CN105690802A - Preparation method and application of carbon-fiber-reinforced macromolecule-based composite - Google Patents
Preparation method and application of carbon-fiber-reinforced macromolecule-based composite Download PDFInfo
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- CN105690802A CN105690802A CN201610084022.XA CN201610084022A CN105690802A CN 105690802 A CN105690802 A CN 105690802A CN 201610084022 A CN201610084022 A CN 201610084022A CN 105690802 A CN105690802 A CN 105690802A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
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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
Abstract
The invention discloses a preparation method and application of a carbon-fiber-reinforced macromolecule-based composite. A saline solution required by an inorganic compound is put in a reaction kettle, a base material used for inducting an alternating magnetic field is put in the reaction kettle, the reaction kettle is sealed and then put into water-heat induction heating equipment, then the reaction kettle is cooled to the room temperature, and the base material loaded with the inorganic compound is taken out to be cleaned and dried; and finally, hot press molding is conducted on the base material, and the carbon-fiber-reinforced macromolecule-based composite is obtained. According to the method and application, the water-heat induction heating technology is applied to surface grafting of a carbon fiber, and the defect that the carbon fiber cannot be combined with other components easily due to surface inertia of the carbon fiber is overcome. In addition, under the action of the alternating magnetic field, multiple kinds of nanometer materials are promoted to grow on the surface of the carbon fiber due to the high temperature of the carbon fiber, more engaged position points are provided for bonding of the carbon fiber and resin, and interfacial bonding of the carbon fiber and the resin and the mechanical performance of the composite are improved.
Description
[technical field]
The invention belongs to the preparing technical field of composite, relate to preparation method and the application of a kind of carbon fibre reinforced high-molecular based composites。
[background technology]
Carbon fiber be often used as because of the combination property of its excellence (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.) polymer-based composite reinforcing material [Zhou Xiya compiles. composite. Beijing: Chemical Industry Press, 2005.01.]。But because carbon fibre surface energy is little, the shortcomings such as, interfacial combined function poor with the wellability of resin matrix is poor, the mechanical property of composite prepared therefrom often differs relatively big [ChoiI, LeeDG.Surfacemodificationofcarbonfiber/epoxycompositeswi thrandomlyorientedaramidfiberfeltforadhesionstrengthenha ncement.CompositesPartA:AppliedScienceandManufacturing.2 013 with theoretical value；48:1-8.]。
Therefore, suitably carbon fiber surface is processed, it is possible to improve the interface cohesion of carbon fiber and macromolecule matrix to a great extent。Chinese scholars is for the construction features of carbon fiber surface, propose multiple method carbon fiber surface is processed, can be divided mainly into [the Liu Baoying such as oxidizing process, plasma processing method, coating and modified by nano particles method, Wang Xiaojun, Yang Jie, Deng. carbon fiber surface modification progress [J]. chemical research, 2015,26 (2): 111-120.]。Oxidizing process mainly includes liquid phase oxidation, vapour phase oxidation process and electrochemical oxidation process etc., dominant mechanism is under the effect of oxidant, the exposure of carbon fiber produces many oxygen-containing polar functional groups with hydrophilicity, it can occur to be combined well with macromolecule, but the intensity of carbon fiber there will be decline。The mechanism of Cement Composite Treated by Plasma is the plasma bombardment carbon fiber surface utilizing plasma generator to produce, thus increasing degree of roughness and the surface area of fiber exposure, and produce oxygen-containing polar functional group at fiber surface, thus improving fiber and macromolecule matrix wellability [MaK each other, WangB, ChenP, etal.Plasmatreatmentofcarbonfibers:Non-equilibriumdynami cadsorptionanditseffectonthemechanicalpropertiesofRTMfab ricatedcomposites [J] .AppliedSurfaceScience, 2011, 257 (9): 3824-3830.]。Owing to carbon fiber surface receives damage, thus its intensity also there will be decline to a certain extent。Coating carbon fiber surface prepare a kind of can with carbon fiber and macromolecule generation physical-chemical reaction, there is the intermediate layer of certain thickness, structure and shear strength, and then the boundary strength of reinforced composite, common processing method has coupling agent coating, sol-gal process, sizing agent coating and vapour deposition process etc., but these methods are relatively complicated。
