CN116751388A - High-strength conductive cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane and preparation method thereof - Google Patents
High-strength conductive cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane and preparation method thereof Download PDFInfo
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 186
- 239000004760 aramid Substances 0.000 title claims abstract description 173
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 173
- 239000001913 cellulose Substances 0.000 title claims abstract description 136
- 229920002678 cellulose Polymers 0.000 title claims abstract description 136
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 123
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 123
- 239000002131 composite material Substances 0.000 title claims abstract description 119
- 239000012528 membrane Substances 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000002159 nanocrystal Substances 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims description 140
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 104
- 239000007788 liquid Substances 0.000 claims description 102
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 100
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 68
- 238000001914 filtration Methods 0.000 claims description 50
- 238000001035 drying Methods 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 238000007865 diluting Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 abstract description 37
- 230000008859 change Effects 0.000 abstract description 9
- 239000011540 sensing material Substances 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 2
- 238000000707 layer-by-layer assembly Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 73
- 229910021641 deionized water Inorganic materials 0.000 description 73
- 229920006231 aramid fiber Polymers 0.000 description 25
- 238000001132 ultrasonic dispersion Methods 0.000 description 25
- 229920000271 Kevlar® Polymers 0.000 description 13
- 239000000835 fiber Substances 0.000 description 13
- 239000004761 kevlar Substances 0.000 description 13
- 239000004677 Nylon Substances 0.000 description 12
- 239000002238 carbon nanotube film Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 229920001778 nylon Polymers 0.000 description 12
- 239000000463 material Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
- C08J2401/04—Oxycellulose; Hydrocellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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Abstract
The invention discloses a high-strength conductive cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane and a preparation method and application thereof, and relates to the fields of composite materials and intelligent sensing materials. The method adopts a vacuum auxiliary suction filtration layer-by-layer assembly method to assemble cellulose nanocrystals, carbon nanotubes and aramid nanofibers into a conductive multilayer composite film, and uses glutaraldehyde for crosslinking. The conductive cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane prepared by the method provided by the invention has excellent mechanical strength, humidity stability and conductivity, and the relative resistance of the composite membrane can be correspondingly changed along with the change of humidity; meanwhile, the relative resistance of the composite film can also be changed in response to the folding or straightening state of the composite film, and good humidity sensing and motion sensing performances are presented.
Description
Technical Field
The invention relates to the technical field of preparation of multifunctional sensing materials, in particular to a high-strength conductive cellulose nanocrystalline/carbon nano tube/aramid nanofiber composite membrane as well as a preparation method and application thereof.
Background
Cellulose nanocrystals (cellulose nanocrystals, CNC) are natural rod-like nanomaterials with high specific surface area, low density, high aspect ratio characteristics. CNC prepared by acid hydrolysis of wood pulp has a rich hydrophilic group and shows extreme sensitivity to water. Dried CNCs are typically stacked in a spiral arrangement with unique optical characteristics; CNC, which is stably dispersed in water, has the property of cholesteric liquid crystals. Based on the sensitivity of CNCs to humidity and the characteristic of generating internal structural changes to the external environment, various CNC film-based sensing materials have been developed for use in humidity sensors, stress-strain sensors, motion sensors, and the like.
However, applying CNC to sensors presents certain challenges. First, pure CNC films are brittle, poor in water resistance, poor in mechanical properties, and cannot meet the mechanical property requirements for applications in complex environments. Secondly, the CNC-based sensing material transmits sensing signals through optical signals or shape change, the optical signals and the shape change signals need specific collecting means, the sensing signals and the shape change signals are difficult to effectively and continuously capture, for example, color change cannot be accurately observed in dark conditions, and errors exist in the visual observation of the deformation degree of the CNC material. Such as by converting these signals into electrical signals, can be systematically collected and detected to achieve efficient and accurate conversion of the external environmental signals into sensing signals. Therefore, the development of the multifunctional CNC film material which has high strength and good humidity stability and can convert external environment signals into electrical signals has very important value for the application of CNC-based sensors.
Aramid nanofibers (aramid nanofibers, ANF) are widely used as a novel high performance nanofiber for the preparation of high strength composites. Glutaraldehyde is widely used as a crosslinking agent for preparing high-strength CNC materials by a crosslinking reaction with hydroxyl groups on the surface of CNC. In order to enable CNC materials to more effectively transfer ambient information, it is a common idea to prepare conductive cellulose nanocrystalline materials. Carbon nanotubes are widely used as sensing materials due to their high conductivity, electrical sensitivity and stability. The anisotropy of CNC and excellent conductivity of the carbon nano tube can provide a new design strategy for a multifunctional sensor with low cost and simple preparation method. The combination of cellulose nanocrystals, aramid nanofibers and carbon nanotubes is expected to produce high strength cellulose sensing materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a high-strength conductive cellulose nanocrystalline/carbon nano tube/aramid nanofiber composite membrane as well as a preparation method and application thereof.
The invention provides the following technical scheme:
the invention provides a preparation method of a high-strength conductive cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane, which comprises the following steps:
(1) Adding a certain amount of aramid nanofibers and potassium hydroxide into dimethyl sulfoxide, and stirring to form an aramid nanofiber/dimethyl sulfoxide/potassium hydroxide solution;
(2) Adding water into the aramid nanofiber/dimethyl sulfoxide/potassium hydroxide solution, vigorously stirring to form a uniform dispersion, then carrying out vacuum filtration, repeatedly dispersing with water and carrying out vacuum filtration to remove dimethyl sulfoxide and potassium hydroxide, and finally dispersing the aramid nanofiber into a certain amount of water to form an aramid nanofiber dispersion;
(3) Adding glutaraldehyde into a certain amount of the aramid nanofiber dispersion liquid obtained in the step (2) to form an aramid nanofiber/glutaraldehyde dispersion liquid;
(4) Adding cellulose nanocrystalline powder and carbon nanotube powder into water, stirring and carrying out ultrasonic treatment for a certain time to form uniform dispersion;
(5) Diluting a certain amount of the aramid nanofiber/glutaraldehyde dispersion liquid obtained in the step (3), carrying out ultrasonic treatment, transferring to a vacuum auxiliary filtering device, and carrying out vacuum auxiliary filtering until water is pumped to dryness to obtain an aramid nanofiber/glutaraldehyde film;
(6) Diluting a certain amount of cellulose nanocrystalline/carbon nanotube dispersion liquid in the step (4), transferring to a vacuum auxiliary filtering device in the step (5) after ultrasonic treatment, and performing vacuum auxiliary filtering until water is pumped to dryness to obtain a composite membrane;
(7) And (3) sequentially repeating the steps (5) and (6) for a plurality of times, so that the topmost layer and the bottommost layer of the prepared composite film are all aramid nanofibers, and the cellulose nanocrystal/carbon nanotube/aramid nanofiber composite film is obtained after drying.
