CN101787208A - Method for preparing rare-earth modified polyethylene fiber polyimide composite materials - Google Patents
Method for preparing rare-earth modified polyethylene fiber polyimide composite materials Download PDFInfo
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- CN101787208A CN101787208A CN 201010135901 CN201010135901A CN101787208A CN 101787208 A CN101787208 A CN 101787208A CN 201010135901 CN201010135901 CN 201010135901 CN 201010135901 A CN201010135901 A CN 201010135901A CN 101787208 A CN101787208 A CN 101787208A
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Abstract
The invention relates to a method for preparing rare-earth modified polyethylene fiber polyimide composite materials in the technical field of composite materials. The method comprises the following steps: immersing polyethylene fibers in a rare-earth modifier, and drying the obtained polyethylene fibers; stirring the polyethylene fibers with polyimide powder, and putting the mixed powder into a vulcanizing press mould for forming; raising the furnace temperature to 270 DEG C and preserving the heat for 80 minutes; performing preplasticization on preformed blanks for forming molded materials; and reducing the temperature along with a furnace to below 180 DEG C, taking the composite materials after compression molding out along with the mould, and cooling to room temperature to prepare polyethylene fiber polyimide wear-resisting composite materials. The method has the advantages of simple process, low cost and no environmental pollution, and the prepared rare-earth modified polyethylene fiber polyimide composite materials have good mechanical property and tribological performance.
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 polyethylene fiber polyimide composite materials.
Background technology
Thermoplastic polyimide (PI) matrix material not only has corrosion-resistant, nontoxicity, also has the not available characteristics of processing and using of repeating of same with thermosetting compound material, avoids producing the three wastes, helps environmental protection, thereby extremely people's attention, and development rapidly.PI has outstanding thermostability, good shock resistance, radioprotective and solvent resistance, under extreme environments such as high temperature, high-low pressure and high speed good friction and wear behavior is arranged, and is the very potential body material that is applied to tribological field of a class.But pure PI is not suitable for using as friction materials separately because of lower tension, ultimate compression strength, and can obtain the PI matrix material of mechanical property and frictional behaviour excellence behind the adding fortifying fibre.
Superhigh molecular weight polyethylene fibers has height-oriented extended-chain configuration, compares with carbon fiber, aramid fiber, and the intensity of superhigh molecular weight polyethylene fibers is higher, and weight is lighter, and density has only 0.97 gram centimeter
3Chemical stability is better, has very strong unreactiveness, strong acid, strong base solution and organic solvent to its intensity without any influence; Have good weather and UV resistant performance, after Exposure to Sunlight in 1500 hours, the fibre strength conservation rate is still up to 80%, and lower temperature resistance is good, and use temperature can be low to moderate 150 ℃; In addition, wear-resisting resistance to bend(ing) energy, tension force fatigue property, cutting resistance can also be very outstanding.Polyethylene has methylene radical, and (CH2-CH2-) chemical structure of continuous macromolecular chain, the used raw material UHMWPE of polyethylene fibre has the non-crystalline region of a large amount of random coils and the crystalline structure of folded chain.When super times of drawing-off, the height-oriented macromole of crystalline region and non-crystalline region that makes of its macromolecular chain fully stretches, and has formed the supramolecular structure of the uncrimping chain of highly crystalline.The high-performance of polyethylene fibre is because its this supramolecular structure determines fully.The superhigh molecular weight polyethylene fibers plastics have the excellent properties that general matrix material does not have, and are a kind of brand-new hi tech and new materials, have good commercial development and application prospect.Superhigh molecular weight polyethylene fibers provides a brand-brand-new way for the enhancing modified of polyimide.
But, because the smooth surface of polyethylene fibre axial height orientation (>95%) and degree of crystallinity height (>99%), itself form by simple methylene radical, make fiber surface not only without any the reactive behavior point, can't with the resin formation chemical bonding, make its surface energy low and difficult, do not have coarse surface again, so just seriously limited its application in polymer matrix composites for forming the mechanical engagement point by resin wetted.Therefore modification is carried out on the surface of polyethylene fibre and handled, the adhesiveproperties of raising and resin matrix enlarges the application in matrix material, is very important research direction of polyethylene fibre always.
