CN104385627B - Advanced resin-based composite material with anti-lightning surface function layer, and preparation method thereof - Google Patents
Advanced resin-based composite material with anti-lightning surface function layer, and preparation method thereof Download PDFInfo
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- CN104385627B CN104385627B CN201410542585.XA CN201410542585A CN104385627B CN 104385627 B CN104385627 B CN 104385627B CN 201410542585 A CN201410542585 A CN 201410542585A CN 104385627 B CN104385627 B CN 104385627B
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- 239000000805 composite resin Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 76
- 229920005989 resin Polymers 0.000 claims abstract description 76
- 238000000465 moulding Methods 0.000 claims abstract description 56
- 239000004744 fabric Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000000835 fiber Substances 0.000 claims abstract description 24
- 238000007731 hot pressing Methods 0.000 claims abstract description 11
- 238000007598 dipping method Methods 0.000 claims abstract description 9
- 239000002346 layers by function Substances 0.000 claims description 50
- 239000010410 layer Substances 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 239000012467 final product Substances 0.000 claims description 18
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- 238000003756 stirring Methods 0.000 claims description 16
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 12
- 239000004917 carbon fiber Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 11
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 9
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- 239000000203 mixture Substances 0.000 claims description 7
- 239000002048 multi walled nanotube Substances 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
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- 238000007789 sealing Methods 0.000 claims description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004026 adhesive bonding Methods 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- -1 polyethylene Ketopyrrolidine Polymers 0.000 claims 3
- 150000001721 carbon Chemical class 0.000 claims 1
- 239000002109 single walled nanotube Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 35
- 238000005056 compaction Methods 0.000 abstract description 5
- 230000037237 body shape Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000003822 epoxy resin Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
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- 239000002184 metal Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
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- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
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- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- APTZNLHMIGJTEW-UHFFFAOYSA-N pyraflufen-ethyl Chemical compound C1=C(Cl)C(OCC(=O)OCC)=CC(C=2C(=C(OC(F)F)N(C)N=2)Cl)=C1F APTZNLHMIGJTEW-UHFFFAOYSA-N 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
- B29C70/345—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation using matched moulds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/36—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and impregnating by casting, e.g. vacuum casting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Moulding By Coating Moulds (AREA)
- Reinforced Plastic Materials (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses an advanced resin-based composite material with an anti-lightning surface function layer, and a preparation method thereof. The method comprises the following steps: cutting a prepreg layer by layer according to the requirements of the shape, size and mechanical performances of a composite material structure member, sequentially paving the layers of the cut prepreg in a die, and carrying out pre-compaction molding; paving the pre-compaction molded prepreg with one or more layers of dry fiber fabrics based on the main body shape of the preliminarily formed composite structure member; injecting a prepared function resin system into a sealed die cavity, dipping fiber fabrics in the die cavity, or coating the surface of each of layers of the dry fiber fabrics with the liquid function resin system to preliminarily form a three dimensional conductive function layer; carrying out hot pressing molding on the pre-compaction molded prepreg and the conductive function layer in the die to co-solidify the above two materials in order to realize overall molding; and opening the die to obtain the fiber reinforced resin-based composite material structure member with the anti-lightning surface function layer.
Description
Technical field
The invention belongs to Material Field, particularly to the Advanced Resin-based Composites with anti-lightning surface functional layer and
Preparation method.
Background technology
Advanced Resin-based Composites, compared with traditional material, show many superior at aspects such as performance, design, molding
Characteristic, such as: Advanced Resin-based Composites have excellent static state and dynamic mechanical, its specific strength and specific modulus are
Steel and 3～5 times of even more highs of aluminium alloy, and the fatigue strength of carbon fiber reinforced epoxy resin-based composite may be up to
90% static strength, and the fatigue strength of steel and aluminium alloy only can reach 50% about static strength.Just because of advanced
Composite has excellent mechanical property, such that it is able to significantly mitigate the weight of structural member, such as on aircaft configuration
Can be with loss of weight 25%～30%.The designability of Advanced Resin-based Composites is strong, by select different high-performance fibers and
High performance resin using in addition molding and the regulation and control of suitable Technology, it is possible to obtain various structures and multiple performance advanced
Composite.Increase and decrease various material components by suitable, it is possible to achieve the structure-function integration of composite.Large complicated
Composite material structural member can also be Integratively formed, thus reducing the number of product component and connector.