Owing to the introducing of nano-particle can dramatically improve the properties (including tribological property and mechanical performance etc.) of composite, nano-particle obtains the extensive concern of field of compound material researcher。In field of compound material, the introducing of nano-particle can be divided mainly into: mechanical blending method, fiber surface grafting and sedimentation etc.。Adopting mechanical blending method and sedimentation can only be incorporated in composite material by physical means by the nano-particle synthesized, this is prone to cause that nano-particle is reunited。Additionally, due to the raising of interface cohesion mainly relies on nanometer size effect to realize, thus this combination is weak。。
Therefore, find that a kind of technique is simple and easy to control, excellent interface can also be obtained under the premise not damaging this body structure of carbon fiber combine, and the preparation method that one-step method grows nano-particle at carbon fiber surface can be realized seem very meaningful。
[summary of the invention]
It is an object of the invention to provide the preparation method of a kind of carbon fibre reinforced high-molecular based composites and application, this method technique is simple and easy to control, a step can realize nano material synthesis on carbon fiber and growth the interface cohesion that can be effectively improved in composite between each component。
For achieving the above object, the present invention is by the following technical solutions:
A kind of preparation method of carbon fibre reinforced high-molecular based composites, it is characterised in that: comprise the following steps:
(1) the saline solution C required for preparation inorganic compound；
(2) solution C of step (1) is placed in reactor, and in reactor, place carbon cloth D, being sealed by reactor is placed in hydro-thermal induction heating equipment, under the effect of sensing alternating magnetic field, saline solution C becomes inorganic compound, and load is on carbon cloth D surface, then reactor is cooled to room temperature, the carbon cloth being loaded with inorganic compound is taken out, cleans, dry；
(3) it is placed in the carbon cloth that step (2) obtains in binder additives to impregnate to take out after 10～60min and dries；
(4) carbon cloth that step (3) obtains is carried out hot-forming on vulcanizer, the hot pressing temperature controlling vulcanizer is 150～180 DEG C, hot pressing time is 10～20min, hot pressing pressure is 3～8MPa, namely obtains having the carbon fibre reinforced high-molecular based composites that excellent interface combines。
Preferably, the count of described carbon cloth is 1K, 3K, 6K or 12K, and braiding structure is plain weave, twill, satin weave or unidirectional cloth。
Preferably, the binder additives of described step (3) is the macromolecular material with thermosetting or thermoplasticity and heat-resisting resistance to chemical attack。
Preferably, described binder additives solution can be thermosetting resin, including unsaturated polyester (UP), epoxy resin, phenolic resin, furane resins, polyimide resin and organic siliconresin etc.；Can also be thermoplastic resin, including polyolefin, polyamide, Merlon, polyformaldehyde, polyphenylene oxide, polyphenylene sulfide, polyether-ether-ketone。
Preferably, described binder additives solution is realized by the mode of spraying or sucking filtration。
Preferably, described carbon cloth is before putting into reactor, first it is carried out pretreatment, to remove the Organic substance on its surface, the method for pretreatment is: takes out after being placed in acetone soln by carbon cloth ultrasonic cleaning 2～10h, cleans post-drying with deionized water, then the carbon cloth after drying is placed in potassium permanganate solution or salpeter solution and soaks 12～36h or carbon cloth carries out calcination processing under atmospheric condition, finally, carbon cloth deionized water is carried out, dry。
Preferably, the induction frequencies of described hydro-thermal sensing heating is 10～500KHz, and faradic current is in the scope of 0～1200A。
Preferably, described inorganic compound include oxide, sulfide or other, described oxide includes metal-oxide and nonmetal oxide, described metal-oxide includes copper oxide, zinc oxide, manganese oxide, titanium oxide, aluminium oxide, molybdenum oxide, tungsten oxide or other metal-oxides, and described nonmetal oxide includes silicon oxide, calcium oxide or other inorganic non-metallic oxides；Described sulfide includes molybdenum sulfide, tungsten sulfide, vanadic sulfide, copper sulfide, iron sulfide or other sulfide, and described other include hydroxyapatite, phosphoric acid pick, calcium silicates or yttrium silicate。
