CN115233320B - Preparation method of high-conductivity special-shaped composite fiber - Google Patents
Preparation method of high-conductivity special-shaped composite fiber Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 124
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000009987 spinning Methods 0.000 claims abstract description 53
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 33
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
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- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 17
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- 238000009998 heat setting Methods 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 238000005345 coagulation Methods 0.000 claims description 8
- 230000015271 coagulation Effects 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000000265 homogenisation Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 15
- 239000002086 nanomaterial Substances 0.000 abstract description 10
- 239000011231 conductive filler Substances 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
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- 238000010586 diagram Methods 0.000 description 4
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- 239000012466 permeate Substances 0.000 description 2
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Classifications
-
- 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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
-
- 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
- D01D5/06—Wet spinning methods
-
- 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
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention relates to the technical field of carbon nanotube conductive fiber preparation, in particular to a preparation method of a high-conductivity special-shaped composite fiber based on carbon nanomaterial modification. The method comprises the following steps: (1) Adding carboxylated carbon nanotubes into dimethyl sulfoxide solvent to achieve homogeneous distribution, adding polyacrylonitrile powder, and dissolving to obtain spinning solution; (2) Injecting the spinning solution into dimethyl sulfoxide coagulating bath to form nascent fiber; drawing the formed nascent fiber to a drawing bath by a first drawing machine, and drawing the nascent fiber to a collector by a second drawing machine for collection to obtain a drawn fiber; (3) And washing the drawn fiber with water, drying under the condition of keeping the pre-tension, and then heating to shape at an elevated temperature to obtain the high-conductivity special-shaped composite fiber. The high-conductivity special-shaped composite fiber prepared by the invention has good mechanical property and conductivity, realizes the construction of a high-efficiency perfect conductive network by a small amount of conductive filler, and has wide application range.
Description
Technical Field
The invention relates to the technical field of carbon nanotube conductive fiber preparation, in particular to a preparation method of a high-conductivity special-shaped composite fiber based on carbon nanomaterial modification.
Background
With the continuous research and development and innovation of intelligent textiles, the excellent and unique properties of the intelligent textiles bring great convenience to the life of people. Conductive fiber as one of the main materials for manufacturing intelligent textiles has attracted extensive attention from the world of materials at home and abroad, and has been studied and developed in the process of resistingThe cold-proof clothing, the electric heating product, the sensor, the capacitor and the like have good application prospect. The conductive fiber has specific resistance of 10 under standard condition of relative humidity of 60% and temperature of 20deg.C 7 And omega cm or less. In general, most polymer fibers are insulators, and thus, it is necessary to add conductive fillers such as carbon black, graphene, carbon nanotubes, metal nanowires, metal oxide nanoparticles, and the like to prepare the conductive fibers. The carbon-based conductive fibers may be classified into carbon black-filled conductive fibers, carbon nanotube-filled conductive fibers, and graphene-filled conductive fibers, from the filler component. Carbon black and a polymer matrix form a conductive network path in a point contact mode, the conductive performance is relatively poor, and carbon black often needs a large addition amount to form a conductive network, and sometimes the mechanical performance of fibers can be reduced. The strong van der Waals force exists between graphene sheets, stacking and agglomeration phenomena are easy to occur, the graphene sheets are difficult to uniformly disperse into a fiber matrix, the high conductivity performance of graphene is affected, and the graphene sheets are more expensive compared with other carbon nano materials. Compared with other carbon nano materials, the carbon nano tube has the characteristic of extremely large length-diameter ratio, is easier to mutually overlap to form a conductive network, can form a continuous phase structure in the fiber, is uniformly distributed in the axial direction of the fiber, and ensures that the interface of two phases is stable so as to form a complete and continuous conductive path. This does not affect the original physical and mechanical properties of the fiber, but also gives the fiber excellent electrical conductivity.