Further, in the step (1), the concentration of the aramid nanofiber in the aramid nanofiber/dimethyl sulfoxide/potassium hydroxide solution is 0.1 mg/mL-3.0 mg/mL, the concentration of potassium hydroxide is 1.0 mg/mL-5.0 mg/mL, the stirring temperature is 20-30 ℃, and the stirring speed is 1000-1500 r/min.
Further, in the step (2), the mass percentage of the aramid nanofiber dispersion liquid is 0.25-1.00 wt% of the mass percentage of the aramid nanofiber.
Further, in the step (3), the aramid nanofiber dispersion liquid is 0.5-10 mL, and glutaraldehyde and water with the volume fraction of 50% are added to prepare a dispersion liquid with the glutaraldehyde concentration of 0.05-5.0%.
Further, in the step (4), the cellulose nanocrystalline/carbon nanotube dispersion liquid is controlled to be 0.1-2.0 wt% according to the mass percentage, the carbon nanotube is controlled to be 0.01-0.10 wt%, the stirring time is 10-30 min, and the ultrasonic time is 10-30 min.
Further, in the step (5), the aramid nanofiber/glutaraldehyde dispersion is diluted, namely a certain amount of the aramid nanofiber/glutaraldehyde dispersion is diluted to 5-10 mL by water, and the dispersion is subjected to ultrasonic dispersion for 5-30 min.
In the step (6), the cellulose nano-crystal/carbon nano-tube dispersion liquid is diluted, a certain amount of the cellulose nano-crystal/carbon nano-tube dispersion liquid is diluted to 10-20 mL by water, and the cellulose nano-crystal/carbon nano-tube dispersion liquid is dispersed for 5-30 min by ultrasonic.
Further, in the step (7), the cellulose nanocrystal/carbon nanotube/aramid nanofiber composite film is dried for 6 to 24 hours at room temperature and then dried for 0 to 12 hours at the temperature of 30 to 80 ℃.
The invention also provides the cellulose nanocrystal/carbon nanotube/aramid nanofiber composite membrane prepared by the method, wherein the aramid nanofiber accounts for 20-40 wt%, the cellulose nanocrystal accounts for 40-70 wt%, and the carbon nanotube accounts for 5-40 wt%. The three components of the composite film are not fixedly matched, and the proportions shown in the examples below are combined within the above range, but the composite film prepared by the invention is not limited to the proportions described in the examples.
The invention also provides application of the cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane in a sensor, and the cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane can be used for humidity sensing and motion sensing.
The invention has the following beneficial effects:
1. according to the invention, the carbon nano tube is added into the cellulose nano crystal for dispersion, then the cellulose nano crystal/carbon nano tube dispersion liquid and the aramid nano fiber dispersion liquid are assembled into the composite membrane with a multi-layer structure through vacuum auxiliary filtration layer by layer, glutaraldehyde is added for crosslinking in the preparation process of the membrane, the composite of the aramid nano fiber and the crosslinking of glutaraldehyde obviously improve the strength of the cellulose nano crystal composite membrane, the carbon nano tube is added to enable the composite membrane to have excellent conductivity, and the high-strength conductive cellulose nano crystal/carbon nano tube/aramid nano fiber composite membrane is prepared through a method of introducing the reinforcing component and the conductive component.
2. The relative resistance of the composite film prepared by the invention can correspondingly change along with the change of the humidity of the film surface, so that the sensing capability of the humidity is shown, in addition, the composite film can also change the relative resistance of the film after being folded and then being bent and straightened, and the motion sensing capability is shown.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without the need of invasive 7 efforts for a person skilled in the art.
FIG. 1 is a flow chart of the preparation of a cellulose nanocrystal/carbon nanotube/aramid nanofiber composite membrane in an embodiment of the invention;
FIG. 2 is a scanning electron microscope image of the cellulose nanocrystal/carbon nanotube/aramid nanofiber composite film prepared in example 1 of the present invention;
FIG. 3 is a humidity sensing test of a cellulose nanocrystal/carbon nanotube/aramid nanofiber composite membrane prepared in example 1 of the present invention;
fig. 4 is a motion sensing test of a cellulose nanocrystal/carbon nanotube/aramid nanofiber composite membrane prepared in example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation method of the high-strength conductive cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane provided by the embodiment of the invention comprises the following steps:
(1) Adding a certain amount of aramid nanofibers and potassium hydroxide into dimethyl sulfoxide, and stirring to form an aramid nanofiber/dimethyl sulfoxide/potassium hydroxide solution;
(2) Adding water into the aramid nanofiber/dimethyl sulfoxide/potassium hydroxide solution, vigorously stirring to form a uniform dispersion, then carrying out vacuum filtration, repeatedly dispersing with water and carrying out vacuum filtration to remove dimethyl sulfoxide and potassium hydroxide, and finally dispersing the aramid nanofiber into a certain amount of water to form an aramid nanofiber dispersion;
(3) Adding glutaraldehyde into a certain amount of the aramid nanofiber dispersion liquid obtained in the step (2) to form an aramid nanofiber/glutaraldehyde dispersion liquid;
(4) Adding cellulose nanocrystalline powder and carbon nanotube powder into ionized water, stirring and carrying out ultrasonic treatment for a certain time to form uniform dispersion;
(5) Diluting a certain amount of the aramid nanofiber/glutaraldehyde dispersion liquid obtained in the step (3), carrying out ultrasonic treatment, transferring to a vacuum auxiliary filtering device, and carrying out vacuum auxiliary filtering for a certain time until water is pumped out to obtain an aramid nanofiber/glutaraldehyde film;
(6) Diluting a certain amount of cellulose nanocrystalline/carbon nanotube dispersion liquid in the step (4), transferring to a vacuum auxiliary filtering device in the step (5) after ultrasonic treatment, and vacuum auxiliary filtering for a certain time until water is pumped out to obtain a composite membrane;
(7) And (3) sequentially repeating the steps (5) and (6) for a plurality of times, so that the topmost layer and the bottommost layer of the prepared composite film are all aramid nanofibers, and the cellulose nanocrystal/carbon nanotube/aramid nanofiber composite film is obtained after drying.