Preferably, the packing ratio of described reactor is 40～80%。
A kind of a kind of carbon fibre reinforced high-molecular based composites prepared according to said method, it is applied on automatic clutch for car。
Compared with prior art, the present invention at least has the advantages that the present invention will be applied to carbon fiber surface engrafted nanometer material in hydro-thermal induction heating technique, provides a kind of brand-new preparation method to nano-material modified carbon fibre reinforced high-molecular based composites。The method manufacturing cycle is short, technique is simple and easy to control, it is not necessary to subsequent treatment and environmentally friendly, thus is more easily implemented industrialized production。
[accompanying drawing explanation]
Fig. 1 is MnO prepared by the present invention2Scanning electron microscope (SEM) photo with 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。
[detailed description of the invention]
Embodiment 1
The preparation method of a kind of carbon fibre reinforced high-molecular based composites, comprises the following steps:
Step one: weigh 0.5～5gA (A can be the salt needed for the synthesis of metal oxide such as potassium permanganate, ammonium molybdate, sodium tungstate, zinc chloride, copper chloride, titanium chloride, aluminum chloride), it is dissolved in 40～80mlB solvent (can be water, ethanol, propanol and ethylene glycol etc.), it is configured to the C solution that molar concentration is 0.01～5mol/L, regulates its pH value for acidity；
Step 2: take out after being placed in acetone soln by carbon cloth ultrasonic cleaning 2～10h, clean post-drying with deionized water。Then by dry after carbon cloth be placed in the potassium permanganate solution of 0.1～2mol/L soak 12～36h (soak potassium permanganate solution purpose be remove carbon fiber surface Organic substance, it is of course also possible to adopt salpeter solution process or carry out calcination processing under atmospheric condition)。Finally, the carbon cloth deionized water after immersion treatment is carried out, obtains carbon cloth D after drying；The count of described carbon cloth is 1K, 3K, 6K or 12K, and braiding structure is plain weave, twill, satin weave or unidirectional cloth；
Step 3: C solution is proceeded in reactor, and add the carbon cloth D of step 2, seal and be placed in hydro-thermal induction heating equipment, under the induction frequencies of 10～500KHz and the output current condition of 0～1200A, react 10min～24h, then naturally cool to room temperature。Carbon cloth is taken out, clean 3～6 times with deionized water, and at 60～100 DEG C, dry 12～24h, growth can be obtained and have the carbon cloth F of product E (E is the metal-oxide synthesized by raw material A, it is possible to be the metal-oxides such as copper oxide, zinc oxide, manganese oxide, titanium oxide, aluminium oxide, molybdenum oxide and tungsten oxide)；Hydrothermal temperature can sense heating by batch (-type) and realize, and the control of Hydro-thermal pressure can be realized by the packing ratio (40～80%) of reactor；
Step 4: be placed in the carbon cloth F of step 3 in the binder additives solution of 20～50wt% to impregnate to take out after 10～60min and dry。Repeated impregnations-drying operation is until the mass fraction of binder additives reaches 20～60%, described binder additives solution to have thermosetting or thermoplasticity, and heat-resisting resistance to chemical attack, for instance resin solution, its objective is carbon cloth F is joined together to form the carbon cloth with some strength；Described binder additives solution can be thermosetting resin, including unsaturated polyester (UP), epoxy resin, phenolic resin, furane resins, polyimide resin and organic siliconresin etc.；Can also be thermoplastic resin, including polyolefin, polyamide, Merlon, polyformaldehyde, polyphenylene oxide, polyphenylene sulfide, polyether-ether-ketone etc.；Additionally, macromolecule matrix can also be rubber；The interpolation of described resin can also be realized by the mode of spraying or sucking filtration；
Step 5: carbon cloth F step 4 obtained is hot-forming on vulcanizer, the hot pressing temperature controlling vulcanizer is 150～180 DEG C, hot pressing time is 10～20min, and hot pressing pressure is 3～8MPa, namely obtains having the carbon fibre reinforced high-molecular based composites that excellent interface combines。
Embodiment 2
Step one: by B solution (B can be the organic or inorganic sulfur source solution such as thioacetamide, sodium sulfide, cupferron, sodium diethyldithiocarbamate, sulphuric acid, the ammonium peroxydisulfate) Homogeneous phase mixing of the solution A (A can be the salt needed for the synthesizing sulfides such as ammonium molybdate, sodium tungstate, folk prescription acid sodium, copper chloride, iron chloride) of 0.01～5mol/L and 0.01～5mol/L, and regulate its pH value for acidity, obtain mixed liquor C；