Based on above characteristic, fiber-reinforced resin matrix compound material is in Aero-Space, automobile, naval vessel and other transport services
In be increasingly widely applied.Especially, in aircaft configuration composite consumption steady growth in 30 years of past,
For example, in Boeing b787 and Air Passenger a350-xwb, the consumption of composite exceedes the 50% of aircraft weight.But it is as being combined
Extensive application on aircaft configuration for the material, the b787 accident taking place frequently in recent years has caused international community to composite safety
With the query of reliability, ignite including the anti-lightning characteristic of composite material structural member, anti-ice hail and impact resistance characteristic, fuel tank lightning
Problem, fire-retardant with resistance cigarette characteristic etc..Here both it had been related to the mechanics problem of composite, further related to its functional characteristic such as conduction
The problems such as heat conduction.
Carbon fibre composite not only assumes anisotropy in terms of mechanical property, and in terms of conduction and heat conduction is also in
Reveal significant anisotropy.Three, space direction (i.e. vertical fibers direction and overlay thickness side along along machine direction, laying
To) thermal resistance and resistance different, have the difference of several orders of magnitude.Generally in laying along carbon fiber direction resistivity
Little, resistivity on overlay thickness direction is maximum, about along machine direction resistivity 103～105Times.Based on compound
Material is conductive on overlay thickness direction, the present situation of heat conductivility difference, and the anti-lightning being badly in need of research and development structure-function integration is combined
Material and its moulding technique.
The method that conventional anti-lightning is damaged is to cover layer of metal net on the composite material structural member surface of aircraft, but
Such a process increases the weight of structural member, deviate from light-weighted design object phase；Metal and resin boundary surface intensity difference, both
Thermal coefficient of expansion mismatch it is easy to lead to the stripping of wire netting；In the complex geometry position of composite material structural member paving
The difficulty covering wire netting is big, and the difficulty of structure-function integration molding is big.
With the constantly improve of nano material rationale, preparation technology and commercial application technology etc., such as silver is received
Rice noodle, CNT and Graphene etc. have the nano material of excellent properties to receive more and more in terms of conductive and heat-conductive
Concern.Wherein, CNT has light weight, big draw ratio, stable chemical property, excellent mechanical property and conductive and heat-conductive
Performance, the advantages of high electric current density can be born, it is a kind of high performance conductive modified nano material.
The nano material such as CNT can be incorporated in polymer matrix composites in the following way at present:
(1) CNT is distributed in the matrix resin of liquid, then prepares fiber using liquid molding technique
Composite.In this molding process, resin and fiber, by impregnating to realize being combined, have mixed carbon nanotube filler
Complicated percolation in multiple dimensioned porous media for the resin and the dipping to fiber, the Chemosensitive area of resin and curing reaction are all
Final composite property is had a significant impact, thus increased the difficulty of liquid molding process planning, complexity and can not
Control factor.Additionally, all adding expensive CNT in whole composite material structural member, material cost is led to substantially to increase
Plus.
(2) by the method for physics or chemistry, CNT is attached to reinforcing fiber bundles or the fabric of dry state
Surface, and then and liquid resin composite molding, or being attached directly to the surface of fiber/resin prepreg, to pass through lamination hotter
Pressure mode is preparing composite.The essential defect of this process is: for the former, conductive and heat-conductive modification only occurs at fibre
On dimension bundle and the interface of surrounding resin or on the interface with surrounding resin for the fabric, between fibre bundle or fabric
Between resin relative to enrichment region it is impossible to improve resin conductive, lead to can not set up on overlay thickness direction and effectively lead
Electric network；For the latter, conductive and heat-conductive modification only occurs on the lamination interface of adjacent two prepreg, and CNT
It is difficult to the resin-rich area entering within every layer of prepreg it is impossible to improve the resin conductive within every layer of prepreg, therefore can not
Effective conductive network is set up on overlay thickness direction.Additionally, in each interlayer region of whole composite material structural member
All add expensive CNT, lead to material cost substantially to increase.
