CN107503121B - Supercritical CO under action of aramid fiber tension in motion state2Modification method and apparatus - Google Patents
Supercritical CO under action of aramid fiber tension in motion state2Modification method and apparatus Download PDFInfo
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- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
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Abstract
The invention relates to supercritical CO of aramid fiber in motion state under the action of tension2The fluid modifying method and apparatus is that under the action of tension, the aramid fiber in motion state is mixed with supercritical CO dissolved with cross-linking agent2And carrying out swelling reaction on the fluid to obtain the modified aramid fiber. Specifically, the aramid fiber and the crosslinking agent are placed in a reaction container, the aramid fiber is not contacted with the crosslinking agent, and the aramid fiber generates tension due to the difference of the front and back movement speeds; then introducing carbon dioxide gas into the reaction vessel until supercritical carbon dioxide fluid is generated; and carrying out swelling reaction on the supercritical carbon dioxide fluid carrying the dissolved crosslinking agent and the aramid fiber in a motion state to obtain the modified aramid fiber. The method effectively improves the mechanical property of the aramid fiber, realizes batch continuous treatment or one-time multiple tension treatment, is simple and convenient to operate, has the advantages of economy, environmental protection, controllable reaction, short reaction time, simple separation of a solvent and a product and the like, and has great industrial application value.
Description
Technical Field
The invention belongs to the field of fiber modification, and relates to supercritical CO under the action of aramid fiber tension in a motion state2A modification method and apparatus.
Background
Para-aramid fiber is also called Poly-p-phenylene-terephthamide (PPTA) fiber for short, has excellent performances of ultrahigh strength, high modulus, high temperature resistance, acid and alkali resistance, light weight and the like, is widely applied to the fields of advanced strategic weapons, national defense and military industry, aerospace, major engineering construction, soldier bulletproof protection, automobiles, optical fiber reinforcement, cables and the like, and is an important strategic material indispensable to national safety, economic construction and scientific and technological progress.
The high modulus aramid fiber generally has the advantages that the crystallization orientation is generated inside the fiber by means of hot stretching treatment, so that the modulus of the fiber is improved, but the tensile strength of the aramid fiber is reduced due to the fact that the stretching temperature is too high and even exceeds 500 ℃ and the molecular chain of the aramid fiber is broken.
The application number is CN201310419414.3, the name is a method for improving mechanical property of aramid fiber by stretching orientation in supercritical fluid, and the method is characterized in that PPTA molecular chains in the aramid fiber under the action of certain tension are damaged by using a part of supercritical carbon dioxide fluid, so that the molecular chains are further oriented to obtain the aramid fiber with better property. The method ensures that the aramid fiber is in a stretching state in the reaction process, the molecular chain orientation degree and the crystallinity degree are increased along with the change of stretching tension, the crystal grains become larger, and the crystallization tends to be complete. However, it is not indicated that the method is suitable for the aramid fiber in a moving state, and the technical effect same as or similar to that of the method is achieved.
The application number is CN201310419417.7, the name is aramid fiber in CO2The method for improving the mechanical property by stretching orientation and chemical crosslinking in the supercritical fluid utilizes the swelling and carrying effect of the supercritical carbon dioxide fluid, and the fiber is in a stretching state due to the tension effect, so that the orientation degree and the crystallinity of a molecular chain are increased, the crystallization tends to be complete, and the chemical crosslinking is generated at the same time, so that the crosslinking and branching degree among macromolecules are increased, and the mechanical property is improved. However, the method also does not indicate whether the aramid fiber in a motion state is suitable or not, and the technical effect which is the same as or similar to that of the method is achieved.
Therefore, whether the fiber in motion state is suitable for the carbon dioxide fluid modification technology under the action of tension to improve the mechanical property of the fiber and improve the industrialization of fiber modification still needs to be further researched.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides supercritical CO under the action of the tension of aramid fiber in a motion state2A modification method and apparatus.
The technical scheme of the invention is as follows: supercritical CO under action of aramid fiber tension in motion state2The modification method comprises the following steps that aramid fiber in a motion state is subjected to tension action and supercritical CO dissolved with a cross-linking agent2The fluid undergoes a swelling reaction to obtainTo obtain the modified aramid fiber. Under the action of tension, the aramid fiber is in a stretching state, the molecular chain orientation degree and the crystallinity of the aramid fiber change along with the change of the tension, the crystallization tends to be complete, and the arrangement of an amorphous area is more regular. At the same time, supercritical CO is utilized2The swelling and carrying effects of (A) are brought into the crosslinking agent inside and on the surface of the fiber, and the crosslinking and branching degree among macromolecules is increased by utilizing the grafting and chain extension reactions, so that the mechanical property of the fiber is improved.
