CN110714337B - Preparation method of CNTs coating sensing fabric based on different fabric textures - Google Patents

Preparation method of CNTs coating sensing fabric based on different fabric textures Download PDF

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CN110714337B
CN110714337B CN201910938896.0A CN201910938896A CN110714337B CN 110714337 B CN110714337 B CN 110714337B CN 201910938896 A CN201910938896 A CN 201910938896A CN 110714337 B CN110714337 B CN 110714337B
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fabric
cnts
coating
temperature
conductive
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CN110714337A (en
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邹梨花
杨莉
孙妍妍
阮芳涛
徐珍珍
花月
刘英存
曹昊天
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Anhui Polytechnic University
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • D01F9/225—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles from stabilised polyacrylonitriles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0006—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using woven fabrics
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
    • G01D5/00—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable
    • G01D5/12—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable using electric or magnetic means
    • G01D5/14—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable using electric or magnetic means influencing the magnitude of a current or voltage
    • G01D5/16—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable using electric or magnetic means influencing the magnitude of a current or voltage by varying resistance
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/04—Properties of the materials having electrical or magnetic properties
    • D06N2209/041—Conductive
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2213/00—Others characteristics
    • D06N2213/02—All layers being of the same kind of material, e.g. all layers being of polyolefins, all layers being of polyesters

Abstract

The invention discloses a preparation method of a CNTs coating sensing fabric based on different fabric textures, which comprises the steps of alkali liquor treatment, carbon nanotube dispersion and coating adsorption, moisture absorption, conductive sealing film preparation and the like. The carbon nano tubes can be uniformly and densely adsorbed on the fabric, so that the conductive network on the surface of the fabric is dense, the surfaces of the CNTs, the CNTs grafted long carbon fibers and the cotton fibers are coated with the starch-based water-absorbent resin, after moisture absorption, the water-containing starch-based water-absorbent resin is used as a conductive medium, the CNTs grafted long carbon fibers and the conductive sealing film are further conducted to form a three-dimensional conductive network, and the overall resistance of the coated fabric is remarkably reduced. The silicone rubber matrix of the conductive sealing film can isolate the inner layer and the outer layer of the fabric after being crosslinked, can keep the stability of the water content of the starch-based water-absorbent resin, and can maintain the stability of the conductive sensing performance.

Description

Preparation method of CNTs coating sensing fabric based on different fabric textures
Technical Field
The invention belongs to the technical field of flexible fabric sensors, and particularly relates to a preparation method of a CNTs coating sensing fabric based on different fabric textures.
Background
The preparation process of the dipping coating of the fabric sensor is economical and convenient, and is easy for large-scale production. The Carbon Nanotubes (CNTs) have the characteristics of good conductivity, corrosion resistance, light weight and the like, and have excellent physical and chemical properties, so that the carbon nanotubes are an ideal coating. The knitted fabric has good elastic recovery performance, wrinkle resistance and air permeability, and is comfortable to wear. Therefore, the coated fabric product obtained by coating the CNTs dispersion liquid on the knitted fabric has the characteristics of soft hand feeling, excellent elasticity, excellent air permeability and excellent conductivity, and the production process is simple, so that a good way is provided for the preparation of the fabric sensor.
At present, conductive fabrics made of conductive fibers such as metal and metal oxide fibers, carbon fibers and the like, which are purely spun or blended, conductive fabrics made of metal coating fabrics and organic conductive coatings and the like mainly appear on the market, but the metal fibers have the problems of poor wear resistance, poor toughness and easy corrosion, and the metal coating fabrics have the problems of easy corrosion and easy shedding. In the aspect of conductive fiber fabric, chinese patent CN104819734A utilizes polyaniline composite conductive yarn and spandex monofilament to weave a fabric resistance sensor. The chinese patent CN108045032A utilizes the graphene conductive filament, the graphene conductive staple fiber, the common filament and the common staple fiber to prepare the conductive woven fabric and the conductive non-woven fabric, so as to combine into the conductive sensing fabric.
Metal fibers and inorganic fibers are used in the development of fabric sensors as a good conductive material, but they have the disadvantages of poor wear resistance, easy breakage under the action of tensile, shearing and the like, and adverse effects on the operating performance of a weaving machine due to the conductivity. A fabric sensor woven with metal fibers has poor wearing feeling due to poor fiber flexibility.