In order to ensure the safety that Advanced Resin-based Composites are applied on the aerospace vehicles such as aircraft, meet with thunder and lightning
Electric current can be guided rapidly in the surface region of the controllable thickness of composite material structural member in the case of impact and not damage
Composite materials property, and can have significant advantage at aspects such as manufacturing cost control, Technology enforcements, invent one
Plant the Advanced Resin-based Composites with anti-lightning surface functional layer and its integral forming technique method.
Content of the invention:
In order to solve the problems, such as above-mentioned Advanced Resin-based Composites lightning damage at low cost, design is a kind of to be carried the present invention
There are carbon fiber enhancement resin base composite material and its integral forming technique method of anti-lightning surface functional layer, this surface functional layer
Achieve the overlap joint of three-dimensional conductive network, can be fast in the surface region of the controllable thickness of composite material structural member by lightning current
Speed guides and not damaged composite material mechanical property.This functional layer can be fitted the surface of complex structural member well simultaneously, keeps away
Exempt from the problems such as wire netting in conventional art is poor with interfacial shear strength, profiling is difficult.
For solving above-mentioned technical problem, the present invention is achieved by the following technical solutions:
The present invention provides a kind of Advanced Resin-based Composites with anti-lightning surface functional layer, makes as follows
Standby:
(1) prepare functional resin: polyvinylpyrrolidonepowder powder is added in liquid resin, constant temperature stirs 1～2h, then plus
Enter conductive modified particle, after constant temperature stirs 2～4h, ultrasonic Treatment 4～6h, obtain final product the functional resin of mix homogeneously；Described poly-
Vinylpyrrolidone and liquid resinous mass ratio are 1～10:1000, described conductive modified particle and liquid resinous mass ratio
For 1～10:1000；
(2) prepreg is successively cut and order is laid in mould, carry out pre-compacted molding in hot press, obtain final product pre-
The prepreg of compaction moulding, as shown in Figure 1；
(3) one layer or several layers of dry state carbon fibre fabric are coated with the prepreg of the pre-compacted molding that step (2) obtains,
Matched moulds；
(4) add firming agent in the functional resin of preparation in step (1), the weight ratio of firming agent and described functional resin
For 3～8:1000；
(5), in the die cavity that the functional resin adding firming agent in step (4) is sealed by injection system injection, fully soak
Stain dry state carbon fiber, obtains final product the fabric after functional resin dipping, and every layer of glue content accounts for the 30～40% of this layer of gross mass；
(6) functional resin that will obtain in the prepreg of pre-compacted molding in step (2) and step (5) in a mold
Fabric after dipping is hot-forming together, makes two sections of material co-curing, realizes global formation；
(7) mold, obtain final product the fiber-reinforced resin matrix compound material with anti-lightning surface functional layer.
In step (1), described constant temperature stirring and ultrasonic processing technique condition are: in water bath with thermostatic control at 60 DEG C～80 DEG C
Mechanical agitation, supersonic frequency is 120khz.
In step (1), described conductive modified particle is single wall or the carbon nanometer of multi-walled carbon nano-tubes, any surface modification
Pipe (for example: nickel-plating carbon nanotube), Graphene, the covalent bond product of nano silver wire, CNT and Graphene.
In step (2), the process conditions carrying out pre-compacted molding in described hot press are in 65 DEG C～85 DEG C of temperature, pressure
Carry out pre-compacted molding 15～30min under 0.1～0.25mpa, obtain the prepreg of pre-compacted molding.
In step (2), the thickness in monolayer of the described prepreg of pre-compacted molding is 0.1～0.2mm.
In step (3), the thickness of described dry state carbon fibre fabric is 0.2～0.4mm, and the dry state carbon described in multilamellar is fine
Dimensional fabric is coated with composition surface functional layer, surface functional layer thickness account for the prepreg gross thickness of described pre-compacted molding 1/8～
1/4.
In step (4), described firming agent is diethylenetriamines.
