CN1206277C - Preparation method of rare earth modified fanglun fiber/epoxy composite material - Google Patents
Preparation method of rare earth modified fanglun fiber/epoxy composite material Download PDFInfo
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- CN1206277C CN1206277C CN 03141664 CN03141664A CN1206277C CN 1206277 C CN1206277 C CN 1206277C CN 03141664 CN03141664 CN 03141664 CN 03141664 A CN03141664 A CN 03141664A CN 1206277 C CN1206277 C CN 1206277C
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Abstract
The present invention relates to a method for preparing rare earth modified aramid fiber/epoxy composite material. Aramid fiber is pretreated to remove a surface protecting coating and organic substances firstly, and then rare earth modifying agents are adopted to modify the surface of the aramid fiber. Glue solution is prepared according to the categories of epoxy resin and curing agents by a specific proportion, and after the fiber is dipped in the glue solution, a flat plate type core mold is used for the parallel winding around a circumferential digital control winding machine. After solvent in resin is baked by an infrared lamp, the aramid fiber is cut into unidirectional fiber prepreg fabric, and the prepreg fabric is folded according to a certain laying mode and then is put into the flat plate mold to be molded through hot pressing. The rare earth modifying agent comprises rare earth compounds, ethanol, ethylenediamine tetraacetic acid, ammonium chloride, nitric acid and urea. The technological method of the present invention has the advantages of simplicity, low cost and no environmental pollution, and the composite material prepared by the technological method of the present invention has a favorable mechanical property.
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 aramid fiber/epoxy composite material preparation method, be to adopt through the aramid fiber filling epoxy resin of rare-earth modifier surface modification treatment to make matrix material specifically, can improve the bonding force at the interface of aramid fiber/epoxy composite material, and then improve the practical engineering application value of matrix material.
Background technology:
Aramid fiber is a kind of high performance organic fibre, has that superelevation is strong, characteristics such as ultra high modulus, high temperature resistant and light specific gravity.The general organic fibre of its strength ratio is high more than 3 times, and modulus is 10 times of nylon, 9 times of terylene; Its relative intensity is equivalent to 6～7 times of steel wire, and modulus is about 2～3 times in steel wire and glass fibre, and proportion has only about 1/5 of steel wire.Characteristics such as aramid fiber has good shock resistance and fatigue performance, good dielectricity, chemical stability, low bulk, low heat conduction, do not fire, molten, available ordinary loom is woven into fabric, and its intensity of braiding back is not less than 90% of protofibril intensity.Therefore, aramid fiber can be as the strongthener of high performance composite.
The aramid fiber reinforced composite is widely used in fields such as Aeronautics and Astronautics, shipbuilding, automobile and building, and especially at aerospace field, aramid fiber has remarkable advantages as the strongthener of matrix material.The third stage engine of three stage motors of the motor-driven intercontinental missile of MX continental rise of the U.S. and novel latent ground " trident II " D5 guided missile has all adopted the fibre-reinforced Resins, epoxy of Kevlar to twine housing.The motor-driven intercontinental missile of the SS-24 of USSR (Union of Soviet Socialist Republics), SS-25 solid engines housings at different levels have all adopted aramid fiber/epoxy composite material in a large number.Aramid fiber/epoxy composite material is also in large quantities 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.
The aramid fiber surface activity is low, the crystallinity height, and smooth surface, bad with the wetting property of Resins, epoxy, this will cause the interface binding power between fiber and the resin matrix poor, thereby influence the performance of performance of composites.Therefore, must carry out surface modification treatment to fiber.The selection of aramid fiber surface treatment process must be considered the resin matrix of matrix material, selects corresponding surface treatment method according to different resin matrixes.The method that aramid fiber surface modification is handled mainly contains three kinds:
(1) by chemical processes such as use coupling agents, between fiber surface and resin matrix, forms the chemical bond combination.
(2) make fiber surface become coarse by methods such as etching, grafting, oxidations, thereby increase surface-area, increase the mechanical bond power of fiber and resin with the resin matrix contact.