CNTs is a carbon sixty allotrope newly found in recent years, can reach the nanometer level, and has the characteristics of good electrical conductivity, thermal conductivity, mechanical property, light weight and the like. The fabric has the characteristics of soft hand feeling, good elasticity and good air permeability, and the method for coating and finishing the fabric by using the CNTs dispersion liquid prepared from the CNTs and the dispersing agent can endow the fabric with excellent conductivity and ensure the comfort of the fabric, thereby providing a good way for preparing the fabric sensor.
In the prior art of preparing a coating conductive sensing fabric by using CNTs and a fabric, the CNTs are mostly adsorbed by adopting direct fabric adsorption or adsorbed after being coated by polyaniline in situ, when the CNTs are directly adsorbed, the CNTs in the fabric are mostly lapped by Van der Waals force to form a conductive structure, the conductive structure is loose, the lapping contact area is small, and the resistance of the fabric with the conductive structure is generally high; when the polyaniline in-situ coating method is used for preparing the conductive coating fabric, the polyaniline is non-conductive or has weak conductivity, so that the overall resistance of the fabric is higher, the conductivity is unsatisfactory, and further improvement steps are needed.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at various problems and defects existing in the preparation process of the CNTs coating sensing fabric at present, the invention provides a preparation method of the CNTs coating sensing fabric based on different fabric textures.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a CNTs coating sensing fabric based on different fabric textures comprises the following steps:
(1) soaking cotton fabrics with different fabric textures in alkali liquor, performing water bath constant temperature treatment, washing to be neutral, and then drying; the cotton fabric is woven by blended yarns of CNTs grafted long carbon fibers and cotton fibers;
(2) preparing a carbon nano tube dispersion liquid: dissolving 0.2-1.0 g of anhydrous starch-based water-absorbent resin in 50 mLN-methyl pyrrolidone to obtain a coating solution, heating to 60 ℃, dispersing carbon nanotubes in the coating solution, adding a surfactant, wherein the final concentration ratio of the carbon nanotubes to the surfactant is 1: 1-3, and performing ultrasonic treatment to obtain a carbon nanotube dispersion solution;
(3) flatly paving the cotton fabric dried in the step (1) in a container containing the carbon nano tube dispersion liquid, then carrying out constant-temperature oscillation treatment on the cotton fabric for 5 hours, and taking out and drying the cotton fabric subjected to the oscillation impregnation treatment;
(4) after drying, under the conditions of constant temperature and constant humidity of 25 ℃ and 100% relative humidity, absorbing moisture for 1-10 hours until the water content is 1-5 wt%;
(5) and uniformly coating the upper surface layer and the lower surface layer of the cotton fabric after moisture absorption with CNTs-containing silicon rubber to form a conductive sealing film, thus obtaining the CNTs coating sensing fabric with different fabric textures.
Preferably, the preparation method of the CNTs grafted long carbon fiber comprises the following steps:
(A) placing the PAN-based carbon fiber in a CVD furnace, and calcining for 1h at 450 ℃ under the protection of nitrogen to remove a surface sizing agent;
(B) modifying the surface of the desized carbon fiber by using an electrochemical anodic oxidation method: the electrolyte solution used was 5wt% NH4H2PO4The wire feeding speed of the aqueous solution is 40cm/min, the current is 0.3-0.5A, and the corresponding electrochemical treatment strength is 70-150C/g respectively;
(C) washing the electrochemically modified carbon fiber sample with deionized water for 5min, drying at 120 deg.C for 10min, and introducing Co (NO) with final concentration of 0.05M3)2·6H2Soaking in O ethanol solution for 3min, guiding out, drying in a drying device at 80 deg.C for 10min, and collecting carbon fiber with catalyst coating by a filament collecting machine;
(D) putting the carbon fiber sample attached with the catalyst coating into an FRD-400-CVD deposition furnace, introducing 10L/min high-purity nitrogen, raising the furnace temperature to 450 ℃ at 10 ℃/min, and closing N2Introducing 10L/min hydrogen to reduce for 1h, heating the furnace temperature to 550 ℃ at the heating rate of 25 ℃/min, and introducing C2H2、H2And N2The mixed gas is subjected to vapor deposition for 10min at the introduction rate of C2H2/H2/N2＝6/6/12L/min；
(E) After the deposition is finished, C is closed2H2And H2And cooling the furnace temperature to room temperature under the protection of high-purity nitrogen of 10L/min to obtain the CNTs grafted long carbon fiber, wherein the air pressure in the furnace is constant at 0.02MPa in the whole reaction process.