In step (6), described heat pressing process is first in 65 DEG C～85 DEG C hot pressing 20～40min, then 120 DEG C～
135 DEG C of hot pressing 1h；Pressure is 0.1～0.3mpa.
A kind of preparation method of the Advanced Resin-based Composites with anti-lightning surface functional layer, upper except adopting
Outside injecting glue technology after the matched moulds stated, can also be comprised the steps: using gluing technology before matched moulds
(1) prepare functional resin: polyvinylpyrrolidonepowder powder is added in liquid resin, constant temperature stirs 1～2h, then plus
Enter conductive modified particle, after constant temperature stirs 2～4h, ultrasonic Treatment 4～6h, obtain final product the functional resin of mix homogeneously；Described poly-
Vinylpyrrolidone and liquid resinous mass ratio are 1～10:1000, described conductive modified particle and liquid resinous mass ratio
For 1～10:1000；
(2) prepreg is successively cut and order is laid in mould, carry out pre-compacted molding in hot press, obtain final product pre-
The prepreg of compaction moulding；
(3) add firming agent in the functional resin of preparation in step (1), the weight ratio of firming agent and described functional resin
For 3～8:1000；
(4) one layer or several layers of carbon fibre fabric are coated with the prepreg of the pre-compacted molding that step (2) obtains, close
Mould, hot-press solidifying molding；Prepared by described one layer or several layers of carbon fibre fabric surface-coated step (3) before being coated with
Functional resin；
(5) mold, obtain final product the fiber-reinforced resin matrix compound material with anti-lightning surface functional layer.
Advanced Resin-based Composites integral forming technique method with anti-lightning surface functional layer proposed by the present invention
It is that prepreg is successively cut according to the geomery of composite material structural member and the requirement of mechanical property, order in mould
Lay each layer prepreg having cut, then pre-compacted molding.In the body shape preliminarily forming composite material structural member
On the basis of again one layer or several layers of dry state fabric are coated with the prepreg of pre-compacted molding.By the work(preparing
Can inject in the die cavity of sealing by resin system, the fabric in dipping die cavity, or the fabric surface in every layer of dry state
The functional resin system of coating liquid, preliminarily forms three-dimensional conductive functional layer.In a mold by the preimpregnation of pre-compacted molding
Material is hot-forming together with conductive functional layers, makes two sections of material co-curing, realizes global formation.Finally die sinking obtains with anti-
The fiber-reinforced resin matrix compound material structural member of thunderbolt surface functional layer.
The carbon fiber enhancement resin base composite material that Fig. 2 gives the conductive functional layers modified with nickel-plating carbon nanotube is put down
Plate (a) and the Ultrasonic C-scanning after hitting through same manual simulation lightning current without the modified flat part (b) of function of surface
Figure.From described Ultrasonic C-scanning contrast picture it can be seen that surface functional layer makes the damaged area in composite wood charge level substantially subtract
Little.
Fig. 3 gives the ultrasonic b scanning comparison diagram of (a), (b) plate center cross section.From described ultrasonic b scanning contrast
Picture be it can be seen that surface functional layer can play the effect of good surface diffusing on flat part surface, it is to avoid thunder and lightning flows to
Enter inside flat board, so that the damage on thickness of composite material direction is obviously reduced.
The invention has the advantages that:
1. to be prepared with anti-lightning surface functional layer using liquid molding technique coupling prepreg forming technique
Composite material structural member, is so combined adjustment on original ripe liquid molding process planning, prepreg moulding process
Just can achieve the global formation of structure-function integrated composite, exploitativeness is strong, is not required to newly added equipment and mould, preparation
Low cost.
2. build anti-lightning functional layer in the surface region of the controllable thickness of composite material structural member, be effectively saved valency
The consumption of the expensive conductive modified nano material of lattice, has special advantage in material cost.
3. more it is essential that the three-dimensional conductive heat conduction strengthening that this material and Technology achieve conductive functional layers changes
Property, not only can form current lead-through network in roofing but also on overlay thickness direction, significantly improve composite wood
The anti-lightning effect of material structural member.
Brief description
Fig. 1 is mould and the technical process schematic diagram of the embodiment of the present invention.