Step 2: the carbon nano-fiber weighing 0.1g～5g is placed in moulding press, under the pressure of 2Mpa～15Mpa, stand 10min～60min, the carbon nano-fiber sheet D that thickness is 0.5mm～10mm can be obtained, then it is clearly respectively washed 3～6 times with ethanol and deionized water, and dry at 60～100 DEG C；
Step 3: C solution is proceeded in reactor, and add the carbon nano-fiber sheet D of step 2, sealing is placed in hydro-thermal induction heating equipment, reacts 10min～24h, then naturally cool to room temperature under the induction frequencies of 10～500KHz and the output current condition of 0～1200A。Nanofiber sheet D is taken out, clean 3～6 times with deionized water, and at 60～100 DEG C, dry 12～24h, growth can be obtained and have the carbon nano-fiber sheet F of product E (E is the product generated after being reacted by A and B, it is possible to be molybdenum sulfide, tungsten sulfide, vanadic sulfide, copper sulfide, iron sulfide sulfides)。
Step 4: the carbon nano-fiber sheet F of step 3 is pulverized, is put in 50～500ml water, under the frequency of 10～40KHz, ultrasonic 30min～3h, then under 60～100 DEG C of conditions drying to fully decentralized carbon nano-fiber；
Step 5: by 0.5～2g step 4 disperse after carbon nano-fiber and 10～20g binder additives powder body F Homogeneous phase mixing after pour in hot pressing die, 100～200 DEG C, hot pressing pressure be 2～10MPa when hot pressing 1～4h。In hot pressing, exit once every 10min, with the gas that macromolecule of fully draining produces in hot pressing。Thermo-compressed naturally cools to room temperature after touch, can obtain having the nano carbon fiber/inorganic sulfide that excellent interface combines and work in coordination with the polymer-based composite of enhancing。
In embodiments of the present invention, the process of described step 4 and step 5 can also adopt the step 4 of embodiment 1 and the mode of step 5 to process。
Embodiment 3
Step one: weigh 0.5～5gA (A can be the salt needed for the synthetic non-metallic oxide such as tetraethyl orthosilicate, calcium carbonate), it is dissolved in 40～80mlB solvent (can be water, ethanol, propanol and ethylene glycol etc.), it is configured to the C solution that molar concentration is 0.01～5mol/L, regulates its pH value for alkalescence；
Step 2: take out after being placed in acetone soln by chopped carbon fiber (length 100um～800um, diameter 10～20um) ultrasonic cleaning 2～10h, clean post-drying with deionized water。Then the chopped carbon fiber after drying is placed in the salpeter solution of 0.1～2mol/L and soaks 12～36h。Finally, the chopped carbon fiber deionized water after immersion treatment is carried out, dries；
Step 3: the chopped carbon fiber weighing 1g～6g step 2 is dissolved in 50～200ml water, by sand core funnel Suction filtration device, it is carried out sucking filtration, namely obtains having certain thickness chopped carbon fiber sheet D；
Step 4: C solution is proceeded in reactor, and add the chopped carbon fiber sheet D of step 3, sealing is placed in hydro-thermal induction heating equipment, reacts 10min～24h, then naturally cool to room temperature under the induction frequencies of 10～500KHz and the output current condition of 0～1200A。Chopped carbon fiber sheet D is taken out, clean 3～6 times with deionized water, and at 60～100 DEG C, dry 12～24h, can obtain growth has the chopped carbon fiber sheet F of product E (E is the nonmetal oxide synthesized by A, it is possible to for the inorganic non-metallic oxide such as silicon oxide, calcium oxide)。
Step 5: be placed in the chopped carbon fiber sheet F of step 4 in the binder additives solution of 20～50wt% to impregnate to take out after 10～60min and dry。Repeated impregnations-drying operation is until the mass fraction of binder additives reaches 20～60%；
Step 6: by the chopped carbon fiber sheet F of step 5 on vulcanizer hot-forming, the hot pressing temperature controlling vulcanizer is 150～180 DEG C, hot pressing time is 10～20min, hot pressing pressure is 3～8MPa, namely obtains having chopped carbon fiber/inorganic non-metallic oxide enhancing polymer-based composite that excellent interface combines。
In embodiments of the present invention, the process of described step 4 and step 5 can also adopt the step 4 of embodiment 2 and the mode of step 5 to process。
Embodiment 4
Step one: (A can be calcium chloride by the solution A of 0.01～5mol/L, basic zirconium chloride, calcium nitrate, Yttrium trinitrate etc.) and B solution (B can be potassium dihydrogen phosphate, phosphoric acid, the tetraethyl orthosilicate etc.) Homogeneous phase mixing of 0.01～5mol/L, and regulate its pH value for alkalescence, obtain mixed liquor C；
