CN1051328C - Carbon fibre reinforced high-molecular composite material and preparing process thereof - Google Patents
Carbon fibre reinforced high-molecular composite material and preparing process thereof Download PDFInfo
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- CN1051328C CN1051328C CN94104725A CN94104725A CN1051328C CN 1051328 C CN1051328 C CN 1051328C CN 94104725 A CN94104725 A CN 94104725A CN 94104725 A CN94104725 A CN 94104725A CN 1051328 C CN1051328 C CN 1051328C
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- composite material
- carbon cloth
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Abstract
The present invention relates to a carbon fiber reinforced high molecular composite material with high strength, low-density, wear resistance and self lubrication. The composite material is prepared from aromatic heterocyclic polymer, such as teflon, polyarylether sulfone, polysulfone, etc., high temperature resistant soluble polymer, such as polyimide, etc., carbon cloth, a surface modifier of the carbon cloth, etc. The composite material has high workability, favorable physical and mechanical properties and favorable wear resistant and self-lubricating properties under the working conditions of high speed, great PV value and dry friction and is suitable for specific environment, such as low temperature environment, vacuum environment, irradiation environment, corrosion environment, etc.
Description
The invention relates to a kind of high-strength low-density wear-resistant self-lubricating carbon fibre reinforced high-molecular material and preparation technology.
Self-lubricating material all has certain scope of application, an important measurement index is its limit PV value under DRY SLIDING, common macromolecule self-lubricating composite and the limit PV value of other conventional integrated solid lubricating composite under DRY SLIDING generally are no more than 3～5MPa.m/8, how solving lubrication problem and material adaptability problem under the bigger PV value operating mode (promptly harsher working condition) under the DRY SLIDING, is the great technical barrier of the solution that development presses for of current hard-core technology.
Carbon fibre reinforced high-molecular composite material has obtained in the sophisticated technology field to use widely as a kind of type material, has solved the great technical barrier that many other conventional materials cann't be solved.But carbon fibre reinforced high-molecular composite material mainly was as structured material in the past, the emphasis of research also is to lay particular emphasis on the specific tenacity that improves material etc., with it as the antifriction self-lubricating material that uses under the extreme operating condition condition, consider its tribological property from The Nomenclature Composition and Structure of Complexes, do not see document and patent report as yet.
The carbon fibre reinforced high-molecular composite material that the purpose of this invention is to provide a kind of high strength, low density, wear-resistant self-lubricating solves the adaptability problem and relevant friction problem of the material under at a high speed big PV value metal to-metal contact working condition and the particular surroundings.
Another object of the present invention provides the preparation technology of above-mentioned wear-resistant self-lubricating carbon fibre reinforced high-molecular composite material.
Purpose of the present invention realizes by following measure.
The composition of carbon fibre reinforced high-molecular composite material of the present invention (wt%):
Carbon cloth 35～80
Polyether sulphone 0～60
Polysulfones 0～40
Polyimide 0～50
Tetrafluoroethylene 0～30
Coupling agent 0～2
The composition that the present invention preferentially selects for use (wt%):
Carbon cloth 45～65
Polyether sulphone 35～50
Polysulfones 5～20
Tetrafluoroethylene 5～15
Coupling agent 0.5～1.5
The carbon cloth that above-mentioned carbon fibre reinforced high-molecular composite material is selected for use is preferably hole count less than strong among the 3K or high-strength polyacrylonitrile carbon cloth, gluing carbon cloth, Graphite cloth, pitch prill carbon cloth.
The viscosity of polyether sulphone is η=0.16～0.90.Preferentially select the modified polyarylether sulfone PES-C of having circle type side group on its main chain for use, its structural formula is as (I)
The viscosity of used polysulfones is preferably η=0.15～0.60.
Polyimide is a soluble polyimide
Preferably less than 8 μ m, purity is greater than 95% for the granularity of tetrafluoroethylene.
Preparation technology of the present invention is as follows:
To commercially available carbon cloth come unstuck processing, be about to carbon cloth and be soaked in capacity dimethylbenzene or the acetone solvent 24 hours, clean and oven dry with acetone then.
2. take by weighing each component in following ratio (wt%)
Carbon cloth 35～80
Polyether sulphone 0～60
Polysulfones 0～40
Polyimide 0～50
Tetrafluoroethylene 0～30
3. will mix by 2 polyether sulphones that taken by weighing, polysulfones, tetrafluoroethylene, and add an amount of solvent, ball milling or high-speed stirring are disperseed, and are mixed with uniform preimpregnation (precoating) sizing material, and viscosity is advisable easily to flow.The solvent that is added can be one or more in dimethyl formamide, N,N-DIMETHYLACETAMIDE and the chlorinated hydrocarbon solvent.