Placing aramid fiber and a cross-linking agent in a reaction container, wherein the aramid fiber is not in contact with the cross-linking agent, and filling carbon dioxide gas into the reaction container until supercritical carbon dioxide fluid is generated; the aramid fiber generates tension due to the difference of the front and back movement speeds, and the supercritical carbon dioxide fluid carries the dissolved cross-linking agent to perform swelling reaction with the aramid fiber in a movement state, so that the modified aramid fiber is obtained. The swelling reaction means that the light stabilizer carried by the supercritical carbon dioxide is contacted with the aramid fiber in a gas infiltration manner.
The tension is 2-100 CN. The tension is preferably 4 to 50CN, more preferably 4 to 20 CN.
The front and back movement speed of the aramid fiber is 0.5-40 r/min. The front and back movement speed of the aramid fiber is preferably 4-20 r/min, and more preferably 2-10 r/min.
The supercritical carbon dioxide fluid is generated under the conditions of 50-250 ℃ and 5-16 Mpa. Due to the temperature being CO2An important index of the supercritical fluid state is that the CO can be realized only when the temperature is more than 31 ℃ and certain pressure is matched2And temperature and pressure affect CO2The concentration in the autoclave, in turn, affects the concentration of the crosslinking agent. Preferably, the supercritical carbon dioxide fluid is generated under the conditions of the temperature of 80-100 ℃ and the pressure of 8-12 MPa.
The reaction vessel is heated by electrical heating or oil bath heating to a temperature at which supercritical carbon dioxide fluid is produced.
The swelling reaction time is 20-120 min. Preferably, the swelling reaction time is 30-90 min.
After the swelling reaction is finished, the pressure of the reaction vessel is relieved. Specifically, the pressure relief time is 1-10 min, and preferably 1-5 min.
The aramid fiber is para-aramid Kevlar, Nomex fiber, Twaron fiber, Technora fiber, aramid III fiber or F-12 fiber.
The cross-linking agent is isocyanate compound or paraphthaloyl chloride.
The addition amount of the cross-linking agent is 2-8% of the mass of the introduced carbon dioxide. Preferably, the addition amount of the cross-linking agent is 2.5-5% of the mass of the introduced carbon dioxide.
Before introducing carbon dioxide gas into the reaction vessel, the exhaust treatment is carried out. Specifically, the mode of the exhaust treatment is vacuum-pumping, and the purpose of the exhaust treatment is to remove air in the closed container and eliminate the influence of active gas such as oxygen in the air on the experiment.
The aramid fiber is cleaned and dried, specifically, the aramid fiber is placed in an organic solvent, and is subjected to constant-temperature ultrasonic washing and vacuum drying. The organic solvent is acetone, the ultrasonic temperature is 70-100 ℃, and the ultrasonic time is 1-5 hours; the drying temperature is 70-100 ℃, and the drying time is 6-10 h. Preferably, the ultrasonic temperature is 85-95 ℃, and the ultrasonic time is 1-3 h; the drying temperature is 75-85 ℃, and the drying time is 7.5-8.5 h. Further preferably, the ultrasonic temperature is 90 ℃, and the ultrasonic time is 2 h; the drying temperature is 80 ℃, and the drying time is 8 h.
The modified aramid fiber is cleaned and dried, specifically, the modified aramid fiber is placed in an organic solvent, washed at a constant temperature to a constant weight and then dried in vacuum. The organic solvent is acetone, ethanol or methanol, the washing temperature is 70-100 ℃, the drying temperature is 70-120 ℃, and the drying time is 1-5 h. Preferably, the washing temperature is 75-95 ℃, the drying temperature is 75-95 ℃, and the drying time is 1-3 h. Further preferably, the washing temperature is 80 ℃, the drying temperature is 80 ℃, and the drying time is 1-2 h.