The specific preparation flow chart is shown in fig. 1, the vacuum auxiliary filtering device used in the embodiment of the invention is common laboratory equipment (the prior equipment is not described any more, and related connection structures are not described), the aramid fiber used is commercially purchased Kevlar short fiber, the cellulose nanocrystalline is prepared by a sulfuric acid hydrolysis method, and the source is commercially purchased.
The invention is illustrated by the following specific examples:
example 1
3g of Kevlar staple fiber and 1.5g of potassium hydroxide were added to 300mL of dimethyl sulfoxide, and stirred at 25℃for 7 days to obtain an aramid nanofiber/dimethyl sulfoxide solution. 10mL of aramid nanofiber/dimethyl sulfoxide solution is measured, and a large amount of deionized water is added to be vigorously stirred for 24 hours, so that an aramid nanofiber dispersion is obtained. Filtration and dispersion with deionized water was repeated twice. Finally, 50% glutaraldehyde solution and proper deionized water are added to obtain aramid fiber/glutaraldehyde dispersion liquid, wherein the weight of the aramid fiber nano-fiber is 0.25% and the weight of the glutaraldehyde is 0.05%.
0.1g of cellulose nanocrystalline and 0.01g of carbon nanotube are weighed and added into 40mL of deionized water, and the mixture is stirred for 10min and then dispersed for 10min by ultrasonic to obtain cellulose nanocrystalline/carbon nanotube dispersion liquid.
2mL of aramid nanofiber/glutaraldehyde dispersion liquid is measured, 3mL of deionized water is added, ultrasonic dispersion is carried out for 5min, and the aramid nanofiber membrane is obtained through vacuum auxiliary suction filtration treatment, wherein a sand core funnel is adopted by a suction filtration device, and the membrane is a nylon membrane with the aperture of 0.22 mu m. Continuously measuring 6mL of cellulose nano-crystal/carbon nano-tube dispersion liquid, adding 9mL of deionized water, performing ultrasonic dispersion for 5min, and filtering to form a cellulose nano-crystal/carbon nano-tube film layer. And then respectively and alternately filtering the aramid nanofiber/glutaraldehyde dispersion liquid and the cellulose nanocrystal/carbon nanotube dispersion liquid to finally obtain the composite membrane with the total layer number of 5. And drying the composite membrane for 24 hours at room temperature after the suction filtration is finished, and finally drying the composite membrane for 6 hours in a blast drying oven at 50 ℃ to obtain the glutaraldehyde crosslinked cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane.
Example 2
3g of Kevlar staple fiber and 1.5g of potassium hydroxide were added to 300mL of dimethyl sulfoxide, and stirred at 25℃for 7 days to obtain an aramid nanofiber/dimethyl sulfoxide solution. 10mL of aramid nanofiber/dimethyl sulfoxide solution is measured, and a large amount of deionized water is added to be vigorously stirred for 24 hours, so that an aramid nanofiber dispersion is obtained. Filtration and dispersion with deionized water was repeated twice. Finally, 50% glutaraldehyde solution and proper deionized water are added to obtain aramid fiber/glutaraldehyde dispersion liquid, wherein the weight of the aramid fiber nano-fiber is 0.25% and the weight of the glutaraldehyde is 1.0%.
0.1g of cellulose nanocrystalline and 0.01g of carbon nanotube are weighed and added into 40mL of deionized water, and the mixture is stirred for 10min and then dispersed for 10min by ultrasonic to obtain cellulose nanocrystalline/carbon nanotube dispersion liquid.
2mL of aramid nanofiber/glutaraldehyde dispersion liquid is measured, 3mL of deionized water is added, ultrasonic dispersion is carried out for 5min, and the aramid nanofiber membrane is obtained through vacuum auxiliary suction filtration treatment, wherein a sand core funnel is adopted by a suction filtration device, and the membrane is a nylon membrane with the aperture of 0.22 mu m. Continuously measuring 6mL of cellulose nano-crystal/carbon nano-tube dispersion liquid, adding 9mL of deionized water, performing ultrasonic dispersion for 5min, and filtering to form a cellulose nano-crystal/carbon nano-tube film layer. And then respectively and alternately filtering the aramid nanofiber/glutaraldehyde dispersion liquid and the cellulose nanocrystal/carbon nanotube dispersion liquid to finally obtain the composite membrane with the total layer number of 5. And drying the composite membrane for 24 hours at room temperature after the suction filtration is finished, and finally drying the composite membrane for 6 hours in a blast drying oven at 50 ℃ to obtain the glutaraldehyde crosslinked cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane.
