CN1597774A - Preparation process for composite of rare earth modified carbon-fibre / epoxy resin - Google Patents
Preparation process for composite of rare earth modified carbon-fibre / epoxy resin Download PDFInfo
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- CN1597774A CN1597774A CNA2004100536621A CN200410053662A CN1597774A CN 1597774 A CN1597774 A CN 1597774A CN A2004100536621 A CNA2004100536621 A CN A2004100536621A CN 200410053662 A CN200410053662 A CN 200410053662A CN 1597774 A CN1597774 A CN 1597774A
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- carbon fiber
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- epoxy resin
- rare earth
- epoxy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/248—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using pre-treated fibres
Abstract
The invention is a method for preparing rare-earth modified carbon fiber/epoxy resin composite, firstly preprocessing carbon fiber to eliminate residual organic substance on the surface, modified processing the surface of the carbon fiber by rare-earth modifier at room temperature, then compounding the processed carbon fiber with epoxy resin to make preimpregnated material and controlling the volume percent of glue to the preimpregnated material in 35%-45%, then spreading the preimprengated material according to a certain mode and layer number, heat-press-curing forming, and making the composite, where the rare-earth modifier has the components: rare-earth compound, alcohol, editic acid, ammonium chloride, nitric acid and urea.
Description
Technical field
The present invention relates to a kind of composite material and preparation method thereof, relate in particular to a kind of rare earth modified carbon fiber/epoxy resin composite material preparation method, to prepare matrix material through the filled with carbon fibers Resins, epoxy of rare-earth modifier for treatment, with the bonding force at the interface of improving carbon fiber/epoxy resin composite material, and then the practical engineering application that improves matrix material is worth.
Background technology
Carbon fiber has characteristics such as specific tenacity is big, Young's modulus is high, thermotolerance is high, chemical stability is good, is preparation performance resins based composites fortifying fibre commonly used.Carbon fibre reinforced composite has excellent mechanical property, and light weight, is widely used in fields such as Aeronautics and Astronautics, shipbuilding, automobile and building, and especially at aerospace field, carbon fiber has remarkable advantages as the strongthener of matrix material.Carbon Fiber is widely used as the material of making aircraft, as engine bin, central cowling, wing and fuselage nose cone, hanger nose cone, yaw rudder and elevating rudder trailing edge, escapement and window etc.
But, carbon planes of molecules in the carbon fiber is parallel-oriented along fibre axis, the surface is unreactiveness, and the affinity between the epoxy resin-base is relatively poor, be difficult to form chemical bond connection and interfacial layer and have immiscible component, interface binding intensity is low, and compound tense forms space and defective easily on the interface, strengthen body and matrix resin and be difficult to be formed with effective adhesive, influence the performance of composite material combination property.Along with progress of modern technology, more and more higher to the performance requriements of material.For tribological property and the mechanical property that improves carbon-fibre reinforced epoxy resin composite material, further widen its range of application, must further investigate its manufacture craft and surface interface treatment process.The interface is the very important microtexture of matrix material, it is the tie that plus load transmits to strongthener from matrix, directly influence the performance of material, for this reason, must be according to the kind and the characteristics of fiber and resin matrix, select appropriate means for use, modification is carried out on the surface of carbon fiber to be handled, improve the wetting property between fiber and the matrix, between fiber and matrix, form Chemical bond, to improve the interface bond strength between chopped carbon fiber and the epoxy resin-base, obtain to have the Carbon Fiber of good mechanical property.
At present, mainly use oxidation style, sedimentation, electropolymerization and electrodip process, Cement Composite Treated by Plasma waits the interface binding power that improves carbon fiber and polymeric matrix, to improve the over-all properties of carbon fiber reinforced polymer matrix material.These methods have been improved the bonding force of interfacial phase to a certain extent, improved the use value of matrix material, but do not reach the ideal effect, exist the effect instability, degenerate easily, shortcoming such as, poor processability big, cause the interface binding power of matrix material relatively poor fibre-tendering.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of rare earth modified carbon fiber/epoxy resin composite material preparation method is provided, it is simple to have technology, the characteristics of low-cost high-efficiency, can well improve the interface binding power of chopped carbon fiber and epoxy resin-base, thereby improve the over-all properties of matrix material.