Supercritical CO of aramid fiber in motion state under tension2The fluid modification device comprises a high-pressure reaction kettle, a raw yarn winding frame, a modified yarn winding frame, a yarn guide roller, a raw yarn stirrer and a stirrer which are arranged in the inner cavity of the high-pressure reaction kettle, and a modified yarn stirrer and a mechanical sensor which are arranged outside the high-pressure reaction kettle;
the precursor winding frame, the precursor stirrer and the stirrer are fixed at the bottom of the high-pressure reaction kettle, the modified filament winding frame and the modified filament stirrer are fixed at the kettle cover of the high-pressure reaction kettle, and the godet roller is positioned between the precursor winding frame and the modified filament winding frame;
the precursor winding frame is connected with the precursor stirrer and is provided with a spring leaf; the modified wire winding frame is connected with the modified wire stirrer;
the kettle cover of the high-pressure reaction kettle is also provided with an air inlet and an air outlet.
When the modified aramid fiber winding frame is used, unmodified aramid fibers are wound on the precursor winding frame, and the free ends of the aramid fibers to be modified are fixed on the modified precursor winding frame. When the reaction kettle is in supercritical CO2During the state, through the speed of motion of the aramid fiber that is located on modified silk winding frame and protofilament winding frame of the rotational speed control of regulation and control modified silk winding frame and protofilament winding frame, the rotational speed of modified silk winding frame is greater than protofilament winding frame, consequently produces tension effect to the aramid fiber that is located between modified winding frame and protofilament winding frame, accomplishes aramid fiber and at supercritical CO2And crosslinking modification under the action of tension, and timely winding the modified aramid fiber on a modified yarn winding frame, so that the aramid fiber is convenient to recover. And the godet roller is arranged between the precursor winding frame and the modified yarn winding frame and is used for controlling the winding direction of the fibers on the modified yarn winding frame.
Compared with the prior art, the invention has the following beneficial effects:
1. the method of the invention is to apply tension to the moving aramid fiber to ensure that the moving aramid fiber is in stretching treatment and is subjected to supercritical CO2Effectively carries the cross-linking agent to enter the surface and the interior of the fiber, and further orientation and crystallization occur in the fiber, thereby improving the tensile strength and the tensile modulus of the fiber. And the orientation degree and the crystallinity degree of molecular chains of the aramid fibers in a stretching state change along with the change of tension, the crystallization tends to be complete, and the arrangement of an amorphous area is more regular.
2. The method of the invention reduces the requirements of temperature, pressure and dosage of the cross-linking agent for modifying the aramid fiber to improve the mechanical property thereof, and saves the production of finished products.
3. Compared with unmodified aramid fibers, the tensile strength of the modified aramid fibers is improved by 8.07-20.37%, the modulus is improved by 2.5-22.28%, and the mechanical properties of the modified aramid fibers are effectively improved, namely, when the aramid fibers are in a motion state, the aramid fibers are subjected to stretching and crosslinking modification, and the mechanical properties of the fibers can be still well improved.
4. The method can realize batch continuous treatment or one-time multi-tension treatment on the aramid fiber in motion, is simple and convenient to operate, has the advantages of economy, environmental protection, controllable reaction, short reaction time, simple separation of solvent and products and the like, and has great industrial application value.
Drawings
FIG. 1 is a schematic view of the structure of a high-pressure reactor used in the present invention.
The method comprises the following steps of 1-high-pressure reaction kettle, 2-spring piece, 3-precursor winding frame, 4-modified-filament winding frame, 5-mechanical sensor, 6-kettle bottom, 7-air inlet, 8-air outlet, 9-kettle cover, 10-modified-filament stirrer, 11-godet roller, 12-precursor stirrer and 13-stirrer.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
As shown in fig. 1, a high-pressure reactor 1 used in the present invention includes a raw filament winding frame 3, a modified filament winding frame 4, a godet 11, a raw filament stirrer 12 and a stirrer 13 which are arranged in an inner cavity, and a modified filament stirrer 10 and a mechanical sensor 5 which are arranged outside, wherein the raw filament winding frame 3, the raw filament stirrer 12 and the stirrer 13 are fixed at a bottom 6 of the reactor, the modified filament winding frame 4 is fixed at a cover 9 of the reactor, the godet 11 is located between the raw filament winding frame 3 and the modified filament winding frame 4, the godet 11 is used for controlling a winding direction of fibers on the modified filament winding frame, and the modified filament stirrer 10 is fixed at the cover 9 of the reactor; the precursor winding frame 3 is connected with a precursor stirrer 12 and is provided with a spring piece 2 for controlling the rotating speed of the precursor winding frame; the modified wire winding frame 4 is connected with a modified wire stirrer 10 fixed on the kettle cover 9 and used for controlling the rotating speed of the modified wire winding frame; the mechanical sensor 5 is connected with the outside of the high-pressure reaction kettle 1 and is used for monitoring the tension of the fiber; the kettle cover 9 is also provided with an air inlet 7 and an air outlet 8 which are respectively used for introducing and discharging air; and the stirrer 13 is arranged on the kettle bottom 6 and is used for stirring reaction substances except the aramid fibers in the reaction kettle.
