CN104894837A - Ultrasonic-assisted chemical modification method for aramid fibers - Google Patents
Ultrasonic-assisted chemical modification method for aramid fibers Download PDFInfo
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Abstract
The invention relates to an ultrasonic-assisted chemical modification method for aramid fibers and belongs to the technical field of chemical synthetic fiber modification. The method includes preparation of a surface modification treatment agent, ultrasonic-assisted catalytic reaction preparation, surface modification treatment and washing drying, a specific acyl chloride active reagent is dissolved in an anhydrous strong-polar organic solvent which is in chemical grafting reaction with the aramid fibers under the action of ultrasonic catalysis, polar groups are introduced to the fiber surfaces, interfacial properties of the aramid fibers and an epoxy resin matrix are improved significantly, impregnated filament strength of the modified aramid fiber can reach 5.4GPa, and interlaminar shear strength can reach 52-60MPa. In addition, the method is simple in process, short in time, low in production cost and beneficial to industrial production, and total production time is less than 10min.
Description
Technical field
The present invention relates to a kind of chemical modification method of fiber, more particularly, the present invention relates to a kind of ultrasonic assistant chemical modification method of aramid fiber, belong to chemical synthetic fiber technical field of modification.
Background technology
P-aramid fiber for reinforcing material mainly contains two kinds.A kind of is carry out polymer " PPTA " prepared by polymerisation, i.e. aramid II by monomer p-phenylene diamine and paraphthaloyl chloride.Another kind on aramid II molecular structure basis, introduces Third monomer " 5 (6)-amido-2-(4-aminocarbonyl phenyl) benzimidazole " carry out polymer prepared by copolymerization, i.e. aramid fiber III.Relative to aramid II, aramid IIII fiber mechanical property is better.Aramid fiber is mainly used in the fields such as defence and military, telecommunications, civil construction, product of rubber and plastic.
Although aramid fiber excellent in mechanical performance, because fiber surface lacks active group, surface property is poor.When aramid fiber makes composite, between fiber surface and resin matrix, bonding force is more weak, affects composite property, restriction composite range of application.So need to carry out surface modification to aramid fiber, introduce chemical active radical at aramid fiber surface, improve fiber surface energy, the adhesive power between fortifying fibre and resin matrix interface, improve fibre reinforced composites application performance.
The patent of invention of application number 201310224440.0 discloses and a kind ofly adopts the cleaning fluid in ultrasonic wave to carry out surface cleaning processing 0.5-3 minute to aramid fiber, reaches technology aramid fiber being implemented to modification.The patent of invention of application number 201210070232.5 discloses a kind of by selecting the several of the one or any ratio in amide-type organic solvent to be ultrasonic treatment media, under ul-trasonic irradiation, make amide solvent swollen fiber surface, reduce the adhesion point between aramid fiber monofilament simultaneously, improve the technology of fiber surface state.The feature of these two kinds of technology is all under certain dicyandiamide solution, makes full use of hyperacoustic cavitation effect and carries out fibrillating process to fiber surface, improves fiber and resin matrix contact area improves composite property by improving fiber surface area.These class methods belong to ultrasonic wave physical modification technology.
Open source literature " the ultrasonic continuous modification process in aramid fiber/epoxy composite material interface " (aeronautical material journal, Vol.23, No.1,49-51) propose and preparing in aramid fiber reinforced composite process, use ultrasonic technique, by ultrasonic energy, force resin wetting fibre, improve wettability between the two, improve composite material interface performance.This method also belongs to ultrasonic wave physical modification technology, improves fiber surface performance limited extent.
It is CN101407995 that State Intellectual Property Office discloses a publication number in 2009.4.15, and the invention that name is called " aramid fiber surface modified method ", this invention relates to a kind of aramid fiber surface modified method.Comprise the steps: the surface treatment of (1) aramid fiber; (2) hydrolysis of aramid fiber; (3) interfacial polymerization grafting liquid crystal monomer 4 is adopted, 4-dihydroxy-α, α '-dimethylbenzyl connection nitrogen: 1. prepare aqueous phase: neutral position aramid fiber will be hydrolyzed into, 4,4-dihydroxy-α, α '-dimethylbenzyl connection nitrogen, NaOH and quaternary amine is soluble in water; 2. organic phase is prepared: be dissolved in by dicarboxylic acid chloride in organic solvent; 3. organic phase is poured into rapidly in aqueous phase, rapid stirring, react, in the precipitating agent that product is poured into, stir, filter, then carry out washing and purify, until washing lotion clarification, after carrying out drying, namely obtain modification of aramid fiber.Make aramid fiber surface with the rigidity side chain of liquid crystal property, form tree fork shape microscopic appearance, contribute to the adhesion strengthening aramid fiber and matrix, improve mechanical property.
