CN101838442A - Preparation method of rare earth modified glass fiber epoxy resin composite material - Google Patents
Preparation method of rare earth modified glass fiber epoxy resin composite material Download PDFInfo
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- CN101838442A CN101838442A CN201010213814A CN201010213814A CN101838442A CN 101838442 A CN101838442 A CN 101838442A CN 201010213814 A CN201010213814 A CN 201010213814A CN 201010213814 A CN201010213814 A CN 201010213814A CN 101838442 A CN101838442 A CN 101838442A
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Abstract
The invention discloses a preparation method of a rare earth modified glass fiber epoxy resin composite material in the technical field of composite materials, which comprises the following steps: firstly, carrying out ablation pretreatment on a glass fiber to ensure that the organic residual quantity on the surface is below 1 percent; adopting a rare earth modifier for treating, immersing the glass fiber into the rare earth modifier at room temperature, soaking the mixture for 2-4 hours, filtering and parching; mechanically blending a chopped or powdery glass fiber with epoxy resin powder; then placing the mixed powder into a vulcanizing press die for forming; and taking out the composite material formed by die press with the die and cooling along with room temperature to obtain a rare earth modified glass fiber epoxy resin wearable composite material. The invention has the advantages of simple process method, low cost and no pollution on the environment. The composite material prepared by adopting the process method has excellent mechanical property.
Description
Technical field
That the present invention relates to is a kind of preparation method of technical field of composite materials, in particular a kind of preparation method of rare-earth-modified glass-fiber epoxy-resin composite materials.
Background technology
The main component of glass fibre is SiO
2, B
2O
3, and the oxide compound of sodium, potassium, calcium, aluminium etc.In general, the chemical stability of glass is relatively good, and characteristics such as that glass fibre has is high temperature resistant, high strength, high elastic coefficient, creep resistance are the most frequently used fortifying fibres of preparation performance resins based composites.The excellent high temperature resistance that the glass fiber reinforced epoxy resin matrix material has, anti-irradiation, high strength than and high ratio of rigidity, self-lubricating, wear-resisting, antifatigue and characteristics such as corrosion-resistant, potential is used and to be comprised automobile and fuel system component, bearing, electronic component, anti scuffing shell etc., the other characteristic of this matrix material is good flame resistance, energy recycling, highly heat-resistant and dimensional stabilizing etc., be widely used in fields such as automobile, building materials, packing, transportation, chemical industry, shipbuilding, furniture, Aeronautics and Astronautics, can be used as structured material and friction materials.
But, affinity between glass fibre and the thermoplastic resin matrix is relatively poor, lacks chemical bonding and interfacial layer and has immiscible component, and interface binding intensity is low, compound tense forms space and defective easily on the interface, strengthen body and matrix resin and be difficult to be formed with effective adhesive.Composite material interface is the tie that wild phase and matrix are got in touch, and also is the bridge of wild phase performance effective capacity.For this reason, must be by to methods such as the physics of the surface modification of glass fibre and matrix, chemical modifications, improve the wetting property between fiber and the matrix, even between fiber and matrix, form Chemical bond, to improve the interface combination degree between fiber and the matrix, obtain the high matrix material of interlaminar shear strength.
At present, mainly use oxidation style, sedimentation, electropolymerization and electrodip process, Cement Composite Treated by Plasma waits the interface binding power that improves glass fibre and polymeric matrix, to improve the over-all properties of glass fibre reinforced polymer composites.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 glass-fiber epoxy-resin composite materials preparation method is provided, the present invention will be filled into Resins, epoxy and be prepared into matrix material through the glass fibre of rare-earth modifier for treatment, with the bonding force at the interface of improving glass-fiber epoxy-resin composite materials, and then the practical engineering application that improves matrix material is worth; It is simple to have technology, the characteristics of low-cost high-efficiency.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
1. at first, to the glass fibre pre-treatment of ablating, make its surface organic matter residual quantity below 1%;
2. adopt rare-earth modifier for treatment, glass fibre is at room temperature immersed in the rare-earth modifier, soaked 2～4 hours, after the filtration, oven dry;
3. the weak point after will handling is cut or mealy glass fibre carries out mechanical blending with the Resins, epoxy powder, then mixed powder is put into plate vulcanization machine die for molding;
4. the matrix material after the compression molding is taken out together with mould,, obtain the glass-epoxy wearing composite material with the room temperature cooling.
Described ablation pre-treatment is meant: ablated in 450～600 ℃ 0.5～1 hour.
The weight percentages of components of described rare-earth modifier 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%.