Preferably, the preparation method of the conductive sealing film is as follows:
(a) weighing 300mg of carbon nanotube, adding the carbon nanotube into 30m of 1 toluene solvent, stirring for 5min on a magnetic stirrer, then ultrasonically dispersing for 30min in an ultrasonic cleaning machine, then adding 10g of component A of Dow Corning Sylgard184PDMS silicone elastomer, magnetically stirring for 5min, ultrasonically dispersing for 30min, then adding 1g of component B of silicone rubber curing agent according to the mass ratio of 10:1, magnetically stirring for 5min, ultrasonically dispersing for 30min, and standing for 10min to obtain the silicone rubber containing CNTs;
(b) uniformly coating the CNTs-containing silicon rubber on the upper surface layer and the lower surface layer of the cotton fabric after moisture absorption, horizontally placing the cotton fabric in a vacuum oven with the relative vacuum degree of 0.05Mpa and the temperature of 40 ℃, taking out the cotton fabric after 40min, horizontally placing the cotton fabric in a fume hood for 12h to thoroughly volatilize toluene, and finally horizontally placing the cotton fabric in a constant-temperature blast drying oven with the temperature of 35 ℃ to cure for 4h to obtain a smooth and flat conductive sealing film without bubbles on the surface of the cotton fabric.
Preferably, the different fabric weaves are plain knitting, 1+1 rib, 2+2 rib; the alkali liquor is NaOH solution, and the concentration of the NaOH solution is 10 g/L; the water bath constant temperature treatment temperature in the step (1) is 60-70 ℃; the drying temperature in the step (1) is 60-80 ℃.
Preferably, the surfactant in the step (2) is sodium dodecyl benzene sulfonate; the final concentration of the carbon nano-tubes in the step (2) is 3-11 mg/mL, the final concentration of the surfactant is 3-22 mg/mL, the ultrasonic treatment time is 30-90 min, and the ultrasonic treatment temperature is 30-60 ℃.
Preferably, the bath ratio of the cotton fabric soaked in the carbon nanotube dispersion liquid in the step (3) is 1: 30-1: 40.
Preferably, the temperature of the shaking impregnation in the step (3) is 30-60 ℃ and the time is 30 min.
Preferably, the drying temperature in the step (3) is 60-80 ℃, and the time is 1.5-2 h.
Preferably, the method further comprises the step 4 after the step 3 is circularly repeated.
The invention has the following beneficial effects:
1. the prepared flexible fabric sensor with better conductivity has the advantages of thin and light coating fabric, good conductivity effect, controllable thickness, adjustable structure, simple requirement on required experimental operation conditions, low energy consumption, no need of expensive equipment and low production cost, and can be industrially produced on the traditional sizing or printing and dyeing equipment. The carbon nanotube coated fabric also has the characteristics of softness and comfort, and the defects of heavy weight and poor comfort of the traditional metal fiber fabric are avoided.
2. The carbon nano tubes can be uniformly and densely adsorbed on the fabric by using a simple dipping-coating process, so that the conductive network on the surface of the fabric is dense, the surfaces of the CNTs, the CNTs grafted long carbon fibers and the cotton fibers are coated with the starch-based water-absorbent resin, after moisture absorption, the water-containing starch-based water-absorbent resin is used as a conductive medium, the CNTs grafted long carbon fibers and the conductive sealing film are further conducted to form a three-dimensional conductive network, and the overall resistance of the coated fabric is remarkably reduced.
