CN107880494A - A kind of carbon fibre initial rinse fabric and preparation method thereof and metal fiber composite - Google Patents
A kind of carbon fibre initial rinse fabric and preparation method thereof and metal fiber composite Download PDFInfo
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- CN107880494A CN107880494A CN201610870696.2A CN201610870696A CN107880494A CN 107880494 A CN107880494 A CN 107880494A CN 201610870696 A CN201610870696 A CN 201610870696A CN 107880494 A CN107880494 A CN 107880494A
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- 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
- C08L63/10—Epoxy resins modified by unsaturated compounds
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary 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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/04—Electrophoretic coating characterised by the process with organic material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
- C25D13/16—Wires; Strips; Foils
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention provides a kind of carbon fibre initial rinse fabric, the prepreg cloth includes carbon fiber and the electrophoresis resin layer for being attached to carbon fiber surface and the thermoplastic resin layer for wrapping up the Carbon fibe and the electrophoresis resin layer.The preimpregnation effect of the carbon fibre initial rinse fabric of the present invention is good.
Description
Technical field
The invention belongs to field of compound material, more particularly it relates to a kind of carbon fibre initial rinse fabric and its preparation side
Method and metal fiber composite.
Background technology
The excellent processability of the existing aluminium alloy of Fiber Reinforced Metal Laminates and the height of impact resistance and fibre reinforced composites
Intensity and fatigue-resistance characteristics, also overcome aluminum alloy materials fatigue strength is low and fibre reinforced composites ductility plus
The shortcomings that work is poor, and impact strength is low and cost is high, it is a kind of new structural material.
Fiber Reinforced Metal Laminates are by high duty metal（Aluminium alloy, titanium alloy）Thin layer and reinforcing fiber layer are alternately laid,
A kind of interply hybrid composites structure that certain curing process is formed.The main preparation methods metallic plate of Fiber Reinforced Metal Laminates
It is laminated to be formed with Fiber prepreg.The preparation method of Fiber prepreg mainly includes melting preimpregnation and reaction preimpregnation.Wherein melt
Preimpregnation is directly by molten resin by pretreated fiber cloth, or molten resin is directly coated on into fiber cloth surface, or
Resin is made after film and is affixed on fiber cloth surface, is made by pressurization and/or heating in resin infiltrated fiber；It is by thermoplastic to react dipping
Property resin monomer or oligomer heating melting, add catalyst formed blend melt after be sprayed at silvalin belt surface, make it
Silvalin band is sufficiently impregnated, then silvalin band heats up, makes the monomer or oligomer initiated polymerization of thermoplastic resin.It is molten
The major defect for melting preimpregnation is that dipping effect is limited, and viscosity is larger after being primarily due to thermoplastic resin melting, it is difficult to is entered fine
Tie up gap；On the other hand, the compatibility of resin and fiber is poor；Reaction dipping is due to fine using monomer or oligomer melt impregnation
High polymer is aggregated into after dimension again, effect of impregnation is preferable, but because subsequently to ensure polymerization effect, it is desirable to condition is harsh, gathers simultaneously
In compound easily residual small molecule, stomata it is bad.
The content of the invention
It is contemplated that above-mentioned problem is directed to, so as to provide a kind of resin and the good carbon fiber of fiber prepreg effect
Prepreg cloth and preparation method thereof and metal fiber composite.
The first aspect of the present invention provides a kind of carbon fibre initial rinse fabric, and the prepreg cloth includes carbon fiber and is attached to carbon
The electrophoresis resin layer of fiber surface and the thermoplastic resin layer for wrapping up the Carbon fibe and the electrophoresis resin layer.The present invention's
The preimpregnation effect of carbon fibre initial rinse fabric is good.