The polyethylene fibre surface processing method of bibliographical information mainly contains physical method, chemical process, plasma body, radiation crosslinking, corona discharge etc. at present.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of rare-earth modified polyethylene fiber polyimide composite materials is provided, it is simple to have technology, the characteristics of low-cost high-efficiency, can well improve the interface binding power of polyethylene fiber peacekeeping polyimide matrix, thereby improve the over-all properties of matrix material.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
1. polyethylene fibre is immersed and soak 3~5 hours in the rare-earth modifier, the baking oven of again polyethylene fibre that obtains being put into 120 ℃ is fully dried;
2. the polyethylene fibre after will handling carries out the powerful stirring of machinery with the polyimide powder, and the volume percent of control polyethylene fibre is 15~40% of a mixed powder, after stirring mixed powder is put into plate vulcanization machine die for molding;
3. furnace temperature is warming up to about 270 ℃, kept 80 minutes;
4. the premolding blank is carried out preformed, pressure-controlling is at 12~15MPa, is warming up to 330~350 ℃ with 1 ℃ minute speed again, is incubated 65 minutes, makes the molding compound moulding;
5. adopt subsequently with the stove temperature reduction way and cool to 180 ℃, pressure remains under the constant pressure in whole process;
6. when temperature drops to below 180 ℃, pressure is removed, the matrix material after the compression molding is taken out together with mould,, make the polyethylene fiber polyimide wearing composite material with the room temperature cooling.
The weight percentages of components of described rare-earth modifier is: rare earth compound 2~8%, ethanol 83~95%, ethylenediamine tetraacetic acid (EDTA) 0.2~1.0%, ammonium chloride 0.5~2%, nitric acid 0.5~1%, urea 1.8~5%.
Described rare earth compound is Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or cerium oxide.
Described polyimide is a thermoplastic polyimide.
The present invention at room temperature adopts rare-earth modifier that polyethylene fibre is carried out surface modification treatment earlier, polyethylene fibre oven dry back after will handling then is compound with polyimide, obtain rare-earth modified polyethylene fiber polyimide composite materials through hot compression molding, make polyethylene fiber polyimide composite materials sample or part by mechanical workout again.Adopt through rare earth surface-treated polyethylene fibre filled polyimide matrix material, to obtain than higher interface binding power the hardness of raising polyimide resin matrix, and then the mechanical property and the abrasion resistance properties of raising matrix material.
The present invention adopts the rare-earth modifier for treatment polyethylene fibre, can improve the interface binding power of matrix material better, improve the dispersiveness of polyethylene fibre, thereby improve the tribological property and the mechanical property of matrix material more significantly, and the rare-earth modifier for treatment processing method is simple, and cost is low, environmentally safe, handle the back polyethylene fibre and can not bond together good manufacturability.The present invention is applicable to that polyethylene fibre strengthens composite polyimide material, adopts the matrix material of the inventive method preparation, and wear resistance is good, and especially the anti impact wear-proof ability significantly improves, and its tensile strength, flexural strength and impelling strength are significantly improved.
Embodiment
Below by specific embodiment technical scheme of the present invention is further described, but do not constitute limitation of the invention.
Embodiment 1:
Used starting material comprise: the GCPI that polyimide resin powder, Changzhou extensively become plastics company limited to produce
TMType, 150 orders.Polyethylene fibre: Ningbo Dacheng New Material Co., Ltd.
Each weight percentages of components is as follows in the rare-earth modifier:
Lanthanum trichloride 5%, ethanol 90%, ethylenediamine tetraacetic acid (EDTA) 0.5%, ammonium chloride 1%, nitric acid 0.6%, urea 2.9%.
Each component volume percent of starting material is as follows:
Polyimide: 80%
Polyethylene fibre: 20%
Earlier polyethylene fibre is carried out pre-treatment, polyethylene fibre is at room temperature immersed in the above-mentioned rare-earth modifier, soaked 3.5 hours.Secondly the baking oven of the polyethylene fibre that obtains being put into 120 ℃ is fully dried.Polyethylene fibre after will handling then carries out the powerful stirring of machinery with the polyimide powder according to aforementioned proportion, after stirring mixed powder is put into plate vulcanization machine die for molding, earlier furnace temperature is warming up to about 270 ℃, kept 80 minutes, the premolding blank is carried out preformed, this moment, pressure-controlling was about 12MPa, and then be warming up to about 330 ℃ with 1 ℃ minute speed, be incubated 65 minutes, make the molding compound moulding, lower the temperature subsequently, employing is with the stove temperature reduction way, cool to 180 ℃, concrete temperature fall time is decided on envrionment conditions, and pressure remains at 12MPa in whole process, after temperature drops to below 180 ℃, pressure is removed, matrix material after the compression molding is taken out together with mould,, obtain rare-earth modified polyethylene fiber polyimide composite materials with the room temperature cooling.