3. The CNTs graft structure formed on the surface of the long carbon fiber through chemical deposition can reduce the resistance generated by natural lapping of the CNTs and the main carbon fiber, after the CNTs and the main carbon fiber are blended into yarn, the long carbon fiber can be used as a framework of a conductive network, the deposited CNTs and the adsorbed CNTs can be lapped to form a branch conductive structure, and the branch conductive structure can be communicated with other main carbon fiber to form a three-dimensional conductive network;
4. by increasing the times of adsorbing the coating, the conductivity of the fabric is continuously improved; the conductivity of the fabric is continuously improved by increasing the concentration of the carbon nano tubes in the dispersion liquid; in the three fabric tissues, the plain structure has the optimal conductivity, and the 2+2 rib coating knitted fabric has the optimal sensing performance.
5. The inner layer and the outer layer of the fabric can be isolated after the silicon rubber matrix of the conductive sealing film is crosslinked, the stability of the water content of the starch-based water-absorbent resin can be kept, excessive water absorption expansion or drying water loss is prevented, the water content of a conductive medium is kept stable, the stability of the conductive sensing performance is maintained, meanwhile, the whole thickness of the fabric is increased after the conductive sealing film is coated, the silicon rubber is not conductive, if CNTs are not added, the resistance of the fabric is increased inevitably, therefore, the conductive sealing film is prepared from liquid CNTs-containing silicon rubber, the CNTs contained in the conductive sealing film can be conducted with the CNTs adsorbed in the fabric, a three-dimensional conductive network is formed by combining the CNTs grafted long carbon fibers in the yarn, and the problem of resistance increase caused by coating a film layer is solved.
Drawings
FIG. 1 is a scanning electron microscope picture of the cotton fabric finished in the step (4) when the concentration of the carbon nano tubes in the carbon nano tube dispersion liquid is 3mg/mL and the concentration of sodium dodecyl benzene sulfonate is 3 mg/mL;
FIG. 2 is a scanning electron microscope picture of the cotton fabric finished in the step (4) when the concentration of the carbon nano tubes in the carbon nano tube dispersion liquid is 6mg/mL and the concentration of sodium dodecyl benzene sulfonate is 18 mg/mL;
FIG. 3 is a scanning electron microscope picture of the cotton fabric finished in the step (4) when the concentration of the carbon nanotubes in the carbon nanotube dispersion liquid is 11mg/mL and the concentration of sodium dodecylbenzenesulfonate is 22 mg/mL;
FIG. 4 is a scanning electron microscope image of the carbon nanotube coated fabric finished in steps (3) + (4) in example 2;
FIG. 5 is a scanning electron microscope image of the carbon nanotube coated fabric finished in step (3). times.3 + (4) in example 2;
FIG. 6 is a scanning electron microscope image of the carbon nanotube coated fabric finished in step (3). times.5 + (4) in example 2;
FIG. 7 is a strain sensing curve of a plain cotton fabric finished in the steps (3) + (4) in example 1;
FIG. 8 is a strain sensing curve of 1+1 rib cotton fabric finished in the steps (3) + (4) in example 1;
FIG. 9 is a strain sensing curve of 2+2 rib cotton fabric finished in the steps (3) + (4) in example 1;
Detailed Description
The following examples are included to provide further detailed description of the present invention and to provide those skilled in the art with a more complete, concise, and exact understanding of the principles and spirit of the invention.
Example 1: the CNTs coating sensing fabric is prepared by the following method:
firstly, preparing and preparing raw materials:
the preparation method of the CNTs grafted long carbon fiber comprises the following steps:
(A) placing the PAN-based carbon fiber in a CVD furnace, and calcining for 1h at 450 ℃ under the protection of nitrogen to remove a surface sizing agent;
(B) modifying the surface of the desized carbon fiber by using an electrochemical anodic oxidation method: the electrolyte solution used was 5wt% NH4H2PO4 water solution, the wire moving speed is 30cm/min, the current is 0.3A, and the corresponding electrochemical treatment intensity is 70C/g respectively; and leading the carbon fibers into the electrolyte through the anode roller and the polytetrafluoroethylene guide roller, and leading the carbon fibers out through the second polytetrafluoroethylene roller to finish surface modification. The current density is changed by adjusting the voltage of a direct-current power supply, the modification time of the carbon fiber is changed by adjusting the wire moving speed, and the pretreatment process suitable for the T700 carbon fiber is optimized and determined.
