EP1591569B1 - Procédé pour la production de nanofibres - Google Patents

Procédé pour la production de nanofibres Download PDF

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Publication number
EP1591569B1
EP1591569B1 EP04460033A EP04460033A EP1591569B1 EP 1591569 B1 EP1591569 B1 EP 1591569B1 EP 04460033 A EP04460033 A EP 04460033A EP 04460033 A EP04460033 A EP 04460033A EP 1591569 B1 EP1591569 B1 EP 1591569B1
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EP
European Patent Office
Prior art keywords
fibres
solution
capillary
electrostatic field
linked
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Not-in-force
Application number
EP04460033A
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German (de)
English (en)
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EP1591569A1 (fr
Inventor
Piotr Kulpinski
Bogumil Laszkiewicz
Piotr Czarnecki
Barbara Niekraszewicz
Marcin Rubacha
Bogdan Peczek
Jolanta Jedrzejczak
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Politechnika Lodzka
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Politechnika Lodzka
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Priority to PL04460033T priority Critical patent/PL1591569T3/pl
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    • 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
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0046—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by coagulation, i.e. wet electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof

Definitions

  • the subject of the present invention is a process for the production of nanofibres with a diameter below 500 nm, in electrostatic field.
  • a process for the formation of fibres from a spinning solution of cellulose acetate in the mixture of acetone and ethyl alcohol in electrostatic field is known from Patent Specification U.S. 1 975 504 .
  • the spun fibres are collected on a moving metallic tape.
  • Patent Application P-362101 a process for the production of nanofibres from solutions of natural polymers in non-volatile solvents, preferably from cellulose solution in N-methylmorpholine-N-oxide, in electrostatic field generated between a metallic capillary, feeding the spinning solution, linked to a current source, and an earthed electrode placed under it or between an electrode linked to a current source and, place inside the feeding capillary and the earthed electrode.
  • Nanofibres formed in electric field from polymer solutions in non-volatile solvents contain large quantities of solvent and show a strong tendency towards sticking and changing shape.
  • the process for the production of nanofibres with a diameter below 500 nm consisting in preparing a spinning solution of natural polymer in a non-volatile solvent, especially of cellulose in N-methylmorpholine-N-oxide, feeding this solution by means of a metallic capillary, linked to a current source, to electrostatic field in which fibres are formed from the solution, winding the resultant fibres onto a take-up device, according to the present invention, is characterised by the fact that these fibres are formed in electrostatic field generated between a feeding capillary and placed under it moving coagulation bath linked to earth, followed by transporting the formed fibres on the surface of the moving coagulation bath to remove the non-volatile solvent and to solidify the fibres, which are finally taken-up in a usual way by a rotating drum or a tape moving on rotating rollers.
  • a coagulation bath water containing an addition of a surface-active agent is preferably used, and besides as a coagulation bath there is used water, water
  • fibres are formed in electrostatic field generated between a feeding capillary and placed under it, rotationally mounted, metallic structure linked to earth.
  • the formed fibres are led into a space between elements of this structure, where fibres are subjected to the coagulating action of a hot steam stream and finally the coagulated fibres are taken up.
  • fibres are formed in electrostatic filed generated between a feeding capillary and moving under it woven fabric, beneath which is placed an earthed and cooled electrode.
  • the formed fibres are directed onto the moving fabric, where they are coagulated with a hot stream of steam first and then with a water stream that rinses off the solvent; finally, the coagulated fibres are taken up.
  • the nanofibres produced by the process according to the present invention contain no solvent and show no tendency towards sticking and changing shape.
  • a spinning solution was prepared from 1 part of cellulose with a degree of polymerisation (DP) of about 800 in 35 parts of N-methylmorpholine-N-oxide (NMMO) and 6.5 parts of water with 0.1 parts of a stabiliser.