The operation of this reation kettle is: the aramid fiber to be modified and the cross-linking agent are placed in the reaction kettle in advance and are not in contact with each other, wherein the aramid fiber to be modified is wound on the precursor winding frame 3, and the free end of the aramid fiber to be modified is fixed on the modified filament winding frame 4. When the reaction kettle is in supercritical CO2During the state, simultaneously respectively controlling the spring piece and the stirrer for respectively controlling the movement speed of the aramid fiber on the modified filament winding frame 4 and the precursor winding frame 3, so as to generate tension effect on the aramid fiber between the modified filament winding frame 4 and the precursor winding frame 3, and finish the aramid fiber in the supercritical CO2And crosslinking modification under the action of tension, and timely winding the modified aramid fiber on the modified yarn winding frame 4, so that the aramid fiber is convenient to recover.
Example 1
(1) And (3) putting 5g of Kevlar49 fiber into acetone, ultrasonically washing for 2h at 90 ℃, taking out, and vacuum drying for 8h at 80 ℃.
(2) The Kevlar49 fiber washed and dried in step (1) and 0.5g of o-toluene diisocyanate were placed in a reaction kettle as shown in FIG. 1, wherein the Kevlar49 fiber was wound on a raw filament winding frame, and the free ends of the Kevlar49 fiber were fixed on a modified filament winding frame.
(3) Heating a 2L high-pressure reaction kettle to 80 ℃ by using an oil bath heating mode, firstly vacuumizing to remove air in the kettle, and then filling CO into a container2The pressure in the reaction kettle is 12Mpa, and the supercritical CO is positioned in the kettle2In a state that the adding amount of the o-toluene diisocyanate is equal to the mass of the carbon dioxide in the reaction kettle2 percent, at the moment, the precursor winding frame and the modified yarn winding frame are rotated simultaneously, and Kevlar49 fiber is wound to the modified yarn winding frame from the precursor winding frame through a godet roller and is mixed with supercritical CO dissolved with o-toluene diisocyanate2And after the fluid swelling reaction is carried out for 40min, the pressure in the high-pressure reaction kettle is discharged to normal pressure for 4min, and the modified Kevlar49 fiber is obtained. The rotating speed of the protofilament winding shaft is 4r/min, the rotating speed of the modified filament winding frame is 6r/min, and the Kevlar49 fiber tension measured by a mechanical sensor is 10 CN.
(4) The modified Kevlar49 fiber was washed with acetone at 80 ℃ for 1 hour to constant weight and then dried under vacuum at 80 ℃ for 1 hour.
(5) Testing the mechanical property of the fiber by using a monofilament strength tester, wherein the monofilament tensile strength of the Kevlar49 fiber is 22.3CN/dtex, and the modulus is 780.5 CN/dtex; the mechanical property tensile strength of the modified Kevlar49 fiber is 24.1CN/dtex, and the modulus is 800.2 CN/dtex. Compared with Kevlar49 fiber, the tensile strength of the modified Kevlar49 fiber is improved by 8.07 percent, and the modulus is improved by 2.5 percent.
Example 2
(1) Taking 5.5g Kevlar29 fiber, putting into acetone, ultrasonically washing at 90 ℃ for 2h, taking out, and vacuum drying at 80 ℃ for 8 h.
(2) And (2) putting the cleaned and dried Kevlar29 fiber obtained in the step (1) and 0.6g of 1, 6-hexamethylene diisocyanate into a reaction kettle, wherein the Kevlar29 fiber is wound on a raw filament winding frame, and the free end of the Kevlar29 fiber is fixed on a modified filament winding frame.