Above-mentioned prior art grafted monomers is 4,4-dihydroxy-α mainly, α '-dimethylbenzyl connection nitrogen, the dicarboxylic acid chloride used is a kind of assisted reaction reagent, plays mainly 4, the 4-dihydroxy-α of modifying function in this technology, α '-dimethylbenzyl connection nitrogen, mechanical property improves more limited.Above-mentioned prior art can only process aramid fiber powder and staple fiber, cannot process aramid filament fiber.In addition, the chemical reaction velocity of the interfacial polymerization of above-mentioned technology is slow, operation is many, and technological process is oversize, and first fiber wash process needs 1-5h, then fiber hydrolysis reaction needed 4-9h, then chemical graft reaction needed 5-30min, last vacuumize needs 16-24h, and this technology production time is oversize, production cost is too high, does not have industrial applications and is worth.
Summary of the invention
The present invention is intended to solve existing ultrasonic wave physical modification to raising aramid fiber surface performance limited extent, and existing chemical modification method operation is too many, oversize problem consuming time, a kind of ultrasonic assistant chemical modification method of aramid fiber is provided, the method operation is simple, consuming time short, effectively can implant chemical active radical at aramid fiber surface, significantly improve fiber surface performance, improve the mechanical property of cementability between aramid fiber and epoxy resin-base and aramid fiber.
For achieving the above object, the technical solution used in the present invention is as follows:
A ultrasonic assistant chemical modification method for aramid fiber, is characterized in that: comprise following processing step:
A, the agent of preparation surface modification treatment
Under inert gas shielding, by acyl chloride active reaction agent dissolves in anhydrous strong polar organic solvent, be mixed with surface modification treatment agent; Described acyl chloride active reaction reagent is several mixing of any one or arbitrary proportion in chloroacetic chloride, propionyl chloride, chloracetyl chloride, dichloroacetyl chloride, trichloro-acetic chloride, thionyl chloride; Described strong polar organic solvent is several mixing of any one or arbitrary proportion in 1-METHYLPYRROLIDONE, DMA, DMF, dimethyl sulfoxide (DMSO);
B, ultrasonic wave added catalytic reaction prepare
The surface modification treatment agent above-mentioned preparation completed imports in the supersonic generator of inert gas shielding;
C, surface modification treatment
Aramid fiber enters in surface modification treatment agent by interval or continued operation form, under Catalyzed by Ultrasonic Wave effect, carry out chemical graft reaction;
D, washing drying
Modification of aramid fiber product is obtained after the reacted aramid fiber of chemical graft is by washing, drying.
In step, described inert gas is any one in nitrogen, helium, argon gas in the present invention.Wherein be more preferably high-purity nitrogen.
In step, described acyl chloride active reaction reagent is one in chloroacetic chloride, chloracetyl chloride or the mixing of both arbitrary proportions in the present invention.
In step, described strong polar organic solvent is one in 1-METHYLPYRROLIDONE, DMA or the mixing of both arbitrary proportions in the present invention.
In step, the described concentration of volume percent of acyl chloride active reaction agent dissolves in anhydrous strong polar organic solvent is 10-40% in the present invention.Wherein preferred concentration of volume percent is 20-30%.
In stepb, the power of described supersonic generator is 1-5kW in the present invention.
The present invention is in step C, and described hyperacoustic frequency is 30-80KHz.
The present invention is in step C, and the described reaction time of carrying out chemical graft reaction is 1-5min, and reaction temperature is 20-50 DEG C.
In step D, described washing adopts the deionized water of 80-90 DEG C to wash, and the temperature of described drying is 130-150 DEG C in the present invention.
Supersonic generator of the present invention has corrosion resistance characteristic, container inside lining polytetrafluoro material, prevents highly acid chemism reaction reagent to ultrasonic instrument corrosion and damage.