Example 3
3g of Kevlar staple fiber and 1.5g of potassium hydroxide were added to 300mL of dimethyl sulfoxide, and stirred at 25℃for 7 days to obtain an aramid nanofiber/dimethyl sulfoxide solution. 10mL of aramid nanofiber/dimethyl sulfoxide solution is measured, and a large amount of deionized water is added to be vigorously stirred for 24 hours, so that an aramid nanofiber dispersion is obtained. Filtration and dispersion with deionized water was repeated twice. Finally, 50% glutaraldehyde solution and proper deionized water are added to obtain aramid fiber/glutaraldehyde dispersion liquid, wherein the aramid fiber nano fiber accounts for 0.25wt% and the glutaraldehyde accounts for 2.0%.
0.1g of cellulose nanocrystalline and 0.01g of carbon nanotube are weighed and added into 40mL of deionized water, and the mixture is stirred for 10min and then dispersed for 10min by ultrasonic to obtain cellulose nanocrystalline/carbon nanotube dispersion liquid.
2mL of aramid nanofiber/glutaraldehyde dispersion liquid is measured, 3mL of deionized water is added, ultrasonic dispersion is carried out for 5min, and the aramid nanofiber membrane is obtained through vacuum auxiliary suction filtration treatment, wherein a sand core funnel is adopted by a suction filtration device, and the membrane is a nylon membrane with the aperture of 0.22 mu m. Continuously measuring 6mL of cellulose nano-crystal/carbon nano-tube dispersion liquid, adding 9mL of deionized water, performing ultrasonic dispersion for 5min, and filtering to form a cellulose nano-crystal/carbon nano-tube film layer. And then respectively and alternately filtering the aramid nanofiber/glutaraldehyde dispersion liquid and the cellulose nanocrystal/carbon nanotube dispersion liquid to finally obtain the composite membrane with the total layer number of 5. And drying the composite membrane for 24 hours at room temperature after the suction filtration is finished, and finally drying the composite membrane for 6 hours in a blast drying oven at 50 ℃ to obtain the glutaraldehyde crosslinked cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane.
Example 4
3g of Kevlar staple fiber and 1.5g of potassium hydroxide were added to 300mL of dimethyl sulfoxide, and stirred at 25℃for 7 days to obtain an aramid nanofiber/dimethyl sulfoxide solution. 10mL of aramid nanofiber/dimethyl sulfoxide solution is measured, and a large amount of deionized water is added to be vigorously stirred for 24 hours, so that an aramid nanofiber dispersion is obtained. Filtration and dispersion with deionized water was repeated twice. Finally, 50% glutaraldehyde solution and proper deionized water are added to obtain aramid fiber/glutaraldehyde dispersion liquid, wherein the aramid fiber nano fiber accounts for 0.25wt% and the glutaraldehyde accounts for 3.0%.
0.1g of cellulose nanocrystalline and 0.01g of carbon nanotube are weighed and added into 40mL of deionized water, and the mixture is stirred for 10min and then dispersed for 10min by ultrasonic to obtain cellulose nanocrystalline/carbon nanotube dispersion liquid.
2mL of aramid nanofiber/glutaraldehyde dispersion liquid is measured, 3mL of deionized water is added, ultrasonic dispersion is carried out for 5min, and the aramid nanofiber membrane is obtained through vacuum auxiliary suction filtration treatment, wherein a sand core funnel is adopted by a suction filtration device, and the membrane is a nylon membrane with the aperture of 0.22 mu m. Continuously measuring 6mL of cellulose nano-crystal/carbon nano-tube dispersion liquid, adding 9mL of deionized water, performing ultrasonic dispersion for 5min, and filtering to form a cellulose nano-crystal/carbon nano-tube film layer. And then respectively and alternately filtering the aramid nanofiber/glutaraldehyde dispersion liquid and the cellulose nanocrystal/carbon nanotube dispersion liquid to finally obtain the composite membrane with the total layer number of 5. And drying the composite membrane for 24 hours at room temperature after the suction filtration is finished, and finally drying the composite membrane for 6 hours in a blast drying oven at 50 ℃ to obtain the glutaraldehyde crosslinked cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane.
Example 5
3g of Kevlar staple fiber and 1.5g of potassium hydroxide were added to 300mL of dimethyl sulfoxide, and stirred at 25℃for 7 days to obtain an aramid nanofiber/dimethyl sulfoxide solution. 10mL of aramid nanofiber/dimethyl sulfoxide solution is measured, and a large amount of deionized water is added to be vigorously stirred for 24 hours, so that an aramid nanofiber dispersion is obtained. Filtration and dispersion with deionized water was repeated twice. Finally, 50% glutaraldehyde solution and proper deionized water are added to obtain aramid fiber/glutaraldehyde dispersion liquid, wherein the aramid fiber nano fiber accounts for 0.25wt% and the glutaraldehyde accounts for 5.0%.
0.1g of cellulose nanocrystalline and 0.01g of carbon nanotube are weighed and added into 40mL of deionized water, and the mixture is stirred for 10min and then dispersed for 10min by ultrasonic to obtain cellulose nanocrystalline/carbon nanotube dispersion liquid.
2mL of aramid nanofiber/glutaraldehyde dispersion liquid is measured, 3mL of deionized water is added, ultrasonic dispersion is carried out for 5min, and the aramid nanofiber membrane is obtained through vacuum auxiliary suction filtration treatment, wherein a sand core funnel is adopted by a suction filtration device, and the membrane is a nylon membrane with the aperture of 0.22 mu m. Continuously measuring 6mL of cellulose nano-crystal/carbon nano-tube dispersion liquid, adding 9mL of deionized water, performing ultrasonic dispersion for 5min, and filtering to form a cellulose nano-crystal/carbon nano-tube film layer. And then respectively and alternately filtering the aramid nanofiber/glutaraldehyde dispersion liquid and the cellulose nanocrystal/carbon nanotube dispersion liquid to finally obtain the composite membrane with the total layer number of 5. And drying the composite membrane for 24 hours at room temperature after the suction filtration is finished, and finally drying the composite membrane for 6 hours in a blast drying oven at 50 ℃ to obtain the glutaraldehyde crosslinked cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane.
