CN105690807B - A kind of preparation method and application of carbon fibre reinforced high-molecular based composites - Google Patents
A kind of preparation method and application of carbon fibre reinforced high-molecular based composites Download PDFInfo
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- CN105690807B CN105690807B CN201610083838.0A CN201610083838A CN105690807B CN 105690807 B CN105690807 B CN 105690807B CN 201610083838 A CN201610083838 A CN 201610083838A CN 105690807 B CN105690807 B CN 105690807B
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- 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
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
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- 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
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/26—Component parts, details or accessories; Auxiliary operations
- B29C51/46—Measuring, controlling or regulating
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- 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
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Abstract
The invention discloses a kind of preparation method and applications of carbon fibre reinforced high-molecular based composites, the required salting liquid of inorganic compound is placed in reaction kettle, and it places to sense the basis material of alternating magnetic field in reaction kettle, reaction kettle sealing is placed in hydro-thermal induction heating equipment, then reaction kettle is cooled to room temperature, to load has the basis material taking-up of inorganic compound, cleaning, drying；Finally it is carried out hot-forming, you can.Hydro-thermal induction heating technique is applied to the surface grafting of carbon fiber by the present invention, and overcome that the surface inertness of carbon fiber brings is not easy with other components are combined the shortcomings that.In addition, under the action of alternating magnetic field, the high temperature of carbon fiber promotes growth of a variety of nano materials on its surface, provides more ratcheting sites for carbon fiber and resin-bonded, improves the mechanical performance of the interface cohesion and composite material between them.
Description
【Technical field】
The invention belongs to the preparing technical fields of composite material, are related to a kind of carbon fibre reinforced high-molecular based composites
Preparation method and application.
【Background technology】
Carbon fiber because its excellent comprehensive performance (high specific modulus and the ratio of strength to weight, low thermal expansion, high conductivity, high heat conduction,
Wear-resisting and high temperature resistant etc.) and be often used as the reinforcing material of polymer-based composite [Zhou Xiya compiles composite material Beijing：
Chemical Industry Press, 2005.01.].However because carbon fibre surface energy is small, and the wellability of resin matrix is poor, interfacial bonding property
Can be poor the shortcomings of, the mechanical property of composite material prepared therefrom often differs larger [Choi I, Lee with theoretical value
DG.Surface modification of carbon fiber/epoxy composites with randomly
oriented aramid fiber felt for adhesion strength enhancement.Composites Part
A:Applied Science and Manufacturing.2013；48:1-8.].
Therefore, suitably carbon fiber surface is handled, can largely improves carbon fiber and macromolecule matrix
Interface cohesion.Domestic and foreign scholars are directed to the design feature of carbon fiber surface, it is proposed that a variety of methods carry out carbon fiber surface
Processing, can be divided mainly into [Liu Baoying, king's filial piety such as oxidizing process, plasma processing method, coating and modified by nano particles method
Army, Yang Jie wait carbon fiber surface modifications progress [J] chemical research, 2015,26 (2)：111-120.].Oxidizing process is main
Including liquid phase oxidation, vapour phase oxidation process and electrochemical oxidation process etc., dominant mechanism be under the action of oxidant, carbon fiber
Exposure generates many oxygen-containing polar functional groups with hydrophilicity, can occur to be combined well with macromolecule, still
The intensity of carbon fiber will appear decline.The mechanism of corona treatment is banged using the plasma that plasma generator generates
Carbon fiber surface is hit, so as to increase the degree of roughness of fiber exposure and surface area, and oxygen-containing polarity official is generated in fiber surface
Can group, so as to improve fiber and mutual wellability [Ma K, Wang B, Chen P, the et al.Plasma of macromolecule matrix
treatment of carbon fibers:Non-equilibrium dynamic adsorption and its effect
on the mechanical properties of RTM fabricated composites[J].Applied Surface
Science,2011,257(9):3824-3830.].Since carbon fiber surface receives damage, thus its intensity is to a certain degree
On also will appear decline.Coating is to prepare one kind in carbon fiber surface physical chemistry can to occur with carbon fiber and macromolecule anti-
It answers, there is the middle layer of certain thickness, structure and shear strength, and then enhance the boundary strength of composite material, common place
Reason method has coupling agent coating, sol-gal process, sizing agent coating and vapour deposition process etc., however these methods compare
It is more complicated.