Described rare earth compound is Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or cerium oxide.
Described glass fibre is an alkali free glass fibre; Described Resins, epoxy is thermoplastic epoxy or thermosetting epoxy resin.
The constituent mass per-cent of described mixed powder: Resins, epoxy 35～45%, glass fibre, 10～20%, surplus: the auxiliary material that comprises molybdenumdisulphide and/or mineral dye.
Described moulding, earlier furnace temperature is warming up to about 280 ℃, kept 60 minutes, the premolding blank is carried out preformed, pressure-controlling is at 10～14MPa, and then be warming up to 320～360 ℃ with 60 ℃ hours speed, be incubated 1 hour, adopt subsequently with the stove temperature reduction way and cool to 200 ℃, pressure remains under the constant pressure in whole process, after dropping to below 200 ℃, temperature pressure is removed stripping forming.
The present invention carries out pre-treatment to remove the organism of remained on surface to glass fibre earlier, at room temperature adopt rare-earth modifier that glass fibre is carried out surface modification treatment again, kind according to Resins, epoxy and solidifying agent, according to certain prescription and proportional arrangement glue, glass fibre after handling is immersed epoxy resin adhesive liquid make prepreg, then the after heat of prepreg lamination is pressed solidly the type of changing into, make the glass fibre epoxy composite material.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 fiberglass surfacing treating processes, be adsorbed on of the form appearance of a part of rare earth element of fiberglass surfacing with active rare earth atom, they might enter the top layer and reside in fault location by the fiberglass surfacing defective, 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 fiberglass surfacing, thereby help the absorption of rare earth atom more, and surface adsorption concentration is greatly improved, and have promoted the fiberglass surfacing treating processes.The formation at active rare earth atom and active rare-earth center has been played clean activatory effect to fiberglass surfacing, can further improve the interface binding power between glass fibre and the Resins, epoxy.The active rare earth atom of fiberglass surfacing is the real source that rare earth element plays a role.Can improve the interfacial combined function of glass-fiber epoxy-resin composite materials by the chemical action that takes place with glass fibre and matrix resin.
The present invention is applicable to various glass fiber reinforced epoxy resin matrix materials, and wherein glass fibre comprises the PAN base and the asphaltic base short glass fiber of various models, as T-300 etc.Resins, epoxy comprises the bisphenol A type epoxy resin and the non-bisphenol-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 adopted the rare-earth modifier for treatment fiberglass surfacing, 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 glass fibre 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 embodiments of the invention are elaborated: present embodiment has provided detailed embodiment and process being to implement under the prerequisite with the technical solution of the present invention, but protection scope of the present invention is not limited to following embodiment.
The solidifying agent that following examples are used is conventional to look different glass fibre kind and definite concrete ratio, solidifying agent adopts the imidazoles high reactivity solidifying agent in the conventional arts such as imidazoles, glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, can make epoxy resin cure in the following short period of time of middle temperature.
Embodiment 1:
Used starting material comprise: Resins, epoxy, and the E-51 bisphenol A type epoxy resin that Shanghai factory produces, solidifying agent is 593 modified aromatic amine curing agents (ambient cure); Glass fibre, the high strong type of no coating PAN base, the carbon element factory, Jilin produces.
Each weight percentages of components is as follows in the rare-earth modifier:
Lanthanum trichloride: 2%, ethanol: 93%, ethylenediamine tetraacetic acid (EDTA) (EDTA): 2%, ammonium chloride: 1%, nitric acid: 0.5%, urea: 1.5%.
Earlier glass fibre 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, glass fibre is at room temperature immersed in the properties-correcting agent, soaked 2 hours, after the filtration, oven dry.
According to Resins, epoxy: solidifying agent is 4: 1 a proportional arrangement epoxy glue solution, glass fibre and Resins, epoxy after handling is compound, make unidirectional pre-immersion material, the 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, 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: Resins, epoxy is that the Shanghai factory production trade mark is the Resins, epoxy (618 resin) of E-51; Glass fibre: T-300, coatingsurface is handled glass fibre, and toray company produces; 2-ethyl-4 Methylimidazole that solidifying agent Tianjin chemical reagent factory produces.
Each weight percentages of components in the rare-earth modifier: Cerium II Chloride 7%; Ethanol 76%; Ethylenediamine tetraacetic acid (EDTA) (EDTA) 9%; Ammonium chloride 5%; Nitric acid 1%; Urea 2%.
Earlier glass fibre 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, glass fibre is at room temperature immersed in the properties-correcting agent, soaked 3 hours, after the filtration, oven dry.