(C) Washing the electrochemically modified carbon fiber sample with deionized water for 5min, drying at 120 deg.C for 10min, and introducing Co (NO) with final concentration of 0.05M3)2·6H2Soaking in O ethanol solution for 3min, guiding out, drying in a drying device at 80 deg.C for 10min, and collecting carbon fiber with catalyst coating by a filament collecting machine;
(D) putting the carbon fiber sample attached with the catalyst coating into an FRD-400-CVD deposition furnace, introducing 10L/min high-purity nitrogen, raising the furnace temperature to 450 ℃ at 10 ℃/min, and closing N2Introducing 10L/min hydrogen to reduce for 1h, heating the furnace temperature to 550 ℃ at the heating rate of 25 ℃/min, and introducing C2H2、H2And N2The mixed gas is subjected to vapor deposition for 10min at the introduction rate of C2H2/H2/N2＝6/6/12L/min；
(E) After the deposition is finished, C is closed2H2And H2And cooling the furnace temperature to room temperature under the protection of high-purity nitrogen of 10L/min to obtain the CNTs grafted long carbon fiber, wherein the air pressure in the furnace is constant at 0.02MPa in the whole reaction process.
The yarns adopted by the cotton fabrics are formed by blending CNTs grafted long carbon fibers and cotton fibers, the CNTs grafted long carbon fibers and the cotton fibers are blended according to the weight ratio of 1:3 to prepare the yarns, and the specific method refers to the method disclosed in the Chinese patent CN 101864631A. It should be noted that, in the present invention, the conductive fabric prepared by the dip-coating technique has no specific limitation and requirement on the material, size, shape, etc. of the substrate, and different choices are made according to specific situations, and may be a cotton fabric in the examples, or other cellulose fabrics or materials.
The silicone rubber is a Dow Corning Sylgard184PDMS silicone elastomer, the main component is polydimethylsiloxane, the silicone rubber is a two-component addition type silicone rubber, the two-component addition type silicone rubber comprises a liquid basic component A and a curing agent B, the A and the B are completely mixed according to the weight ratio of 10:1 to prepare solid silicone rubber, and metal platinum is used as a catalyst in the curing process of the A and the B, and exists in the B. At 25 deg.C, the density is 1.03g/cm3, and the volume resistivity is 2.9x 1014Omega/cm, dynamic viscosity of 3000 centipoises.
Secondly, preparing a CNTs coating sensing fabric:
(1) plain knitted cotton fabric (Ctn) with size of 10 × 10cm2The thickness is about 0.3mm, the degree of mesh is 70, the number of lines is 112, the fabric is dipped in 10g/L NaOH aqueous solution, the fabric is washed to be neutral after being processed by water bath at the constant temperature of 60 ℃, the surface of the fabric is clean, the adsorption of the carbon nano tube is facilitated after the alkali etching, and then the fabric is dried at the temperature of 60 ℃; the cotton fabric is woven by blended yarns of CNTs grafted long carbon fibers and cotton fibers; because the strain sensing needs larger deformation capacity, the knitted fabric with larger deformation capacity is selected as the fabric tissue, and the woven fabric is not selected.