Example 6
3g of Kevlar staple fiber and 1.5g of potassium hydroxide were added to 300mL of dimethyl sulfoxide, and stirred at 25℃for 7 days to obtain an aramid nanofiber/dimethyl sulfoxide solution. 10mL of aramid nanofiber/dimethyl sulfoxide solution is measured, and a large amount of deionized water is added to be vigorously stirred for 24 hours, so that an aramid nanofiber dispersion is obtained. Filtration and dispersion with deionized water was repeated twice. Finally, 50% glutaraldehyde solution and proper deionized water are added to obtain aramid fiber/glutaraldehyde dispersion liquid with the concentration of glutaraldehyde of 5.0%, wherein the concentration of the aramid fiber nano fiber is 0.25 wt%.
0.1g of cellulose nanocrystalline and 0.02g of carbon nanotube are weighed and added into 40mL of deionized water, and the mixture is stirred for 10min and then dispersed for 10min by ultrasonic to obtain cellulose nanocrystalline/carbon nanotube dispersion liquid.
2mL of aramid nanofiber/glutaraldehyde dispersion liquid is measured, 3mL of deionized water is added, ultrasonic dispersion is carried out for 5min, and the aramid nanofiber membrane is obtained through vacuum auxiliary suction filtration treatment, wherein a sand core funnel is adopted by a suction filtration device, and the membrane is a nylon membrane with the aperture of 0.22 mu m. Continuously measuring 6mL of cellulose nano-crystal/carbon nano-tube dispersion liquid, adding 9mL of deionized water, performing ultrasonic dispersion for 5min, and filtering to form a cellulose nano-crystal/carbon nano-tube film layer. And then respectively and alternately filtering the aramid nanofiber/glutaraldehyde dispersion liquid and the cellulose nanocrystal/carbon nanotube dispersion liquid to finally obtain the composite membrane with the total layer number of 5. And drying the composite membrane for 24 hours at room temperature after the suction filtration is finished, and finally drying the composite membrane for 6 hours in a blast drying oven at 50 ℃ to obtain the glutaraldehyde crosslinked cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane.
Example 7
3g of Kevlar staple fiber and 1.5g of potassium hydroxide were added to 300mL of dimethyl sulfoxide, and stirred at 25℃for 7 days to obtain an aramid nanofiber/dimethyl sulfoxide solution. 10mL of aramid nanofiber/dimethyl sulfoxide solution is measured, and a large amount of deionized water is added to be vigorously stirred for 24 hours, so that an aramid nanofiber dispersion is obtained. Filtration and dispersion with deionized water was repeated twice. Finally, 50% glutaraldehyde solution and proper deionized water are added to obtain aramid fiber/glutaraldehyde dispersion liquid, wherein the aramid fiber nano fiber accounts for 0.25wt% and the glutaraldehyde accounts for 5.0%.
0.1g of cellulose nanocrystalline and 0.05g of carbon nanotube are weighed and added into 40mL of deionized water, and the mixture is stirred for 10min and then dispersed for 10min by ultrasonic to obtain cellulose nanocrystalline/carbon nanotube dispersion liquid.
2mL of aramid nanofiber/glutaraldehyde dispersion liquid is measured, 3mL of deionized water is added, ultrasonic dispersion is carried out for 5min, and the aramid nanofiber membrane is obtained through vacuum auxiliary suction filtration treatment, wherein a sand core funnel is adopted by a suction filtration device, and the membrane is a nylon membrane with the aperture of 0.22 mu m. Continuously measuring 6mL of cellulose nano-crystal/carbon nano-tube dispersion liquid, adding 9mL of deionized water, performing ultrasonic dispersion for 5min, and filtering to form a cellulose nano-crystal/carbon nano-tube film layer. And then respectively and alternately filtering the aramid nanofiber/glutaraldehyde dispersion liquid and the cellulose nanocrystal/carbon nanotube dispersion liquid to finally obtain the composite membrane with the total layer number of 5. And drying the composite membrane for 24 hours at room temperature after the suction filtration is finished, and finally drying the composite membrane for 6 hours in a blast drying oven at 50 ℃ to obtain the glutaraldehyde crosslinked cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane.
Example 8
3g of Kevlar staple fiber and 1.5g of potassium hydroxide were added to 300mL of dimethyl sulfoxide, and stirred at 25℃for 7 days to obtain an aramid nanofiber/dimethyl sulfoxide solution. 10mL of aramid nanofiber/dimethyl sulfoxide solution is measured, and a large amount of deionized water is added to be vigorously stirred for 24 hours, so that an aramid nanofiber dispersion is obtained. Filtration and dispersion with deionized water was repeated twice. Finally, 50% glutaraldehyde solution and proper deionized water are added to obtain aramid fiber/glutaraldehyde dispersion liquid, wherein the aramid fiber nano fiber accounts for 0.25wt% and the glutaraldehyde accounts for 5.0%.
0.1g of cellulose nanocrystalline and 0.10g of carbon nanotube are weighed and added into 40mL of deionized water, and the mixture is stirred for 10min and then dispersed for 10min by ultrasonic to obtain cellulose nanocrystalline/carbon nanotube dispersion liquid.
2mL of aramid nanofiber/glutaraldehyde dispersion liquid is measured, 3mL of deionized water is added, ultrasonic dispersion is carried out for 5min, and the aramid nanofiber membrane is obtained through vacuum auxiliary suction filtration treatment, wherein a sand core funnel is adopted by a suction filtration device, and the membrane is a nylon membrane with the aperture of 0.22 mu m. Continuously measuring 6mL of cellulose nano-crystal/carbon nano-tube dispersion liquid, adding 9mL of deionized water, performing ultrasonic dispersion for 5min, and filtering to form a cellulose nano-crystal/carbon nano-tube film layer. And then respectively and alternately filtering the aramid nanofiber/glutaraldehyde dispersion liquid and the cellulose nanocrystal/carbon nanotube dispersion liquid to finally obtain the composite membrane with the total layer number of 5. And drying the composite membrane for 24 hours at room temperature after the suction filtration is finished, and finally drying the composite membrane for 6 hours in a blast drying oven at 50 ℃ to obtain the glutaraldehyde crosslinked cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane.