Currently, the methods for preparing carbon-based conductive fibers are roughly classified into a coating method and a spinning method. The coating method is to load conductive substances on the surfaces of fibers to realize the conductive function of the fibers, but the conductive fibers are only formed by attaching conductive components on the surfaces of the fibers, and the interface firmness is poor, so that the conductive components are easy to fall off after repeated friction and washing, the conductivity of the fibers is greatly reduced, and the normal use is influenced. The spinning method is to blend the conductive material and the high polymer for spinning to prepare the conductive fiber, and the spinning method comprises wet spinning, electrostatic spinning, melt spinning, air-jet spinning and the like. Among them, wet spinning is one of the effective and simple methods for preparing high-conductivity composite fibers. Compared with the traditional coating method and other spinning methods, the carbon-based conductive fiber prepared by the wet spinning technology has more excellent and stable performances. However, because of the problems of low carbon nano conductive filler loading, uneven distribution, poor interface compatibility, discontinuous conductive network and the like in the polymer matrix, the conductivity of the prepared carbon conductive fiber is far lower than that of the carbon nano tube fiber and the metal conductive fiber. This is mainly because a small amount of conductive filler is disadvantageous in constructing a conductive network, the conductive network structure of the formed fiber is not sufficiently connected, defects are generated in forming a conductive path, and the conductive performance is poor, but if too much conductive filler is added, the spinnability of the mixed spinning solution is significantly affected. Thus, the key to success is whether the conductive network can be effectively built into the fibrous polymer matrix.
Therefore, the problem to be solved at present is to construct a high-efficiency perfect conductive network with a small amount of conductive filler, and prepare conductive fibers with more excellent performance so as to meet the requirement of industrial production.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a high-conductivity special-shaped composite fiber based on carbon nanomaterial modification, wherein the prepared high-conductivity special-shaped composite fiber has good mechanical property and conductivity, realizes construction of a high-efficiency perfect conductive network by a small amount of conductive filler, and has wide application range.
The preparation method of the high-conductivity special-shaped composite fiber comprises the following steps:
(1) Adding carboxylated carbon nanotubes into dimethyl sulfoxide solvent to achieve homogeneous distribution, adding polyacrylonitrile powder, dissolving, and stirring uniformly to obtain spinning solution;
the carboxylated carbon nanotubes are added into dimethyl sulfoxide solvent, and the homogenization is promoted by ultrasonic treatment, and the ultrasonic treatment conditions are as follows: the frequency is 40-50 kHz, the temperature is 25-30 ℃ and the time is 2-3 hours;
stirring mechanical stirrer, stirring conditions: the rotating speed is 250-300 rpm, the temperature is 25-30 ℃ and the time is 8-10 h;
the spinning solution comprises the following components in percentage by weight: 20-22 wt%, 1.2-1.4 wt% and 76.6-78.8 wt%.
(2) Injecting the spinning solution into dimethyl sulfoxide coagulating bath to form nascent fiber; drawing the formed nascent fiber to a drawing bath by a first drawing machine while injecting, and drawing the nascent fiber to a collector for collection by a second drawing machine to obtain a drawn fiber;
the spinning solution injection mode adopts an injection mode that an injection pump advances an injector, the inner diameter of a used needle head is 400-800 mu m, and the injection rate is 0.1-0.3 ml/min;
the coagulation bath is as follows: 50-70wt% dimethyl sulfoxide aqueous solution, and a coagulating bath temperature: 25-30 ℃;
the stretching bath is as follows: 5-10wt% dimethyl sulfoxide aqueous solution, stretching bath temperature: 25-30 ℃;
the speed of the first drawing machine is 5-6 rpm, the speed of the second drawing machine is 9-10.8 rpm, and the collection speed of the collector is 12.9-16.2 rpm.
The primary fiber is passed through a drawing bath to increase the degree of orientation, strength of the fiber, removal of organic solvents, and improved washing efficiency of the drawn fiber.
(3) Repeatedly cleaning the drawn fiber with deionized water, and drying at the drying temperature of 80-100 ℃ under the pre-tension of 0.02-0.05N for 20-30 min; and then the temperature is increased to 105-130 ℃, the pre-tension is kept unchanged, and the heat setting is carried out for 3-8 min, so that the high-conductivity special-shaped composite fiber is obtained.
