CN103590233A - Method for interfacial modification of carbon fiber by cryogenic treatment - Google Patents
Method for interfacial modification of carbon fiber by cryogenic treatment Download PDFInfo
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- CN103590233A CN103590233A CN201310534440.0A CN201310534440A CN103590233A CN 103590233 A CN103590233 A CN 103590233A CN 201310534440 A CN201310534440 A CN 201310534440A CN 103590233 A CN103590233 A CN 103590233A
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Abstract
The invention provides a method for interfacial modification of carbon fiber by cryogenic treatment. The method is characterized by specifically comprising the steps of: placing a carbon fiber sample in cryogenic treatment equipment with a cryogenic medium, and sealing the container; setting the cryogenic treatment technological parameters as: a cooling rate of 1DEG C/min-5DEG C/min, a treatment temperature constantly ranging from -100DEG C to -200 DEG C, and a treatment time of 3h-15h; and performing temperature regaining, thus obtaining modified carbon fiber. Without loss of carbon fiber mechanical properties, the method provided by the invention can increase the surface roughness so as to reach the purpose of improving the interface bonding performance of carbon fiber and resin. The improvement of the interface bonding performance enables uniform transfer of a composite material internal stress, thus satisfying the higher requirements of high performance carbon fiber reinforced resin composite materials.
Description
Technical field
The present invention relates to a kind of carbon fiber be carried out to subzero treatment to improve the method for modifying of its combination property, belong to high-performance fiber modification field.
Background technology
Carbon fiber is to be accompanied by the development of military project cause and the new material of growing up, and belongs to new high-tech product.The intrinsic intrinsic property not only with material with carbon element, has both again the soft machinability of textile fabric, is fortifying fibre of new generation.It is excellent mechanical property and the dynamic property such as high specific strength, high ratio modulus, low-density, linear expansion coefficient are little, creep resistant, antifatigue because having; Good chemical resistance, the outstanding hot property such as high temperature resistant, low temperature resistant, conduction, heat transfer and thermal coefficient of expansion are little and good dielectric properties and be subject to extensive concern.As fibre reinforced composites, aspect density and intensity, there is more significant advantage.Compare with traditional metal materials, carbon fibre composite quality is light, and intensity is high, and toughness is high, has obvious advantage.Compare with the silicon based fiber composite that is all new material, the TENSILE STRENGTH of carbon based fibers is about its 3-7 doubly.Therefore rely on its good performance, in every field such as Aero-Space, automobile, structural fortification, new energy development, leisure goodss, be widely used.But, the resistance to impact of carbon fiber is poor, easily damage, smooth surface, inertia are large, surface can be low, have chemically active functional group few, under strong acid effect, be oxidized, the shortcomings such as metallic carbide, carburizing and electrochemical corrosion phenomenon can occur during with metal composite, in interface, have more defect, thereby directly affected the mechanical property of composite, limited the high performance performance of carbon fiber.
At present, carbon fiber modifying generally adopts chemical method and physical method.Chemical modification is by methods such as oxidation processes, chemical grafts, by add specific functional group to carbon fiber surface, changes its performance; And physical technique is generally to rely on plasma, ray-laser treatment, coating processing etc. to pass through the comprehensive function of etching, activation and grafting at fiber surface, improve the physics and chemistry state of fiber surface, increase the free energy of fiber surface, and then reach the object that improves the adhesion strength between fiber and matrix.
Subzero treatment claims again ultralow temperature to process or super sub-cold treatment, and it is the extension of conventional cold treatment.Cryogenic treatment process is generally considered to be usings liquid nitrogen as deep cooling medium, treated sample is contained in certain container, different materials is by its specific temperature lowering curve, control rate of temperature fall, lentamente sample is dropped to liquid nitrogen temperature, insulation certain hour, then press heating curve, be slowly raised to the processing procedure of room temperature.This technique is not only mainly used in ferrous material and alloy thereof, nonferrous materials and alloy etc. thereof, can make metal tools all demonstrate improvement to a certain degree at the aspects such as stability of abrasive wear resistant weld deposit, anticorrosive wearing and tearing, minimizing internal stress and raising material.Up to now, cryogenic treatment process is applied to, in the modification of carbon fiber performance, have not been reported.Summary of the invention
Technical problem to be solved by this invention is to provide a kind of simple to operate, increases carbon fiber surface surface roughness, so improve its with resin matrix interface between gluing performance, the cryogenic treatment process of raising carbon fiber combination property.