Since the introducing of nano particle can dramatically improve the properties of composite material (including tribological property and machine
Tool performance etc.), nano particle obtains the extensive concern of field of compound material researcher.In field of compound material, nano particle
Introducing can be divided mainly into：Mechanical blending method, fiber surface grafting and sedimentation etc..It can only using mechanical blending method and sedimentation
The nano particle synthesized is introduced by physical means in composite material material, this is easy to cause nano particle that group occurs
It is poly-.Further, since the raising of interface cohesion is mainly realized by nanometer size effect, thus this combination is weak..
Therefore, find it is a kind of it is simple for process it is easily-controllable, can also obtain under the premise of carbon fiber this body structure is not damaged it is excellent
Interface cohesion, and can realize that one-step method seems very significant in the preparation method of carbon fiber surface growth nano particle.
【Invention content】
The purpose of the present invention is to provide a kind of preparation method and application of carbon fibre reinforced high-molecular based composites, this
Kind of method is simple for process easily-controllable, can a step realize synthesis and growth of the nano material on carbon fiber, and can be effectively improved
Interface cohesion in composite material between each component.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of carbon fibre reinforced high-molecular based composites, includes the following steps：
(1) the required salting liquid C of inorganic compound is prepared, and adjusts its Ph as alkalinity；
(2) solution C of step (1) is placed in reaction kettle, and chopped carbon fiber piece D is added in reaction kettle, will reacted
Kettle sealing is placed in hydro-thermal induction heating equipment, and under the action of alternating magnetic field is sensed, salting liquid C becomes inorganic compound,
And chopped carbon fiber piece D surfaces are supported on, then reaction kettle is cooled to room temperature, load is had to the chopped carbon fibre of inorganic compound
It ties up piece to take out, cleaning, drying；
(3) the chopped carbon fiber piece D that step (2) obtains is placed in the binder additives that weight percent is 20~50%
It is impregnated in solution, is then dried；
(4) the chopped carbon fiber piece that step (3) obtains is controlled into the hot pressing temperature of vulcanizer in hot-forming on vulcanizer
It it is 150~180 DEG C, hot pressing time is 10~20min, and hot pressing pressure is 3~8MPa to get short to being combined with excellent interface
Cut carbon fiber/inorganic nonmetal oxide enhancing polymer-based composite.
Preferably, the binder additives of the step (4) are with thermosetting property or thermoplasticity and heat-resisting resistant to chemical etching
High molecular material.
Preferably, the binder additives can be thermosetting resin, including unsaturated polyester (UP), epoxy resin, phenolic aldehyde
Resin, furane resins, polyimide resin and organic siliconresin etc.；May be thermoplastic resin, including polyolefin, polyamides
Amine, makrolon, polyformaldehyde, polyphenylene oxide, polyphenylene sulfide, polyether-ether-ketone.
Preferably, the binder additives are realized by way of spraying or filtering.
Preferably, the chopped carbon fiber piece D is obtained according to following methods：Chopped carbon fiber is used successively first
After acetone, deionized water cleaning, then drying is placed it in the salpeter solution of 0.1~2mol/L and is impregnated, then uses deionized water
Cleaning, drying, it is finally that chopped carbon fiber is soluble in water, it is filtered by sand core funnel Suction filtration device.
Preferably, the induction frequencies of the hydro-thermal sensing heating are 10~500KHz, sense the model that electric current is 0~1200A
In enclosing.
Preferably, the inorganic compound include oxide, sulfide or other, the oxide include metal oxide
And nonmetal oxide, the metal oxide include copper oxide, zinc oxide, manganese oxide, titanium oxide, aluminium oxide, molybdenum oxide, oxygen
Change tungsten or other metal oxides, the nonmetal oxide includes silica, calcium oxide or other inorganic non-metallic oxides；
The sulfide includes molybdenum sulfide, tungsten sulfide, vanadic sulfide, copper sulfide, iron sulfide or other sulfide, and described other include hydroxyl
Apatite, phosphoric acid pick, calcium silicates or yttrium silicate.
