CN117344457A - Method for preparing para-aramid nanofiber membrane by air-flow assisted drafting coaxial spinning - Google Patents
Method for preparing para-aramid nanofiber membrane by air-flow assisted drafting coaxial spinning Download PDFInfo
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- CN117344457A CN117344457A CN202311331460.8A CN202311331460A CN117344457A CN 117344457 A CN117344457 A CN 117344457A CN 202311331460 A CN202311331460 A CN 202311331460A CN 117344457 A CN117344457 A CN 117344457A
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- 238000009987 spinning Methods 0.000 title claims abstract description 55
- 239000012528 membrane Substances 0.000 title claims abstract description 37
- 239000002121 nanofiber Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 26
- 239000000835 fiber Substances 0.000 claims abstract description 44
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 claims abstract description 21
- 239000000725 suspension Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 239000010410 layer Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000012792 core layer Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 239000004760 aramid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 108010025899 gelatin film Proteins 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000352 supercritical drying Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/009—Condensation or reaction polymers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/016—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the fineness
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a method for preparing a para-aramid nanofiber membrane by air-assisted drafting and coaxial spinning, which comprises the following steps: the PPTA short fiber is dried after being ultrasonically treated in absolute ethyl alcohol, and is dissolved in a proton removing system to obtain an ANF suspension; PEO powder is dissolved in N, N-dimethylformamide to obtain PEO solution, the PEO solution is respectively injected into a pipeline corresponding to a coaxial spinning needle head, coaxial spinning is carried out by air flow auxiliary drafting, a fiber membrane is formed by depositing on a water bath receiving net, and the pure ANFM is obtained by washing and drying. The ANFM obtained by the coaxial spinning through the air-assisted traction and stretching not only maintains the excellent performance of macroscopic PPTA fibers, but also has the characteristics of small fiber diameter size, high membrane porosity and the like which are special for ANFs, and can be applied to the fields of lithium ion battery diaphragms, heat insulation, filtration and the like.
Description
Technical Field
The invention belongs to the field of nanofiber preparation, and particularly relates to a method for preparing a para-aramid nanofiber membrane by air-assisted drafting and coaxial spinning.
Background
Para-aramid fiber, namely poly-paraphenylene terephthalamide (PPTA) fiber, is a quasi-reticular cross-linked high polymer, has excellent performances of high strength, high modulus, high temperature resistance, corrosion resistance and the like, can be used for preparing high-strength and light-weight honeycomb structural materials, high-temperature resistant insulating materials, high-performance materials for electronic communication equipment and the like, and is widely applied to the fields of aerospace, traffic electric power, national defense and military and the like, and plays a significant role in the modern industry.
With the continued innovation and development of nanotechnology, aramid Nanofibers (ANF) have also been a focus of attention. When the material is small to the nanometer scale, small-size effects, surface effects, quantum size effects and macroscopic quantum tunneling effects are exhibited due to changes in physical and chemical properties of the material itself. Nanofibers generally exhibit unique properties not found in the original materials, based on maintaining the original macroscopic materials, due to variations in size, morphology and structure. However, because the PPTA chopped fiber has high surface molecular chain arrangement orientation degree and high crystallinity, the hydrogen on the amide group is difficult to react with other atoms due to the large steric hindrance of the benzene ring, in addition, the fiber surface is smooth, the specific surface area is small, the chemical inertia of the chemical active group is lacking, the chemical inertia is strong, the physical engagement point with a matrix is avoided, and the like, so that the PPTA fiber is not easy to be dissolved by a common organic solvent, is not easy to be cracked into aramid nanofibers, and greatly influences the application of the aramid nanofibers in the field of composite materials.