In order to solve the problems of the technologies described above, the invention provides a kind of subzero treatment and carbon fiber is carried out to the method for interface modification, it is characterized in that, concrete steps comprise: carbon fiber sample are positioned in the deep cold treatment apparatus with deep cooling medium, container is airtight; Cryogenic treatment process parameter is set: cooling rate is 1 ℃/min-5 ℃/min, and treatment temperature is subzero 100 ℃ to subzero 200 ℃ of constant temperature, and the processing time is 3 hours-15 hours; Rise again, obtain modified carbon fiber.
Preferably, described carbon fiber is organic fiber base carbon fibre.
More preferably, described carbon fiber is polyacrylonitrile-based carbon fibre, asphalt base carbon fiber, cellulose base carbon fiber or phenolic resins base carbon fibre.
Preferably, described deep cooling medium is liquid nitrogen.
Preferably, the described process choosing temperature programming of rising again is risen again or carbon fiber is taken out from deep cold treatment apparatus to nature and rise again.
Subzero treatment of the present invention, being equal to ultralow temperature processes or super sub-cold treatment, refer to processed object is placed in to specific, controlled low temperature environment, the heterogeneous microstructure of its material is changed, thereby reach a kind of technology that improves or improve material property.
Cryogenics application of the present invention is usingd liquid nitrogen conventionally as low-temperature receiver, utilizes its phase transformation (gasification) heat absorption to obtain low temperature environment.Nitrogen is one of main composition in atmosphere, nonpoisonous and tasteless, thereby the application environmental sound of cryogenics, belongs to green manufacture technology category.
Compared with prior art, the invention has the beneficial effects as follows:
1, the present invention is placed in deep cooling medium through a series of modification by carbon fiber, improves the adhesive power of itself and resin.The present invention can not lose under the prerequisite of carbon fiber mechanical property, increases the object that its surperficial roughness reaches the interfacial adhesion performance that improves carbon fiber and resin.The raising of interfacial adhesion performance can make the stress of composite inner evenly transmit, and meets the higher demand that high-performance carbon fibre strengthens resin composite materials.The present invention can not only improve the interfacial combined function of carbon fibre resin, also comprises the combination properties such as surface friction property, surface roughness, tensile property, abrasion resistance properties.
2, in the present invention, the carbon fiber through subzero treatment has more excellent comprehensive mechanical property, can meet the application demand in different field, improves the service life of carbon fibre material simultaneously.
3, in the present invention, carbon fiber crocking resistance and the tensile property through subzero treatment is significantly improved, and fully excavated the potentiality of carbon fibre material.
4, in the present invention carbon fiber through subzero treatment rear surface roughening, when showing to increase and the contact area of resin matrix also increase, be conducive to carbon fiber and resin and form good adhesive interface, improve the combination property of aramid fiber reinforced composite.
5, cryogenic treatment process process of the present invention and deep cold treatment apparatus are simple in structure, compare with other modification process, more save the energy and production cost, have good development prospect.
6, subzero treatment technology of the present invention is usingd liquid nitrogen as low-temperature receiver, utilizes its phase transformation (gasification) heat absorption to obtain low temperature environment, nonpoisonous and tasteless, environmental friendliness, belongs to green manufacture technology category.
7, the present invention is owing to adopting subzero treatment, can improve under the abrasion resistance properties of carbon fiber and the prerequisite of tensile property, improve significantly the adhesive property of carbon fiber and resin matrix simultaneously, can significantly improve the whole mechanical property of carbon fiber-reinforced resin composite materials, and process is simple, easy to operate, the production cost that reduces modified technique, has significant economic benefit and social benefit, has good prospects for commercial application.