Wherein, carboxylated carbon nanotubes are commercially available, and the purity is more than 95% without further treatment, and the diameter is as follows: 5-15nm, length: 10-30 mu m, and carboxylation content: 3.86wt%, conductivity > 100S/cm.
The invention prepares the high-conductivity special-shaped composite fiber by using a wet spinning technology and adopting an in-situ doping method by regulating and controlling various technological parameters of spinning. The high-conductivity special-shaped composite fiber prepared by the invention overcomes the difficult problem that a small amount of conductive filler is doped to cause the non-communication and fault of a constructed conductive network, and realizes the successful construction of the high-efficiency conductive network in a fiber polymer matrix. The intermolecular polar acting force between polyacrylonitrile and carboxylated carbon nano tube is utilized to induce the carboxylated carbon nano tube to grow and migrate to the surface of the fiber and effectively permeate and transition to one axial side of the fiber, so that the special-shaped composite fiber with higher tensile strength, certain elongation at break, better flexibility and high conductivity is prepared. The conductive special-shaped fiber is analyzed along a transverse structure, one side of the conductive special-shaped fiber is enriched with a conductive network structure, and the movable electrons are concentrated by the semi-conductive path structure to form a perfect and continuous conductive path, and the mechanical property of the fiber is effectively guaranteed by the other side of the conductive special-shaped fiber, so that the fiber has good conductivity and flexibility.
The preparation mechanism of the conductive special-shaped composite fiber is as follows: when the thin flow of the spinning solution enters the coagulating bath, the concentration difference exists between the spinning solution and the dimethyl sulfoxide solution in the coagulating bath, so that the dimethyl sulfoxide in the spinning solution can enter the coagulating bath, the water in the coagulating bath can enter the thin flow of the spinning solution, and when the concentration of the dimethyl sulfoxide in the spinning solution is reduced to a certain value, the thin flow of the spinning solution can be subjected to phase separation to form the primary fiber with enrichment holes on one side of the section. The holes on one side are formed because water molecules penetrate through the skin layer and the core layer of the primary fiber, and compared with polyacrylonitrile and the carbon nano tube, the water molecules have smaller molecular weight and energy, so that the water molecules jump to the upper side of the central axis of the primary fiber under the action of gravity to form the holes. At this time, through the first drafting, the polyacrylonitrile and the carbon nano tube are oriented, and because the carboxylated carbon nano tube has hydrophilicity, the carboxylated carbon nano tube can preferentially permeate and transition to the side with holes to fill the holes, and meanwhile, the polyacrylonitrile is oriented on the side without holes. Then, through a second drawing bath, the nascent fiber is further oriented, so that the carboxylated carbon nano-tube is enriched on one side of the fiber, and the high-conductivity special-shaped composite fiber with the eccentric form, namely the axial asymmetric conductive network enrichment structure, is formed.
Compared with the prior art, the invention has the following beneficial effects:
1. the high-conductivity special-shaped composite fiber has good mechanical property and conductivity;
2. the invention constructs a high-efficiency perfect conductive network with low cost and a small amount of conductive filler, thus realizing the preparation of the special-shaped composite fiber with high conductivity;
3. the high-conductivity special-shaped composite fiber disclosed by the invention has a wide application range and has great application potential in the fields of cold-resistant and warm-keeping clothes, electric heating products, thermal physiotherapy health-care products, sensors, capacitors and the like.
Drawings
FIG. 1 is a schematic view of a highly conductive profiled composite fiber structure of the present invention;
FIG. 2 is a schematic diagram of the process flow of the present invention;
FIG. 3 is a cross-sectional FE-SEM image of a fiber according to example 1 of the present invention;
FIG. 4 is a FE-SEM diagram of the portion A of FIG. 3;
fig. 5, FE-SEM images of part B of fig. 3;
FIG. 6 is an FE-SEM diagram of portion C of FIG. 3;
FIG. 7 is a surface FE-SEM image of a fiber according to example 1 of the present invention;
FE-SEM images of part D in fig. 8 and 7;
FIG. 9, stress-strain curve for example 1 of the present invention;
fig. 10 is an electrical property diagram of example 1 of the present invention.
Detailed Description
The technical scheme of the invention will be clearly and completely described below with reference to the accompanying drawings and examples.