For realizing such purpose, in the technical scheme of the present invention, earlier carbon fiber is carried out pre-treatment to remove the organism of remained on surface, at room temperature adopt rare-earth modifier that carbon fiber is carried out surface modification treatment again, in Resins, epoxy, add weight percent then and be 5～25% solidifying agent and be made into epoxy glue solution, carbon fiber after handling is immersed epoxy resin adhesive liquid make prepreg, the gel content volume percent of prepreg is 35～45%, then with (10～300 layers of prepreg laminations, according to member thickness needs) after heat presses solidly the type of changing into, and makes Carbon Fiber.Wherein, the component of rare-earth modifier comprises rare earth compound, ethanol, ethylenediamine tetraacetic acid (EDTA), ammonium chloride, nitric acid and urea.
Owing to 4f layer structure and electronegativity that rare earth element is special are less, rare earth element itself has outstanding chemically reactive, in the surface treatment of carbon fibers process, be adsorbed on of the form appearance of a part of rare earth element of carbon fiber surface with active rare earth atom, they might enter the top layer and reside in fault location by carbon fiber surface defect, and rare earth atom is because electronegativity is extremely low, with H, O extremely strong chemical affinity is arranged, can be used as negative electricity central suction atom on every side, become the active centre.Some rare earth atoms carry out physical adsorption at the place, active centre and form the activation body, and are producing the distortion district near carbon fiber surface, thereby help the absorption of rare earth atom more, and surface adsorption concentration is greatly improved, and have promoted the surface treatment of carbon fibers process.The formation at active rare earth atom and active rare-earth center has been played clean activatory effect to carbon fiber surface, can further improve the interface binding power between carbon fiber and the Resins, epoxy.The active rare earth atom of carbon fiber surface is the real source that rare earth element plays a role.Can improve the interfacial combined function of carbon fiber/epoxy resin composite material by the chemical action that takes place with carbon fiber and matrix resin.
Composite material and preparation method thereof of the present invention is specific as follows:
At first, carbon fiber is carried out pre-treatment, in 450～600 ℃ of muffle furnaces, ablated 0.5～1 hour, make its surface organic matter residual quantity below 1%.Adopt rare-earth modifier for treatment then, carbon fiber is at room temperature immersed in the properties-correcting agent, soaked 2～4 hours, after the filtration, oven dry.
In Resins, epoxy, add weight percent and be 5～25% solidifying agent and be made into epoxy glue solution, behind the carbon fiber impregnation after handling, make unidirectional pre-immersion material, the gel content volume percent is 35～45% in the control prepreg, then with behind the prepreg lamination (10～300 layers, according to member thickness needs) be placed on hot-press solidifying moulding in the pressing machine, again by being machined into carbon fiber/epoxy resin composite material sample or member.
The weight percentages of components of the rare-earth modifier that the present invention adopts is:
Rare earth compound: 2～10%
Ethanol: 75～95%
Ethylenediamine tetraacetic acid (EDTA) (EDTA): 1～10%
Ammonium chloride: 1～5%
Nitric acid: 0.5～1%
Urea: 0.5～2%
Rare earth compound of the present invention can be Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or cerium oxide.
The present invention is applicable to various carbon-fibre reinforced epoxy resin composite materials, and wherein carbon fiber comprises the polypropylene itrile group and the asphaltic base chopped carbon fiber of various models, as T-300 etc.Resins, epoxy comprises the bisphenol A type epoxy resin of the various trades mark, as 618, E-44, F-51, F-44, F-46 etc.Solidifying agent comprises the aromatic amine or the imidazole curing agent of the various trades mark.
The present invention has significant effect.Adopted the rare-earth modifier for treatment carbon fiber surface, can improve the interface binding power of matrix material better, thereby improve the mechanical property of matrix material more significantly, and the rare-earth modifier for treatment processing method is simple, cost is low, environmentally safe is handled the back carbon fiber and can not bonded together good manufacturability.Adopt the composite materials property of method preparation of the present invention good, tensile strength, flexural strength and impelling strength are significantly improved.
Embodiment
Below by specific embodiment technical scheme of the present invention is further described.