(3) Heating a 2L high-pressure reaction kettle to 80 ℃ by using an oil bath heating mode, firstly vacuumizing to remove air in the kettle, and then filling CO into a container2The pressure in the reaction kettle is 12Mpa, and the supercritical CO is positioned in the kettle2In the state, the adding amount of the 1, 6-hexamethylene diisocyanate is 2.9% of the mass of the carbon dioxide in the reaction kettle, at the same time, the precursor winding frame and the modified yarn winding frame are rotated, and the Kevlar29 fiber is mixed with the supercritical CO dissolved with the 1, 6-hexamethylene diisocyanate in the process of winding the precursor winding frame and the modified yarn winding frame through the godet roller2And after the fluid swelling reaction is carried out for 40min, discharging the pressure in the high-pressure reaction kettle to normal pressure for 2min to obtain the modified Kevlar29 fiber. The rotating speed of the protofilament winding shaft is 4rAnd/min, the rotating speed of the modified yarn winding frame is 6r/min, and the Kevlar29 fiber tension measured by a mechanical sensor is 10 CN.
(4) The modified Kevlar29 fiber was washed with acetone at 80 ℃ for 1 hour to constant weight and then dried under vacuum at 80 ℃ for 1 hour.
(5) Testing the mechanical property of the fiber by using a monofilament strength tester, wherein the monofilament tensile strength of the Kevlar29 fiber is 18.5CN/dtex, and the modulus is 480.6 CN/dtex; the mechanical property tensile strength of the modified Kevlar29 fiber is 20.1CN/dtex, and the modulus is 520.2 CN/dtex. Compared with Kevlar29 fiber, the tensile strength of the modified Kevlar29 fiber is improved by 8.65 percent, and the modulus is improved by 8.24 percent.
Example 3
(1) And (3) putting 5.3g of aramid fiber III into acetone, ultrasonically washing for 2h at 90 ℃, taking out, and vacuum drying for 8h at 80 ℃.
(2) And (2) placing the aramid fiber III cleaned and dried in the step (1) and 1.5g of 2, 4-toluene diisocyanate crosslinking modifier into a reaction kettle, wherein the aramid fiber III is wound on a precursor winding frame, and the free end of the aramid fiber III is fixed on a modified yarn winding frame.
(3) Heating a 2L high-pressure reaction kettle to 80 ℃ by using an oil bath heating mode, firstly vacuumizing to remove air in the kettle, and then filling CO into a container2The pressure in the reaction kettle is 14Mpa, and the supercritical CO is positioned in the kettle2In this state, the amount of 2, 4-tolylene diisocyanate added was 6.1% by mass of carbon dioxide in the reaction vessel. At the moment, the precursor winding frame and the modified yarn winding frame are rotated simultaneously, and the aramid fiber III fiber is wound to the modified yarn winding frame from the precursor winding frame through the godet roller and is mixed with supercritical CO dissolved with 2, 4-toluene diisocyanate2And (3) after the fluid swelling reaction is carried out for 90min, discharging the pressure in the high-pressure reaction kettle to normal pressure for 5min, thus obtaining the modified aramid fiber III. The rotating speed of the precursor filament winding shaft is 2r/min, the rotating speed of the modified filament winding frame is 5r/min, and the tension of the aramid fiber III measured by a mechanical sensor is 15 CN.
(4) And cleaning the modified aramid fiber III with acetone at 80 ℃ for 1h to constant weight, and then carrying out vacuum drying at 80 ℃ for 2 h.
(5) Testing the mechanical property of the aramid fiber III fiber by using a monofilament strength tester, wherein the monofilament tensile strength of the aramid fiber III fiber is 29.4CN/dtex, and the modulus is 1090.2 CN/dtex; the mechanical property tensile strength of the modified aramid fiber III is 32.5CN/dtex, and the modulus is 1320.2 CN/dtex. Compared with aramid fiber III, the tensile strength of the modified aramid fiber III is improved by 10.54%, and the modulus is improved by 21.10%.
Example 4
(1) And (3) putting 5.0g of Nomex fiber into acetone, ultrasonically washing at 90 ℃ for 2h, taking out, and vacuum drying at 80 ℃ for 8 h.
(2) And (2) placing the cleaned and dried Nomex fiber in the step (1) and 1.0g of terephthaloyl chloride crosslinking modifier into a reaction kettle, wherein the Nomex fiber is wound on a protofilament winding frame, and the free end of the Nomex fiber is fixed on a modified filament winding frame.