  • This solution was placed in container 2 of the feeding device shown in Fig. 1 , heated to 105°C, terminated with a metallic capillary 1 with a diameter of 0.4 mm linked to current source 3 under a voltage of 6 kV.
  • the solution was fed by means of capillary 1 to electrostatic field generated between capillary 1 and placed under it earthed tub 4 containing a coagulating bath. The distance between capillary 1 and bath 4 was 10 cm.
  • the stream of polymer solution drawn in electrostatic field and cooled was directed onto the surface of coagulation bath 4 consisting of water with an addition of a surface-active agent at a temperature of 10°C.
  • bath 4 the solvent is rinsed off and fibres are solidified.
  • the reduced rate of taking off fibres from bath 4 brings about the formation, on its surface, of a cellulose film composed from fibres with a thickness of 150 nm.
  • a spinning solution was prepared from 1 part of cellulose with a DP of about 800 in 16.0 parts of NMMO and 3.0 parts of water with 0.1 part of a stabiliser. This solution was placed in container 2 of the feeding device shown in Fig.2 , heated to 125°C, terminated with metallic capillary 1 with a diameter of 0.6 mm linked to current source 3 under a voltage of 17 kV. The solution was fed be means of capillary 1 into electrostatic field generated between capillary 1 and placed under it earthed tub with flowing through it coagulating bath 4 . The tub was equipped with rotating drum 5 . The distance between capillary 1 and bath 4 was 12 cm.
  • the drawn in electrostatic field and cooled stream of polymer solution was directed onto the surface of flowing coagulation bath 4 consisting of water containing a surface-active agent, cooled down to a temperature of 5°C.
  • bath 4 the solvent was rinsed off and fibres were solidified.
  • the formed fibres in the form of tow 6 were wound on drum 5 pulling the fibres out from the surface of bath 4, which prevented the formation of cellulose film on the surface of bath 4.
  • the produced nanofibres showed a thickness of 70 nm.
  • a spinning solution was prepared from 1 part of cellulose with a DP of about 800 in 30.4 parts of NMMO and 3.1 parts of water with 0.1 part of a stabiliser.
  • the solution was placed in contained 2 of the feeding device shown in Fig. 3 , heated to a temperature of 116°C, terminated with metallic capillary 1 with a diameter of 0.8 mm, linked to current source 3 under a voltage of 19 kV.
  • the solution was fed by means of capillary 1 into electrostatic field generated between capillary 1 and placed under it tub 5 containing coagulation bath 4.
  • the distance between capillary 1 and bath 4 was 8 cm.
  • hole 6 In the bottom of bath 5 containing bath 4 was made hole 6 with attached to its edges earthed discharging stub pipe 7 ( Fig.
  • bath 4 the solvent was rinsed off and fibres were solidified, and then the formed nanofibres with bath 4 flowed out into discharging stub pipe 7, in which they were twisted into a thread with a thickness of 1 cm by the guide and wound uniformly on drum 8 .
  • Nanofibres were formed from the spinning solution prepared as in Example III, using the equipment as in Example III ( Fig. 5 ) with a difference that the thread formed by means of the guide in stub pipe 7 was taken up on tape 9 stretched on two rollers moving both around and along the rotation axis.
  • a spinning solution was prepared from 1 part of cellulose with a DP of about 800 in 35.5 parts of NMMO and 6.5 parts of water containing 0.1 parts of stabiliser and 0.2 parts of fullerenes.
  • the solution was placed in container 2 of the feeding device shown in Fig. 6 , heated to a temperature 115°C, terminated with metallic capillary 1 with a diameter of 0.9 mm, linked to current source 3 under a voltage of 17 kV.
  • the solution was fed by means of capillary 1 into electrostatic field generated between capillary 1 and placed under it earthed tub 4 with coagulating bath 5 flowing through it.
  • the distance between capillary 1 and bath 5 was equal to 8 cm.
  • the resultant nanofibres, together with bath 5 flowed out from tub 4 on the surface of rotating drum 6.
  • the produced nanofibres showed a thickness of 290 nm.
  • Nanofibres were formed from a spinning solution prepared as in Example V, in the equipment as in Example V ( Fig. 7 ) with the difference that the produced fibres together with bath 5 flowed out from tub 4 onto the surface of tape 6 stretched on two rotating rollers.
  • a spinning solution was prepared from 1 part of cellulose with a DP of about 800 in 35.5 parts of NMMO and 6.5 parts of water containing 0.1 part of stabiliser.