Second aspect of the present invention provides the preparation method of carbon fibre initial rinse fabric, the described method comprises the following steps：
S1, using carbon fiber as negative pole electrophoresis is carried out in electrophoresis liquid；
S2, by thermoplastic resin powder and by step S1 processing after carbon fiber carry out it is hot-forming；
In the preparation method of the carbon fibre initial rinse fabric of the present invention, electrophoresis liquid used contains underfill resin layer and solvent, and controls electricity
The electro kinetic potential of underfill resin layer is -40 ~ -10mV in swimming liquid, can cover one layer of underfill resin layer in fiber surface, and reach good
Coating effect, while underfill resin layer is not only and fiber has good combination, and has good phase with thermoplastic resin powder
Capacitive, so that resin has good effect of impregnation with fiber.
Third aspect present invention provides a kind of carbon fibre initial rinse fabric being prepared by preparation method described above.
Fourth aspect present invention provides a kind of metal fiber composite, and the metal fiber composite is included successively
The metal level and fibrous layer of stacking, wherein, the fibrous layer is to be formed by carbon fibre initial rinse fabric of the present invention by hot pressing.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Fig. 1 is the structural representation of the carbon fibre initial rinse fabric of one embodiment of the present invention.
Embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only explaining
The present invention, it is not intended to limit the present invention.
As shown in figure 1, the invention provides a kind of carbon fibre initial rinse fabric, the prepreg cloth includes carbon fiber 1 and is attached to
The electrophoresis resin layer 2 of carbon fiber surface and the thermoplastic resin layer 3 for wrapping up the Carbon fibe and the electrophoresis resin layer.
According to carbon fibre initial rinse fabric provided by the present invention, resin used is acrylic acid tree in the electrophoresis resin layer
Fat, epoxy resin, or at least one of thermoplastic resin handled through peroxidating, sulfonation or radiation grafting.Bottom tree
It is thermoplastic resin used in lipid layer, including but not limited to polystyrene, polyformaldehyde, polyphenylene sulfide, makrolon, polyamide, poly-
Acid imide, polyether-ether-ketone.
The surface for the resin for handling to obtain by the above method can produce ion, reaction or/and Compatibilizing groups, these from
Son, reaction or/and Compatibilizing groups can make the resin particle surfaces of no ion matrix produce ionic group progress electrophoresis.And propylene
Just contain these ions, reaction or/and Compatibilizing groups in acid resin and epoxy resin this body structure.
In the present invention, in order to further improve the effect of electrophoresis, it is preferable that resin used in the electrophoresis resin layer
Mean molecule quantity is 1000-20000.
According to carbon fibre initial rinse fabric provided by the present invention, in order to further improve the mechanical property of electrophoresis resin layer and carry
High voltage electrophoresis effect, it is preferable that affiliated resin bed contains nano-particle, and the nano-particle is CNT, metal oxide, stone
Black alkene, at least one of nano-calcium carbonate and nano silicon.
According to carbon fibre initial rinse fabric provided by the present invention, the thermoplastic resin layer is polystyrene resin layer, poly- first
Urea formaldehyde layer, polyphenylene sulfide resin lipid layer, polycarbonate resin, polyamide resin layer, polyimide resin layer and polyether-ether-ketone
At least one of resin bed.
According to carbon fibre initial rinse fabric provided by the present invention, in order that the mechanical property of obtained prepreg cloth is more preferable, preferably
Ground, on the basis of the gross weight of the prepreg cloth, the content of the electrophoresis resin layer is 1-5wt%, and the thermoplastic resin contains
Measure as 30-40wt%.
Present invention also offers a kind of preparation method of carbon fibre initial rinse fabric, the described method comprises the following steps：
S1, using carbon fiber as anode electrophoresis is carried out in electrophoresis liquid；
S2, by thermoplastic resin powder and by step S1 processing after carbon fiber carry out it is hot-forming；
The electrophoresis liquid contains underfill resin layer and solvent, and the electro kinetic potential of underfill resin layer is -40 ~ -10mV in the electrophoresis liquid.
In the present invention, inventor is drawn by substantial amounts of experiment, and in electrophoresis, the electro kinetic potential of underfill resin layer is imitated to electrophoresis
Fruit has a great influence, if electro kinetic potential is less than -40mV, the speed of electrophoretic coating is too fast, can make the uneven of fiber surface coat film
Densification, if current potential is higher than in -10mV, underfill resin layer is promoted to move without enough power, so as to reach the purpose of electrophoresis.This
The electro kinetic potential that underfill resin layer in electrophoresis liquid is controlled in invention is -40 ~ -10mV, can cover one layer of coating effect in fiber surface
The good underfill resin layer of fruit, while underfill resin layer is not only and fiber has good combination, and have with thermoplastic resin powder good
Good compatibility, so that resin has good effect of impregnation with fiber.