Step 2: take out after being placed in acetone soln by long carbon fiber (length is more than 800um) ultrasonic cleaning 2～10h, clean post-drying with deionized water。Then the long carbon fiber after drying is arranged in the salpeter solution of 0.1～2mol/L and soaks 12～36h。Finally, the long carbon fiber deionized water after immersion treatment is carried out, dries；
Step 3: the long carbon fiber weighing 1g～6g step 2 is dissolved in 50～200ml water, by sand core funnel Suction filtration device, it is carried out sucking filtration and obtain long carbon fiber filter cake, then pass through the mode of mold pressing, under the pressure of 2Mpa～15Mpa, stand 10min～60min, then it is clearly respectively washed 3～6 times with ethanol and deionized water, and dry at 60～100 DEG C, the long carbon fiber sheet D that thickness is 0.5mm～10mm can be obtained；
Step 4: C solution is proceeded in reactor, and add the long carbon fiber sheet D of step 3, sealing is placed in hydro-thermal induction heating equipment, reacts 10min～24h, then naturally cool to room temperature under the induction frequencies of 10～500KHz and the output current condition of 0～1200A。Long carbon fiber sheet D is taken out, clean 3～6 times with deionized water, and at 60～100 DEG C dry 12～24h, can obtain growth has product E (E is the product generated after being reacted by A and B, it is possible to for the long carbon fiber sheet F of hydroxyapatite, phosphoric acid pick, calcium silicates and yttrium silicate etc.。
Step 5: by the long carbon fiber sheet F of step 4 through tentatively pulverizing, be put in 100～500ml water, under the speed conditions of 50～1000r/min, after discongesting time 60～120min, dries under 60～100 DEG C of conditions, is namely uniformly discongested long carbon fiber。
Step 6: pour in hot pressing die after the long carbon fiber that 0.5～2g step 5 is uniformly discongested and 10～20g binder additives powder body F Homogeneous phase mixing, 100～200 DEG C, hot pressing pressure be 2～10MPa when hot pressing 1～4h。In hot pressing, exit once every 10min, with the gas that macromolecule of fully draining produces in hot pressing。Thermo-compressed naturally cools to room temperature after touch, can obtain having long carbon fiber/inorganic compound salt that excellent interface combines and work in coordination with the polymer-based composite of enhancing。
In embodiments of the present invention, the process of described step 4 and step 5 can also adopt the step 4 of embodiment 1 and the mode of step 5 to process。
In various embodiments of the invention, the method in blocks of described carbon plate, it is different for different carbon fiber materials, specifically, for the method that the fiber that carbon nano-fiber and chopped carbon fiber equidimension are less mainly adopts mold pressing, and method long fibre mainly being adopted to sucking filtration, in order to obtain the carbon plate that thickness is controlled, even need to adopt sucking filtration and mold pressing and method。
In tableting process, the bond strength in order to improve carbon plate can add some binder additives, and these additives should have the characteristic insoluble in reaction dissolvent, is prone to the feature removed with organic solvent after also possessing high temperature resistant and reaction。
Prepared carbon plate needs to process through dispersion to revert back pulverulence, this dispersion can not adopt ball milling, and the method that stirring should be adopted, by adjusting mode and the speed of stirring, under not destroying the premise of inorganic compound of carbon fiber surface growth, it dispersed is opened。
Water in hydro-thermal sensing can also change the organic solvents such as ethanol, propanol and ethylene glycol into, makes hydro-thermal reaction change into solvent thermal reaction。
In hydro-thermal reaction system, the organic solvent of addition anion or cationic surface active agent and opposed polarity etc. (enuatrol, triethanolamine, octadecylene, oleic acid, oleyl amine etc.) are as Morphological control agent, to reach to control the purpose of carbon fiber surface inorganic compound structure。
In order to enable inorganic compound better at carbon fiber surface nucleating growth, it is possible in advance carbon fiber is carried out surface treatment, such as surface carboxyl groups, hydroxylating etc.。The carbon cloth of inorganic compound is had, it is possible to be overlapped fixing by two-layer carbon cloth, it is also possible to be fixed on by carbon cloth on glass plate or ceramic wafer in order to obtain only one side growth。
The composite of present invention synthesis can apply to the fields such as thermal protection system, light structures part, ultracapacitor, ion secondary battery and auto parts and components。Wherein involved performance includes hot property, electrical property, mechanical performance and chemical property etc.。