Preferably, the packing ratio of the reaction kettle is 40~80%.
A kind of a kind of carbon fibre reinforced high-molecular based composites prepared according to above method, it is automatic to be applied to automobile
On brake block.
Compared with prior art, the present invention at least has the advantages that：The present invention will be in hydro-thermal induction heating technique
Applied to carbon fiber surface engrafted nanometer material, one is provided to nano-material modified carbon fibre reinforced high-molecular based composites
The completely new preparation method of kind.It is this method short preparation period, simple for process easily-controllable, without subsequent processing and environmentally friendly, thus
It is more easily implemented industrialized production.
【Description of the drawings】
Fig. 1 is MnO prepared by the present invention2With scanning electron microscope (SEM) photo of carbon fiber composite structure.
Fig. 2 is the SEM photograph of the embodiment of the present invention 1.
Fig. 3 is the SEM photograph of the embodiment of the present invention 4.
Fig. 4 is the SEM photograph of the embodiment of the present invention 3.
Fig. 5 is the SEM photograph of the embodiment of the present invention 2.
【Specific embodiment】
Embodiment 1
A kind of preparation method of carbon fibre reinforced high-molecular based composites, includes the following steps：
Step 1：Weighing 0.5~5gA, (A can be potassium permanganate, ammonium molybdate, sodium tungstate, zinc chloride, copper chloride, chlorination
Salt needed for the synthesis of metal oxide such as titanium, aluminium chloride), be dissolved in 40~80mlB solvents (can be water, ethyl alcohol, propyl alcohol and
Ethylene glycol etc.), the C solution that molar concentration is 0.01~5mol/L is configured to, adjusts its pH value as acidity；
Step 2：Carbon cloth is placed in acetone soln after being cleaned by ultrasonic 2~10h and taken out, dried after being cleaned with deionized water.
Then the carbon cloth after drying is placed in the liquor potassic permanganate of 0.1~2mol/L and impregnates 12~36h (immersion liquor potassic permanganates
Purpose be remove carbon fiber surface organic matter, it is of course also possible to use salpeter solution processing or under atmospheric condition into
Row calcination processing).Finally, the carbon cloth after immersion treatment with deionized water is cleaned, carbon cloth D is obtained after dry；The carbon
The count of cloth is 1K, 3K, 6K or 12K, and braiding structure is plain weave, twill, satin weave or unidirectional cloth；
Step 3：C solution is transferred in reaction kettle, and adds in the carbon cloth D of step 2, sealing is placed on hydro-thermal sensing heating
In equipment, 10min~for 24 hours is reacted under the conditions of the induction frequencies of 10~500KHz and the output current of 0~1200A, then from
So it is cooled to room temperature.Carbon cloth is taken out, is cleaned 3~6 times with deionized water, and dry 12 at 60~100 DEG C~for 24 hours, you can
Obtain growth have product E (E is the metal oxide synthesized by raw material A, can be copper oxide, zinc oxide, manganese oxide, titanium oxide,
The metal oxides such as aluminium oxide, molybdenum oxide and tungsten oxide) carbon cloth F；Hydrothermal temperature can by intermittent sensing heating come
It realizes, the control of Hydro-thermal pressure can be realized by the packing ratio (40~80%) of reaction kettle；
Step 4：The carbon cloth F of step 3 is placed in 10~60min of dipping in the binder additives solution of 20~50wt%
Drying is taken out afterwards.Repeated impregnations-drying operation reaches 20~60% until the mass fraction of binder additives, the binding agent
Additive solution will have thermosetting property or thermoplasticity, and heat-resisting resistant to chemical etching, such as resin solution, and the purpose is to by carbon cloth F
It is joined together to form the carbon cloth with some strength；The binder additives can be thermosetting resin, including insatiable hunger
With polyester, epoxy resin, phenolic resin, furane resins, polyimide resin and organic siliconresin etc.；May be thermoplasticity
Resin, including polyolefin, polyamide, makrolon, polyformaldehyde, polyphenylene oxide, polyphenylene sulfide, polyether-ether-ketone etc.；In addition, macromolecule
Matrix can also be rubber；The addition of the resin can also be realized by way of spraying or filtering；
Step 5：By the carbon cloth F that step 4 obtains in hot-forming on vulcanizer, the hot pressing temperature for controlling vulcanizer is
150~180 DEG C, hot pressing time is 10~20min, and hot pressing pressure is 3~8MPa to get fine to the carbon combined with excellent interface
Dimension enhancing polymer-based composite.