According to preparation method provided by the present invention, in order to allow underfill resin layer to be preferably deposited on the surface of carbon fiber, together
When do not influence the motion of underfill resin layer in a solvent, it is preferable that on the basis of the gross weight of the electrophoresis liquid, in the electrophoresis liquid
The weight content of underfill resin layer is 30-50wt%.
In the present invention, the positive pole used in the electrophoresis has no particular limits, and can be positive electrode commonly used in the art,
Such as carbon-point or stainless steel.
In the present invention, the solvent has no particular limits, as long as the underfill resin layer can be dissolved, such as can be
Water or ethanol etc..
According to preparation method provided by the present invention, in electrophoresis, a small amount of solvent or small can be deposited on the surface of carbon fiber
Molecular substance, and these materials can be converted into gas in hot pressing, produce stomata or bubble, influence the performance of prepreg cloth, this hair
In bright, it is preferable that first carbon fiber is dried after electrophoresis, removes solvent and small-molecule substance；In order to faster and better
Energy consumption is saved while removing solvent and small-molecule substance, it is highly preferred that the condition of the drying is：It is true in 60-120 DEG C take out
Sky dries 30-60min.
According to preparation method provided by the present invention, one layer of epoxy family macromolecule is all contained on general commercially available fiber cloth surface
Coating, and the polymeric coating layer of the epoxies can influence the deposition of the resin of follow-up electrophoresis, generally require and be removed；It is simultaneously
The combination of the resin of increase carbon fiber surface and electrophoretic deposition, use to carbon fiber progress coupling processing to increase in the present invention
The group that carbon fibre surface energy is combined with electrophoresis resin；Preferably, locate before being carried out before the step S1 to the carbon fiber
Reason, the pre-treatment include organic solvent cleaning and degumming and coupling agent treatment.
According to preparation method provided by the present invention, the underfill resin layer has no particular limits, and can be that this area is normal
Various resins, in order to increase underfill resin layer and carbon fiber and the adhesion of thermoplastic resin powder, it is preferable that the bottom
Resin is acrylic acid, epoxy resin, or at least one in the thermoplastic resin handled through peroxidating, sulfonation or radiation grafting
Kind.The thermoplastic resin of the underfill resin layer includes but is not limited to polystyrene, polyformaldehyde, polyphenylene sulfide, makrolon, poly-
Acid amides, polyimides, polyether-ether-ketone.
The surface for the resin for handling to obtain by the above method can produce ion, reaction or/and Compatibilizing groups, these from
Son, reaction or/and Compatibilizing groups can make the resin particle surfaces of no ion matrix produce ionic group progress electrophoresis.And propylene
Just contain these ions, reaction or/and Compatibilizing groups in acid resin and epoxy resin this body structure.
In the present invention, the oxidation refers to：Using oxidant such as oxygen, ozone, potassium permanganate, concentrated nitric acid, concentrated sulfuric acid etc.
Resin is handled, the radical oxidations such as the part methyl in resin is converted into ionic group.
In the present invention, the sulfonation refers to：Using dense sulfuric acid treatment resin, make to produce sulfonate group in resin.
In the present invention, the radiation grafting refers to：Resin ion is subjected to plasma resonance, produces activated centre, then
It is graft-polymerized with small molecules such as acrylic acid, epoxies.
According to preparation method provided by the present invention, the thermoplastic resin powder has no particular limits, and can be this
The conventional various thermoplastic resin powders in field, it is preferable that the thermoplastic resin powder is Polystyrene powder, polyformaldehyde powder
One kind in end, pps powder, polycarbonate powder, polyamide powder, polyimide powder and polyether-ether-ketone powder.Institute
The mean molecule quantity for stating thermoplastic resin powder is 5000-50000.It is highly preferred that in order to further improve underfill resin layer and heat
The adhesion of plastic resin powder, the thermoplastic resin powder and the underfill resin layer are similar resin.The similar resin
It is the low-molecular-weight resin consistent with thermoplastic resin powder's backbone structure to refer to underfill resin layer.