Embodiment 1:
Used starting material comprise: Resins, epoxy, the E-51 bisphenol A type epoxy resin that Shanghai Resin Factory produces; Solidifying agent is 593 modified aromatic amine curing agents (ambient cure); Carbon fiber, the high strong type of no coating polypropylene itrile group, the carbon element factory, Jilin produces; Rare-earth modifier is prepared according to following weight percent:
Lanthanum trichloride: 2%, ethanol: 93%, ethylenediamine tetraacetic acid (EDTA) (EDTA): 2%, ammonium chloride: 1%, nitric acid: 0.5%, urea: 1.5%.
Earlier carbon fiber is carried out pre-treatment, in 450 ℃ of muffle furnaces, ablated 1 hour, make its surface organic matter residual quantity below 1%.Adopt above-mentioned rare-earth modifier for treatment then, carbon fiber is at room temperature immersed in the properties-correcting agent, soaked 2 hours, after the filtration, oven dry.
The adding weight percent is 20% solidifying agent in Resins, epoxy, be made into epoxy glue solution, carbon fiber and Resins, epoxy after handling is compound, make unidirectional pre-immersion material, the volume percent content of Resins, epoxy is 35% in the control prepreg, according to unidirectional ply sequence prepreg is spread 25 layers, press curing moulding on pressing machine, hot pressing condition is 30 ℃, 50MPa, and the time is 15 hours.
According to GB3354-82 standard testing matrix material tensile strength is 1570MPa.
Embodiment 2:
Used starting material are: Resins, epoxy is that Shanghai Resin Factory's production trade mark is the Resins, epoxy (618 resin) of E-51; Carbon fiber: T-300, the coatingsurface Treatment of Carbon, toray company produces; 2-ethyl-4 Methylimidazole that solidifying agent Tianjin chemical reagent factory produces; Rare-earth modifier is prepared by following mass percent:
Cerium II Chloride 7%; Ethanol 76%; Ethylenediamine tetraacetic acid (EDTA) (EDTA) 9%; Ammonium chloride 5%; Nitric acid 1%; Urea 2%.
Earlier carbon fiber is carried out pre-treatment, in 550 ℃ of muffle furnaces, ablated 0.5 hour, make its surface organic matter residual quantity below 1%.Adopt above-mentioned rare-earth modifier for treatment then, carbon fiber is at room temperature immersed in the properties-correcting agent, soaked 3 hours, after the filtration, oven dry.
The adding weight percent is 7% solidifying agent preparation epoxy glue solution in Resins, epoxy, the carbon fiber that the modification of learning from else's experience is handled immerses epoxy glue solution, make unidirectional pre-immersion material, the Resins, epoxy volume percent content is 40% in the prepreg, then that 16 layers of preimpregnation cloth are superimposed according to unidirectional ply sequence, it is hot-forming to put into flat plate mold, and hot pressing condition is as follows: at room temperature at the uniform velocity be warming up to 50 ℃, be incubated 0.5 hour, this moment is plus-pressure not.After fully soaking into, be warming up to 75 ℃, be incubated after 5 minutes, pressurization 80MPa continues to be warming up to 100 ℃, is incubated 3 hours, is cooled to room temperature then.
According to GB3356-82 standard testing matrix material flexural strength is 1220MPa.
Embodiment 3
Material only changes the proportioning of rare-earth modifier with embodiment 1: lanthanum trioxide 10%; Ethanol 82%; Ethylenediamine tetraacetic acid (EDTA) (EDTA) 5%; Ammonium chloride 2%; Nitric acid 0.5%; Urea 0.5%.
Earlier carbon fiber is carried out pre-treatment, in 600 ℃ of muffle furnaces, ablated 0.5 hour, make its surface organic matter residual quantity below 1%.Adopt above-mentioned rare-earth modifier for treatment then, carbon fiber is at room temperature immersed in the properties-correcting agent, soaked 4 hours, after the filtration, oven dry.
The matrix material manufacture craft is with embodiment 1, and test compound material bending intensity is 54.0MPa.