(3) by the active group of Cement Composite Treated by Plasma increase fiber surface, improve the chemically reactive of fiber surface, thus the interface binding power of fortifying fibre and resin.
At present, research of aramid fiber surface treatment process and engineering Application Research have obtained preliminary achievement, but also there are some problems, for example: plasma surface treatment is a kind of method that can carry out continuously, but processing speed slow (only being 0.7m/min) can not (6～10m/s) be complementary with impregnation speed; Make fiber surface become coarse by methods such as etching, oxidations,, can cause damage, influence the intensity of fiber itself fiber though improved the mechanical bond power of fiber and Resins, epoxy; Coupling agent treatment method technology is simple, can carry out mass disposal, but the interfacial layer of coupling agent treatment can decompose under higher working temperature, and the shock resistance at interface, irradiation ability are relatively poor, cause composite property to descend, and fiber bonds together easily after the coupling agent treatment, and industrialness is bad; The treatment effect of most surfaces treatment process is not ideal enough, and the strength conversion ratio of fiber in matrix material is low.
Summary of the invention:
The objective of the invention is at the deficiencies in the prior art, a kind of rare earth modified aramid fiber/epoxy composite material preparation method is provided, it is simple to have technology, low-cost, high-efficiency characteristics, can well improve the interface binding power of aramid fiber and epoxy resin-base, thereby improve the mechanical property of aramid fiber/epoxy composite material.
For realizing such purpose; in the technical scheme of the present invention; at first aramid fiber surface is cleaned pre-treatment; remove coating for surface protection and organism; adopt rare-earth modifier then; at room temperature aramid fiber is soaked modification and handle, after the oven dry, make matrix material with the epoxy resin-matrix volume recombination.Owing to 4f layer structure and electronegativity that rare earth element is special are less, rare earth element itself has outstanding chemically reactive, adopt rare-earth modifier for treatment, can increase the concentration of aramid fiber surface active group, improve the wetting property of fiber and resin matrix, thereby improve the interface binding power of aramid fiber/epoxy composite material.
Aramid fiber of the present invention/epoxy composite material preparation method is specific as follows:
At first, aramid fiber is carried out pre-treatment, adopt the cleaning that refluxes successively of acetone, toluene, three kinds of reagent of deionized water respectively, every kind of agent treated time is 3 hours, dries under 110 ℃ of conditions in baking oven then.
To immerse in the rare-earth modifier through pretreated fiber, immersion treatment 2～4 hours was dried 3～5 hours under 90～110 ℃ of conditions in baking oven.
The weight percentages of components of the rare-earth modifier that the present invention adopts is:
Rare earth compound: 0.1～2%
Ethanol: 96～99.7%
Ethylenediamine tetraacetic acid (EDTA) (EDTA): 0.05～0.5%
Ammonium chloride: 0.1～1%
Nitric acid: 0.02～0.5%
Urea: 0.03～1%
Rare earth compound of the present invention can be Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or cerium oxide.
Add solidifying agent and be mixed with epoxy glue solution in Resins, epoxy, the weight percent of Resins, epoxy and solidifying agent is 100: 7～25, decides according to the kind of Resins, epoxy and solidifying agent.The aramid fiber that the modification of learning from else's experience is handled immerses epoxy glue solution, and the volume percent of epoxy glue solution and aramid fiber is 1: 1.5～4.Behind the impregnation, adopt flat core on the hoop numerical control winding machine, to carry out wound in parallel, behind the roasting solvent that goes in the resin of infrared lamp, cut into unidirectional fibre preimpregnation cloth, again that preimpregnation cloth is superimposed according to unidirectional ply sequence, it is hot-forming to put into flat plate mold, different according to the kind of Resins, epoxy and solidifying agent, hot pressed condition is 50～100 ℃, and pressure is 50～80MPa.
Can make aramid fiber/epoxy laminated composite through above-mentioned technology.