It should be noted that: in actual operation, the temperature control allows a fluctuation temperature difference of 2 ℃, other raw materials are commercially available except special description, for example, the carboxyl carbon nano tube is commercially available, no further oxidation treatment is needed, and the purity is more than 95%; diameter: 5-15nm, length: 10-30 mu m, carboxylation content: 3.86wt%, conductivity > 100S/cm.
Example 1
The preparation method of the high-conductivity special-shaped composite fiber comprises the following steps:
(1) Adding carboxylated carbon nanotubes into dimethyl sulfoxide solvent, and performing ultrasonic treatment with ultrasonic cleaning agent at 40kHz and 30 ℃ for 3 hours to achieve homogeneous distribution. And adding polyacrylonitrile powder, dissolving, uniformly stirring under a mechanical stirrer, and stirring at the rotating speed of 250rpm for 10 hours at the temperature of 25 ℃ to obtain spinning solution.
The spinning solution comprises the following components in percentage by weight: 20wt%,1.2wt% and 78.8wt%.
(2) The spinning dope was sucked up by a syringe, a needle (model: 21G) having an inner diameter of about 500 μm was provided, and the spinning dope was extruded into a dimethyl sulfoxide coagulation bath at an injection rate of 0.2ml/min by a syringe pump, and the process conditions were: dimethyl sulfoxide: 60wt%; water: 40wt%; temperature: 25 ℃.
After the spinning dope is injected into the coagulating bath, the phase separation is carried out to coagulate into filaments, and the nascent fiber is formed. Simultaneously, the as-formed nascent fiber was drawn into a drawing bath at 5rpm with a first drawing machine, process conditions: dimethyl sulfoxide: 5wt% of water: 95wt%; temperature: 25 ℃. After passing through the drawing bath, drawn with a second drawing machine at 9rpm to a collector set at a speed of 16.2rpm to obtain drawn fibers.
(3) Repeatedly cleaning the drawn fiber with deionized water, drying for 30min under the conditions of pre-tension of 0.05N and 80 ℃, and performing heat setting for 8min under the conditions of pre-tension of 0.05N and 130 ℃ to obtain the high-conductivity special-shaped composite fiber.
Example 2
The preparation method of the high-conductivity special-shaped composite fiber based on carbon nanomaterial modification provided by the invention comprises the following steps:
(1) Adding carboxylated carbon nanotubes into dimethyl sulfoxide solvent, and performing ultrasonic treatment with ultrasonic cleaning agent at 50kHz and 30 ℃ for 3 hours to achieve homogeneous distribution. And adding polyacrylonitrile powder, dissolving, uniformly stirring under a mechanical stirrer, and stirring at a rotating speed of 300rpm for 10 hours at 25 ℃ to obtain spinning solution.
The spinning solution comprises the following components in percentage by weight: 22wt%,1.4wt% and 76.6wt%.
(2) The spinning dope was sucked up with a syringe, equipped with a needle (model: 18G) having an inner diameter of about 800 μm, and the spinning dope was extruded into a dimethyl sulfoxide coagulation bath with a syringe pump at an injection rate of 0.3ml/min, process conditions: dimethyl sulfoxide: 70wt%; water: 30wt%; temperature: 25 ℃.
After the spinning dope is injected into the coagulating bath, the phase separation is carried out to coagulate into filaments, and the nascent fiber is formed. Simultaneously, the as-formed nascent fiber was drawn into a drawing bath at 6rpm with a first drawing machine, process conditions: dimethyl sulfoxide: 10wt% of water: 90wt%; temperature: 25 ℃. After passing through the drawing bath, drawn with a second drawing machine at 10.8rpm to a collector set at 16.2rpm to obtain drawn fibers.
(3) Repeatedly cleaning the drawn fiber with deionized water, drying for 30min under the conditions of pre-tension of 0.05N and 100 ℃, and performing heat setting for 8min under the conditions of pre-tension of 0.05N and 130 ℃ to obtain the high-conductivity special-shaped composite fiber.