As seen from Figure 1, the inventive method the carbon fiber surface homoepitaxial prepared nanometer MnO one layer finer and close2Granule。
The invention provides a kind of carbon fibre reinforced high-molecular based composites adopting the preparation of hydro-thermal induction technology to have excellent interface combination。Regulate its pH value after solution A and B solution being mixed and obtain C solution, then C solution proceeded in reactor and add carbon cloth or carbon plate, react in induction heating equipment after sealing, finally by reacted carbon cloth impregnating resin hot-press solidifying, can obtain that there is the carbon fibre reinforced high-molecular based composites that excellent interface combines。By changing output electric current and packing ratio, the control of reaction temperature and pressure can be realized, add response time, the adjustment of pH and introducing morphology control agent in reaction system, it is possible to achieve the control to product E structure, and then prepare the composite with different performance。Meanwhile, by selecting different reactants, it is possible to obtain the composite of enhancing worked in coordination with by different nano-particle/carbon fibers。
Hydro-thermal induction heating technique is applied to the surface grafting of carbon fiber by the present invention, it is possible to substantially overcome the shortcoming not easily combined that the surface inertness of carbon fiber brings with other components。In addition, under the effect of alternating magnetic field, the high temperature of carbon fiber can promote multiple nano material (in the growth on its surface, to provide more meshing site for carbon fiber and resin-bonded, and then improve the mechanical performance of the interface cohesion between them and composite。This invented technology is simple and easy to control, provides a kind of brand-new preparation method for nano-material modified composite。
Its concrete having the beneficial effect that:
(1) carbon fiber is quickly heated to higher temperature under the effect of alternating magnetic field, provide site for reactant nucleation and accelerate the growth of crystal, thus prepared composite chemical composition is homogeneous, purity is higher, crystal morphology rule, particle diameter is less and is evenly distributed, and interface cohesion is excellent；
(2) nano-particle firm growth on carbon fiber, has been provided in association with more meshing point for carbon fiber and resin, also improves fault interface energy and the storage modulus of material, thus this composite has the mechanical performance of excellence；
(3) the method to carbon fiber almost without infringement because the intensity of carbon fiber will not be weakened；
(4) temperature that carbon fiber surface is higher makes the nano material of synthesis have higher degree of crystallinity, because without carrying out post processing, this simplify whole preparation process and environmentally friendly。
Claims (10)
1. the preparation method of a carbon fibre reinforced high-molecular based composites, it is characterised in that: comprise the following steps:
(1) the saline solution C required for preparation inorganic compound；
(2) solution C of step (1) is placed in reactor, and in reactor, place carbon cloth D, being sealed by reactor is placed in hydro-thermal induction heating equipment, under the effect of sensing alternating magnetic field, saline solution C becomes inorganic compound, and load is on carbon cloth D surface, then reactor is cooled to room temperature, the carbon cloth being loaded with inorganic compound is taken out, cleans, dry；
(3) it is placed in the carbon cloth that step (2) obtains in binder additives to impregnate to take out after 10～60min and dries；
(4) carbon cloth that step (3) obtains is carried out hot-forming on vulcanizer, the hot pressing temperature controlling vulcanizer is 150～180 DEG C, hot pressing time is 10～20min, hot pressing pressure is 3～8MPa, namely obtains having the carbon fibre reinforced high-molecular based composites that excellent interface combines。
2. the preparation method of a kind of carbon fibre reinforced high-molecular based composites according to claim 1, it is characterised in that: the count of described carbon cloth is 1K, 3K, 6K or 12K, and braiding structure is plain weave, twill, satin weave or unidirectional cloth。
3. the preparation method of a kind of carbon fibre reinforced high-molecular based composites according to claim 1, it is characterised in that: the binder additives of described step (3) is the macromolecular material with thermosetting or thermoplasticity and heat-resisting resistance to chemical attack。