According to preparation method provided by the present invention, in order that the gap increase knot that thermoplastic resin is immersed between carbon fiber
The angle being easy to get with joint efforts and from raw material, it is preferable that the D50 of the thermoplastic resin powder is 5-20 microns.
According to preparation method provided by the present invention, in order to further improve the performance of electrophoresis liquid, it is preferable that the electrophoresis
Also include at least one of surfactant, dispersant, defoamer and pH adjusting agent etc. in liquid.The surfactant, divide
Powder, defoamer have no particular limits, and can be various surfactants commonly used in the art, dispersant, defoamer.Such as table
Face activating agent is stearic acid, neopelex, fatty acid glycerine acid esters etc.；Dispersant can be alkylphenol-polyethenoxy
Ether（Such as OP-10, TX-19）, vinyl bis-stearamides, glyceryl monostearate etc.；Defoamer can be tributyl phosphate, two
Methylsiloxane, polypropylene ethylene oxide glycerin ether etc..
In the present invention, in order to ensure that the electro kinetic potential of underfill resin layer ion carries out electrophoresis, and prevent resin particle from reuniting, it is excellent
Selection of land, the pH of the electrophoresis liquid is 6-9.
According to preparation method provided by the present invention, the condition of the electrophoresis has no particular limits, as long as can be by institute
State underfill resin layer and be deposited on carbon fiber surface, in of the invention, the condition of the electrophoresis is：Voltage is 60-80V, and the time is
10-30min, temperature are 30-80 DEG C.
According to preparation method provided by the present invention, the condition of the hot pressing has no particular limits, as long as can be by carbon
Fiber combines well with thermoplastic resin powder, and the condition of such as described hot pressing is：Temperature is 280-380 DEG C, and pressure is
15-35MPa。
In the present invention, thermoplastic resin powder and the carbon fiber after step S1 processing are subjected to heat in the step S2
Molded specific method is the both sides for the carbon fiber that thermoplastic resin powder is placed in after step S1 processing, to carry out double
Rod hot pressing, temperature set 280-330 DEG C, preferably 300-310 DEG C, reach expected tree by adjusting roller gap and hot pressing number
Fat content, cut after being cooled down after the completion of hot pressing and obtain prepreg.
Present invention also offers the carbon fibre initial rinse fabric that a kind of preparation method described above is prepared.
Present invention also offers a kind of metal fiber composite, the metal fiber composite includes what is stacked gradually
Metal level and fibrous layer, wherein, the fibrous layer is to be formed by carbon fibre initial rinse fabric of the present invention by hot pressing.
According to metal fiber composite provided by the present invention, it is preferable that the metal level is selected from aluminium alloy plate, titanium closes
One kind in golden plate and steel plate；The thickness of the metal level is 0.1-3mm.
In the present invention, by that in one layer of underfill resin layer of carbon fiber surface elder generation electrophoretic deposition, underfill resin layer can be made uniform
There is good adhesion coated in carbon fiber surface, and with carbon fiber.Then thermoplastic resin is wrapped up again on underfill resin layer layer
Fat, underfill resin layer can have good compatibility with thermoplastic resin, so that resin has good effect of impregnation with fiber.
The present invention is described in further detail below by specific embodiment.
The method of testing of the electro kinetic potential of electrophoresis liquid：With Zeta potential tester（Malvern company, model Zetasizer
nanozs-90）Test the electro kinetic potential of electrophoresis liquid.Specifically method of testing is：Take the electrophoresis liquid configured appropriate（2ml）It is placed in glass
In glass measuring cell, tester is put into, accesses electrode, opens runs software afterwards, selects Zeta potential test item to measure.