Claims (3)
1, a kind of rare earth modified carbon fiber/epoxy resin composite material preparation method, it is characterized in that earlier carbon fiber being placed in 450～600 ℃ of muffle furnaces ablating 0.5～1 hour, make its surface organic matter residual quantity below 1%, then carbon fiber is at room temperature immersed and soak 2～4 hours in the rare-earth modifier, filter the back oven dry; In Resins, epoxy, add weight percent and be 5～25% solidifying agent and be made into epoxy glue solution, carbon fiber impregnation after handling is made unidirectional pre-immersion material, the gel content volume percent of control prepreg is 35～45%, then the after heat of prepreg lamination is pressed solidly the type of changing into, wherein, the weight percentages of components of rare-earth modifier is: rare earth compound 2～10%, ethanol 75～95%, ethylenediamine tetraacetic acid (EDTA) 1～10%, ammonium chloride 1～5%, nitric acid 0.5～1%, urea 0.5～2%.
2, rare earth modified carbon fiber as claimed in claim 1/epoxy resin composite material preparation method is characterized in that described rare earth compound is Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or cerium oxide.
3, rare earth modified carbon fiber as claimed in claim 1/epoxy resin composite material preparation method, it is characterized in that described carbon fiber is polypropylene itrile group and asphalt base carbon fiber, Resins, epoxy comprises bisphenol A type epoxy resin, and solidifying agent comprises aromatic amine or imidazole curing agent.
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| CNB2004100536621A CN1243047C (en) | 2004-08-12 | 2004-08-12 | Preparation process for composite of rare earth modified carbon-fibre / epoxy resin |
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| CNB2004100536621A CN1243047C (en) | 2004-08-12 | 2004-08-12 | Preparation process for composite of rare earth modified carbon-fibre / epoxy resin |
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| CN1597774A true CN1597774A (en) | 2005-03-23 |
| CN1243047C CN1243047C (en) | 2006-02-22 |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314725C (en) * | 2005-09-05 | 2007-05-09 | 天津大学 | Novel light-wave absorbing carbon fiber composite material preparation method |
| CN100368471C (en) * | 2006-01-12 | 2008-02-13 | 上海交通大学 | Preparation method of rare earth modified carbon fiber/ polypropylene composite material |
| CN100450316C (en) * | 2006-04-14 | 2009-01-07 | 李家俊 | Modified processing method of carbon fibre electrothermal wire |
| CN101781444A (en) * | 2010-03-31 | 2010-07-21 | 上海交通大学 | Method for preparing rare-earth-modified glass-fiber epoxy-resin composite materials |
| CN101851394A (en) * | 2010-05-27 | 2010-10-06 | 哈尔滨工业大学 | Hollow carbon fiber felt epoxy resin composite material and preparation method thereof |
| CN101859903A (en) * | 2010-06-11 | 2010-10-13 | 湖南维邦新能源有限公司 | Carbon electrode material treating agent and method for treating electrode materials by using same |
| CN102351556A (en) * | 2011-06-16 | 2012-02-15 | 西北工业大学 | Preparation method of rare earth toughening carbon/carbon composite material |
| CN102702543A (en) * | 2012-05-28 | 2012-10-03 | 哈尔滨工程大学 | Method for improving interface toughness of basalt fiber and epoxy composite material and rare earth processing liquid |
| CN104342936A (en) * | 2013-07-26 | 2015-02-11 | 永虹科技股份有限公司 | Carbon-fiber surface oiling agent replacing method |
| CN104369386A (en) * | 2014-10-31 | 2015-02-25 | 荣成复合材料有限公司 | Novel engine tappet |
| CN104402482A (en) * | 2014-10-31 | 2015-03-11 | 荣成复合材料有限公司 | Composite material engine cylinder |
| CN104403344A (en) * | 2014-10-31 | 2015-03-11 | 荣成复合材料有限公司 | Composite material engine connecting rod |