The Advantageous Effects that the present invention brings:
1, the invention solves existing ultrasonic wave physical modification to raising aramid fiber surface performance limited extent, and existing chemical modification method operation is too many, oversize problem consuming time, specific acyl chloride active agent is adopted to be dissolved in anhydrous strong polar organic solvent, chemical graft reaction is carried out with aramid fiber under Catalyzed by Ultrasonic Wave effect, polar group is introduced at fiber surface, significantly improve the interface performance between aramid fiber and epoxy resin-base, 5.4GPa can be reached through modified aramid fiber impregnation silk intensity, interlaminar shear strength can reach 52-60MPa.Operation of the present invention is simple in addition, and consuming time short, the production time is less than 10min altogether, and production cost is low, is beneficial to suitability for industrialized production.
2, hyperacoustic in the present invention " cavitation effect " contributes to aramid fiber and carries out swelling in strong polar organic solvent, and produces fibrillating effect, improves pulp freeness, is conducive to aramid fiber and resin matrix fully bonds.
3, industrial implementation method of the present invention is flexible, and intermittently operated namely can be adopted also can to adopt continued operation.Output less employing batch process method; Output then adopts continous treatment process comparatively greatly.
4, the inventive method can change flexibility and the dispersiveness of aramid fiber simultaneously, modified fiber surface stable performance, unattenuated.
5, the present invention can process aramid fiber powder and staple fiber, also can process aramid filament fiber, and mainly process filament fiber.
6, monoacid acyl chlorides (as chloroacetic chloride, propionyl chloride, chloracetyl chloride, dichloroacetyl chloride, trichloro-acetic chloride, the thionyl chloride) reactivity of the present invention's use is strong, and reaction speed is fast.
7, the present invention in step, and preferred acyl chloride active reaction reagent is one in chloroacetic chloride, chloracetyl chloride or the mixing of both arbitrary proportions.Chloroacetic chloride, chloracetyl chloride are active strong, and density is less, and price is more economical, are conducive to large-scale industrial application.
8, the present invention in step, and preferred strong polar organic solvent is one in 1-METHYLPYRROLIDONE, DMA or the mixing of both arbitrary proportions.Preferred solvent polarity is stronger, has better swelling action to aramid fiber, is conducive to acyl chlorides and fiber carries out graft reaction, is also conducive to ultrasonic wave and carries out physical modification effect to fiber.
9, the present invention in step, and the concentration of volume percent of preferred acyl chloride active reaction agent dissolves in anhydrous strong polar organic solvent is 10-40%.Wherein preferred concentration of volume percent is 20-30%.Aforementioned preferred concentration both ensure that chemical reaction velocity did not slow down, and can not produce waste again, can not reduce the swelling action of organic solvent to fiber.Preferred concentration effect is better.
10, the present invention in stepb, and the power of preferred supersonic generator is 1-5kW.This power bracket can provide enough reaction activities for reaction reagent, can not produce too many heat, can prevent temperature of reaction system from raising fast.
11, the present invention in stepb, and preferred hyperacoustic frequency is 30-80KHz.The selection of above-mentioned special ultrasonic ripple frequency ensure that hyperacoustic penetration power, decreases ultrasonic wave decay in media as well; Enough mechanical oscillation active forces can be produced simultaneously, ensure the fibrillating effect to aramid fiber.
12, the present invention is in step C, and the reaction time of preferably carrying out chemical graft reaction is 1-5min, and reaction temperature is 20-50 DEG C.Being combined in of above-mentioned reaction time and reaction temperature can prevent reaction reagent with solvent evaporates, can not affect work condition environment while enhancing productivity.
Detailed description of the invention
embodiment 1
A ultrasonic assistant chemical modification method for aramid fiber, comprises following processing step:
A, the agent of preparation surface modification treatment
Under inert gas shielding, by acyl chloride active reaction agent dissolves in anhydrous strong polar organic solvent, be mixed with surface modification treatment agent; Described acyl chloride active reaction reagent is several mixing of any one or arbitrary proportion in chloroacetic chloride, propionyl chloride, chloracetyl chloride, dichloroacetyl chloride, trichloro-acetic chloride, thionyl chloride; Described strong polar organic solvent is several mixing of any one or arbitrary proportion in 1-METHYLPYRROLIDONE, DMA, DMF, dimethyl sulfoxide (DMSO);
B, ultrasonic wave added catalytic reaction prepare
The surface modification treatment agent above-mentioned preparation completed imports in the supersonic generator of inert gas shielding;
C, surface modification treatment
Aramid fiber enters in surface modification treatment agent by interval or continued operation form, under Catalyzed by Ultrasonic Wave effect, carry out chemical graft reaction;
D, washing drying
Modification of aramid fiber product is obtained after the reacted aramid fiber of chemical graft is by washing, drying.