Embodiment 1
1st, electrophoresis liquid is configured
By 3 parts of defoamer tributyl phosphate, 100 parts of 6 parts of dispersant OP-10 and water are added in electrolytic cell, and device height is whisked with machinery
After 6 min of speed stirring, epoxy acrylic resin E-20 is added in high-speed stirred（Molecular weight 1000）50 parts, continue after adding
15min is stirred, ability cathode electrophoresis liquid A1 is made（Electrophoresis liquid A1 electro kinetic potential is -21mV）；
2nd, surface treatment of carbon fibers
Carbon cloth is soaked to 10min in acetone and carries out degumming process, deionized water is cleared up afterwards, then using silane coupler
KH-550 processing, dry the carbon fiber B1 after being handled；
3rd, electrophoretic deposition
Using carbon fiber B1 as anode, stainless steel is negative electrode, and electrophoresis, electrophoretic voltage 72V, sedimentation time are carried out in electrophoresis liquid A1
15min, temperature are 50 DEG C, then obtain products C 1；
4th, dry
C1 is dried into 50min in drying box in 80 DEG C vacuumize, until the small molecule volatilization such as solvent is complete, obtains product D1；
5th, hot pressing
Using thermoplastic resin PPS powder（D50 is 8 μm, molecular weight 8000）, D1 sides are first set into PPS powder, afterwards by double
Roller carries out hot pressing, afterwards manual reverse side or by twist rollers, overleaf lays PPS powder, hot pressing, hot pressing are carried out again by double roller
Temperature is 310 DEG C, and pressure is adjusted to 20MPa by adjusting roller gap, and roller linear velocity is 10mm/s, adjusts hot pressing number
Reach expected resin content（35%-40%）, cut after being cooled down after the completion of hot pressing and obtain prepreg cloth P1.
Embodiment 2
Method according to embodiment 1 prepares prepreg cloth P2, and difference is：
Configure electrophoresis liquid：
By 3 parts of defoamer tributyl phosphate, 100 parts of 6 parts of dispersant OP-10 and water are added in electrolytic cell, and device height is whisked with machinery
After 6 min of speed stirring, epoxy acrylic resin E-20 is added in high-speed stirred（Molecular weight 1000）50 parts, continue after adding
15min is stirred, adds nano silicon（8 μm of diameter）10 parts, continue to stir 20min under 50KHz ultrasonications, the moon is made
Pole electrophoresis liquid A2（Electrophoresis liquid A2 electro kinetic potential is -28mV）.
Embodiment 3
Method according to embodiment 1 prepares prepreg cloth P3, and difference is：
Configure electrophoresis liquid：By PPS powder（D50 is 10 μm, molecular weight 8000）40 parts, 100 parts of ethanol, 3 parts of triethylamine, lemon
8 parts of acid, is formulated as suspension, using HCl and NaOH conditions its pH to 7.5, is placed in ultrasound and disperses 30-50min, electrophoresis is made
Liquid A3（Electrophoresis liquid A3 electro kinetic potential is -18mV）.
Embodiment 4
Method according to embodiment 1 prepares prepreg cloth P4, and difference is：
Configure electrophoresis liquid：PPS powder (D50 is 5 μm, molecular weight 8000) is placed in 30min in the concentrated sulfuric acid, it is anti-to carry out sulfonation
Should, first cleaned afterwards with dichloroethanes, then cleaned with deionized water；By CNT（External diameter 20-30nm, length 3-5 μ
m）It is placed in the concentrated sulfuric acid, 30min is reacted under 50KHz ultrasonications, and just have deionized water cleaning under above ultrasonication；
Above-mentioned 40 parts treated of PPS powder, 100 parts of ethanol, 3 parts of triethylamine, 8 parts of citric acid, CNT 4 are used afterwards
Part, suspension is formulated as, using HCl and NaOH conditions its pH to 9, is placed in ultrasound and disperses 30min, electrophoresis liquid A4 is made（Electricity
Swimming liquid A4 electro kinetic potential is -25mV）.