  • the solution was placed in container 2 of the feeding device shown in Fig. 8 , heated to a temperature of 95°C, terminated with metallic capillary 1 with a diameter of 0.4 mm linked to current source 3 under a voltage of 8 kV.
  • the solution was fed by means of capillary 1 into electrostatic field generated between capillary 1 and a stainless steel structure placed under it. This structure consisted of two perpendicular frames 4 placed one in the other and linked to earth. The distance between capillary 1 and frames 4 was equal to 15 cm.
  • the stream of polymer solution drawn in electrostatic field and cooled was directed to the metallic structure and coagulated with hot steam 5 that removed the solvent and solidified the fibres. Steam was discharged from the space of fibre formation through offtake 6 . The solidified fibres were taken up by means of devices shown in Fig. 9 . The produced nanofibres showed a thickness of 160 nm.
  • a spinning solution was prepared from 1 part of cellulose with a DP of about 800 in 35.5 parts of NMMO and 6.0 parts of water containing 0.1 part of stabiliser.
  • the solution was placed in container 2 of the feeding device shown in Fig. 10 , heated to a temperature of 98°C, terminated with metallic capillary 1 with a diameter 0.4 mm linked to current source 3 under a voltage of 11 kV.
  • the solution was fed by means of capillary 1 into electrostatic field generated between capillary 1 and placed under it stainless steel structure composed of two rotating rings 4 situated in parallel and linked to earth. The distance between capillary 1 and rings 4 was equal to 16 cm.
  • the stream of polymer solution drawn in electrostatic field and cooled was directed onto the metallic structure and coagulated by hot steam 5 that removed the solvent and solidified the fibres, which were deposited within the space between rings 4 ( Fig. 11 ). Steam was discharged from the space of fibre formation through offtake 6. The produced nanofibres showed a thickness of 120 nm.
  • Nanofibres were formed from a spinning solution as in Example VIII proceeding as in Example VII with the difference that the stainless steel structure used was composed of three rings situated in parallel and four rings situated in parallel ( Fig. 12 ).
  • a spinning solution was prepared from 1 part of cellulose with a DP of about 800 in 26.5 parts of NMMO and 6.0 parts of water containing 0.1 parts of stabiliser and 0.18 parts of silica nanoparticles with a grain diameter of 9 nm.
  • This solution was placed in container 2 of the feeding device shown in Fig. 13 , heated to a temperature of 105°C, terminated with metallic capillary 1 with a diameter of 0.4 mm, linked to current source 3 under a voltage of 27 kV.
  • the solution was fed by means of capillary 1 into electrostatic field generated between capillary 1 and moving under it fabric 4, under which earthed and cooled electrode 5 was placed.
  • the distance between capillary 1 and fabric 4 was equal to 12 cm.
  • the stream of polymer solution drawn in electrostatic field and cooled was directed onto moving fabric 4, on which it was coagulated first with hot steam stream 6 and then with stream 7 of rinsing solvent NMMO.
  • the space of fibre formation was separated from the steam blow-in zone with impermeable screen 8.
  • the produced nanofibres showed a thickness of 150 nm.
  • a spinning solution was prepared from 1 part of cellulose with a DP of about 800 in 35.5 parts of NMMO and 6.5 parts of water containing 0.1 parts of stabiliser and 0.15 parts of Fe 3 O 4 with a grain diameter of 9nm.
  • This solution was placed in container 2 of the feeding device shown in Fig. 14 , heated to a temperature of 109°C, terminated with metallic capillary 1 with a diameter of 0.6 mm, linked to current source 3 under a voltage of 12 kV.
  • the solution was fed by means of capillary 1 into electrostatic field generated between capillary 1 and placed under it tub with flowing coagulating bath 4 composed of water and a surface-active agent cooled to a temperature of 23°C. Under the surface of bath 4, earthed ring 5 was placed.
  • the distance between capillary 1 and bath 4 was equal to 7 cm.
  • the stream of polymer solution drawn in electric field and cooled was directed onto the surface of coagulating bath 4 flowing through the tub where the solvent was rinsed off and the fibres were solidified.
  • the fibres formed on the surface of bath 4 were transported by means of rotating roller 6, placed under ring 5, onto roller 8 to take up the formed fibres in the form of tow 7. Rollers 6 and 8 rotated with a speed that ensured a continuous take-up of fibres from the surface of bath 4.
  • the produced nanofibres showed a thickness of 350 nm.