In above-mentioned basic technical scheme, specific acyl chloride active agent is adopted to be dissolved in anhydrous strong polar organic solvent, chemical graft reaction is carried out with aramid fiber under Catalyzed by Ultrasonic Wave effect, polar group is introduced at fiber surface, significantly improve the interface performance between aramid fiber and epoxy resin-base, can reach 5.4GPa through modified aramid fiber impregnation silk intensity, interlaminar shear strength can reach 52-60MPa.
embodiment 2
On the basis of embodiment 1:
Preferably, in step, described inert gas is any one in nitrogen, helium, argon gas.
In the selection of acyl chloride active reaction reagent and strong polar organic solvent:
Preferably, in step, described acyl chloride active reaction reagent is one in chloroacetic chloride, chloracetyl chloride or the mixing of both arbitrary proportions.
Preferably or further, in step, described strong polar organic solvent is one in 1-METHYLPYRROLIDONE, DMA or the mixing of both arbitrary proportions.
embodiment 3
On the basis of embodiment 1, the selection of technological parameter is as follows:
Preferably, in step, the described concentration of volume percent of acyl chloride active reaction agent dissolves in anhydrous strong polar organic solvent is 10%.
Preferably, in stepb, the power of described supersonic generator is 1kW.
Preferably, in step C, described hyperacoustic frequency is 30KHz.
Preferably or further, in step C, the described reaction time of carrying out chemical graft reaction is 1min, and reaction temperature is 20 DEG C.
Preferably, in step D, described washing adopts the deionized water of 80 DEG C to wash, and the temperature of described drying is 130 DEG C.
embodiment 4
On the basis of embodiment 1, the selection of technological parameter is as follows:
Preferably, in step, the described concentration of volume percent of acyl chloride active reaction agent dissolves in anhydrous strong polar organic solvent is 40%.
Preferably, in stepb, the power of described supersonic generator is 5kW.
Preferably, in step C, described hyperacoustic frequency is 80KHz.
Preferably or further, in step C, the described reaction time of carrying out chemical graft reaction is 5min, and reaction temperature is 50 DEG C.
Preferably, in step D, described washing adopts the deionized water of 90 DEG C to wash, and the temperature of described drying is 150 DEG C.
embodiment 5
On the basis of embodiment 1, the selection of technological parameter is as follows:
Preferably, in step, the described concentration of volume percent of acyl chloride active reaction agent dissolves in anhydrous strong polar organic solvent is 25%.
Preferably, in stepb, the power of described supersonic generator is 3kW.
Preferably, in step C, described hyperacoustic frequency is 55KHz.
Preferably or further, in step C, the described reaction time of carrying out chemical graft reaction is 3min, and reaction temperature is 35 DEG C.
Preferably, in step D, described washing adopts the deionized water of 85 DEG C to wash, and the temperature of described drying is 140 DEG C.
embodiment 6
On the basis of embodiment 1, the selection of technological parameter is as follows:
Preferably, in step, the described concentration of volume percent of acyl chloride active reaction agent dissolves in anhydrous strong polar organic solvent is 20%.
Preferably, in stepb, the power of described supersonic generator is 2kW.
Preferably, in step C, described hyperacoustic frequency is 65KHz.
Preferably or further, in step C, the described reaction time of carrying out chemical graft reaction is 4.5min, and reaction temperature is 21 DEG C.
Preferably, in step D, described washing adopts the deionized water of 88 DEG C to wash, and the temperature of described drying is 145 DEG C.
embodiment 7
The ultrasonic assistant chemical modification method of aramid fiber, technical process is as follows:
Under nitrogen protection, be dissolved in by chloracetyl chloride in DMA, chloracetyl chloride in the solution volumn concentration is 40%.