Wherein, 1. go up mould, 2. sealing ring, 3. descend mould, 4. the prepreg of pre-compacted molding, 5. glue injection channel, 6. dry
State fabric, 7. carries the composite material structural member of anti-lightning surface functional layer.
Fig. 2 is the carbon fiber enhancement resin base composite material flat part of the conductive functional layers modified with nickel-plating carbon nanotube
(a) and the Ultrasonic C-scanning figure after hitting through same manual simulation lightning current without the modified flat part (b) of function of surface.
Fig. 3 is the carbon fiber enhancement resin base composite material flat part of the conductive functional layers modified with nickel-plating carbon nanotube
(a) and the center cross-sectional after hitting through same manual simulation lightning current without the modified flat part (b) of function of surface
Ultrasonic b scans comparison diagram.
Specific embodiment
1 the present invention will be further elaborated below in conjunction with the accompanying drawings.It should be noted that the description below is merely to solve
Release the present invention, its content is not defined.
Embodiment 1:
(1) in the mono- neck round-bottom flask of the 250ml already equipped with agitator, the dry pvp powder of 0.1g and 100ml are added
Liquid-state epoxy resin, heated and stirred 1h in 60 DEG C of water-bath, add the nickel-plating carbon nanotube that 0.1g is dried, in 60 DEG C of water
In bath, heating is stirred for 2h.Through 120khz ultrasonic Treatment 4h.The epoxy being added with multi-walled carbon nano-tubes being uniformly mixed
Resin.
(2) prepreg is cut into 150mm*100mm size and be successively coated with 29 layers in mould.
Set hot press temperature as 65 DEG C, pressure is 0.1mpa, pre-compacted molding 15min, obtains the pre- of pre-compacted molding
Leaching material.
(3) upper surface in pre-compacted molded body is coated with one layer of a size of 150mm*100mm thickness is the Unidirectional of 0.3mm
Fabric, matched moulds.
In this embodiment, surface functional layer thickness accounts for the 1/8 of gross thickness.
(4) add firming agent diethylenetriamines 5g in the functional resin preparing in step (1), and stir.
(5), in the die cavity that the resin preparing is sealed by injection system injection, it is sufficiently impregnated with dry state carbon fiber.Or
By the functional resin matched moulds again of the carbon fibre fabric surface-coated liquid of dry state before step (3) matched moulds.Every layer of glue content controls
30%.
(6) hot-forming together with conductive functional layers to the prepreg of pre-compacted molding in mould, make two parts material
Material co-curing, realizes global formation.Using heat pressing process be 65 DEG C first hot pressing 20min, then 120 DEG C of hot pressing 1h；Pressure
For 0.1mpa.
(7) die sinking obtains the fiber-reinforced resin matrix compound material structural member with anti-lightning surface functional layer.
Embodiment 2:
(1) in the mono- neck round-bottom flask of the 250ml already equipped with agitator, the dry pvp powder of 0.1g and 100ml are added
Liquid-state epoxy resin, heated and stirred 1h in 70 DEG C of water-bath, add 0.1g nano silver wire, heat again in 70 DEG C of water-bath
Stirring 2h.Through 120khz ultrasonic Treatment 6h.The epoxy resin being added with multi-walled carbon nano-tubes being uniformly mixed.
(2) prepreg is cut into 150mm*100mm size and be successively coated with 29 layers in mould.
Set hot press temperature as 75 DEG C, pressure is 0.15mpa, pre-compacted molding 20min, obtains the pre- of pre-compacted molding
Leaching material.
(3) upper surface in pre-compacted molded body is coated with one layer of a size of 150mm*100mm thickness is the Unidirectional of 0.3mm
Fabric, matched moulds.
In this embodiment, surface functional layer thickness accounts for the 1/8 of gross thickness.
(4) add firming agent diethylenetriamines 5g in the functional resin preparing in step (1), and stir.
(5), in the die cavity that the resin preparing is sealed by injection system injection, it is sufficiently impregnated with dry state carbon fiber.Or
By the functional resin matched moulds again of the carbon fibre fabric surface-coated liquid of dry state before step (3) matched moulds.Every layer of glue content controls
30%.