4. the preparation method of a kind of carbon fibre reinforced high-molecular based composites according to claim 3, it is characterized in that: described binder additives can be thermosetting resin, including unsaturated polyester (UP), epoxy resin, phenolic resin, furane resins, polyimide resin and organic siliconresin etc.；Can also be thermoplastic resin, including polyolefin, polyamide, Merlon, polyformaldehyde, polyphenylene oxide, polyphenylene sulfide, polyether-ether-ketone。
5. the preparation method of a kind of carbon fibre reinforced high-molecular based composites according to claim 1 or 3 or 4, it is characterised in that: described binder additives solution is realized by the mode of spraying or sucking filtration。
6. the preparation method of a kind of carbon fibre reinforced high-molecular based composites according to claim 2, it is characterized in that: described carbon cloth is before putting into reactor, first it is carried out pretreatment, to remove the Organic substance on its surface, the method of pretreatment is: take out after being placed in acetone soln by carbon cloth ultrasonic cleaning 2～10h, post-drying is cleaned with deionized water, then the carbon cloth after drying is placed in potassium permanganate solution or salpeter solution and soaks 12～36h or carbon cloth carries out calcination processing under atmospheric condition, finally, carbon cloth deionized water is carried out, dry。
7. the preparation method of a kind of carbon fibre reinforced high-molecular based composites according to claim 1, it is characterised in that: the induction frequencies of described hydro-thermal sensing heating is 10～500KHz, and faradic current is in the scope of 0～1200A。
8. the preparation method of a kind of carbon fibre reinforced high-molecular based composites according to claim 1, it is characterized in that: described inorganic compound include oxide, sulfide or other, described oxide includes metal-oxide and nonmetal oxide, described metal-oxide includes copper oxide, zinc oxide, manganese oxide, titanium oxide, aluminium oxide, molybdenum oxide, tungsten oxide or other metal-oxides, and described nonmetal oxide includes silicon oxide, calcium oxide or other inorganic non-metallic oxides；Described sulfide includes molybdenum sulfide, tungsten sulfide, vanadic sulfide, copper sulfide, iron sulfide or other sulfide, and described other include hydroxyapatite, phosphoric acid pick, calcium silicates or yttrium silicate。
9. the preparation method of a kind of carbon fibre reinforced high-molecular based composites according to claim 8, it is characterised in that: the packing ratio of described reactor is 40～80%。
10. a kind of carbon fibre reinforced high-molecular based composites that prepared by the method according to claim 1 to 9, it is applied on automatic clutch for car。
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| CN106147498A (en) * | 2016-07-18 | 2016-11-23 | 张和庆 | A kind of wear-resistant clutch surface sheet stock soaks coating processed |
| CN106957510A (en) * | 2017-03-24 | 2017-07-18 | 陕西科技大学 | A kind of titanium dioxide nano-rod is modified the preparation method of carbon cloth reinforced resin based composites |
| CN110914490A (en) * | 2017-03-23 | 2020-03-24 | 波士顿材料公司 | Fiber reinforced composite, method thereof and articles containing the composite |
| US11479656B2 (en) | 2019-07-10 | 2022-10-25 | Boston Materials, Inc. | Systems and methods for forming short-fiber films, composites comprising thermosets, and other composites |
| US11840028B2 (en) | 2018-12-10 | 2023-12-12 | Boston Materials, Inc. | Systems and methods for carbon fiber alignment and fiber-reinforced composites |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106147498A (en) * | 2016-07-18 | 2016-11-23 | 张和庆 | A kind of wear-resistant clutch surface sheet stock soaks coating processed |
| CN110914490A (en) * | 2017-03-23 | 2020-03-24 | 波士顿材料公司 | Fiber reinforced composite, method thereof and articles containing the composite |
| CN106957510A (en) * | 2017-03-24 | 2017-07-18 | 陕西科技大学 | A kind of titanium dioxide nano-rod is modified the preparation method of carbon cloth reinforced resin based composites |
| CN106957510B (en) * | 2017-03-24 | 2018-11-30 | 陕西科技大学 | A kind of preparation method of the modified carbon cloth reinforced resin based composites of titanium dioxide nano-rod |
| US11840028B2 (en) | 2018-12-10 | 2023-12-12 | Boston Materials, Inc. | Systems and methods for carbon fiber alignment and fiber-reinforced composites |
| US11479656B2 (en) | 2019-07-10 | 2022-10-25 | Boston Materials, Inc. | Systems and methods for forming short-fiber films, composites comprising thermosets, and other composites |
| US11767415B2 (en) | 2019-07-10 | 2023-09-26 | Boston Materials, Inc. | Systems and methods for forming short-fiber films, composites comprising thermosets, and other composites |
| US11820880B2 (en) | 2019-07-10 | 2023-11-21 | Boston Materials, Inc. | Compositions and methods for carbon fiber-metal and other composites |
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