Example 9
3g of Kevlar staple fiber and 1.5g of potassium hydroxide were added to 300mL of dimethyl sulfoxide, and stirred at 25℃for 7 days to obtain an aramid nanofiber/dimethyl sulfoxide solution. 10mL of aramid nanofiber/dimethyl sulfoxide solution is measured, and a large amount of deionized water is added to be vigorously stirred for 24 hours, so that an aramid nanofiber dispersion is obtained. Filtration and dispersion with deionized water was repeated twice. Finally, 50% glutaraldehyde solution and proper deionized water are added to obtain aramid fiber/glutaraldehyde dispersion liquid, wherein the weight of the aramid fiber nano-fiber is 0.25% and the weight of the glutaraldehyde is 0.05%.
0.1g of cellulose nanocrystalline and 0.10g of carbon nanotube are weighed and added into 40mL of deionized water, and the mixture is stirred for 10min and then dispersed for 10min by ultrasonic to obtain cellulose nanocrystalline/carbon nanotube dispersion liquid.
2mL of aramid nanofiber/glutaraldehyde dispersion liquid is measured, 3mL of deionized water is added, ultrasonic dispersion is carried out for 5min, and the aramid nanofiber membrane is obtained through vacuum auxiliary suction filtration treatment, wherein a sand core funnel is adopted by a suction filtration device, and the membrane is a nylon membrane with the aperture of 0.22 mu m. Continuously measuring 6mL of cellulose nano-crystal/carbon nano-tube dispersion liquid, adding 9mL of deionized water, performing ultrasonic dispersion for 5min, and filtering to form a cellulose nano-crystal/carbon nano-tube film layer. And then respectively and alternately filtering the aramid nanofiber/glutaraldehyde dispersion liquid and the cellulose nanocrystal/carbon nanotube dispersion liquid to finally obtain the composite membrane with the total layer number of 5. And drying the composite membrane for 24 hours at room temperature after the suction filtration is finished, and finally drying the composite membrane for 6 hours in a blast drying oven at 50 ℃ to obtain the glutaraldehyde crosslinked cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane.
Example 10
3g of Kevlar staple fiber and 1.5g of potassium hydroxide were added to 300mL of dimethyl sulfoxide, and stirred at 25℃for 7 days to obtain an aramid nanofiber/dimethyl sulfoxide solution. 10mL of aramid nanofiber/dimethyl sulfoxide solution is measured, and a large amount of deionized water is added to be vigorously stirred for 24 hours, so that an aramid nanofiber dispersion is obtained. Filtration and dispersion with deionized water was repeated twice. Finally, 50% glutaraldehyde solution and proper deionized water are added to obtain aramid fiber/glutaraldehyde dispersion liquid, wherein the aramid fiber nano fiber accounts for 0.25wt% and the glutaraldehyde accounts for 5.0%.
0.1g of cellulose nanocrystalline and 0.10g of carbon nanotube are weighed and added into 40mL of deionized water, and the mixture is stirred for 10min and then dispersed for 10min by ultrasonic to obtain cellulose nanocrystalline/carbon nanotube dispersion liquid.
2mL of aramid nanofiber/glutaraldehyde dispersion liquid is measured, 3mL of deionized water is added, ultrasonic dispersion is carried out for 5min, and the aramid nanofiber membrane is obtained through vacuum auxiliary suction filtration treatment, wherein a sand core funnel is adopted by a suction filtration device, and the membrane is a nylon membrane with the aperture of 0.22 mu m. Continuously measuring 6mL of cellulose nano-crystal/carbon nano-tube dispersion liquid, adding 9mL of deionized water, performing ultrasonic dispersion for 5min, and filtering to form a cellulose nano-crystal/carbon nano-tube film layer. And then respectively and alternately filtering the aramid nanofiber/glutaraldehyde dispersion liquid and the cellulose nanocrystal/carbon nanotube dispersion liquid to finally obtain the composite membrane with the total layer number of 5. Drying the composite membrane for 48 hours at room temperature after the suction filtration is completed, and obtaining the glutaraldehyde crosslinked cellulose nanocrystalline/carbon nano tube/aramid nanofiber composite membrane.
Example 11
3g of Kevlar staple fiber and 1.5g of potassium hydroxide were added to 300mL of dimethyl sulfoxide, and stirred at 25℃for 7 days to obtain an aramid nanofiber/dimethyl sulfoxide solution. 10mL of aramid nanofiber/dimethyl sulfoxide solution is measured, and a large amount of deionized water is added to be vigorously stirred for 24 hours, so that an aramid nanofiber dispersion is obtained. Filtration and dispersion with deionized water was repeated twice. Finally, 50% glutaraldehyde solution and proper deionized water are added to obtain aramid fiber/glutaraldehyde dispersion liquid, wherein the weight of the aramid fiber nano-fiber is 0.25% and the weight of the glutaraldehyde is 0.05%.
0.1g of cellulose nanocrystalline and 0.10g of carbon nanotube are weighed and added into 40mL of deionized water, and the mixture is stirred for 10min and then dispersed for 10min by ultrasonic to obtain cellulose nanocrystalline/carbon nanotube dispersion liquid.