The surface treatment agent solution above-mentioned preparation completed with delivery pump is sent in the supersonic generator of inert gas shielding.Under nitrogen protection, aramid fiber is put into ultrasonic device, under Catalyzed by Ultrasonic Wave effect, carry out chemical graft reaction with chloroacetic chloride.Supersonic generator power 1kW, ultrasonic frequency 30KHz, reaction time 5min, reaction temperature 30 DEG C.
Fiber after Surface grafting reaction completes, by after 85 DEG C of deionized water washings, obtains sonochemistry modified fibre after drying under 150 DEG C of conditions.
embodiment 8
The ultrasonic assistant chemical modification method of aramid fiber, technical process is as follows:
Under helium protection, be dissolved in by chloracetyl chloride in 1-METHYLPYRROLIDONE, chloroacetic chloride in the solution volumn concentration is 10%.
The surface treatment agent solution above-mentioned preparation completed with delivery pump is sent in the supersonic generator of inert gas shielding.Under helium protection, aramid fiber is put into ultrasonic device, under Catalyzed by Ultrasonic Wave effect, carries out chemical graft reaction with chloracetyl chloride.Supersonic generator power 5kW, ultrasonic frequency 80KHz, reaction time 2min, reaction temperature 20 DEG C.
Fiber after Surface grafting reaction completes, by after 85 DEG C of deionized water washings, obtains sonochemistry modified fibre after drying under 130 DEG C of conditions.
embodiment 9
The ultrasonic assistant chemical modification method of aramid fiber, technical process is as follows:
Under argon shield, be dissolved in by thionyl chloride in DMF, thionyl chloride in the solution volumn concentration is 20%.
The surface treatment agent solution above-mentioned preparation completed with delivery pump is sent in the supersonic generator of inert gas shielding.Under argon shield, aramid fiber is put into ultrasonic device, under Catalyzed by Ultrasonic Wave effect, carry out chemical graft reaction with thionyl chloride.Supersonic generator power 3kW, ultrasonic frequency 60KHz, reaction time 1min, reaction temperature 50 DEG C.
Fiber after Surface grafting reaction completes, by after 90 DEG C of deionized water washings, obtains sonochemistry modified fibre after drying under 135 DEG C of conditions.
embodiment 10
The ultrasonic assistant chemical modification method of aramid fiber, technical process is as follows:
Under argon shield, be dissolved in by dichloroacetyl chloride in dimethyl sulfoxide (DMSO), dichloroacetyl chloride in the solution volumn concentration is 30%.
The surface treatment agent solution above-mentioned preparation completed with delivery pump is sent in the supersonic generator of inert gas shielding.Under argon shield, aramid fiber is put into ultrasonic device, under Catalyzed by Ultrasonic Wave effect, carry out chemical graft reaction with dichloroacetyl chloride.Supersonic generator power 2kW, ultrasonic frequency 50KHz, reaction time 3min, reaction temperature 30 DEG C.
Fiber after Surface grafting reaction completes, by after 80 DEG C of deionized water washings, obtains sonochemistry modified fibre after drying under 145 DEG C of conditions.
embodiment 11
The ultrasonic assistant chemical modification method of aramid fiber, technical process is as follows:
Under nitrogen protection, be dissolved in by trichloro-acetic chloride in dimethyl sulfoxide (DMSO), trichloro-acetic chloride in the solution volumn concentration is 25%.
The surface treatment agent solution above-mentioned preparation completed with delivery pump is sent in the supersonic generator of inert gas shielding.Under nitrogen protection, aramid fiber is put into ultrasonic device, under Catalyzed by Ultrasonic Wave effect, carry out chemical graft reaction with trichloro-acetic chloride.Supersonic generator power 5kW, ultrasonic frequency 60KHz, reaction time 1.5min, reaction temperature 35 DEG C.
Fiber after Surface grafting reaction completes, by after 85 DEG C of deionized water washings, obtains sonochemistry modified fibre after drying under 130 DEG C of conditions.
embodiment 12
The ultrasonic assistant chemical modification method of aramid fiber, technical process is as follows:
Under nitrogen protection, be dissolved in by propionyl chloride in DMA, propionyl chloride in the solution volumn concentration is 32%.
The surface treatment agent solution above-mentioned preparation completed with delivery pump is sent in the supersonic generator of inert gas shielding.Under nitrogen protection, aramid fiber is put into ultrasonic device, under Catalyzed by Ultrasonic Wave effect, carry out chemical graft reaction with propionyl chloride.Supersonic generator power 2.5kW, ultrasonic frequency 60KHz, reaction time 3min, reaction temperature 30 DEG C.