Resins, epoxy and solidifying agent are prepared glue according to 100: 7 weight ratio, the glass fibre that the modification of learning from else's experience is handled immerses epoxy glue solution, make unidirectional pre-immersion material, prepreg contains Resins, epoxy 40%, 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 glass fibre 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, glass fibre 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 (7)
1. the preparation method of a rare-earth-modified glass-fiber epoxy-resin composite materials is characterized in that, comprises the steps:
1. at first, to the glass fibre pre-treatment of ablating, make its surface organic matter residual quantity below 1%;
2. adopt rare-earth modifier for treatment, glass fibre is at room temperature immersed in the rare-earth modifier, soaked 2～4 hours, after the filtration, oven dry;
3. the weak point after will handling is cut or mealy glass fibre carries out mechanical blending with the Resins, epoxy powder, then mixed powder is put into plate vulcanization machine die for molding;
4. the matrix material after the compression molding is taken out together with mould,, obtain the glass-epoxy wearing composite material with the room temperature cooling.
2. the preparation method of rare-earth-modified glass-fiber epoxy-resin composite materials as claimed in claim 1 is characterized in that, described ablation pre-treatment is meant: ablated in 450～600 ℃ 0.5～1 hour.
3. the preparation method of rare-earth-modified glass-fiber epoxy-resin composite materials as claimed in claim 1, it is characterized in that the weight percentages of components of described 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%.
4. the preparation method of rare-earth-modified glass-fiber epoxy-resin composite materials as claimed in claim 1 is characterized in that, described rare earth compound is Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or cerium oxide.
5. the preparation method of rare-earth-modified glass-fiber epoxy-resin composite materials as claimed in claim 1 is characterized in that, described glass fibre is an alkali free glass fibre, and Resins, epoxy is thermoplastic epoxy or thermosetting epoxy resin.
6. the preparation method of rare-earth-modified glass-fiber epoxy-resin composite materials as claimed in claim 1, it is characterized in that, the constituent mass per-cent of described mixed powder: Resins, epoxy 35～45%, glass fibre, 10～20%, surplus: the auxiliary material that comprises molybdenumdisulphide and/or mineral dye.
7. the preparation method of rare-earth-modified glass-fiber epoxy-resin composite materials as claimed in claim 1, it is characterized in that, described moulding, earlier furnace temperature is warming up to about 280 ℃, kept 60 minutes, the premolding blank is carried out preformed, pressure-controlling is at 10～14MPa, and then be warming up to 320～360 ℃ with 60 ℃ hours speed, be incubated 1 hour, adopt subsequently with the stove temperature reduction way and cool to 200 ℃, pressure remains under the constant pressure in whole process, after dropping to below 200 ℃, temperature pressure is removed stripping forming.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010213814A CN101838442A (en) | 2010-06-30 | 2010-06-30 | Preparation method of rare earth modified glass fiber epoxy resin composite material |
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|---|---|---|---|
| CN201010213814A CN101838442A (en) | 2010-06-30 | 2010-06-30 | Preparation method of rare earth modified glass fiber epoxy resin composite material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103758906A (en) * | 2014-01-17 | 2014-04-30 | 广州大学 | Fiber reinforced epoxy resin/rubber laminated isolation bearing and production method thereof |
| CN103772921A (en) * | 2012-10-22 | 2014-05-07 | 黑龙江鑫达企业集团有限公司 | Glass fiber reinforced poly(ethylene terephthalate)/polycarbonate alloy |
| CN108659410A (en) * | 2017-03-31 | 2018-10-16 | 南京工业大学 | Rare earth modified superfine glass fiber/fluoropolymer composite material and preparation method |
-
2010
- 2010-06-30 CN CN201010213814A patent/CN101838442A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772921A (en) * | 2012-10-22 | 2014-05-07 | 黑龙江鑫达企业集团有限公司 | Glass fiber reinforced poly(ethylene terephthalate)/polycarbonate alloy |
| CN103772921B (en) * | 2012-10-22 | 2016-06-29 | 黑龙江鑫达企业集团有限公司 | A kind of fiberglass reinforced polyethyleneterephthalate/polycarbonate alloy |
| CN103758906A (en) * | 2014-01-17 | 2014-04-30 | 广州大学 | Fiber reinforced epoxy resin/rubber laminated isolation bearing and production method thereof |
| CN108659410A (en) * | 2017-03-31 | 2018-10-16 | 南京工业大学 | Rare earth modified superfine glass fiber/fluoropolymer composite material and preparation method |
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Open date: 20100922 |