(6) hot-forming together with conductive functional layers to the prepreg of pre-compacted molding in mould, make two parts material
Material co-curing, realizes global formation.Using heat pressing process be 70 DEG C first hot pressing 30min, then 125 DEG C of hot pressing 1h；Pressure
For 0.2mpa.
(7) die sinking obtains the fiber-reinforced resin matrix compound material structural member with anti-lightning surface functional layer.
Embodiment 3:
(1) in the mono- neck round-bottom flask of the 250ml already equipped with agitator, the dry pvp powder of 0.1g and 100ml are added
Liquid-state epoxy resin, heated and stirred 2h in 80 DEG C of water-bath, add 0.1g multi-walled carbon nano-tubes, add in 80 DEG C of water-bath
Heat is stirred for 4h.Through 120khz ultrasonic Treatment 6h.The epoxy resin being added with multi-walled carbon nano-tubes being uniformly mixed.
(2) prepreg is cut into 150mm*100mm size and be successively coated with 29 layers in mould.
Set hot press temperature as 85 DEG C, pressure is 0.25mpa, pre-compacted molding 30min, obtains the pre- of pre-compacted molding
Leaching material.
(3) upper surface in pre-compacted molded body is coated with one layer of a size of 150mm*100mm thickness is the Unidirectional of 0.3mm
Fabric, matched moulds.
In this embodiment, surface functional layer thickness accounts for the 1/8 of gross thickness.
(4) add firming agent diethylenetriamines 5g in the functional resin preparing in step (1), and stir.
(5), in the die cavity that the resin preparing is sealed by injection system injection, it is sufficiently impregnated with dry state carbon fiber.Or
By the functional resin matched moulds again of the carbon fibre fabric surface-coated liquid of dry state before step (3) matched moulds.Every layer of glue content controls
30%.
(6) hot-forming together with conductive functional layers to the prepreg of pre-compacted molding in mould, make two parts material
Material co-curing, realizes global formation.Using heat pressing process be 85 DEG C first hot pressing 40min, then 135 DEG C of hot pressing 1h；Pressure
For 0.3mpa.
(7) die sinking obtains the fiber-reinforced resin matrix compound material structural member with anti-lightning surface functional layer.
Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not model is protected to the present invention
The restriction enclosed, one of ordinary skill in the art should be understood that on the basis of technical scheme, and those skilled in the art are not
Need to pay the various modifications that creative work can make or deformation still within protection scope of the present invention.
Claims (11)
1. a kind of Advanced Resin-based Composites with anti-lightning surface functional layer are it is characterised in that prepare as follows:
(1) prepare functional resin: polyvinylpyrrolidonepowder powder is added in liquid resin, constant temperature stirs 1～2h, adds and leads
Electric modified particle, after constant temperature stirs 2～4h, ultrasonic Treatment 4～6h, obtain final product the functional resin of mix homogeneously；Described polyethylene
Ketopyrrolidine and liquid resinous mass ratio are 1～10:1000, and described conductive modified particle and liquid resinous mass ratio are 1
～10:1000；
(2) prepreg is successively cut and order is laid in mould, carry out pre-compacted molding in hot press, obtain final product pre-compacted
The prepreg of molding；
(3) one layer or several layers of dry state carbon fibre fabric are coated with the prepreg of the pre-compacted molding that step (2) obtains, close
Mould；
(4) add firming agent in the functional resin of preparation in step (1), the weight of firming agent and described functional resin ratio is for 3
～8:1000；
(5), in the die cavity sealing the functional resin adding firming agent in step (4) by injection system injection, it is sufficiently impregnated with doing
State carbon fiber, obtains final product the fabric after functional resin dipping, and every layer of glue content accounts for the 30～40% of this layer of gross mass；
(6) in a mold by the functional resin obtaining in the prepreg of pre-compacted molding in step (2) and step (5) dipping
Fabric afterwards is hot-forming together, makes two sections of material co-curing, realizes global formation；
(7) mold, obtain final product the fiber-reinforced resin matrix compound material with anti-lightning surface functional layer.