Embodiment 5
Method according to embodiment 1 prepares prepreg cloth P5, and difference is：
Configure electrophoresis liquid：PP powder (D50 be 10 μm, molecular weight 15000) is placed in 140 DEG C, in the electrocaloric effect of air atmosphere
2H is stood, oxidation reaction is carried out, afterwards using above-mentioned 40 parts treated of PP powder, 100 parts of ethanol, 3 parts of triethylamine, citric acid
8 parts, suspension is formulated as, using HCl and NaOH conditions its pH to 9, is placed in ultrasound and disperses 30min, electrophoresis liquid A5 is made（Electricity
Swimming liquid A5 electro kinetic potential is -19mV）.
Embodiment 6
Method according to embodiment 1 prepares prepreg cloth P6, and difference is：
PPS powder (8 μm of D50 positions, molecular weight 8000) is carried out at room temperature in air atmosphere60Co radiation treatments, irradiate agent
Measure as 30kGy, radiated time 20min, take 10 parts of PPS powder after radiation treatment afterwards, add 10 parts of acrylic acid, 100 parts
Distilled water, it is graft-polymerized under nitrogen protection, temperature is 80 DEG C, polymerization time 30min, is filtered after the completion of polymerization,
Using above-mentioned 50 parts treated of PPS powder, 100 parts of ethanol, 3 parts of triethylamine, 8 parts of citric acid, suspension is formulated as, used
HCl and NaOH conditions its pH to 9, be placed in ultrasound and disperse 30min, be made electrophoresis liquid A6 (electrophoresis liquid A6 electro kinetic potential for-
22mV)。
Embodiment 7
Prepreg cloth A7 is prepared in the way of embodiment 1, difference is：There is no step 2, surface treatment of carbon fibers.
Embodiment 8
Method according to embodiment 1 prepares prepreg cloth A8, and difference is：There is no step 4, dry.
Embodiment 9
1st, electrophoresis liquid is configured
By 3 parts of defoamer tributyl phosphate, 100 parts of 6 parts of dispersant OP-10 and water are added in electrolytic cell, and device height is whisked with machinery
After 6 min of speed stirring, epoxy resin E-21 is added in high-speed stirred（Molecular weight 1000）50 parts, continue to stir after adding
15min, ability cathode electrophoresis liquid A9 is made（Electrophoresis liquid A9 eletrokinetic potential is -22mV）；
2nd, surface treatment of carbon fibers
Carbon cloth is soaked to 10min in acetone and carries out degumming process, deionized water is cleared up afterwards, then using silane coupler
KH-550 processing, dry the carbon fiber B9 after being handled；
3rd, electrophoretic deposition
Using carbon fiber B9 as negative electrode, stainless steel is anode, and electrophoresis, electrophoretic voltage 60V, sedimentation time are carried out in electrophoresis liquid A9
30min, temperature are 80 DEG C, then obtain products C 9；
4th, dry
C9 is dried into 60min in drying box in 60 DEG C vacuumize, until the small molecule volatilization such as solvent is complete, obtains product D9；
5th, hot pressing
Using the powder of thermoplastics PA 6（D50 is 8 μm, molecular weight 16000）, D9 sides are first set into PPS powder, passed through afterwards
Double roller carries out hot pressing, afterwards manual reverse side or by twist rollers, overleaf lays PPS powder, hot pressing, heat are carried out again by double roller
It is 260 DEG C to press temperature, and pressure is adjusted to 35MPa by adjusting roller gap, and roller linear velocity is 10mm/s, regulation hot pressing time
Number reaches expected resin content（35%-40%）, cut after being cooled down after the completion of hot pressing and obtain prepreg cloth P9.
Embodiment 10
1st, electrophoresis liquid is configured
PPS powder (8 μm of D50 positions, molecular weight 8000) is carried out at room temperature in air atmosphere60Co radiation treatments, irradiate agent
Measure as 30kGy, radiated time 20min, take 10 parts of PPS powder after radiation treatment afterwards, add 10 parts of acrylic acid, 100 parts
Distilled water, it is graft-polymerized under nitrogen protection, temperature is 80 DEG C, polymerization time 30min, is filtered after the completion of polymerization,
Using above-mentioned 50 parts treated of PPS powder, 100 parts of ethanol, 3 parts of triethylamine, 8 parts of citric acid, 4 parts of CNT, it is formulated as
Suspension, using HCl and NaOH conditions its pH to 9, it is placed in ultrasound and disperses 30min, obtained electrophoresis liquid A6 is (electrophoresis liquid A10's
Electro kinetic potential is -30mV).