The matrix material that makes according to the method described above, recording its tensile strength according to standard is 125MPa.
Example in contrast, under identical polyethylene fiber dimension hplc and composite material preparation process condition, strengthening the composite polyimide material tensile strength without the polyethylene fibre of rare earth modified processing is 98MPa.As can be seen, rare-earth modifier for treatment can obviously improve the tensile property of matrix material.
Embodiment 2:
Used starting material comprise: the GCPI that polyimide resin powder, Changzhou extensively become plastics company limited to produce
TMType, 150 orders.Polyethylene fibre: Ningbo Dacheng New Material Co., Ltd.
Each weight percentages of components in the rare-earth modifier: lanthanum trioxide 3%, ethanol 92.7%, ethylenediamine tetraacetic acid (EDTA) 0.3%, ammonium chloride 0.8%, nitric acid 0.7%, urea 2.5%.
Each component volume percent of starting material is as follows:
Polyimide: 75%
Polyethylene fibre: 25%
Earlier polyethylene fibre is carried out pre-treatment, polyethylene fibre is at room temperature immersed in the above-mentioned rare-earth modifier, soaked 4 hours.Secondly the baking oven of the polyethylene fibre that obtains being put into 120 ℃ is fully dried.Polyethylene fibre after will handling then carries out the powerful stirring of machinery with the polyimide powder according to aforementioned proportion, after stirring mixed powder is put into plate vulcanization machine die for molding, earlier furnace temperature is warming up to about 270 ℃, kept 80 minutes, the premolding blank is carried out preformed, this moment, pressure-controlling was about 13.5MPa, and then be warming up to about 340 ℃ with 1 ℃ minute speed, be incubated 65 minutes, make the molding compound moulding, lower the temperature subsequently, employing is with the stove temperature reduction way, cool to 180 ℃, concrete temperature fall time is decided on envrionment conditions, and pressure remains at 13.5MPa in whole process, after temperature drops to below 180 ℃, pressure is removed, matrix material after the compression molding is taken out together with mould,, obtain rare-earth modified polyethylene fiber polyimide composite materials with the room temperature cooling.Above-mentioned materials is machined into the rub(bing)test sample.
Utilize MMD-10 type metope wear testing machine, matrix material is carried out the friction and wear behavior test, and compare with the polyethylene fibre filled polyimide matrix material of handling without rare earth, experimental result shows: the friction and wear behavior of the polyethylene fiber polyimide composite materials of handling through rare earth is better than the polyethylene fiber polyimide composite materials handled without rare earth.
Embodiment 3
Used starting material comprise: the GCPI that polyimide resin powder, Changzhou extensively become plastics company limited to produce
TMType, 150 orders.Polyethylene fibre: Ningbo Dacheng New Material Co., Ltd.
Each weight percentages of components in the rare-earth modifier: cerium oxide 6%, ethanol 86.9%, ethylenediamine tetraacetic acid (EDTA) 0.8%, ammonium chloride 1.5%, nitric acid 0.8%, urea 4%.
Each component volume percent of starting material is as follows:
Polyimide: 78%
Polyethylene fibre: 22%
Earlier polyethylene fibre is carried out pre-treatment, polyethylene fibre is at room temperature immersed in the above-mentioned rare-earth modifier, soaked 5 hours.Secondly the baking oven of the polyethylene fibre that obtains being put into 120 ℃ is fully dried.Polyethylene fibre after will handling then carries out the powerful stirring of machinery with the polyimide powder according to aforementioned proportion, after stirring mixed powder is put into plate vulcanization machine die for molding, earlier furnace temperature is warming up to about 270 ℃, kept 80 minutes, the premolding blank is carried out preformed, this moment, pressure-controlling was about 14MPa, and then be warming up to about 345 ℃ with 1 ℃ minute speed, be incubated 65 minutes, make the molding compound moulding, lower the temperature subsequently, employing is with the stove temperature reduction way, cool to 180 ℃, concrete temperature fall time is decided on envrionment conditions, and pressure remains at 14MPa in whole process, after temperature drops to below 180 ℃, pressure is removed, matrix material after the compression molding is taken out together with mould,, obtain rare-earth modified polyethylene fiber polyimide composite materials with the room temperature cooling.