(2) Preparing a carbon nano tube dispersion liquid: dissolving 0.2g of anhydrous starch-based water-absorbent resin in 50 mLN-methyl pyrrolidone to obtain a coating solution, heating to 60 ℃, dispersing carbon nanotubes in the coating solution, adding a surfactant, carrying out ultrasonic treatment for 30min at the final concentration ratio of the carbon nanotubes to the surfactant of 1:1, obtaining a dispersion solution at the ultrasonic treatment temperature of 30 ℃, and carrying out ultrasonic treatment to obtain a carbon nanotube dispersion solution; in the embodiment, the surfactant is sodium dodecyl benzene sulfonate; the sodium dodecyl benzene sulfonate is an anionic surfactant, can make the fabric surface affinity moisture, the ionic surfactant also has the conductive function at the same time, the final concentration of the carbon nanotube is 3mg/mL, the final concentration of the surfactant is 3 mg/mL;
(3) flatly paving the cotton fabric dried in the step (1) in a container containing the carbon nano tube dispersion liquid, soaking the cotton fabric in the carbon nano tube dispersion liquid at a bath ratio of 1:30, then carrying out constant-temperature vibration treatment for 5 hours for 30 minutes, wherein the vibration soaking temperature is 30 ℃, the vibration frequency is 80 times/minute, taking out the cotton fabric subjected to the vibration soaking treatment, and drying at the drying temperature of 60 ℃ for 1.5 hours;
(4) after the cotton fabric is dried to be absolute dry, exposing the cotton fabric to a constant temperature and humidity condition of 25 ℃ and 100 percent relative humidity, and absorbing moisture for 1 hour until the water content is 2 weight percent;
(5) uniformly coating CNTs-containing silicon rubber on the upper surface layer and the lower surface layer of the cotton fabric after moisture absorption to form a conductive sealing film, and obtaining the CNTs coating sensing fabric with different fabric textures, wherein the specific preparation method of the conductive sealing film comprises the following steps:
(a) the carbon nano tube and PDMS are compounded by adopting a solution mixing method and assisting ultrasonic dispersion to prepare the composite conductive material. Weighing 300mg of carbon nanotubes, adding the carbon nanotubes into 30m of 1 toluene solvent, stirring for 5min on a magnetic stirrer, ultrasonically dispersing for 30min in an ultrasonic cleaning machine, then adding 10g of the component A of the silicone rubber, magnetically stirring for 5min, ultrasonically dispersing for 30min, then adding 1g of the component B of the curing agent of the silicone rubber according to the mass ratio of 10:1, magnetically stirring for 5min, ultrasonically dispersing for 30min, and standing for 10min to obtain liquid silicone rubber containing CNTs;
(b) uniformly coating the CNTs-containing silicon rubber on the upper surface layer and the lower surface layer of the cotton fabric after moisture absorption, wherein the single-side coating amount is 100g/m2And horizontally placing the composite film in a vacuum oven with the relative vacuum degree of 0.05Mpa for removing bubbles and organic solvent toluene in the PDMS/carbon nanotube composite film, setting the temperature to be 40 ℃, taking out the composite film after 40min, horizontally placing the composite film in a fume hood for 12h to completely volatilize toluene, and finally horizontally placing the composite film in a constant-temperature blast drying oven with the temperature of 35 ℃ for curing for 4h to obtain a smooth and flat conductive sealing film without bubbles on the surface of the cotton fabric.
Example 2: the CNTs coating sensing fabric is prepared by the following method:
firstly, preparing and preparing raw materials:
the preparation method of the CNTs grafted long carbon fiber is the same as that of the embodiment 1 except that: the wire moving speed is 40cm/min, the current is 0.5A, and the corresponding electrochemical treatment intensity is 150C/g respectively;
the cotton fabric is prepared by blending CNTs grafted long carbon fiber and cotton fiber in a weight ratio of 1: 5.
The silicone rubber material was the same as in example 1.
Secondly, preparing a CNTs coating sensing fabric:
(1) 1+1 rib cotton fabric (Ctn) with the size of 10 multiplied by 10cm2The thickness is about 0.3mm, the degree of mesh is 70, the number of lines is 112, the fabric is immersed in 10g/L KOH aqueous solution, the fabric is washed to be neutral after being processed by water bath at the constant temperature of 70 ℃, the surface of the fabric is clean, and the fabric is dried at 80 ℃ after being beneficial to the adsorption of the carbon nano tube after being subjected to alkali etching; the cotton fabric is woven by blended yarns of CNTs grafted long carbon fibers and cotton fibers; because the strain sensing needs larger deformation capacity, the knitted fabric with larger deformation capacity is selected as the fabric tissue, and the woven fabric is not selected.