Example 3
The preparation method of the high-conductivity special-shaped composite fiber based on carbon nanomaterial modification provided by the invention comprises the following steps:
(1) Adding carboxylated carbon nanotubes into dimethyl sulfoxide solvent, and performing ultrasonic treatment with ultrasonic cleaning agent at 45kHz and 30 ℃ for 2.5 hours to achieve homogeneous distribution. And adding polyacrylonitrile powder, dissolving, uniformly stirring under a mechanical stirrer, and stirring at the speed of 280rpm for 9 hours at the temperature of 28 ℃ to obtain spinning solution.
The spinning solution comprises the following components in percentage by weight: 21wt%,1.3wt% and 77.7wt%.
(2) Sucking the spinning solution by a syringe, preparing a needle (model: 20G) with an inner diameter of about 600 mu m, extruding the spinning solution into a dimethyl sulfoxide coagulation bath at an injection rate of 0.2ml/min by a syringe pump, and processing conditions: dimethyl sulfoxide: 50wt%; water: 50wt%; temperature: 25 ℃. After the spinning dope is injected into the coagulating bath, the phase separation is carried out to coagulate into filaments, and the nascent fiber is formed. Simultaneously, the as-formed nascent fiber was drawn into a drawing bath at 6rpm with a first drawing machine, process conditions: dimethyl sulfoxide: 7wt% of water: 93 wt.%; temperature: 25 ℃. After passing through the drawing bath, drawn with a second drawing machine at 10rpm to a collector set at 15.5rpm to obtain drawn fibers.
(3) Repeatedly cleaning the drawn fiber with deionized water, drying for 25min under the conditions of pre-tension of 0.03N and 90 ℃, and performing heat setting for 5min under the conditions of pre-tension of 0.03N and 120 ℃ to obtain the high-conductivity special-shaped composite fiber.
Example 4
The preparation method of the high-conductivity special-shaped composite fiber based on carbon nanomaterial modification provided by the invention comprises the following steps:
(1) Adding carboxylated carbon nanotubes into dimethyl sulfoxide solvent, and performing ultrasonic treatment with ultrasonic cleaning agent at 40kHz and 25 ℃ for 2 hours to achieve homogeneous distribution. And adding polyacrylonitrile powder, dissolving, uniformly stirring under a mechanical stirrer, and stirring at the rotating speed of 250rpm for 8 hours at the temperature of 25 ℃ to obtain spinning solution.
The spinning solution comprises the following components in percentage by weight: 20wt%,1.2wt% and 78.8wt%.
(2) Sucking the spinning solution by a syringe, preparing a needle (model: 22G) with an inner diameter of about 400 mu m, extruding the spinning solution into a dimethyl sulfoxide coagulation bath at an injection rate of 0.1ml/min by a syringe pump, and processing conditions: dimethyl sulfoxide: 60wt%; water: 40wt%; temperature: 25 ℃.
After the spinning dope is injected into the coagulating bath, the phase separation is carried out to coagulate into filaments, and the nascent fiber is formed. Simultaneously, the as-formed nascent fiber was drawn into a drawing bath at 5rpm with a first drawing machine, process conditions: dimethyl sulfoxide: 5wt% of water: 95wt%; temperature: 25 ℃. After passing through the drawing bath, drawn with a second drawing machine at 9rpm to a collector set at 14.4rpm to obtain drawn fibers.
(3) Repeatedly cleaning the drawn fiber with deionized water, drying for 20min under the conditions of pre-tension of 0.02N and 80 ℃, and performing heat setting for 3min under the conditions of pre-tension of 0.02N and 105 ℃ to obtain the high-conductivity special-shaped composite fiber.
Example 5
The preparation method of the high-conductivity special-shaped composite fiber based on carbon nanomaterial modification provided by the invention comprises the following steps:
(1) Adding carboxylated carbon nanotubes into dimethyl sulfoxide solvent, and performing ultrasonic treatment with ultrasonic cleaning agent at 45kHz and 25 ℃ for 3 hours to achieve homogeneous distribution. And adding polyacrylonitrile powder, dissolving, uniformly stirring under a mechanical stirrer, and stirring at a rotating speed of 300rpm for 10 hours at 25 ℃ to obtain spinning solution.