4. will carry out surface treatment by 2 carbon cloths that taken by weighing, surface treatment can be adopted acid treatment, Cement Composite Treated by Plasma or coupling agent treatment etc., and acid treatment is used with concentrated nitric acid infusion method, coupling agent treatment and gathered titanate coupling agent or the ultrasonic infusion method of organo-silicon coupling agent acetone soln (concentration 1～2%).
5. use by 3 preimpregnation of being prepared (precoating) sizing materials and carry out gluing and handle carrying out carbon cloth after the surface treatment by 4, photoresist coating process can adopt the comprehensive of sound impregnation or spread coating gluing and above-mentioned two kinds of methods, to sizing material with the preparation of high boiling solvents such as dimethyl formamide, can carry out pre-as heat to sizing material, Controllable Temperature be built in 100～120 ℃.And then carry out gluing, but gluing process mark uses until exhausted until whole sizing materials all over carrying out.
6. the carbon cloths after will carrying out gluing and handle by 5 flatten, and make its drying, drying means can adopt a kind of in the methods such as seasoning, hair dryer dry up, infrared baking, vacuum-drying or several.
7. will be by 6 dried gluing carbon cloths, cut according to mold shape and to make shape, and stack gradually in mould with different carbon cloth weaving directions.
8. high temperature compression moulding to being forced into 10MPa by 7 moulds that install, heats up then, treat that temperature rises to 120 ℃ ± 10 ℃, constant temperature 10 minutes is forced into 30～65MPa then, and continues to be warming up to 290～360 ℃, constant temperature 30～80 minutes, cooling or sharply be cooled to room temperature naturally under the pressurize orderliness then with icing, the demoulding gets final product, and heat-up rate is advisable to be not more than 10 ℃/minute in above-mentioned hot pressing, in addition for preventing that bubble from producing, and should note venting at any time.
It can be polyacrylonitrile carbon cloth, gluing carbon cloth, Graphite cloth, pitch prill carbon cloth etc. that preparation technology of the present invention selects carbon cloth for use, for polymer sizing material (glue) can fully be impregnated between the carbon fiber bundle, except that adopting ultrasonic wave gum dipping process etc., selected carbon cloth hole count should be less than 3K.
It is in order to guarantee that product has excellent intensity and thermotolerance as material of main part that the present invention selects polyimide and high-temperature resistant aromatic heterocycle polymer polyether sulphone for use, also considered simultaneously the feasibility of technology, used polyether sulphone can be various modified polyarylether sulfones, as on its main chain with the polyether sulphone PES-C of circle type side group etc., this material not only has good Technological adaptability, also have excellent mechanical property and resistance to elevated temperatures, its second-order transition temperature reaches 260 ℃, the short-term use temperature can reach 400 ℃, and the molecular structural formula of PES-C is:
The present invention selects polysulfones and polyether sulphone blend for use, and its main purpose is in order to improve the intensity of product, also is in order to improve the pressing process performance secondly.In addition, also considered the matching properties that dissolves each other of these two kinds of materials.
What solid lubricant was selected for use is surface energy and the very low tetrafluoroethylene of frictional coefficient, and its purity is greater than 95%, and granularity is less than 8 μ m, and selecting tetrafluoroethylene for use also is the matching properties of having considered itself and system as solid lubricant.
Behind the hot pressing constant temperature, the selection of the type of cooling can be controlled the crystalline state of macromolecular material in the product among the present invention, and then influences product performance, generally speaking, better flexible with the product of stove naturally cooling, then better with the rigidity of the product of ice quick cooling.
The maximum characteristics of product of the present invention are to have excellent wear-resistant self-lubricating characteristic under at a high speed big PV value metal to-metal contact working condition, and its limit PV value exceeds nearly 10 times of conventional material, can reach about 45MPam/s.This product also has characteristics such as high strength, low density, anti-very low temperature and other particular surroundings simultaneously, and this product also has excellent processability, is suitable for making the small-sized component of different shape.
The main performance index of product of the present invention is as follows:
1. density～1.8
2. bending strength＞400MPa
3. resistance to impact shock＞30KJ/m
2
4. thermal expansivity～5 * 10
-6/ K
-1
5. frictional coefficient＜0.32
6. wear rate＜5 * 10
-7G/mkg
7. Applicable temperature scope-200 ℃～+ 200 ℃
Product of the present invention is applicable to the friction means of making under the at a high speed big PV value metal to-metal contact working condition, the outer space vehicle that can be used for the requirement high-strength low-density, the space station, in man-made satellite and the rocket, as bearing, sealing material, slide block, piston ring and some structure unit: because its low density, thereby be specially adapted to because centrifugal force produces the high speed rotating air pump slide plate of pressure, some member of supercentrifuge: because its radioprotective, vacuum performance and high-temperature behavior are all relatively good, thereby also be applicable to as atomic reactor, some component of vacuum machine: can also be as some component used in the corrosive medium and the liquid hydrogen of under very low temperature, working, liquid nitrogen, the bearing of liquid helium pump, wear ring etc.