2. a kind of preparation method of the Advanced Resin-based Composites with anti-lightning surface functional layer is it is characterised in that include
Following steps:
(1) prepare functional resin: polyvinylpyrrolidonepowder powder is added in liquid resin, constant temperature stirs 1～2h, adds and leads
Electric modified particle, after constant temperature stirs 2～4h, ultrasonic Treatment 4～6h, obtain final product the functional resin of mix homogeneously；Described polyethylene
Ketopyrrolidine and liquid resinous mass ratio are 1～10:1000, and described conductive modified particle and liquid resinous mass ratio are 1
～10:1000；
(2) prepreg is successively cut and order is laid in mould, carry out pre-compacted molding in hot press, obtain final product pre-compacted
The prepreg of molding；
(3) one layer or several layers of dry state carbon fibre fabric are coated with the prepreg of the pre-compacted molding that step (2) obtains, close
Mould；
(4) adding percentage by weight in the functional resin of preparation in step (1) is 0.3～0.8% firming agent；
(5), in the die cavity sealing the functional resin adding firming agent in step (4) by injection system injection, it is sufficiently impregnated with doing
State carbon fiber, obtains final product the fabric after functional resin dipping, and every layer of glue content accounts for the 30～40% of this layer of gross mass；
(6) in a mold by the functional resin obtaining in the prepreg of pre-compacted molding in step (2) and step (5) dipping
Fabric afterwards is hot-forming together, makes two sections of material co-curing, realizes global formation；
(7) mold, obtain final product the fiber-reinforced resin matrix compound material with anti-lightning surface functional layer.
3. carry the preparation method of the Advanced Resin-based Composites of anti-lightning surface functional layer as claimed in claim 2, its
It is characterised by, in step (1), described constant temperature stirring and ultrasonic processing technique condition are: water bath with thermostatic control at 60 DEG C～80 DEG C
Middle mechanical agitation, supersonic frequency is 120khz.
4. carry the preparation method of the Advanced Resin-based Composites of anti-lightning surface functional layer as claimed in claim 2, its
It is characterised by, in step (1), described conductive modified particle is single wall or multi-walled carbon nano-tubes or the modified carbon of any surface is received
The covalent bond product of mitron, Graphene, nano silver wire, CNT and Graphene.
5. carry the preparation method of the Advanced Resin-based Composites of anti-lightning surface functional layer as claimed in claim 2, its
It is characterised by, in step (1), described conductive modified particle is nickel-plating carbon nanotube.
6. carry the preparation method of the Advanced Resin-based Composites of anti-lightning surface functional layer as claimed in claim 2, its
It is characterised by, in step (2), the process conditions carrying out pre-compacted molding in described hot press are in 65 DEG C～85 DEG C of temperature, pressure
Carry out pre-compacted molding 15～30min under power 0.1～0.25mpa, obtain the prepreg of pre-compacted molding.
7. carry the preparation method of the Advanced Resin-based Composites of anti-lightning surface functional layer as claimed in claim 2, its
It is characterised by, in step (2), the thickness in monolayer of the described prepreg of pre-compacted molding is 0.1～0.2mm.
8. carry the preparation method of the Advanced Resin-based Composites of anti-lightning surface functional layer as claimed in claim 2, its
It is characterised by, in step (3), the thickness of described dry state carbon fibre fabric is 0.2～0.4mm, the dry state carbon described in multilamellar
Fabric is coated with composition surface functional layer, and surface functional layer thickness accounts for the 1/8 of the prepreg gross thickness of described pre-compacted molding
～1/4.
9. carry the preparation method of the Advanced Resin-based Composites of anti-lightning surface functional layer as claimed in claim 2, its
It is characterised by, in step (4), described firming agent is diethylenetriamines.