Para-aramid nanofiber membrane (ANFM) is formed by bonding the inside and the between molecules of ANFs, the unique performance and wide application prospect of the ANFM lead to active researches of scientific researchers, and the preparation method of the ANFM is mainly focused on a layer-by-layer self-assembly method and an electrostatic spinning method. Patent document CN106170878A composites ANF with polyethylene oxide (PEO), and obtains a nanocomposite film with high ion flux and good thermal stability by a layer-by-layer self-assembly method (LBL); patent document CN108084468A combines ANF and polydiallyl ammonium dichloromethylation (PDDA), and produces a film with excellent mechanical properties by vacuum assisted LBL process; patent document CN110373814A adds PEO powder into ANF dispersion liquid to prepare spinning liquid, and prepares ANFs/PEO nanofiber membrane by electrostatic spinning technology, which has wide application range.
At present, the layer-by-layer self-assembly method generally needs to be repeated for at least about 200-300 times, which is extremely time-consuming, and the prepared nano composite film sometimes needs to adopt supercritical drying or freeze drying to replace liquid in wet gel with gas, which has the defect of high energy consumption and is not beneficial to environmental protection. In addition, the electrospinning method has a series of defects, such as high melt viscosity, poor conductivity, high electric field intensity, and easy occurrence of electric field breakdown, and the prepared fiber is in micron level, the device is complex, a high-temperature heating device is required, electrostatic interference with a high-voltage device is easy to occur, and the thermal stability of the prepared composite nanofiber membrane is reduced due to the fact that ANF dispersion liquid is blended with PEO and part of PEO is doped in the fiber. The preparation of pure ANFM is advantageous for widening the applications of ANFM if it reduces the energy consumption during the preparation of ANFM and shortens the preparation period. However, PPTA has a high molecular chain rigidity, is not easily fibrillated, shows poor spinnability, and is difficult to form a film by using pure ANF, and even if the film is formed, the film is very fragile, so that the application of the film is greatly limited.
Disclosure of Invention
In order to solve the problems of difficult preparation, long preparation period and high energy consumption of the ANFM in the prior art, the invention aims to provide a method for preparing a para-aramid nanofiber membrane by adopting PEO solution to wrap ANF dispersion liquid and adopting the air-assisted drafting coaxial spinning to prepare the ANFM.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing a para-aramid nanofiber membrane by air-assisted drafting and coaxial spinning, which comprises the following steps:
step 1: the PPTA short fibers are dried after being ultrasonically treated in absolute ethyl alcohol for 2 hours, and the treated PPTA short fibers are dissolved in a proton removing system to obtain an ANF suspension; PEO powder is dissolved in N, N-Dimethylformamide (DMF) to obtain PEO solution;
step 2: the ANF suspension and the spinning aid are respectively injected into a pipeline corresponding to the coaxial spinning needle head, and the ANF suspension comprises the following components: injecting ANF suspension into the injection pump corresponding to the core layer solution channel, injecting PEO solution into the injection pump corresponding to the outer shell layer solution channel, connecting a liquid outlet of the propeller injection pump with a coaxial spinning needle through a liquid inlet pipe, setting a propelling speed, and connecting an air tank, a pressure regulating valve and an air compressor through an air pipe;
step 3: air-assisted drafting co-axial spinning comprising: opening an air compressor, an air inlet, a pressure regulating valve and an injection pump, pushing spinning liquid into a liquid inlet pipe, flowing out from an outlet of a coaxial spinning needle, blowing and spraying high-speed air flow, and depositing in a water bath net curtain to form a film to form a fiber film;
step 4: and taking out the deposited fiber membrane, cleaning the fiber membrane by deionized water to remove PEO, and drying the fiber membrane to obtain the pure ANFM.
Preferably, in step 1, the proton removing system is composed of potassium hydroxide (KOH), dimethyl sulfoxide (DMSO), and absolute ethanol.
Preferably, in the step 1, the fineness of the PPTA short fiber is 200 denier, the concentration is 0.8-1.0 wt%, and the preferable concentration is 1.0wt%; PEO has a molecular weight of 60 ten thousand and a concentration of 5 to 7wt%, preferably 6.5wt%.