Fiber after Surface grafting reaction completes, by after 85 DEG C of deionized water washings, obtains sonochemistry modified fibre after drying under 140 DEG C of conditions.
Claims (9)
1. a ultrasonic assistant chemical modification method for aramid fiber, is characterized in that: comprise following processing step:
A, the agent of preparation surface modification treatment
Under inert gas shielding, by acyl chloride active reaction agent dissolves in anhydrous strong polar organic solvent, be mixed with surface modification treatment agent; Described acyl chloride active reaction reagent is several mixing of any one or arbitrary proportion in chloroacetic chloride, propionyl chloride, chloracetyl chloride, dichloroacetyl chloride, trichloro-acetic chloride, thionyl chloride; Described strong polar organic solvent is several mixing of any one or arbitrary proportion in 1-METHYLPYRROLIDONE, DMA, DMF, dimethyl sulfoxide (DMSO);
B, ultrasonic wave added catalytic reaction prepare
The surface modification treatment agent above-mentioned preparation completed imports in the supersonic generator of inert gas shielding;
C, surface modification treatment
Aramid fiber enters in surface modification treatment agent by interval or continued operation form, under Catalyzed by Ultrasonic Wave effect, carry out chemical graft reaction;
D, washing drying
Modification of aramid fiber product is obtained after the reacted aramid fiber of chemical graft is by washing, drying.
2. the ultrasonic assistant chemical modification method of a kind of aramid fiber according to claim 1, is characterized in that: in step, and described inert gas is any one in nitrogen, helium, argon gas.
3. the ultrasonic assistant chemical modification method of a kind of aramid fiber according to claim 1, is characterized in that: in step, and described acyl chloride active reaction reagent is one in chloroacetic chloride, chloracetyl chloride or the mixing of both arbitrary proportions.
4. the ultrasonic assistant chemical modification method of a kind of aramid fiber according to claim 1 or 3, it is characterized in that: in step, described strong polar organic solvent is one in 1-METHYLPYRROLIDONE, DMA or the mixing of both arbitrary proportions.
5. the ultrasonic assistant chemical modification method of a kind of aramid fiber according to claim 1, is characterized in that: in step, and the described concentration of volume percent of acyl chloride active reaction agent dissolves in anhydrous strong polar organic solvent is 10-40%.
6. the ultrasonic assistant chemical modification method of a kind of aramid fiber according to claim 1, is characterized in that: in stepb, and the power of described supersonic generator is 1-5kW.
7. the ultrasonic assistant chemical modification method of a kind of aramid fiber according to claim 1, is characterized in that: in step C, and described hyperacoustic frequency is 30-80KHz.
8. the ultrasonic assistant chemical modification method of a kind of aramid fiber according to claim 1 or 7, is characterized in that: in step C, and the described reaction time of carrying out chemical graft reaction is 1-5min, and reaction temperature is 20-50 DEG C.
9. the ultrasonic assistant chemical modification method of a kind of aramid fiber according to claim 1, is characterized in that: in step D, and described washing adopts the deionized water of 80-90 DEG C to wash, and the temperature of described drying is 130-150 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407995A (en) * | 2008-11-20 | 2009-04-15 | 沈阳工业大学 | Aramid fiber surface modified method |
| CN102605606A (en) * | 2012-03-16 | 2012-07-25 | 中蓝晨光化工有限公司 | Ultrasonic surface modification treatment method for aramid fibers |
| CN103321037A (en) * | 2013-06-07 | 2013-09-25 | 南通和泰通讯器材有限公司 | Aramid fiber surface treatment process |
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2015
- 2015-06-29 CN CN201510365730.6A patent/CN104894837B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407995A (en) * | 2008-11-20 | 2009-04-15 | 沈阳工业大学 | Aramid fiber surface modified method |
| CN102605606A (en) * | 2012-03-16 | 2012-07-25 | 中蓝晨光化工有限公司 | Ultrasonic surface modification treatment method for aramid fibers |
| CN103321037A (en) * | 2013-06-07 | 2013-09-25 | 南通和泰通讯器材有限公司 | Aramid fiber surface treatment process |
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| 凌新龙等: ""芳纶纤维表面改性研究进展"", 《天津工业大学学报》 * |
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