(2) Preparing a carbon nano tube dispersion liquid: dissolving 1.0g of anhydrous starch-based water-absorbent resin in 50 mLN-methyl pyrrolidone to obtain a coating solution, heating to 60 ℃, dispersing carbon nanotubes in the coating solution, adding a surfactant, carrying out ultrasonic treatment for 90min at the final concentration ratio of the carbon nanotubes to the surfactant of 1:3, obtaining a dispersion solution at the ultrasonic treatment temperature of 60 ℃, and carrying out ultrasonic treatment to obtain a carbon nanotube dispersion solution; in the embodiment, the surfactant is dodecyl benzene sulfonic acid; the final concentration of the carbon nano tube is 6mg/mL, and the final concentration of the surfactant is 18 mg/mL;
(3) flatly paving the cotton fabric dried in the step (1) in a container containing the carbon nano tube dispersion liquid, soaking the cotton fabric in the carbon nano tube dispersion liquid at a bath ratio of 1:40, then carrying out constant-temperature vibration treatment for 5 hours for 30 minutes, wherein the vibration soaking temperature is 60 ℃, the vibration frequency is 80 times/minute, taking out the cotton fabric subjected to the vibration soaking treatment, and drying at 80 ℃ for 2 hours;
(4) after the cotton fabric is dried completely, exposing the cotton fabric to a constant temperature and humidity condition of 25 ℃ and 100 percent relative humidity, and absorbing moisture for 10 hours until the water content is 5 weight percent;
(5) and uniformly coating the upper surface layer and the lower surface layer of the cotton fabric after moisture absorption with CNTs-containing silicon rubber to form a conductive sealing film, thus obtaining the CNTs coating sensing fabric with different fabric textures, wherein the specific preparation method of the conductive sealing film is the same as that of the embodiment 1.
Example 3: the CNTs coating sensing fabric is prepared by the following method:
firstly, preparing and preparing raw materials:
the preparation method of the CNTs grafted long carbon fiber is the same as that of the embodiment 1 except that: the wire moving speed is 35cm/min, the current is 0.4A, and the corresponding electrochemical treatment intensity is 110C/g respectively;
the cotton fabric is prepared by blending CNTs grafted long carbon fiber and cotton fiber in a weight ratio of 1: 4.
The silicone rubber material was the same as in example 1.
Secondly, preparing a CNTs coating sensing fabric:
(1) 2+2 rib cotton fabric (Ctn) with the size of 10 multiplied by 10cm2The thickness is about 0.3mm, the degree of mesh is 70, the number of lines is 112, the fabric is dipped in 10g/L NaOH aqueous solution, the fabric is washed to be neutral after being processed by water bath at the constant temperature of 65 ℃, the surface of the fabric is clean, the adsorption of the carbon nano tube is facilitated after the alkali etching, and then the fabric is dried at the temperature of 70 ℃; the cotton fabric is woven by blended yarns of CNTs grafted long carbon fibers and cotton fibers; because the strain sensing needs larger deformation capacity, the knitted fabric with larger deformation capacity is selected as the fabric tissue, and the woven fabric is not selected.
(2) Preparing a carbon nano tube dispersion liquid: dissolving 0.6g of anhydrous starch-based water-absorbent resin in 50 mLN-methyl pyrrolidone to obtain a coating solution, heating to 60 ℃, dispersing carbon nanotubes in the coating solution, adding a surfactant, carrying out ultrasonic treatment for 60min at a final concentration ratio of the carbon nanotubes to the surfactant of 1:2, obtaining a dispersion solution at an ultrasonic treatment temperature of 45 ℃, and carrying out ultrasonic treatment to obtain a carbon nanotube dispersion solution; in the embodiment, the surfactant is sodium dodecyl benzene sulfonate; the final concentration of the carbon nano tube is 11mg/mL, and the final concentration of the surfactant is 22 mg/mL;
(3) flatly paving the cotton fabric dried in the step (1) in a container containing the carbon nano tube dispersion liquid, soaking the cotton fabric in the carbon nano tube dispersion liquid at a bath ratio of 1:35, then carrying out constant-temperature vibration treatment for 5 hours for 30 minutes, wherein the vibration soaking temperature is 45 ℃, the vibration frequency is 80 times/minute, taking out the cotton fabric subjected to the vibration soaking treatment, and drying at the drying temperature of 70 ℃ for 1.8 hours;
(4) after the cotton fabric is dried to be absolute dry, exposing the cotton fabric to a constant temperature and humidity condition of 25 ℃ and 100 percent relative humidity, and absorbing moisture for 5 hours until the water content is 3.5 percent by weight;
(5) and uniformly coating the upper surface layer and the lower surface layer of the cotton fabric after moisture absorption with CNTs-containing silicon rubber to form a conductive sealing film, thus obtaining the CNTs coating sensing fabric with different fabric textures, wherein the specific preparation method of the conductive sealing film is the same as that of the embodiment 1.