Accompanying drawing explanation
Fig. 1 a is the front surface roughness figure of subzero treatment carbon fiber (T300);
Fig. 1 b is the surface roughness figure after subzero treatment carbon fiber (T300).
The specific embodiment
For the present invention is become apparent, hereby with preferred embodiment, be described in detail below.
Embodiment 1: cryogenic treating process modified polyacrylonitrile-based carbon fiber (T300)
Clean polyacrylonitrile-based carbon fibre (T300) is placed in deep cold treatment apparatus (SLX-100R).The container cover of deep cold treatment apparatus is closely closed, in order to avoid low temperature liquid nitrogen is revealed, affects temperature controlled accuracy and treatment effect, by the Deep Cryogenic Treatment table in table 1, set subzero treatment and the parameter of rising again, carry out subzero treatment after temperature programming rise again.
Table 1 Deep Cryogenic Treatment table
After being disposed, container environment temperature reaches room temperature, and polyacrylonitrile-based carbon fibre (T300) is taken out with special equipment, completes modification process.After subzero treatment, polyacrylonitrile-based carbon fibre (T300) surface roughness obviously increases (as shown in Fig. 1 a and 1b).After tested, polyacrylonitrile-based carbon fibre (T300) improves more than 25% with the interfacial adhesion intensity of thermosetting epoxy resin, and tensile property improves 5% left and right.
Embodiment 2: cryogenic treating process modified polyacrylonitrile-based carbon fiber (T700)
Clean polyacrylonitrile-based carbon fibre (T700) is placed in deep cold treatment apparatus (SLX-100R).The container cover of deep cold treatment apparatus is closely closed, in order to avoid low temperature liquid nitrogen is revealed, affects temperature controlled accuracy and treatment effect, by the Deep Cryogenic Treatment table in table 2, set subzero treatment and the parameter of rising again, carry out subzero treatment after temperature programming rise again.
Table 2 Deep Cryogenic Treatment table
After being disposed, container environment temperature reaches room temperature, and polyacrylonitrile-based carbon fibre (T700) is taken out with special equipment, completes modification process.After subzero treatment, polyacrylonitrile-based carbon fibre (T700) improves more than 25% with the interfacial adhesion intensity of thermosetting epoxy resin, and tensile property improves 5% left and right.
Embodiment 3 cryogenic treating process modified pitch base carbon fibres
Clean asphalt base carbon fiber is placed in deep cold treatment apparatus (SLX-100R).The container cover of deep cold treatment apparatus is closely closed, in order to avoid low temperature liquid nitrogen is revealed, affect temperature controlled accuracy and treatment effect, by Deep Cryogenic Treatment table in table 3, set subzero treatment, carry out carbon fiber being taken out from deep cold treatment apparatus to nature after subzero treatment and rise again.
Table 3 Deep Cryogenic Treatment table
After being disposed, container environment temperature reaches room temperature, and polyacrylonitrile-based carbon fibre is taken out with special equipment, completes modification process.After subzero treatment, the interfacial adhesion intensity of asphalt base carbon fiber and thermosetting epoxy resin improves more than 20%, and tensile property improves 5% left and right.
Claims (5)
1. a method for interface modification is carried out in subzero treatment to carbon fiber, it is characterized in that, concrete steps comprise: carbon fiber sample is positioned in the deep cold treatment apparatus with deep cooling medium, and container is airtight; Cryogenic treatment process parameter is set: cooling rate is 1 ℃/min-5 ℃/min, and treatment temperature is subzero 100 ℃ to subzero 200 ℃ of constant temperature, and the processing time is 3 hours-15 hours; Rise again, obtain modified carbon fiber.
2. the method for interface modification is carried out in subzero treatment as claimed in claim 1 to carbon fiber, it is characterized in that, described carbon fiber is organic fiber base carbon fibre.
3. the method for interface modification is carried out in subzero treatment as claimed in claim 2 to carbon fiber, it is characterized in that, described carbon fiber is polyacrylonitrile-based carbon fibre, asphalt base carbon fiber, cellulose base carbon fiber or phenolic resins base carbon fibre.