2nd, surface treatment of carbon fibers
Carbon cloth is soaked to 10min in acetone and carries out degumming process, deionized water is cleared up afterwards, then using silane coupler
KH-550 processing, dry the carbon fiber B10 after being handled；
3rd, electrophoretic deposition
Using carbon fiber B10 as negative electrode, stainless steel is anode, carries out electrophoresis in electrophoresis liquid A10, electrophoretic voltage 80V, during deposition
Between 10min, temperature be 80 DEG C, then obtain products C 10；
4th, dry
C10 is dried into 30min in drying box in 120 DEG C vacuumize, until the small molecule volatilization such as solvent is complete, obtains product
D10；
5th, hot pressing
Using thermoplastic resin PC powder（D50 is 8 μm, molecular weight 18000）, D10 sides are first set into PPS powder, passed through afterwards
Double roller carries out hot pressing, afterwards manual reverse side or by twist rollers, overleaf lays PPS powder, hot pressing, heat are carried out again by double roller
It is 300 DEG C to press temperature, and pressure is adjusted to 15MPa by adjusting roller gap, and roller linear velocity is 10mm/s, regulation hot pressing time
Number reaches expected resin content（35%-40%）, cut after being cooled down after the completion of hot pressing and obtain prepreg cloth P10.
Comparative example 1
Double rod hot pressing preimpregnation are directly carried out with fiber cloth using above-mentioned PPS powder prepreg cloth CP1 is made.
Comparative example 2
The method impregnated using following reaction prepares prepreg cloth CP2.
Carbon cloth is soaked to 10min in acetone and carries out degumming process, deionized water is cleared up afterwards, drying；
30 parts purified of paradibromobenzene is dissolved in 100 parts of ɑ-chloronaphthalene CNT in a kettle, carries out mechanical agitation, it is completely molten
10 parts of vulcanized sodium after dehydration are added after solution, the fiber cloth flattening after above-mentioned treat is placed in reactor afterwards, heated up
To 290 DEG C, add and add the reaction 14 hours of 5 parts of catalyst sodium phosphate；Taking out surface aggregate has PPS fiber cloth, using going
Ionized water cleans, and drying obtains prepreg cloth.
Performance test
Embodiment 1-10 and comparative example 1-2 prepreg cloth P1-P10 and CP1-CP2 are cut into 10 equirotal sheet materials respectively,
Then respectively by the hot pressing in same flat plate mold after 10 layer of sheet material laminations（300 DEG C, 2.5MPa pressure）, CNC adds respectively afterwards
Work goes out to test batten X1-X10 and CX1-CX2, using ASTM D2344 short beam strength test standards to experiment batten X1-X10 and
CX1-CX2 is tested, and the results are shown in Table 1.
Table 1
。
From table 1 it follows that the interlaminar shear strength ratio use pair for the carbon fibre initial rinse fabric being obtained by the present invention
The interlaminar shear strength for the prepreg cloth that ratio 1-2 method is prepared is big, illustrates the prepreg cloth prepared with the method for the present invention
Adhesion it is more preferable.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description
Point is contained at least one embodiment or example of the present invention.In this manual, to the schematic representation of above-mentioned term not
Necessarily refer to identical embodiment or example.Moreover, specific features, structure, material or the feature of description can be any
One or more embodiments or example in combine in an appropriate manner.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that：Not
In the case of departing from the principle and objective of the present invention a variety of change, modification, replacement and modification can be carried out to these embodiments, this
The scope of invention is limited by claim and its equivalent.
Claims (16)
1. a kind of carbon fibre initial rinse fabric, it is characterised in that the prepreg cloth includes carbon fiber and is attached to the electricity of carbon fiber surface
Swimming resin bed and the thermoplastic resin layer for wrapping up the Carbon fibe and the electrophoresis resin layer.