Embodiment 2
Step 1：By the solution A of 0.01~5mol/L, (A can be ammonium molybdate, sodium tungstate, folk prescription acid sodium, copper chloride, chlorine
Change the salt needed for the synthesizing sulfides such as iron) and the B solution of 0.01~5mol/L (B can be that thioacetamide, vulcanized sodium, copper try
The organic or inorganics sulphur source such as agent, sodium diethyldithiocarbamate, sulfuric acid, ammonium peroxydisulfate solution) uniformly mixing, and adjusting
Its pH value is acidity, obtains mixed liquor C；
Step 2：The carbon nano-fiber for weighing 0.1g~5g is placed in moulding press, quiet under the pressure of 2Mpa~15Mpa
Put 10min~60min, you can obtain thickness be 0.5mm~10mm carbon nano-fiber piece D, then by its with ethyl alcohol and go from
Sub- water is respectively washed clearly 3~6 times, and is dried at 60~100 DEG C；
Step 3：C solution is transferred in reaction kettle, and adds in the carbon nano-fiber piece D of step 2, sealing is placed on hydro-thermal
In induction heating equipment, under the conditions of the induction frequencies of 10~500KHz and the output current of 0~1200A react 10min~
For 24 hours, room temperature is then naturally cooled to.Nanofiber piece D is taken out, is cleaned 3~6 times with deionized water, and at 60~100 DEG C
Dry 12~for 24 hours, you can obtaining growth has product E (E is the product by being generated after A and B reactions, can be molybdenum sulfide, vulcanization
Tungsten, vanadic sulfide, copper sulfide, iron sulfide sulfides) carbon nano-fiber piece F.
Step 4：The carbon nano-fiber piece F of step 3 is pulverized, is put in 50~500ml water, in the frequency of 10~40KHz
Under rate, ultrasonic 30min~3h, then under the conditions of 60~100 DEG C drying to fully decentralized carbon nano-fiber；
Step 5：Carbon nano-fiber and 10~20g binder additives powders F after 0.5~2g step 4 is disperseed is equal
It is poured into hot pressing die after even mixing, 1~4h of hot pressing under conditions of 100~200 DEG C, hot pressing pressure is 2~10MPa.In heat
During pressure, deflate every 10min primary, fully to exhaust the gas that macromolecule generates in hot pressing.Thermo-compression bonding is after touch
Cooled to room temperature, you can obtain the high score of the nano carbon fiber/inorganic sulfide that there is excellent interface to combine collaboration enhancing
Subbase composite material.
In embodiments of the present invention, the process of the step 4 and step 5 can also use four Hes of the step of embodiment 1
The mode of step 5 is handled.
Embodiment 3
Step 1：Weighing 0.5~5gA, (A can be needed for the synthetic non-metallics oxides such as ethyl orthosilicate, calcium carbonate
Salt), (can be water, ethyl alcohol, propyl alcohol and ethylene glycol etc.) be dissolved in 40~80mlB solvents, and it is 0.01 to be configured to molar concentration
The C solution of~5mol/L adjusts its pH value as alkalinity；
Step 2：Chopped carbon fiber (length 100um~800um, 10~20um of diameter) is placed in acetone soln ultrasonic
It takes out after 2~10h of cleaning, is dried after being cleaned with deionized water.Then the chopped carbon fiber after drying is placed in 0.1~2mol/L
Salpeter solution in impregnate 12~36h.Finally, the chopped carbon fiber after immersion treatment with deionized water cleaned, dried；
Step 3：The chopped carbon fiber for weighing 1g~6g step 2 is dissolved in 50~200ml water, is filtered by sand core funnel
Device filters it to get to certain thickness chopped carbon fiber piece D；
Step 4：C solution is transferred in reaction kettle, and adds in the chopped carbon fiber piece D of step 3, sealing is placed on hydro-thermal
In induction heating equipment, under the conditions of the induction frequencies of 10~500KHz and the output current of 0~1200A react 10min~
For 24 hours, room temperature is then naturally cooled to.Chopped carbon fiber piece D is taken out, is cleaned 3~6 times with deionized water, and in 60~100 DEG C
Lower drying 12~for 24 hours, you can obtain growth have product E (E be nonmetal oxide synthesize by A, can for silica, aoxidize
The inorganic non-metallics such as calcium oxide) chopped carbon fiber piece F.