(3) Heating a 2L high-pressure reaction kettle to 100 ℃ by using an oil bath heating mode, firstly vacuumizing to remove air in the kettle, and then filling CO into a container2The pressure in the reaction kettle is 8Mpa, and the kettle is in supercritical CO2In the state, the adding amount of the paraphthaloyl chloride is 5% of the mass of the carbon dioxide in the reaction kettle, at the same time, the protofilament winding frame and the modified filament winding frame are rotated, and the Nomex fiber and the supercritical CO dissolved with the paraphthaloyl chloride are mixed in the process that the Nomex fiber is wound from the protofilament winding frame to the modified filament winding frame through the godet roller2And after the fluid swelling reaction is carried out for 120min, the pressure in the high-pressure reaction kettle is discharged to normal pressure for 8min, and the modified Nomex fiber is obtained. The rotating speed of the protofilament winding shaft is 4r/min, the rotating speed of the modified filament winding frame is 5r/min, and the Nomex fiber tension measured by a mechanical sensor is 4 CN.
(4) The modified Nomex fibers were cleaned with acetone at 80 ℃ for 1h to constant weight, and then vacuum dried at 80 ℃ for 2 h.
(5) Testing the mechanical property of the fiber by using a monofilament strength tester, wherein the monofilament tensile strength of the Nomex fiber is 5.4CN/dtex, and the modulus is 90.2 CN/dtex; the mechanical property tensile strength of the modified Nomex fiber is 6.5CN/dtex, and the modulus is 110.3 CN/dtex. The tensile strength of the modified Nomex fibers was increased by 20.37% and the modulus was increased by 22.28% compared to Nomex fibers.
Claims (3)
1. In tension of moving aramid fiberSupercritical CO under utilization2The fluid modification method is characterized in that aramid fiber and a cross-linking agent are placed in a reaction container, the aramid fiber is not contacted with the cross-linking agent, and carbon dioxide gas is introduced into the reaction container until supercritical carbon dioxide fluid is generated; the aramid fiber generates tension due to the difference of the front and back movement speeds, and the supercritical carbon dioxide fluid carries the dissolved cross-linking agent to perform swelling reaction with the aramid fiber in a movement state to obtain modified aramid fiber; the tension is 4-50 CN, and the front-back movement speed of the aramid fiber is 0.5-40 r/min; the swelling reaction time is 20-120 min; the aramid fiber is para-aramid Kevlar, Nomex fiber, Twaron fiber, Technora fiber, aramid III fiber or F-12 fiber; the cross-linking agent is isocyanate compound or paraphthaloyl chloride.
2. The supercritical CO of claim 12The fluid modification method is characterized in that the supercritical carbon dioxide fluid is generated under the conditions of 50-250 ℃ and 8-16 Mpa.
3. The supercritical CO of claim 12The fluid modification method is characterized in that the addition amount of the cross-linking agent is 2-8% of the mass of the introduced carbon dioxide.
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| JP2006016710A (en) * | 2004-06-30 | 2006-01-19 | Teijin Techno Products Ltd | Method for treating synthetic fiber |
| WO2009000275A3 (en) * | 2007-06-22 | 2009-02-19 | Nanon As | A method of treating a polymer item |
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| CN102587131B (en) * | 2012-02-17 | 2014-04-02 | 东华大学 | Method for modifying interior and surface of aramid fiber through isocyanate in supercritical CO2 |
| CN103469602B (en) * | 2013-09-13 | 2016-01-06 | 东华大学 | A kind of aramid fiber stretch orientation in supercritical fluid improves the method for mechanical property |
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| CN103469573B (en) * | 2013-09-13 | 2015-10-21 | 东华大学 | A kind of aramid fiber is at CO 2improved the method for mechanical property by stretch orientation and chemical crosslinking in supercritical fluid |
| CN103469589B (en) * | 2013-09-13 | 2016-01-06 | 东华大学 | A kind of aramid fiber is at CO 2the method of Graft Epoxy Resin in supercritical fluid |
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| JP2006016710A (en) * | 2004-06-30 | 2006-01-19 | Teijin Techno Products Ltd | Method for treating synthetic fiber |
| WO2009000275A3 (en) * | 2007-06-22 | 2009-02-19 | Nanon As | A method of treating a polymer item |
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