2. carbon fibre initial rinse fabric according to claim 1, it is characterised in that resin used is in the electrophoresis resin layer
Acrylic resin, at least one of epoxy resin and the thermoplastic resin through the processing of peroxidating, sulfonation or radiation grafting.
3. carbon fibre initial rinse fabric according to claim 1 or 2, it is characterised in that the resin used in the electrophoresis resin layer
Mean molecule quantity be 1000-20000.
4. carbon fibre initial rinse fabric according to claim 3, it is characterised in that also received in the electrophoresis resin layer containing inorganic
Rice corpuscles, the inorganic particulate are in CNT, metal oxide, graphene, nano-calcium carbonate and nano silicon
It is at least one.
5. carbon fibre initial rinse fabric according to claim 4, it is characterised in that the thermoplastic resin layer is polystyrene tree
Lipid layer, acetal resin layer, polyphenylene sulfide resin lipid layer, polycarbonate resin, polyamide resin layer, polyimide resin layer and
At least one of polyether-ether-ketone resin layer.
6. carbon fibre initial rinse fabric according to claim 5, it is characterised in that on the basis of the gross weight of the prepreg cloth,
The content of the electrophoresis resin layer is 1-5wt%, and the content of the thermoplastic resin is 30-40wt%.
7. a kind of preparation method of carbon fibre initial rinse fabric, it is characterised in that the described method comprises the following steps：
S1, using carbon fiber as negative pole electrophoresis is carried out in electrophoresis liquid；
S2, by thermoplastic resin powder and by step S1 processing after carbon fiber carry out it is hot-forming；
The electrophoresis liquid contains underfill resin layer and solvent, and the electro kinetic potential of underfill resin layer is -40 ~ -10mV in the electrophoresis liquid.
8. preparation method according to claim 7, it is characterised in that also include after step S1 the carbon after electrophoresis is fine
The step of dimension is dried.
9. preparation method according to claim 7, it is characterised in that carried out before the step S1 to the carbon fiber
Pre-treatment, the pre-treatment include the clear degumming of organic solvent and coupling agent treatment.
10. according to the preparation method described in claim 7-9 any one, it is characterised in that the underfill resin layer is acrylic acid,
At least one of epoxy resin and the thermoplastic resin of acidified, oxidation, sulfonation or radiation grafting processing.
11. preparation method according to claim 10, it is characterised in that the thermoplastic resin powder is polystyrene powder
End, polyformaldehyde powder, pps powder, polycarbonate powder, polyamide powder, polyimide powder and polyether-ether-ketone powder
At least one of.
12. preparation method according to claim 7, it is characterised in that the condition of the electrophoresis is：Voltage is 60-80V,
Time is 10-30min, and temperature is 30-80 DEG C.
13. preparation method according to claim 7, it is characterised in that the condition of the drying is：In 60-120 DEG C take out
It is dried in vacuo 30-60min.
14. preparation method according to claim 7, it is characterised in that the condition of the hot pressing is：Temperature is 280-380
DEG C, pressure 15-35MPa.
A kind of 15. carbon fibre initial rinse fabric that preparation method as described in claim 7-14 any one is prepared.
16. a kind of metal fiber composite, the metal fiber composite includes the metal level and fibrous layer stacked gradually,
Characterized in that, the fibrous layer is to pass through hot pressing as the carbon fibre initial rinse fabric described in claim 1-6 any one or 15
Into.
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| CN109295489A (en) * | 2018-11-19 | 2019-02-01 | 镇江市高等专科学校 | A kind of electrophoresis suspensioning liquid and preparation method thereof for substrate surface layer plated film |
| CN109468852A (en) * | 2017-09-08 | 2019-03-15 | 比亚迪股份有限公司 | A kind of preparation method of fiber prepreg material, fiber prepreg plate and fiber prepreg material |
| CN109535783A (en) * | 2018-11-19 | 2019-03-29 | 江苏科技大学 | A kind of bismuth ferrite electrophoresis suspensioning liquid and its preparation method and application |
| CN109652839A (en) * | 2018-11-26 | 2019-04-19 | 镇江市高等专科学校 | Cu ferrite electrophoresis suspensioning liquid and its preparation method and application |
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