10. carry the preparation method of the Advanced Resin-based Composites of anti-lightning surface functional layer as claimed in claim 2, its
It is characterised by, in step (6), described heat pressing process is first in 65 DEG C～85 DEG C hot pressing 20～40min, then 120 DEG C～
135 DEG C of hot pressing 1h；Pressure is 0.1～0.3mpa.
A kind of 11. preparation methoies of the Advanced Resin-based Composites with anti-lightning surface functional layer are it is characterised in that adopt
Gluing technology before matched moulds, comprises the steps:
(1) prepare functional resin: polyvinylpyrrolidonepowder powder is added in liquid resin, constant temperature stirs 1～2h, adds and leads
Electric modified particle, after constant temperature stirs 2～4h, ultrasonic Treatment 4～6h, obtain final product the functional resin of mix homogeneously；Described polyethylene
Ketopyrrolidine and liquid resinous mass ratio are 1～10:1000, and described conductive modified particle and liquid resinous mass ratio are 1
～10:1000；
(2) prepreg is successively cut and order is laid in mould, carry out pre-compacted molding in hot press, obtain final product pre-compacted
The prepreg of molding；
(3) add firming agent in the functional resin of preparation in step (1), the weight of firming agent and described functional resin ratio is for 3
～8:1000；
(4) one layer or several layers of carbon fibre fabric, matched moulds, heat are coated with the prepreg of the pre-compacted molding that step (2) obtains
Cured molding；The described one layer or several layers of carbon fibre fabric function that before being coated with prepared by surface-coated step (3)
Resin；
(5) mold, obtain final product the fiber-reinforced resin matrix compound material with anti-lightning surface functional layer.
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| CN105086363B (en) * | 2015-07-31 | 2017-12-19 | 山东大学 | The function modified method of composite based on co-curing and Polymerization induced phase separation |
| CN106404065B (en) * | 2016-10-09 | 2019-05-07 | 山东大学 | A kind of fiber-optic grating sensor and its manufacturing method of composite material encapsulation |
| CN106976281B (en) * | 2017-03-21 | 2020-01-21 | 安徽四创电子股份有限公司 | Carbon fiber composite material, preparation method thereof and radar antenna using same |
| CN107141726A (en) * | 2017-06-23 | 2017-09-08 | 北京吉泰亿阳科技有限公司 | Graphene conductive polymer composite, its preparation method and Electric radiant Heating Film therefrom |
| CN109968688B (en) * | 2017-12-27 | 2020-11-24 | 中国科学院宁波材料技术与工程研究所 | Fiber hot-pressing deformable mold |
| CN108381940A (en) * | 2018-02-09 | 2018-08-10 | 西安天运新材料科技有限公司 | A kind of the preparation tooling and method of high mould Pitch-Based Graphite Fibers reinforced resin based composites |
| KR20200135938A (en) * | 2018-03-30 | 2020-12-04 | 도레이 카부시키가이샤 | Manufacturing method of press-formed products |
| CN109466098B (en) * | 2018-07-17 | 2021-09-21 | 广州市勇源冰雪运动用品有限公司 | Shoe body forming method and shoe body |
| CN109676956A (en) * | 2018-11-21 | 2019-04-26 | 哈尔滨飞机工业集团有限责任公司 | A kind of composite flexible beam pressure control forming method |
| CN110077011A (en) * | 2019-05-28 | 2019-08-02 | 天津中天腾世科技有限公司 | A kind of transferable prepreg shell mould tire, mold system and its application method |
| CN110539895B (en) * | 2019-07-26 | 2022-08-30 | 国营芜湖机械厂 | Method for repairing damage of aluminum-sprayed layer on outer surface of composite structure of airplane |
| CN111634023A (en) * | 2020-05-19 | 2020-09-08 | 北京航空航天大学 | Forming method of foldable fiber reinforced resin matrix composite pipe |
| CN113021948B (en) * | 2021-04-09 | 2023-02-03 | 北方长龙新材料技术股份有限公司 | Forming tool and process for continuous fiber reinforced resin matrix composite gear parts |
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| CN101864148A (en) * | 2010-07-13 | 2010-10-20 | 哈尔滨工业大学 | Method for modifying epoxy resins and method for preparing carbon fiber composite by applying modified epoxy resins |
| CN102350800A (en) * | 2011-07-20 | 2012-02-15 | 江苏兆鋆新材料科技有限公司 | HP-RTM technology based method for molding automobile surface external decorative parts |
| US20140212624A1 (en) * | 2011-09-04 | 2014-07-31 | Honda Motor Co., Ltd. | Fiber-reinforced resin member and method for manufacturing fiber-reinforced resin member |
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