| CN104448683A (en) * | 2014-12-02 | 2015-03-25 | 荣成复合材料有限公司 | Method for manufacturing composite-material electromagnetic valve |
| CN104479297A (en) * | 2014-12-24 | 2015-04-01 | 芜湖市汽车产业技术研究院有限公司 | Method for improving interface toughness of epoxy resin carbon fiber composite |
| CN104559283A (en) * | 2014-12-02 | 2015-04-29 | 荣成复合材料有限公司 | Manufacturing method of carbon fiber composite material valve |
| CN106497360A (en) * | 2016-10-26 | 2017-03-15 | 安徽飞达电气科技有限公司 | A kind of organic-inorganic aluminium shell of capacitor high-quality coating paint |
| CN106497361A (en) * | 2016-10-26 | 2017-03-15 | 安徽飞达电气科技有限公司 | A kind of capacitor coating for the characteristic good of resistance to deep-draw and preparation method thereof |
-
2004
- 2004-08-12 CN CNB2004100536621A patent/CN1243047C/en not_active Expired - Fee Related
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314725C (en) * | 2005-09-05 | 2007-05-09 | 天津大学 | Novel light-wave absorbing carbon fiber composite material preparation method |
| CN100368471C (en) * | 2006-01-12 | 2008-02-13 | 上海交通大学 | Preparation method of rare earth modified carbon fiber/ polypropylene composite material |
| CN100450316C (en) * | 2006-04-14 | 2009-01-07 | 李家俊 | Modified processing method of carbon fibre electrothermal wire |
| CN101781444A (en) * | 2010-03-31 | 2010-07-21 | 上海交通大学 | Method for preparing rare-earth-modified glass-fiber epoxy-resin composite materials |
| CN101851394A (en) * | 2010-05-27 | 2010-10-06 | 哈尔滨工业大学 | Hollow carbon fiber felt epoxy resin composite material and preparation method thereof |
| CN101851394B (en) * | 2010-05-27 | 2011-11-16 | 哈尔滨工业大学 | Hollow carbon fiber felt epoxy resin composite material and preparation method thereof |
| CN101859903B (en) * | 2010-06-11 | 2012-09-05 | 大力电工襄阳股份有限公司 | Carbon electrode material treating agent and method for treating electrode materials by using same |
| CN101859903A (en) * | 2010-06-11 | 2010-10-13 | 湖南维邦新能源有限公司 | Carbon electrode material treating agent and method for treating electrode materials by using same |
| CN102351556B (en) * | 2011-06-16 | 2013-06-05 | 西北工业大学 | Preparation method of rare earth toughening carbon/carbon composite material |
| CN102351556A (en) * | 2011-06-16 | 2012-02-15 | 西北工业大学 | Preparation method of rare earth toughening carbon/carbon composite material |
| CN102702543A (en) * | 2012-05-28 | 2012-10-03 | 哈尔滨工程大学 | Method for improving interface toughness of basalt fiber and epoxy composite material and rare earth processing liquid |
| CN104342936A (en) * | 2013-07-26 | 2015-02-11 | 永虹科技股份有限公司 | Carbon-fiber surface oiling agent replacing method |
| CN104342936B (en) * | 2013-07-26 | 2017-04-12 | 永虹先进材料股份有限公司 | Carbon-fiber surface oiling agent replacing method |
| CN104369386A (en) * | 2014-10-31 | 2015-02-25 | 荣成复合材料有限公司 | Novel engine tappet |
| CN104402482A (en) * | 2014-10-31 | 2015-03-11 | 荣成复合材料有限公司 | Composite material engine cylinder |
| CN104403344A (en) * | 2014-10-31 | 2015-03-11 | 荣成复合材料有限公司 | Composite material engine connecting rod |
| CN104448683A (en) * | 2014-12-02 | 2015-03-25 | 荣成复合材料有限公司 | Method for manufacturing composite-material electromagnetic valve |
| CN104559283A (en) * | 2014-12-02 | 2015-04-29 | 荣成复合材料有限公司 | Manufacturing method of carbon fiber composite material valve |
| CN104479297A (en) * | 2014-12-24 | 2015-04-01 | 芜湖市汽车产业技术研究院有限公司 | Method for improving interface toughness of epoxy resin carbon fiber composite |
| CN106497360A (en) * | 2016-10-26 | 2017-03-15 | 安徽飞达电气科技有限公司 | A kind of organic-inorganic aluminium shell of capacitor high-quality coating paint |
| CN106497361A (en) * | 2016-10-26 | 2017-03-15 | 安徽飞达电气科技有限公司 | A kind of capacitor coating for the characteristic good of resistance to deep-draw and preparation method thereof |
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