Step 5：The chopped carbon fiber piece F of step 4 is placed in the binder additives solution of 20~50wt% and is impregnated
Drying is taken out after 10~60min.Repeated impregnations-drying operation reaches 20~60% until the mass fraction of binder additives；
Step 6：By the chopped carbon fiber piece F of step 5 in hot-forming on vulcanizer, the hot pressing temperature of vulcanizer is controlled
It it is 150~180 DEG C, hot pressing time is 10~20min, and hot pressing pressure is 3~8MPa to get short to being combined with excellent interface
Cut carbon fiber/inorganic nonmetal oxide enhancing polymer-based composite.
In embodiments of the present invention, the process of the step 4 and step 5 can also use four Hes of the step of embodiment 2
The mode of step 5 is handled.
Embodiment 4
Step 1：By the solution A of 0.01~5mol/L (A can be calcium chloride, basic zirconium chloride, calcium nitrate, yttrium nitrate etc.)
With B solution (B can be potassium dihydrogen phosphate, phosphoric acid, ethyl orthosilicate etc.) uniformly mixing, and adjust its pH of 0.01~5mol/L
It is worth for alkalinity, obtains mixed liquor C；
Step 2：Long carbon fiber (length is more than 800um) is placed in acetone soln after being cleaned by ultrasonic 2~10h and taken out, used
It is dried after deionized water cleaning.Then the long carbon fiber after drying is arranged in the salpeter solution of 0.1~2mol/L and impregnates 12
~36h.Finally, the long carbon fiber after immersion treatment with deionized water cleaned, dried；
Step 3：The long carbon fiber for weighing 1g~6g step 2 is dissolved in 50~200ml water, is filtered and filled by sand core funnel
It puts and it is filtered to obtain long carbon fiber filter cake, then by way of molding, under the pressure of 2Mpa~15Mpa, stand
Then it with ethyl alcohol and deionized water is respectively washed clearly 3~6 times, and is dried at 60~100 DEG C by 10min~60min, you can obtain
Obtain the long carbon fiber piece D that thickness is 0.5mm~10mm；
Step 4：C solution is transferred in reaction kettle, and adds in the long carbon fiber piece D of step 3, sealing is placed on hydro-thermal sense
It answers in heating equipment, 10min~for 24 hours is reacted under the conditions of the induction frequencies of 10~500KHz and the output current of 0~1200A,
Then room temperature is naturally cooled to.Long carbon fiber piece D is taken out, is cleaned 3~6 times with deionized water, and is dry at 60~100 DEG C
12~for 24 hours, you can obtaining growth has product E (E is by the product that generates after A and B reactions, can be hydroxyapatite, phosphoric acid
The long carbon fiber piece F of pick, calcium silicates and yttrium silicate etc..
Step 5：By the long carbon fiber piece F of step 4 by tentatively pulverizing, it is put in 100~500ml water, 50~
Under the speed conditions of 1000r/min, after discongesting 60~120min of time, dry under the conditions of 60~100 DEG C and dredged to get to uniform
Solve long carbon fiber.
Step 6：The long carbon fiber that 0.5~2g step 5 is uniformly discongested and 10~20g binder additives powders F is equal
It is poured into hot pressing die after even mixing, 1~4h of hot pressing under conditions of 100~200 DEG C, hot pressing pressure is 2~10MPa.In heat
During pressure, deflate every 10min primary, fully to exhaust the gas that macromolecule generates in hot pressing.Thermo-compression bonding is after touch
Cooled to room temperature, you can obtain the high score of the long carbon fiber that there is excellent interface to combine/inorganic compound salt collaboration enhancing
Subbase composite material.