The present invention is applicable to various aramid fiber reinforced epoxy matrix materials, and wherein aramid fiber comprises the Twaron series fiber, Muscovite Terlon fiber, APMOC series fiber, home-made Fanglun l414, F-12 aramid fiber etc. of AKZO company of Kevlar series fiber, the Holland of du pont company.Resins, epoxy comprises bisphenol A type epoxy resin, phenol aldehyde type epoxy resin of the various trades mark etc., as E-51, 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.Adopt aramid fiber ring type filling O compoiste material through rare earth modified processing, can better improve the interface binding power of aramid fiber and Resins, epoxy, thereby can increase substantially the mechanical property of aramid fiber/epoxy composite material, improve the engineering using value of aramid fiber/epoxy composite material.Simultaneously, composite material and preparation method thereof cost of the present invention is low, processing efficiency is high, pollution-free, technology simple, be fit to large-scale commercial production.
Embodiment:
Below by specific embodiment technical scheme of the present invention is further described.
Embodiment 1:
Used raw material comprises: aramid fiber is the F-12 aramid fiber; Resins, epoxy is that Shanghai Resin Factory's production trade mark is the Resins, epoxy (618 resin) of E-51; Solidifying agent adopts 593 (modified aromatic amine) ambient cure agent;
The weight percent of each component of rare-earth modifier is: Lanthanum trichloride: 0.2%, and ethanol: 98.62%, ethylenediamine tetraacetic acid (EDTA) (EDTA): 0.05%, ammonium chloride: 0.1%, nitric acid: 0.03%, urea: 1%.
At first, aramid fiber is carried out pre-treatment, adopt the cleaning that refluxes successively of acetone, toluene, three kinds of reagent of deionized water respectively, every kind of agent treated time is 3 hours, dries under 110 ℃ of conditions in baking oven then.
To immerse in the rare-earth modifier through pretreated fiber, immersion treatment 2 hours was dried 5 hours under 90 ℃ of conditions in baking oven.
Resins, epoxy and solidifying agent are prepared glue according to 100: 25 weight ratio, and the aramid fiber that the modification of learning from else's experience is handled immerses epoxy glue solution, and the volume percent of epoxy glue solution and aramid fiber is 1: 1.6.Behind the fiber impregnation, adopt flat core on the hoop numerical control winding machine, to carry out wound in parallel, behind the roasting solvent that goes in the resin of infrared lamp, cut into unidirectional fibre preimpregnation cloth, again 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 50 ℃, 50MPa.
According to GB3354-82 standard testing matrix material tensile strength is 1980MPa.
Embodiment 2:
Used raw material comprises: E.I.Du Pont Company produces the Kevlar fiber; Resins, epoxy is that Shanghai Resin Factory's production trade mark is the Resins, epoxy (618 resin) of E-51; Solidifying agent is 2-ethyl-4 Methylimidazole that Tianjin chemical reagent factory produces.
The weight percent of each component of rare-earth modifier is: Cerium II Chloride 1%; Ethanol 97.27%; Ethylenediamine tetraacetic acid (EDTA) (EDTA) 0.5%; Ammonium chloride 1%; Nitric acid 0.2%; Urea 0.03%.
The surface preparation of fiber is with embodiment 1.
To immerse in the rare-earth modifier through pretreated fiber, immersion treatment 3 hours was dried 4 hours under 100 ℃ of conditions in baking oven.
Resins, epoxy and solidifying agent are prepared glue according to 100: 7 weight ratio, and the aramid fiber that the modification of learning from else's experience is handled immerses epoxy glue solution, and the volume percent of epoxy glue solution and aramid fiber is 1: 3.8.Behind the fiber impregnation, adopt flat core on the hoop numerical control winding machine, to carry out wound in parallel, behind the roasting solvent that goes in the resin of infrared lamp, cut into unidirectional fibre preimpregnation cloth, again 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 820MPa.
Embodiment 3:
The raw material that adopts only changes rare-earth modifier proportioning and fiber treatment technology with embodiment 2.