4. the method for interface modification is carried out in subzero treatment as claimed in claim 1 to carbon fiber, it is characterized in that, described deep cooling medium is liquid nitrogen.
5. the method for interface modification is carried out in subzero treatment as claimed in claim 1 to carbon fiber, it is characterized in that, the described process choosing temperature programming of rising again is risen again or carbon fiber taken out from deep cold treatment apparatus to nature and rise again.
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104228090A (en) * | 2014-09-15 | 2014-12-24 | 东华大学 | Method for modifying aramid fiber composite by subzero treatment |
CN104231296A (en) * | 2014-09-15 | 2014-12-24 | 东华大学 | Method for modifying carbon fiber composite material by cryogenic treatment |
CN104385507A (en) * | 2014-09-15 | 2015-03-04 | 东华大学 | Method for modification of glass fiber composite material by ultralow temperature treatment |
CN105821644A (en) * | 2016-05-26 | 2016-08-03 | 东华大学 | Preparation method of modified polyphenylene sulfide fibers |
CN105821645A (en) * | 2016-05-26 | 2016-08-03 | 东华大学 | Preparation method of modified high-strength polyarylester fibers |
CN106012537A (en) * | 2016-05-25 | 2016-10-12 | 东华大学 | Method for preparing wear-resistant conductive fibers |
CN107747182A (en) * | 2017-11-08 | 2018-03-02 | 张万虎 | A kind of cryogenic treating process for suppressing wool fabric and shrinking |
CN108951117A (en) * | 2018-08-14 | 2018-12-07 | 泉州师范学院 | A kind of method of modifying of nylon fabric |
CN110184550A (en) * | 2019-07-08 | 2019-08-30 | 南昌航空大学 | A kind of cryogenic treating process of continuous filament reinforced metallic matrix composite |
CN114874023A (en) * | 2022-06-01 | 2022-08-09 | 内蒙古中晶科技研究院有限公司 | Method for preparing carbon-carbon crucible bottom from carbon fiber preform |
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Cited By (13)
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CN104231296A (en) * | 2014-09-15 | 2014-12-24 | 东华大学 | Method for modifying carbon fiber composite material by cryogenic treatment |
CN104385507A (en) * | 2014-09-15 | 2015-03-04 | 东华大学 | Method for modification of glass fiber composite material by ultralow temperature treatment |
CN104228090A (en) * | 2014-09-15 | 2014-12-24 | 东华大学 | Method for modifying aramid fiber composite by subzero treatment |
CN106012537B (en) * | 2016-05-25 | 2018-05-15 | 东华大学 | A kind of preparation method of wear-resistant conductive fiber |
CN106012537A (en) * | 2016-05-25 | 2016-10-12 | 东华大学 | Method for preparing wear-resistant conductive fibers |
CN105821644A (en) * | 2016-05-26 | 2016-08-03 | 东华大学 | Preparation method of modified polyphenylene sulfide fibers |
CN105821645A (en) * | 2016-05-26 | 2016-08-03 | 东华大学 | Preparation method of modified high-strength polyarylester fibers |
CN107747182A (en) * | 2017-11-08 | 2018-03-02 | 张万虎 | A kind of cryogenic treating process for suppressing wool fabric and shrinking |
CN107747182B (en) * | 2017-11-08 | 2020-04-28 | 绍兴兆丽新材料科技有限公司 | Cryogenic treatment method for inhibiting shrinkage of wool fabric |
CN108951117A (en) * | 2018-08-14 | 2018-12-07 | 泉州师范学院 | A kind of method of modifying of nylon fabric |
CN110184550A (en) * | 2019-07-08 | 2019-08-30 | 南昌航空大学 | A kind of cryogenic treating process of continuous filament reinforced metallic matrix composite |
CN114874023A (en) * | 2022-06-01 | 2022-08-09 | 内蒙古中晶科技研究院有限公司 | Method for preparing carbon-carbon crucible bottom from carbon fiber preform |
CN114874023B (en) * | 2022-06-01 | 2022-12-20 | 内蒙古中晶科技研究院有限公司 | Method for preparing carbon-carbon crucible bottom from carbon fiber preform |
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