In embodiments of the present invention, the process of the step 4 and step 5 can also use four Hes of the step of embodiment 1
The mode of step 5 is handled.
In various embodiments of the invention, the method in blocks of the carbon plate, be for different carbon fiber materials it is different,
Specifically, it is mainly to use the method being molded for carbon nano-fiber and the smaller fiber of chopped carbon fiber equidimension, and for
Long fibre is mainly the method for using and filtering, and filters and is molded in order to obtain the controllable carbon plate of thickness or even need to use
And method.
In tableting process, in order to which the bond strength for improving carbon plate can add in some binder additives, these additions
Agent should have the characteristic insoluble in reaction dissolvent, also to have high temperature resistant and be easy to the spy removed with organic solvent after reacting
Point.
Prepared carbon plate needs to revert back pulverulence by decentralized processing, and this dispersion cannot use ball milling, and answer
This is using the method stirred, by adjusting the mode and speed of stirring, in the inorganic compound for not destroying carbon fiber surface growth
Under the premise of, it is uniformly dispersed out.
Water in hydro-thermal sensing can also change the organic solvents such as ethyl alcohol, propyl alcohol and ethylene glycol into, be converted to hydro-thermal reaction
Solvent thermal reaction.
Anion or the organic solvent of cationic surface active agent and opposed polarity are added in hydro-thermal reaction system
It is inorganic to reach control carbon fiber surface Deng (enuatrol, triethanolamine, octadecylene, oleic acid, oleyl amine etc.) as Morphological control agent
The purpose of compound structure.
In order to enable inorganic compound that in carbon fiber surface nucleating growth, table preferably can be carried out to carbon fiber in advance
Surface treatment, such as surface carboxyl groups, hydroxylating.There was only the carbon cloth that single side growth has inorganic compound in order to obtain, it can be by two
Layer carbon cloth is overlapped fixation, can also be fixed on carbon cloth on glass plate or ceramic wafer.
The composite material that the present invention synthesizes can be applied to thermal protection system, light structures part, ultracapacitor, ion two
The fields such as primary cell and auto parts and components.Wherein involved performance includes hot property, electrical property, mechanical performance and electrification
Learn performance etc..
As seen from Figure 1, the carbon fiber surface homoepitaxial prepared by the method for the present invention one layer of finer and close nanometer
MnO2Particle.
The present invention provides a kind of fibre reinforced high scores for being prepared using hydro-thermal induction technology and being combined with excellent interface
Subbase composite material.Its pH value is adjusted after solution A and B solution are mixed and obtains C solution, and then C solution is transferred in reaction kettle
And carbon cloth or carbon plate are added in, it is reacted in induction heating equipment after sealing, finally by the carbon cloth impregnating resin after reaction and heat
It is cured, you can to obtain the carbon fibre reinforced high-molecular based composites that there is excellent interface to combine.By changing output current
And packing ratio, the control of reaction temperature and pressure can be realized, along with the adjustment to reaction time, pH and in reaction system
Middle introducing pattern controlling agent, can realize the control to product E structures, and then prepare the composite material with different performance.
At the same time, by selecting different reactants, the composite material of different nano particles/carbon fiber collaboration enhancing can be obtained.
Hydro-thermal induction heating technique is applied to the surface grafting of carbon fiber by the present invention, can significantly overcome the table of carbon fiber
What face inertia was brought be not easy with other components are combined the shortcomings that.In addition, under the action of alternating magnetic field, the high temperature of carbon fiber can
With promote a variety of nano materials (growth on its surface provides more ratcheting sites for carbon fiber and resin-bonded, and then
Improve the mechanical performance of the interface cohesion and composite material between them.The invented technology is simple and easy to control, is nano-material modified
Composite material provides a kind of completely new preparation method.