The weight percent of each component of rare-earth modifier is: lanthanum trioxide 2%; Ethanol 96.49%; Ethylenediamine tetraacetic acid (EDTA) (EDTA) 0.25%; Ammonium chloride 0.06%; Nitric acid 0.5%; Urea 0.7%.
To immerse in the rare-earth modifier through pretreated fiber, immersion treatment 4 hours was dried 3 hours under 110 ℃ of conditions in baking oven.
The fiber of above-mentioned processing is made unidirectional aramid fiber reinforced epoxy matrix material according to the composite material process planning of embodiment 2.
According to GB3352-82 standard testing matrix material shearing resistance is 73.6MPa.
Claims (1)
1; a kind of rare earth modified aramid fiber/epoxy composite material preparation method; it is characterized in that at first aramid fiber being carried out pre-treatment to remove coating for surface protection and organism; adopt acetone respectively; toluene; the cleaning that refluxes successively of three kinds of reagent of deionized water; every kind of agent treated time is 3 hours; in baking oven, dry under 110 ℃ of conditions then; to immerse in the rare-earth modifier through pretreated fiber; immersion treatment 2～4 hours; in baking oven, dried 3～5 hours under 90～110 ℃ of conditions; in Resins, epoxy, add solidifying agent and be mixed with epoxy glue solution; the weight percent of Resins, epoxy and solidifying agent is 100: 7～25; the aramid fiber that the modification of learning from else's experience is handled immerses epoxy glue solution; the volume percent of epoxy glue solution and aramid fiber is 1: 1.5～4; behind the impregnation; adopt flat core on the hoop numerical control winding machine, to carry out wound in parallel; behind the roasting solvent that goes in the resin of infrared lamp; cut into unidirectional fibre preimpregnation cloth; again that preimpregnation cloth is superimposed according to unidirectional ply sequence; it is hot-forming to put into flat plate mold; hot pressed condition is 50～100 ℃; pressure is 50～80Mpa; wherein; the weight percentages of components of described rare-earth modifier is: the rare earth compound Lanthanum trichloride; Cerium II Chloride; lanthanum trioxide or cerium oxide: 0.1～2%; ethanol: 96～99.7%; ethylenediamine tetraacetic acid (EDTA): 0.05～0.5%; ammonium chloride: 0.1～1%; nitric acid: 0.02～0.5%, urea: 0.03～1%.
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| CN 03141664 CN1206277C (en) | 2003-07-17 | 2003-07-17 | Preparation method of rare earth modified fanglun fiber/epoxy composite material |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366815C (en) * | 2005-01-13 | 2008-02-06 | 福州大学 | Anionic grafting method for modification of aramid fiber surface |
| CN102516570B (en) * | 2011-10-21 | 2014-01-01 | 苏州大学 | Aramid fiber-reinforced rein-based composite material and preparation method thereof |
| 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 |
| CN104131455B (en) * | 2013-05-02 | 2016-02-24 | 黑龙江弘宇短纤维新材料股份有限公司 | A kind of preparation method of the preliminary treatment aramid fiber short fibre for rubber |
| CN103740103A (en) * | 2014-01-24 | 2014-04-23 | 深圳天鼎精细化工制造有限公司 | Aramid fiber/epoxy resin composite material and preparation method thereof |
| CN104404772B (en) * | 2014-12-06 | 2016-09-07 | 苏州大学 | A kind of surface modification aramid fiber and preparation method thereof |
| CN105671932A (en) * | 2016-01-13 | 2016-06-15 | 宁波大学 | Method used for removing sizing agent on surface of aramid fiber, soak solution and leacheate |
| CN110761079B (en) * | 2019-10-09 | 2020-09-04 | 江南大学 | Infrared traceability anti-counterfeiting method for down fibers |
| CN113585183A (en) * | 2021-08-20 | 2021-11-02 | 南京工业大学 | Pier isolation type composite material elastic ship collision prevention bent frame structure system and construction method thereof |
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