Embodiment 1
Take by weighing the gluing carbon cloth 30g after coming unstuck, be soaked in the concentrated nitric acid 24 hours, wash and dry, take by weighing soluble polyimide 20g, tetrafluoroethylene 3g, and adding dimethyl formamide 200ml, ball milling 5 hours is made preimpregnation (precoating) glue and is trembled, and above-mentioned carbon cloth after surface treatment is soaked in this glue, supersound process 5 minutes, take out airing, and paint brush and will remain the pros and cons that sizing material is brushed this carbon cloth, carry out the gluing processing, after treating to finish on whole glues, make its seasoning (＞12h), cut according to mold shape then and make shape, and stack gradually in mould with different carbon cloth weaving directions.Be forced into 10MPa, and be warming up to 120 ℃ ± 10 ℃, constant temperature 10 minutes is forced into 45MPa then, and continues to be warming up to 320 ℃, and constant temperature 60 minutes is cooled to room temperature then naturally under the pressurize condition, and the demoulding gets final product.Material property satisfies These parameters.In above-mentioned hot pressing, heat-up rate is 5 ℃/minute, and the venting in 5 minutes of every interval once.Embodiment 2
Take by weighing the 3K graphite carbon cloth 30g after coming unstuck, be soaked in organo-silicon coupling agent (KH-550) acetone soln of concentration 1% 30 minutes, and dry up with hair dryer, take by weighing polyether sulphone PES) (η=0.63) 20g, polysulfones (PSF) (η=0.24) 4g, tetrafluoroethylene 6g, and adding trichloromethane 250ml, ball milling 5 hours is made the preimpregnation sizing material, pours in the Flat bottom container; Above-mentioned carbon cloth after coupling agent treatment is soaked in this glue, supersound process, when stirring carbon cloth, press stone roller carbon cloth surface with the column type roller, after treating to finish on whole glues, take out carbon cloth and make its maintenance smooth, dry with the infrared lamp baking, cut according to mold shape then and make shape, and stack gradually with different carbon cloth weaving directions and in mould, to be forced into 10MPa, and be warming up to 120 ℃ ± 10 ℃, constant temperature 10 minutes, be forced into 40MPa then, and continue to be warming up to 320 ℃, constant temperature is after 40 minutes, promptly be chilled to room temperature with ice, the demoulding gets final product.Material property satisfies These parameters.Wherein bending strength is greater than 500MPa, and in above-mentioned hot pressing, heat-up rate is 10 ℃/minute, and the venting in 5 minutes of every interval once.Embodiment 3
Take by weighing strong polyacrylonitrile carbon cloth 30g among the 1K after coming unstuck, carry out the air plasma etching processing, take by weighing novel polyether sulphone (PES-C) (η=0.63) 20g, the tetrafluoroethylene 4g that contain circle type side group, and adding N,N-DIMETHYLACETAMIDE 250ml, ball milling 5 hours, make the preimpregnation sizing material, this sizing material is poured in the Flat bottom container, take out after in baking oven, being heated to 120 ℃, above-mentioned carbon cloth after surface treatment is soaked in this glue, supersound process is pressed stone roller carbon cloth surface with the column type roller when stirring carbon cloth; After glue temperature drops to below 50 ℃, again glue is put into baking oven, make its temperature return to 120 ℃, so go round and begin again.After treating to finish on whole glues, take out carbon cloth and also make its maintenance smooth, dry with the infrared lamp baking, cut according to mold shape then and make shape, and stack gradually in mould with different carbon cloth weaving directions.Be forced into 10MPa, and be warming up to 120 ℃ ± 10 ℃, constant temperature 10 minutes is forced into 55MPa then, and continues to be warming up to 350 ℃, and constant temperature 40 minutes is chilled to room temperature with ice then, and the demoulding gets final product.Material property satisfies These parameters.In above-mentioned hot pressing, heat-up rate is 5 ℃/minute, should exit once in 5 minutes at every interval.
Claims (8)
1. carbon fibre reinforced high-molecular composite material is characterized in that forming (weight %) and is:
Carbon cloth 35-80
Polyether sulphone 0-60
Polysulfones 0-40
Polyimide 0-50
Tetrafluoroethylene 0-30
Coupling agent 0-2 wherein coupling agent comprises organo-silicon coupling agent or poly-titanate coupling agent.
2. carbon fibre reinforced high-molecular composite material as claimed in claim 1, the hole count that it is characterized in that carbon cloth be less than 3K, strong or high-strength polyacrylonitrile carbon cloth, gluing carbon cloth, Graphite cloth, pitch prill carbon cloth in can being.
3. carbon fibre reinforced high-molecular composite material as claimed in claim 1, the viscosity that it is characterized in that polyether sulphone is η=0.16-0.90.