Preferably, in step 2, the spinning aid is one of PEO, polyvinylpyrrolidone (PVP) or polyvinyl alcohol (PVA), and more preferably PEO.
Preferably, in the step 2, the pushing speed of the syringe pump corresponding to the ANF suspension is 0.1-0.3 mL/min, more preferably 0.2mL/min; the PEO solution was advanced at a corresponding syringe pump speed of 0.3mL/min.
Preferably, in the step 2, the distance between the receiving net and the spinning needle is 20-40 cm, preferably 30cm; the coaxial spinning needles have an inner diameter of 16G+21G or 17G+22G, more preferably 16G+21G.
Preferably, the preparation method of the ANFM comprises the following steps:
(a) Immersing the PPTA chopped fibers in absolute ethyl alcohol for ultrasonic treatment for 2 hours, drying, adding KOH and the treated PPTA chopped fibers into DMSO and absolute ethyl alcohol, wherein the volume ratio of the absolute ethyl alcohol to the DMSO is 1:20, stirring in a water bath to obtain an ANF suspension with the concentration of 1.0wt%;
(b) PEO powder is added into DMF and stirred in a water bath to obtain PEO solution with the concentration of 6.5 weight percent;
(c) The ANF suspension and PEO solution were injected into the coaxial needle with a ratio of advancing rate of PEO solution to advancing rate of ANF suspension of 3:2, drawing and stretching by air flow assistance to obtain fiber with a core-shell structure, wherein the fiber is randomly deposited in a water bath net curtain to form a film, and the receiving distance is 30cm;
(d) And (3) completely removing PEO by using deionized water for cleaning, and air-drying at room temperature to obtain the pure ANFM.
Compared with the prior art, the method for preparing the para-aramid nanofiber membrane by air-assisted drafting and coaxial spinning has the following beneficial effects:
1. according to the invention, through air flow auxiliary traction stretching coaxial spinning, the obtained ANFM not only maintains the excellent performance of macroscopic PPTA fibers, but also has the characteristics of small fiber diameter size, high membrane porosity and the like which are special for ANFs, and has wide application in the fields of lithium ion battery diaphragms, heat insulation, filtration and the like.
2. The preparation method provided by the invention omits the supercritical drying or freeze drying process in the process of preparing the ANFM by the vacuum auxiliary layer-by-layer self-assembly method, is relatively environment-friendly in preparation process and shorter in preparation process, and can completely remove PEO in the ANFM to obtain the pure ANFM.
3. The preparation method provided by the invention is simple, can be continuously operated, is environment-friendly and moderate in cost, is beneficial to amplifying and industrial production, and the obtained ANFM has the characteristics of light weight, high strength, high flexibility, high chemical stability, high thermal stability and the like, can be applied to extreme environments or special environments, and further expands the application of the materials.
Drawings
Fig. 1 is a schematic diagram of an air-assisted drawing coaxial spinning process in an embodiment.
FIG. 2 is a digital photograph of the para-aramid nanofiber membrane obtained in example 1.
FIG. 3 is a scanning electron micrograph of the para-aramid nanofiber membrane obtained in example 1.
FIG. 4 is a pore size distribution diagram of the para-aramid nanofiber membrane obtained in example 1.
FIG. 5 is a tensile stress-strain curve of the para-aramid nanofiber membrane obtained in example 1.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
As shown in fig. 1, the following embodiment provides a method for preparing a para-aramid nanofiber membrane by air-assisted drawing and coaxial spinning, which comprises the following steps:
(1) Preparation of spinning solution: ultrasonic treating PPTA short fiber in absolute ethyl alcohol for 2h, drying, dissolving the treated PPTA short fiber in a proton removing system to obtain an ANF suspension, wherein the proton removing system consists of KOH, DMSO and absolute ethyl alcohol; PEO powder was dissolved in DMF to give a PEO solution. Preparing ANF suspension liquid and PEO solution with different concentrations by adjusting the weighing quality of PPTA fiber and PEO powder, so as to prepare nanofiber membranes with different performances; wherein the fineness of the PPTA fiber is 200 denier, the concentration is 0.8-1.0 wt%, and the preferable concentration is 1.0wt%; PEO has a molecular weight of 60 ten thousand and a concentration of 5 to 7wt%, preferably 6.5wt%.