The spinning solution comprises the following components in percentage by weight: 22wt%,1.4wt% and 76.6wt%.
(2) The spinning dope was sucked up with a syringe, equipped with a needle (model: 18G) having an inner diameter of about 800 μm, and the spinning dope was extruded into a dimethyl sulfoxide coagulation bath with a syringe pump at an injection rate of 0.2ml/min, process conditions: dimethyl sulfoxide: 70wt%; water: 30wt%; temperature: 30 ℃.
After the spinning dope is injected into the coagulating bath, the phase separation is carried out to coagulate into filaments, and the nascent fiber is formed. Simultaneously, the as-formed nascent fiber was drawn into a drawing bath with a first drawing machine at 5.5rpm, process conditions: dimethyl sulfoxide: 8wt% of water: 92wt%; temperature: 25 ℃. After passing through the drawing bath, drawn with a second drawing machine at 9.9rpm to a collector set at a speed of 12.9rpm to obtain drawn fibers.
(3) Repeatedly cleaning the drawn fiber with deionized water, drying for 30min under the conditions of pre-tension of 0.05N and 100 ℃, and performing heat setting for 8min under the conditions of pre-tension of 0.05N and 130 ℃ to obtain the high-conductivity special-shaped composite fiber.
Example 6
The preparation method of the high-conductivity special-shaped composite fiber based on carbon nanomaterial modification provided by the invention comprises the following steps:
(1) Adding carboxylated carbon nanotubes into dimethyl sulfoxide solvent, and performing ultrasonic treatment with ultrasonic cleaning agent at 45kHz and 25 ℃ for 2.5 hours to obtain homogeneous distribution. And adding polyacrylonitrile powder, dissolving, uniformly stirring under a mechanical stirrer, and stirring at the rotating speed of 250rpm for 9 hours at the temperature of 25 ℃ to obtain spinning solution.
The spinning solution comprises the following components in percentage by weight: 21wt%,1.3wt% and 77.7wt%.
(2) Sucking the spinning solution by a syringe, preparing a needle (model: 20G) with an inner diameter of about 600 mu m, extruding the spinning solution into a dimethyl sulfoxide coagulation bath at an injection rate of 0.3ml/min by a syringe pump, and processing conditions: dimethyl sulfoxide: 55wt%; water: 45wt%; temperature: 25 ℃. After the spinning dope is injected into the coagulating bath, the phase separation is carried out to coagulate into filaments, and the nascent fiber is formed. Simultaneously, the as-formed nascent fiber was drawn into a drawing bath at 6rpm with a first drawing machine, process conditions: dimethyl sulfoxide: 6wt% of water: 94wt%; temperature: 25 ℃. After passing through the drawing bath, drawn with a second drawing machine at 10.2rpm to a collector set at 15.3rpm to obtain drawn fibers.
(3) Repeatedly cleaning the drawn fiber with deionized water, drying for 25min under the conditions of pre-tension of 0.03N and 90 ℃, and performing heat setting for 8min under the conditions of pre-tension of 0.03N and 120 ℃ to obtain the high-conductivity special-shaped composite fiber.
The high-conductivity special-shaped composite fiber structure of the invention is shown in fig. 1, and the process flow of the invention is shown in fig. 2, wherein MWCNTs are carbon nanotubes, and PAN is polyacrylonitrile.
Comparative example 1
This comparative example 1 differs from example 1 in that the collector speed was set to 10.8rpm, all other things being equal to example 1.
Characterization and testing
Taking the conductive fiber prepared in the embodiment 1, observing the surface and cross-section morphology structure of the fiber by using a field emission scanning electron microscope (FE-SEM), and observing the distribution of carboxylated carbon nanotubes on the surface and cross section of the fiber as shown in figures 3-8.
As can be seen from fig. 3, the conductive fiber prepared in example 1 has different phase structures, fig. 4 and fig. 5 show that the carboxylated carbon nanotubes are concentrated on one side of the inside of the fiber, the other side of the fiber is mainly composed of a polymer, the surface morphology of two sides is different, and fig. 6 shows that the carboxylated carbon nanotubes and the cortex polymer form an interface phase, which indicates that the carbon nanotubes transition from the fiber core to the surface, and the eccentric conductive fiber structure is formed.