Claims (4)

  1. Procèdè pour la production de nanofibres de diamètre de moins que 500 nm reposant sur la préparation d'une solution de polymère naturel textile dans le solvant non volatil, en particulier de la cellulose dans la N-méthylmorpholine-N-oxyde, sur le dosage de ladite solution, à l'aide d'un capillaire en métal lié avec une source de courant, au champ électrostatique dans lequel la solution est formée en fibres, sur l'enroulement des fibres finis sur un dispositif récepteur, laquelle façon est caractérisée en ce que les fibres sont formés dans le champ électrostatique généré entre le capillaire de dosage et le bain de coagulation qui est situé sous ledit capillaire et qui se déplace, ledit bain est lié avec l'installation de mise à la terre, après quoi on déplace les fibres formés sur la surface du bain qui se déplace et enfin on reçoit d'une façon connue les fibres coagulés sur le tambour tournant ou sur le ruban tendu sur les rouleaux tournants.
  2. Procèdè selon une revendication No 1 est caractérisé en ce qu'on utilise pour le bain de coagulation l'eau contenant l'additif d'un agent tensioactif, en plus pour le bain de coagulation on utilise l' eau, l'eau avec un solvant, les solvants volatils.
  3. Procèdè pour la production de nanofibres de diamètre de moins que 500 nm reposant sur la préparation d'une solution de polymère naturel textile dans le solvant non volatil, en particulier de la cellulose dans la N-méthylmorpholine-N-oxyde, sur le dosage de ladite solution, à l'aide d'un capillaire en métal lié avec une source de courant, au champ électrostatique dans lequel la solution est formée en fibres, sur l'enroulement des fibres finis sur un dispositif récepteur, laquelle façon est caractérisée en ce que les fibres sont formés dans le champ électrostatique généré entre le capillaire de dosage et une construction en métal fixée à pivot, située sous ledit capillaire et liée avec l' installation de mise à la terre, après quoi on introduit les fibres formés dans l'espace entre les éléments de cette construction où les fibres sont soumis à l'action coagulatrice d'un jet de vapeur d'eau chaude et enfin on reçoit les fibres coagulés.
  4. Procèdè pour la production de nanofibres de diamètre de moins que 500 nm reposant sur la préparation d'une solution de polymère naturel textile dans le solvant non volatil, en particulier de la cellulose dans la N-méthylmorpholine-N-oxyde, sur le dosage de ladite solution, à l'aide d'un capillaire en métal lié avec une source de courant, au champ électrostatique dans lequel la solution est formée en fibres, sur l'enroulement des fibres finis sur un dispositif récepteur, laquelle façon est caractérisée en ce que les fibres sont formés dans le champ électrostatique généré entre le capillaire de dosage et un tissu se déplaçant sous ledit capillaire, sous lequel tissu est mise une électrode mise à la terre et refroidie, après quoi on introduit les fibres formés sur le tissu qui se déplace où les fibres sont premièrement soumis à l'action coagulatrice d'un jet de vapeur d'eau chaude et ensuite à l'action d'un jet de liquide qui élimine le solvant et enfin on reçoit les fibres coagulés.
EP04460033A 2004-04-30 2004-07-26 Procédé pour la production de nanofibres Not-in-force EP1591569B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL04460033T PL1591569T3 (pl) 2004-04-30 2004-07-26 Sposób wytwarzania nanowłókien

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PL36760004 2004-04-30
PL367600A PL212325B1 (pl) 2004-04-30 2004-04-30 Sposób wytwarzania nanowlókien

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EP1591569A1 EP1591569A1 (fr) 2005-11-02
EP1591569B1 true EP1591569B1 (fr) 2009-09-16

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EP (1) EP1591569B1 (fr)
AT (1) ATE443169T1 (fr)
DE (1) DE602004023177D1 (fr)
PL (2) PL212325B1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110106562A (zh) * 2019-04-26 2019-08-09 英鸿纳米科技股份有限公司 一种纳米纤维静电纺丝设备

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG123727A1 (en) * 2004-12-15 2006-07-26 Univ Singapore Nanofiber construct and method of preparing thereof
WO2009150644A2 (fr) * 2008-06-10 2009-12-17 Technion Research & Development Foundation Ltd. Structure non tissée et procédé de fabrication associé
CN102367593B (zh) * 2011-11-30 2013-08-07 福建农林大学 纳米纤维静电纺丝平板抽插式收集器
CN103465628B (zh) * 2013-09-03 2015-10-28 华中科技大学 一种静电喷印纳米纤维直径闭环控制方法及装置
CN103645751B (zh) * 2013-12-09 2016-01-20 华中科技大学 基于基板速度调节的纳米纤维直径控制方法及控制装置
CN108179485B (zh) * 2017-12-05 2021-06-11 合肥国轩高科动力能源有限公司 一种静电纺丝滚筒收集装置
CN115323611B (zh) * 2022-09-02 2023-12-08 南通大学 一种自灭菌高效防寒保暖非织造材料及其制备方法
CN115434036A (zh) * 2022-09-20 2022-12-06 江苏大学 一种螺旋结构导电聚合物纤维人工肌肉制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB364780A (en) * 1929-12-07 1932-01-14 Anton Formhals Improvements in or relating to processes and apparatus for the production of artificial filaments

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110106562A (zh) * 2019-04-26 2019-08-09 英鸿纳米科技股份有限公司 一种纳米纤维静电纺丝设备
CN110106562B (zh) * 2019-04-26 2021-07-30 英鸿纳米科技股份有限公司 一种纳米纤维静电纺丝设备

Also Published As

Publication number Publication date
PL1591569T3 (pl) 2009-12-31
PL367600A1 (en) 2005-10-31
PL212325B1 (pl) 2012-09-28
DE602004023177D1 (de) 2009-10-29
EP1591569A1 (fr) 2005-11-02
ATE443169T1 (de) 2009-10-15

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