4. carbon fibre reinforced high-molecular composite material as claimed in claim 1 is characterized in that polyether sulphone can be the modified polyarylether sulfone PES-C that encloses circle type side group on its main chain, and the structural formula of this compound is (I), and viscosity is η=0.16-0.90.
5. carbon fibre reinforced high-molecular composite material according to claim 1, the viscosity that it is characterized in that used polysulfones is η=0.15-0.60.
6. carbon fibre reinforced high-molecular composite material according to claim 1 is characterized in that polyimide is a soluble polyimide.
7. carbon fibre reinforced high-molecular composite material according to claim 1, the granularity that it is characterized in that tetrafluoroethylene is less than 8 μ m, and purity is greater than 95%.
8. the preparation technology of a carbon fibre reinforced high-molecular composite material is characterized in that:
(1) takes by weighing each component by claim 1;
(2) carbon cloth that takes by weighing by (1) being carried out surface treatment, can be come unstuck processing, plasma etching treatment, acid treatment, coupling agent treatment;
(3) will mix by polyether sulphone, polysulfones, polyimide, the tetrafluoroethylene that (1) takes by weighing, add an amount of solvent, fully disperse and make uniform precoating sizing material, viscosity is advisable easily to flow, and the solvent that is added can be one or more in dimethyl formamide, N,N-DIMETHYLACETAMIDE and the chlorinated hydrocarbon solvent;
(4) sizing material of being prepared with (3) carries out gluing and handles carry out carbon cloth after the surface treatment by (2), and makes its drying.
(5) will be by the gluing carbon cloth after (4) processing, cut according to mold shape and to make shape, and stack gradually in mould, be forced into 10MPa with different carbon cloth weaving directions, be warming up to 120 ℃ ± 10 ℃ then, constant temperature 10 minutes is forced into 30-65MPa then, and continues to be warming up to 290-360 ℃, constant temperature 30-80 minute, cooling or sharply be cooled to room temperature naturally under the pressurize condition then with icing, the demoulding gets final product, and heat-up rate is advisable to be not more than 10 ℃/minute in above-mentioned hot pressing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94104725A CN1051328C (en) | 1994-05-05 | 1994-05-05 | Carbon fibre reinforced high-molecular composite material and preparing process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94104725A CN1051328C (en) | 1994-05-05 | 1994-05-05 | Carbon fibre reinforced high-molecular composite material and preparing process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1111258A CN1111258A (en) | 1995-11-08 |
| CN1051328C true CN1051328C (en) | 2000-04-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94104725A Expired - Fee Related CN1051328C (en) | 1994-05-05 | 1994-05-05 | Carbon fibre reinforced high-molecular composite material and preparing process thereof |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052990C (en) * | 1996-11-01 | 2000-05-31 | 中国科学院长春应用化学研究所 | Preparation of poly(aromatic ether-sulphone)/inorganic particle composite material |
| CN102031087A (en) * | 2010-11-18 | 2011-04-27 | 西北工业大学 | Wet friction material for heavy-duty differential and preparation method thereof |
| CN104945795B (en) * | 2010-11-24 | 2019-05-21 | Ａｇｃ株式会社 | Automobile-use sealing ring or industrial gas compressor sealing ring or sliding component |
| CN102558720A (en) * | 2010-12-07 | 2012-07-11 | 华东理工大学 | High heat conductivity fluoroplastic and its preparation method and application |
| US10626546B2 (en) | 2012-06-24 | 2020-04-21 | Gates Corporation | Carbon cord for reinforced rubber products and the products |
| CN105566919B (en) * | 2015-07-31 | 2019-03-15 | 沈阳理工大学 | A kind of compound heat vulcanized silicone rubber base ablation resistant material of carbon cloth and preparation method thereof |
| WO2019014661A1 (en) * | 2017-07-14 | 2019-01-17 | Arkema Inc | High strength polyvinylidene fluoride composite |
| CN108440961A (en) * | 2018-04-25 | 2018-08-24 | 长沙五犇新材料科技有限公司 | A kind of modified polysulfone composite material and preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5320505A (en) * | 1976-08-09 | 1978-02-24 | Hitachi Ltd | Sound preventing device of rotary electrical machinery |
| JPS5329861A (en) * | 1976-08-30 | 1978-03-20 | Akaiwazawa Toshitaka | Upper high table |
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1994
- 1994-05-05 CN CN94104725A patent/CN1051328C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5320505A (en) * | 1976-08-09 | 1978-02-24 | Hitachi Ltd | Sound preventing device of rotary electrical machinery |
| JPS5329861A (en) * | 1976-08-30 | 1978-03-20 | Akaiwazawa Toshitaka | Upper high table |
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|---|---|
| CN1111258A (en) | 1995-11-08 |
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