As can be further seen from fig. 7 to fig. 8, the carboxylated carbon nanotubes form enrichment on the surface of the fiber, so that the fiber forms a perfect and continuous conductive path, which is beneficial to improving the conductive performance.
The mechanical properties and electrical properties of the fibers prepared in examples 1 to 6 and comparative example 1 were measured: (1) the mechanical properties (breaking strength, breaking elongation and Young modulus) of the fiber are tested by a universal material testing machine; (2) the resistance of the fiber was measured using a semiconductor parameter analyzer and was calculated by the formula: σ=l/(r.s), the conductivity of the fiber is calculated. The stress-strain curves and electrical performance graphs of example 1 are shown in fig. 9-10. The test and calculation results are shown in table 1 below.
Table 1 performance test tables for examples 1 to 6 and comparative example 1
As can be seen from Table 1, the conductive fibers prepared by the method have higher mechanical properties and conductivity, the tensile strength can reach 291MPa, which is 2 times that of comparative example 1, the conductivity can reach 51.6S/cm, which is 100 times that of comparative example 1, and the collector speed is different compared with comparative example 1, so that the tensile multiple of the prepared conductive fibers is different. The stretching multiple has great influence on the orientation of the carbon nano tube in the fiber matrix, and the larger the stretching multiple is, the more regularly the carbon nano tube is arranged in the fiber, and the larger the orientation degree is, so that the conductivity of the fiber is larger, and the conductivity is better.
Claims (5)
1. The preparation method of the high-conductivity special-shaped composite fiber is characterized by comprising the following steps of:
(1) Adding carboxylated carbon nanotubes into dimethyl sulfoxide solvent to achieve homogeneous distribution, adding polyacrylonitrile powder, dissolving, and stirring uniformly to obtain spinning solution;
(2) Injecting the spinning solution into dimethyl sulfoxide coagulating bath to form nascent fiber; drawing the formed nascent fiber to a drawing bath by a first drawing machine while injecting, and drawing the nascent fiber to a collector for collection by a second drawing machine to obtain a drawn fiber;
(3) Washing the drawn fiber with water, drying under pre-tension, then raising the temperature, keeping the pre-tension unchanged, and performing heat setting to obtain the high-conductivity special-shaped composite fiber;
the spinning solution comprises the following components in percentage by weight: 20-22 wt%, 1.2-1.4 wt% and 76.6-78.8 wt%;
the coagulation bath is as follows: 50-70wt% dimethyl sulfoxide aqueous solution, and a coagulating bath temperature: 25-30 ℃;
the stretching bath is as follows: 5-10wt% dimethyl sulfoxide aqueous solution, stretching bath temperature: 25-30 ℃;
the speed of the first drafting machine is 5-6 rpm, the speed of the second drafting machine is 9-10.8 rpm, and the collecting speed of the collector is 12.9-16.2 rpm;
the pre-tension is 0.02-0.05N, the drying temperature is 80-100 ℃, the drying time is 20-30 min, the heat setting temperature is 105-130 ℃, and the heat setting time is 3-8 min.
2. The method for preparing the highly conductive shaped composite fiber according to claim 1, wherein carboxylated carbon nanotubes are added into dimethyl sulfoxide solvent, and homogenization is promoted by ultrasonic treatment under the following conditions: the frequency is 40-50 kHz, the temperature is 25-30 ℃, and the time is 2-3 hours.
3. The method for preparing the highly conductive shaped composite fiber according to claim 1, wherein the stirring conditions are as follows: the rotation speed is 250-300 rpm, the temperature is 25-30 ℃, and the time is 8-10 h.
4. The method for preparing the high-conductivity special-shaped composite fiber according to claim 1, wherein the spinning solution is injected by adopting an injection mode of an injection pump pushing injector, and the inner diameter of a used needle is 400-800 mu m.
5. The method for preparing the high-conductivity shaped composite fiber according to claim 4, wherein the injection rate is 0.1-0.3 ml/min.
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