(2) Spinning preparation: the ANF suspension is injected into the injection pump 2 corresponding to the core layer solution channel, the PEO solution is injected into the injection pump 3 corresponding to the outer layer solution channel, the liquid outlet of the propeller injection pump is connected with the coaxial spinning needle 8 through the liquid inlet pipes 6 and 7, the propelling speed is set, and the air tank 14, the pressure regulating valve 5 and the air compressor 1 are connected through the air pipe 4. The propulsion speed of the ANF suspension injection pump is set to be 0.1-0.3 mL/min, preferably 0.2mL/min; the PEO solution syringe pump advancement rate was fixed at 0.3mL/min.
(3) Spinning: the air compressor 1, the air inlet 9, the pressure regulating valve 5 and the injection pumps 12 and 13 are opened, the spinning solution is pushed into the liquid inlet pipes 6 and 7 and flows out from the outlet of the coaxial spinning needle 8, and then the spinning solution is drawn by air flow and deposited on the water bath net curtain 10 to form the fiber membrane 11. In the process, the distance between the receiving net and the spinning needle and the pressure of the pressure regulating valve are regulated, and coaxial spinning needles with different apertures are replaced, so that the fiber membranes 11 with different structures can be obtained, and the distance between the receiving net and the spinning needle is set to be 20-40 cm, preferably 30cm; the coaxial spinning needle inner diameter is set to 16G+21G or 17G+22G, preferably 16G+21G.
(4) And (3) spinning is finished: taking out the deposited fiber film, cleaning the fiber film in deionized water for 30min for removing PEO in the film, and then drying the fiber film in a 100 ℃ oven to obtain the pure ANFM.
Example 1
The preparation method of the ANFM comprises the following steps; 1.2g of PPTA fiber and 0.6g of KOH are respectively weighed and added into 100mL of LDMSO and 5mL of absolute ethyl alcohol, and then stirred in a water bath kettle at 60 ℃ for 2 hours at the rotating speed of 350rpm/min to obtain a dark red ANF suspension with the concentration of 1.0wt%; then adding PEO powder into DMF, stirring for 3 hours at a speed of 350rpm/min in a water bath at 60 ℃ to obtain a PEO solution with a concentration of 6.5 wt%; and respectively injecting the ANF suspension and the PEO solution into the inner and outer channels of a coaxial needle with the specification of 21G and 16G, drawing the coaxial needle by airflow auxiliary traction to assist in forming fibers, randomly depositing the fibers into a water bath screen to form a gel film, cleaning the gel film in deionized water for 30min to remove PEO, and drying the gel film in a drying oven at 100 ℃ to obtain the ANFM.
As shown in FIGS. 2 to 5, the ANFM prepared in this example has an average pore size of 0.2 μm, an average diameter of ANFs of 20-30nm, and a density of 0.12g/cm 3 The porosity was 62%, the tensile strength was 50MPa, and the elongation at break was 9.2%.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art will appreciate that, in light of the principles of the present invention, improvements and modifications can be made without departing from the scope of the invention.