2mL of aramid nanofiber/glutaraldehyde dispersion liquid is measured, 3mL of deionized water is added, ultrasonic dispersion is carried out for 5min, and the aramid nanofiber membrane is obtained through vacuum auxiliary suction filtration treatment, wherein a sand core funnel is adopted by a suction filtration device, and the membrane is a nylon membrane with the aperture of 0.22 mu m. Continuously measuring 6mL of cellulose nano-crystal/carbon nano-tube dispersion liquid, adding 9mL of deionized water, performing ultrasonic dispersion for 5min, and filtering to form a cellulose nano-crystal/carbon nano-tube film layer. And then respectively and alternately filtering the aramid nanofiber/glutaraldehyde dispersion liquid and the cellulose nanocrystal/carbon nanotube dispersion liquid to finally obtain the composite membrane with the total layer number of 5. Drying the composite membrane for 48 hours at room temperature after the suction filtration is completed, and obtaining the glutaraldehyde crosslinked cellulose nanocrystalline/carbon nano tube/aramid nanofiber composite membrane.
Example 11
3g of Kevlar staple fiber and 1.5g of potassium hydroxide were added to 300mL of dimethyl sulfoxide, and stirred at 25℃for 7 days to obtain an aramid nanofiber/dimethyl sulfoxide solution. 10mL of aramid nanofiber/dimethyl sulfoxide solution is measured, and a large amount of deionized water is added to be vigorously stirred for 24 hours, so that an aramid nanofiber dispersion is obtained. Filtration and dispersion with deionized water was repeated twice. Finally, 50% glutaraldehyde solution and proper deionized water are added to obtain aramid fiber/glutaraldehyde dispersion liquid, wherein the weight of the aramid fiber nano-fiber is 0.25% and the weight of the glutaraldehyde is 0.05%.
0.1g of cellulose nanocrystalline and 0.01g of carbon nanotube are weighed and added into 40mL of deionized water, and the mixture is stirred for 10min and then dispersed for 10min by ultrasonic to obtain cellulose nanocrystalline/carbon nanotube dispersion liquid.
2mL of aramid nanofiber/glutaraldehyde dispersion liquid is measured, 3mL of deionized water is added, ultrasonic dispersion is carried out for 5min, and the aramid nanofiber membrane is obtained through vacuum auxiliary suction filtration treatment, wherein a sand core funnel is adopted by a suction filtration device, and the membrane is a nylon membrane with the aperture of 0.22 mu m. Continuously measuring 6mL of cellulose nano-crystal/carbon nano-tube dispersion liquid, adding 9mL of deionized water, performing ultrasonic dispersion for 5min, and filtering to form a cellulose nano-crystal/carbon nano-tube film layer. And then respectively and alternately filtering the aramid nanofiber/glutaraldehyde dispersion liquid and the cellulose nanocrystal/carbon nanotube dispersion liquid to finally obtain the composite membrane with the total layer number of 5. Drying the composite membrane for 48 hours at room temperature after the suction filtration is completed, and obtaining the glutaraldehyde crosslinked cellulose nanocrystalline/carbon nano tube/aramid nanofiber composite membrane.
The composite film prepared in example 1 was subjected to scanning electron microscopy analysis, and as a result, see fig. 2, from which a layered composite film consisting of aramid nanofibers and cellulose nanocrystalline/carbon nanotube layers can be clearly seen. The aramid nanofibers of the outer layer are tightly combined with the cellulose nanocrystals/carbon nanotube layers, and the enlarged detailed view can see that the short rod-shaped carbon nanotubes are uniformly embedded in the cellulose nanocrystals, and the two uniformly form the conductive layer of the composite film, so that the composite film can be applied in a conductive related manner.
Experimental example 1
This experimental example tests the humidity sensing performance of the cellulose nanocrystal/carbon nanotube/aramid nanofiber composite film of example 1. The composite film of example 1 was cut into strips of 1cm in width and 3cm in length, and the conductive layers were exposed at both ends of the composite film by treatment with tweezers, and a closed loop circuit was connected together with the composite film using a utility meter to detect changes in the resistance value of the composite film. After the circuit is connected, deionized water is dripped on the composite film after the electric meter reading is stable, the resistance reading is recorded at intervals, and after the reading number is stable, water drops on the composite film are sucked away, and the resistance reading is recorded at intervals. After the composite film is completely dried, the actions of dripping and sucking water drops are repeated for a plurality of times, and the resistance reading is recorded. As a result, as shown in FIG. 3, the composite film of example 1 rapidly increased in electrical resistance after being wetted with water. When the water is wiped dry, the resistance can be gradually recovered. Experimental results show that the cellulose nanocrystal/carbon nanotube/aramid nanofiber composite membrane of the embodiment 1 has good humidity sensing performance.
Experimental example 2
This experimental example tested the motion sensing performance of the cellulose nanocrystal/carbon nanotube/aramid nanofiber composite membrane of example 1. The composite film of example 1 was cut into strips of 1cm in width and 3cm in length, and the conductive layers were exposed at both ends of the composite film by treatment with tweezers, and connected together into a closed loop circuit using a utility meter. Folding the composite film until a crease appears, and then repeating the actions of straightening and bending the composite film, and recording the change of the resistance of the composite film. As a result, as shown in fig. 4, the composite film resistance of example 1 also changed regularly in response to the film bending regularly. The composite film resistance becomes large when bent and becomes small when straightened. Experimental results show that the cellulose nanocrystal/carbon nanotube/aramid nanofiber composite membrane of the embodiment 1 has good motion sensing performance.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The preparation method of the high-strength conductive cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane is characterized by comprising the following steps of:
(1) Adding a certain amount of aramid nanofibers and potassium hydroxide into dimethyl sulfoxide, and stirring to form an aramid nanofiber/dimethyl sulfoxide/potassium hydroxide solution;
(2) Adding water into the aramid nanofiber/dimethyl sulfoxide/potassium hydroxide solution, vigorously stirring to form a uniform dispersion, then carrying out vacuum filtration, repeatedly dispersing with water and carrying out vacuum filtration to remove dimethyl sulfoxide and potassium hydroxide, and finally dispersing the aramid nanofiber into a certain amount of water to form an aramid nanofiber dispersion;
(3) Adding glutaraldehyde into a certain amount of the aramid nanofiber dispersion liquid obtained in the step (2) to form an aramid nanofiber/glutaraldehyde dispersion liquid;
(4) Adding cellulose nanocrystalline powder and carbon nanotube powder into water, stirring and carrying out ultrasonic treatment for a certain time to form uniform dispersion;
(5) Diluting a certain amount of the aramid nanofiber/glutaraldehyde dispersion liquid obtained in the step (3), carrying out ultrasonic treatment, transferring to a vacuum auxiliary filtering device, and carrying out vacuum auxiliary filtering until water is pumped to dryness to obtain an aramid nanofiber/glutaraldehyde film;
(6) Diluting a certain amount of cellulose nanocrystalline/carbon nanotube dispersion liquid in the step (4), transferring to a vacuum auxiliary filtering device in the step (5) after ultrasonic treatment, and performing vacuum auxiliary filtering until water is pumped to dryness to obtain a composite membrane;
(7) And (3) sequentially repeating the steps (5) and (6) for a plurality of times, so that the topmost layer and the bottommost layer of the prepared composite film are all aramid nanofibers, and the cellulose nanocrystal/carbon nanotube/aramid nanofiber composite film is obtained after drying.