It specifically has the beneficial effect that：
(1) carbon fiber is quickly heated to higher temperature under the action of alternating magnetic field, is provided for reactant nucleation
Site and the growth for accelerating crystal, because prepared by composite material chemical composition it is uniform, purity is higher, crystal morphology rule,
Grain size is smaller and is evenly distributed, and interface cohesion is excellent；
(2) secured growth of the nano particle on carbon fiber, the combination for carbon fiber and resin provide more ratcheting
Point also improves the fault interface energy and storage modulus of material, thus the composite material has excellent mechanical performance；
(3) this method to carbon fiber almost without damage because the intensity of carbon fiber will not be weakened；
(4) the higher temperature of carbon fiber surface makes the nano material of synthesis have higher crystallinity, because without carrying out
Post processing, this simplifies whole preparation process and environmentally friendly.
Claims (7)
1. a kind of preparation method of carbon fibre reinforced high-molecular based composites, it is characterised in that：Include the following steps：
(1) the required salting liquid C of inorganic compound is prepared, and adjusts its Ph as alkalinity；
(2) solution C of step (1) is placed in reaction kettle, and the addition chopped carbon fiber piece D in reaction kettle, reaction kettle is close
It is honored as a queen and is placed in hydro-thermal induction heating equipment, under the action of alternating magnetic field is sensed, salting liquid C becomes inorganic compound, and bears
Chopped carbon fiber piece D surfaces are loaded in, are then cooled to room temperature reaction kettle, load is had to the chopped carbon fiber piece of inorganic compound
It takes out, cleaning, drying；The induction frequencies of hydro-thermal sensing heating are 10~500KHz, and sensing electric current is in the range of 0~1200A；
The packing ratio of reaction kettle is 40~80%；
(3) the chopped carbon fiber piece D that step (2) obtains is placed in the binder additives solution that weight percent is 20~50%
In impregnated, then dry；
(4) by the chopped carbon fiber piece that step (3) obtains in hot-forming on vulcanizer, the hot pressing temperature for controlling vulcanizer is
150~180 DEG C, hot pressing time is 10~20min, and hot pressing pressure is chopped for 3~8MPa to get to what is combined with excellent interface
Carbon fiber/inorganic nonmetal oxide enhances polymer-based composite.
2. a kind of preparation method of carbon fibre reinforced high-molecular based composites according to claim 1, it is characterised in that：
The binder additives are with thermosetting property or thermoplasticity and heat-resisting high molecular material resistant to chemical etching.
3. a kind of preparation method of carbon fibre reinforced high-molecular based composites according to claim 2, it is characterised in that：
The binder additives can be thermosetting resin, including unsaturated polyester (UP), epoxy resin, phenolic resin, furane resins, gather
Imide resin and organic siliconresin；May be thermoplastic resin, including polyolefin, polyamide, makrolon, poly- first
Aldehyde, polyphenylene oxide, polyphenylene sulfide, polyether-ether-ketone.
4. a kind of preparation method of carbon fibre reinforced high-molecular based composites according to Claims 2 or 3, feature exist
In：The binder additives are realized by way of spraying or filtering.
5. a kind of preparation method of carbon fibre reinforced high-molecular based composites according to claim 1, it is characterised in that：
The chopped carbon fiber piece D is obtained according to following methods：It is clear with acetone, deionized water successively first by chopped carbon fiber
After washing, then drying is placed it in the salpeter solution of 0.1~2mol/L and is impregnated, then cleaned, dried with deionized water, finally
Chopped carbon fiber is soluble in water, it is filtered by sand core funnel Suction filtration device.
6. a kind of preparation method of carbon fibre reinforced high-molecular based composites according to claim 1, it is characterised in that：
The inorganic compound include oxide, sulfide or other, the oxide include metal oxide and nonmetal oxide,
The metal oxide includes copper oxide, zinc oxide, manganese oxide, titanium oxide, aluminium oxide, molybdenum oxide, tungsten oxide or other metals
Oxide, the nonmetal oxide include silica, calcium oxide or other inorganic non-metallic oxides；The sulfide includes
Molybdenum sulfide, tungsten sulfide, vanadic sulfide, copper sulfide, iron sulfide or other sulfide, it is described other include hydroxyapatite, phosphoric acid pick,
Calcium silicates or yttrium silicate.
7. a kind of carbon fibre reinforced high-molecular base prepared by a kind of method as claimed in any of claims 1 to 6 is answered
Condensation material is applied to automobile automatic brake on piece.
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