Claims (9)
1. The method for preparing the para-aramid nanofiber membrane by air-assisted drafting and coaxial spinning is characterized by comprising the following steps of:
step 1: the PPTA short fibers are dried after being ultrasonically treated in absolute ethyl alcohol for 2 hours, and the treated PPTA short fibers are dissolved in a proton removing system to obtain an ANF suspension; PEO powder is dissolved in N, N-dimethylformamide to obtain PEO solution;
step 2: the ANF suspension and the spinning aid are respectively injected into a pipeline corresponding to the coaxial spinning needle head, and the ANF suspension comprises the following components: injecting ANF suspension into the injection pump corresponding to the core layer solution channel, injecting PEO solution into the injection pump corresponding to the outer shell layer solution channel, connecting a liquid outlet of the propeller injection pump with a coaxial spinning needle through a liquid inlet pipe, setting a propelling speed, and connecting an air tank, a pressure regulating valve and an air compressor through an air pipe;
step 3: air-assisted drafting co-axial spinning comprising: opening an air compressor, an air inlet, a pressure regulating valve and an injection pump, pushing spinning liquid into a liquid inlet pipe, flowing out from an outlet of a coaxial spinning needle, drawing by airflow, and depositing on a water bath receiving net to form a fiber membrane;
step 4: and taking out the deposited fiber membrane, cleaning the fiber membrane by deionized water to remove PEO, and drying the fiber membrane to obtain the pure ANFM.
2. The method for preparing para-aramid nanofiber membrane by air-assisted drawing and coaxial spinning according to claim 1, wherein in the step 1, the proton removing system consists of potassium hydroxide, dimethyl sulfoxide and absolute ethyl alcohol.
3. The method for preparing a para-aramid nanofiber membrane by air-assisted drafting and coaxial spinning according to claim 1, wherein in the step 1, the fineness of the PPTA short fiber is 200 denier, and the concentration is 0.8-1.0 wt%; PEO has a molecular weight of 60 ten thousand and a concentration of 5 to 7wt%.
4. A method for preparing para-aramid nanofiber membrane by air-assisted drawing and coaxial spinning according to claim 3, wherein in step 1, the concentration of PPTA short fiber is 1.0wt% and the concentration of PEO is 6.5wt%.
5. The method for preparing para-aramid nanofiber membrane by air-assisted drawing and coaxial spinning according to claim 1, wherein in the step 2, the spinning aid is one of PEO, polyvinylpyrrolidone or polyvinyl alcohol.
6. The method for preparing a para-aramid nanofiber membrane by air-assisted drafting and coaxial spinning according to claim 1, wherein in the step 2, the propelling speed of a syringe pump corresponding to the ANF suspension is 0.1-0.3 mL/min; and/or the syringe pump advancing speed corresponding to the PEO solution is 0.3mL/min.
7. The method for preparing a para-aramid nanofiber membrane by air-assisted drawing and coaxial spinning according to claim 6, wherein in the step 2, the advancing speed of a syringe pump corresponding to the ANF suspension is 0.2mL/min, and the advancing speed of a syringe pump corresponding to the PEO solution is 0.3mL/min.
8. The method for preparing para-aramid nanofiber membrane by air-assisted drafting and coaxial spinning according to claim 1, wherein in the step 2, the distance between the receiving net and the spinning needle is 20-40 cm, and the inner diameter of the coaxial spinning needle is selected from 16g+21g or 17g+22g.
9. The method for preparing para-aramid nanofiber membrane by air-assisted drawing and coaxial spinning according to claim 8, wherein in the step 2, the distance between the receiving net and the spinning needle is 30cm, and the inner diameter of the coaxial spinning needle is 16g+21g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311331460.8A CN117344457A (en) | 2023-10-16 | 2023-10-16 | Method for preparing para-aramid nanofiber membrane by air-flow assisted drafting coaxial spinning |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311331460.8A CN117344457A (en) | 2023-10-16 | 2023-10-16 | Method for preparing para-aramid nanofiber membrane by air-flow assisted drafting coaxial spinning |
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| CN117344457A true CN117344457A (en) | 2024-01-05 |
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| CN202311331460.8A Pending CN117344457A (en) | 2023-10-16 | 2023-10-16 | Method for preparing para-aramid nanofiber membrane by air-flow assisted drafting coaxial spinning |
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