2. The method for preparing the high-strength conductive cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane according to claim 1, which is characterized in that: in the step (1), the concentration of the aramid nanofiber in the aramid nanofiber/dimethyl sulfoxide/potassium hydroxide solution is 0.1-3.0 mg/mL, the concentration of potassium hydroxide is 1.0-5.0 mg/mL, the stirring temperature is 20-30 ℃, and the stirring speed is 1000-1500 r/min.
3. The method for preparing the high-strength conductive cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane according to claim 1, which is characterized in that: in the step (2), the mass percentage of the aramid nanofiber dispersion liquid is 0.25-1.00 wt% of the aramid nanofiber.
4. The method for preparing the high-strength conductive cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane according to claim 1, which is characterized in that: in the step (3), the aramid nanofiber dispersion liquid is 0.5-10 mL, and glutaraldehyde and water with the volume fraction of 50% are added to prepare the dispersion liquid with the glutaraldehyde concentration of 0.05-5.0%.
5. The method for preparing the high-strength conductive cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane according to claim 1, which is characterized in that: in the step (4), the cellulose nanocrystalline/carbon nanotube dispersion liquid is controlled to be 0.1-2.0 wt% and the carbon nanotube is controlled to be 0.01-0.10 wt% according to the mass percentage, the stirring time is 10-30 min, and the ultrasonic time is 10-30 min.
6. The method for preparing the high-strength conductive cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane according to claim 1, which is characterized in that: in the step (5), the aramid nanofiber/glutaraldehyde dispersion liquid is diluted, namely a certain amount of the aramid nanofiber/glutaraldehyde dispersion liquid is diluted to 5-10 mL by water, and the dispersion is carried out for 5-30 min by ultrasonic.
7. The method for preparing the high-strength conductive cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane according to claim 1, which is characterized in that: in the step (6), the cellulose nano-crystal/carbon nano-tube dispersion liquid is diluted, a certain amount of cellulose nano-crystal/carbon nano-tube dispersion liquid is diluted to 10 mL-20 mL by water, and the cellulose nano-crystal/carbon nano-tube dispersion liquid is dispersed for 5 min-30 min by ultrasonic.
8. The method for preparing the high-strength conductive cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite membrane according to claim 1, which is characterized in that: in the step (7), the cellulose nanocrystalline/carbon nanotube/aramid nanofiber composite film is firstly dried for 6-24 hours at room temperature and then dried for 0-12 hours at the temperature of 30-80 ℃.
9. The cellulose nanocrystal/carbon nanotube/aramid nanofiber composite membrane prepared by the method of any one of claims 1 to 8, wherein the aramid nanofiber accounts for 20wt% to 40wt%, the cellulose nanocrystal accounts for 40wt% to 70wt%, and the carbon nanotube accounts for 5wt% to 40wt%.
10. Use of the cellulose nanocrystal/carbon nanotube/aramid nanofiber composite membrane according to claim 9 in sensors for humidity sensing and motion sensing.
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| CN104559175A (en) * | 2014-12-27 | 2015-04-29 | 哈尔滨工业大学 | Preparation method of carbon nano tube-Kevlar nanofiber composite film |
| CN110838415A (en) * | 2019-11-12 | 2020-02-25 | 南京理工大学 | Aramid nanofiber/carbon nanotube/conductive polyaniline composite film material and preparation method thereof |
| CN110964216A (en) * | 2019-12-24 | 2020-04-07 | 陕西科技大学 | ANF (artificial neural fiber) -reinforced HEC (high-energy carbon) film composite material and preparation method thereof |
| CN111292968A (en) * | 2020-02-19 | 2020-06-16 | 南京理工大学 | Flexible self-supporting electrode material with aramid nano-fiber film as substrate and preparation method thereof |
| WO2020194380A1 (en) * | 2019-03-22 | 2020-10-01 | 北越コーポレーション株式会社 | Nanocarbon dispersion liquid, method for producing same, and nanocarbon dispersing agent |
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| CN104559175A (en) * | 2014-12-27 | 2015-04-29 | 哈尔滨工业大学 | Preparation method of carbon nano tube-Kevlar nanofiber composite film |
| WO2020194380A1 (en) * | 2019-03-22 | 2020-10-01 | 北越コーポレーション株式会社 | Nanocarbon dispersion liquid, method for producing same, and nanocarbon dispersing agent |
| CN110838415A (en) * | 2019-11-12 | 2020-02-25 | 南京理工大学 | Aramid nanofiber/carbon nanotube/conductive polyaniline composite film material and preparation method thereof |
| CN110964216A (en) * | 2019-12-24 | 2020-04-07 | 陕西科技大学 | ANF (artificial neural fiber) -reinforced HEC (high-energy carbon) film composite material and preparation method thereof |
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