Above-mentioned matrix material machinery is processed into sample, carries out on the MPV200 type that the is determined at friction wear testing machine of friction coefficient of composite material and abrasion loss, before each test, sample and antithesis ring surface acetone cotton balls scrub.Test-results: frictional coefficient is 0.16, and load is when 500N, and abrasion loss is 215mmg.
Claims (4)
1. the preparation method of a rare-earth modified polyethylene fiber polyimide composite materials is characterized in that, comprises the steps:
1. polyethylene fibre is immersed and soak 3~5 hours in the rare-earth modifier, the baking oven of again polyethylene fibre that obtains being put into 120 ℃ is fully dried;
2. the polyethylene fibre after will handling carries out the powerful stirring of machinery with the polyimide powder, and the volume percent of control polyethylene fibre is 15~40% of a mixed powder, after stirring mixed powder is put into plate vulcanization machine die for molding;
3. furnace temperature is warming up to about 270 ℃, kept 80 minutes;
4. the premolding blank is carried out preformed, pressure-controlling is at 12~15MPa, is warming up to 330~350 ℃ with 1 ℃ minute speed again, is incubated 65 minutes, makes the molding compound moulding;
5. adopt subsequently with the stove temperature reduction way and cool to 180 ℃, pressure remains under the constant pressure in whole process;
6. when temperature drops to below 180 ℃, pressure is removed, the matrix material after the compression molding is taken out together with mould,, make the polyethylene fiber polyimide wearing composite material with the room temperature cooling.
2. according to the preparation method of the rare-earth modified polyethylene fiber polyimide composite materials of claim 1, it is characterized in that, the weight percentages of components of described rare-earth modifier is: rare earth compound 2~8%, ethanol 83~95%, ethylenediamine tetraacetic acid (EDTA) 0.2~1.0%, ammonium chloride 0.5~2%, nitric acid 0.5~1%, urea 1.8~5%.
3. according to the preparation method of the rare-earth modified polyethylene fiber polyimide composite materials of claim 2, it is characterized in that described rare earth compound is Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or cerium oxide.
4. according to the preparation method of the rare-earth modified polyethylene fiber polyimide composite materials of claim 1, it is characterized in that described polyimide is a thermoplastic polyimide.
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Citations (6)
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US6329603B1 (en) * | 1999-04-07 | 2001-12-11 | International Business Machines Corporation | Low CTE power and ground planes |
CN1587319A (en) * | 2004-08-12 | 2005-03-02 | 上海交通大学 | Process for preparing rare-earth modified carbon fiber/polyimide composite material |
CN1730262A (en) * | 2005-06-15 | 2006-02-08 | 沈阳海鑫科技有限公司 | Compression molding technique for thermostable polyimide and its composite material |
CN1793230A (en) * | 2005-12-29 | 2006-06-28 | 上海交通大学 | Process for preparing composite of rare earth modified glass fibre/polyimide |
CN1803922A (en) * | 2005-12-29 | 2006-07-19 | 上海交通大学 | Method for preparing poly(p-phenylene benzobisoxazole)/polyimide composite material |
JP2008095210A (en) * | 2006-10-06 | 2008-04-24 | Nippon Sheet Glass Co Ltd | Insect-repelling sheet and method for producing the same, and method for preventing insect from house |
-
2010
- 2010-03-31 CN CN 201010135901 patent/CN101787208A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6329603B1 (en) * | 1999-04-07 | 2001-12-11 | International Business Machines Corporation | Low CTE power and ground planes |
CN1587319A (en) * | 2004-08-12 | 2005-03-02 | 上海交通大学 | Process for preparing rare-earth modified carbon fiber/polyimide composite material |
CN1730262A (en) * | 2005-06-15 | 2006-02-08 | 沈阳海鑫科技有限公司 | Compression molding technique for thermostable polyimide and its composite material |
CN1793230A (en) * | 2005-12-29 | 2006-06-28 | 上海交通大学 | Process for preparing composite of rare earth modified glass fibre/polyimide |
CN1803922A (en) * | 2005-12-29 | 2006-07-19 | 上海交通大学 | Method for preparing poly(p-phenylene benzobisoxazole)/polyimide composite material |
JP2008095210A (en) * | 2006-10-06 | 2008-04-24 | Nippon Sheet Glass Co Ltd | Insect-repelling sheet and method for producing the same, and method for preventing insect from house |
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