Example 4: the rest was the same as example 2 except that the step (3) was repeated five times in a cycle.
Comparative example 1: the rest was the same as example 3 except that no anhydrous starch-based water-absorbent resin was added in the step (2) and the moisture absorption step was omitted.
Comparative example 2: the rest is the same as the example 3, except that the fabric tissue does not adopt CNTs grafted long carbon fiber and cotton fiber blended yarns, and only adopts the ungrafted ordinary PAN-based carbon fiber and cotton fiber to prepare the fabric.
Comparative example 3: the rest was the same as example 3 except that the step (5) was omitted and the conductive seal film was not prepared.
Comparative example 4: the rest was the same as example 3 except that the conductive sealing film was prepared only from Dow Corning Sylgard184PDMS silicone rubber, with no CNTs added.
Respectively weighing and comparing the dry cotton fabric product obtained in the step (3) in the embodiments 1 to 3 with the dry cotton fabric product obtained in the step (1), calculating the weight gain ratio of the fabric, and investigating the influence of different carbon nanotube dispersion liquid preparation parameters on the carbon nanotube adsorbed by the cotton fabric and the coating (starch-based water-absorbent resin), wherein the results are shown in table 1:
TABLE 1 adsorption of carbon nanotubes and coatings on cotton fabrics with different carbon nanotube dispersion solution preparation parameters
Group of Fabric weight gain (%)
Example 1 5.47
Example 2 5.74
Example 3 5.94
Example 4 7.79
Comparing example 4 with example 3, it can be seen that the adsorption amount of the carbon nanotubes and the coating material can be effectively increased by repeating the adsorption operation of the carbon nanotubes, and other parameters also have an influence on the adsorption effect, but have a small influence.
Taking the final concentration of the carbon nanotubes and the surfactant in the carbon nanotube dispersion liquid as a variable, operating to the step (4) according to the method of the embodiment 3, carrying out electron microscope scanning detection on the surface of the carbon nanotube coated fabric finished by the method in the step (4) and measuring the resistance value:
when the concentration of the carbon nano tube dispersion liquid is 3mg/ml and the concentration of the sodium dodecyl benzene sulfonate is 3mg/ml, the surface electron microscope photo of the cotton fabric is shown in figure 1, and the measured resistance of the finished cotton fabric is 84.17-91.40 kOmega.
When the concentration of the carbon nano tube dispersion liquid is 6mg/ml and the concentration of the sodium dodecyl benzene sulfonate is 18mg/ml, the surface electron microscope photo of the cotton fabric is shown in figure 2, and the measured resistance of the finished cotton fabric is 39.33-51.68 kOmega.
When the concentration of the carbon nano tube dispersion liquid is 11mg/ml and the concentration of the sodium dodecyl benzene sulfonate is 22mg/ml, the surface electron microscope photo of the cotton fabric is shown in figure 3, and the measured resistance of the finished cotton fabric is 25.15-29.38 kOmega.
The resistance test data is an average value calculated after 5 measurements.
It can be seen from fig. 1, 2 and 3 that, when the concentration of the carbon nanotubes is higher, the content of the carbon nanotubes attached to the surface of the fiber is higher, the distribution range on the fiber is wider, and the conductivity is improved. The results of the fabric weight gain in table 1 are also verified here, the carbon nanotubes and the coating are adsorbed on the surface and inside of the fiber, the surface adsorption amount is positively correlated to the overall weight gain of the fabric, the carbon nanotubes and the coating on the surface of the fiber can be used as conductive media after absorbing water, and the CNTs and CNTs grafted long carbon fibers are conducted to form a conductive network, so that the overall resistance of the coated fabric is significantly reduced, therefore, the surface adsorption amount is negatively correlated to the resistance, and further, the overall adsorption amount is negatively correlated to the resistance.
Taking the number of times of repeating the operation step (3) as a variable, operating to the step (4) according to the method of the embodiment 2, carrying out electron microscope scanning detection on the surface of the carbon nanotube coated fabric finished in the step (4) and measuring the resistance value, wherein the results are as follows:
and (3) performing surface electron microscope photos of the finished carbon nanotube coated fabric in the single step (3) as shown in figure 4, and measuring the resistance of the finished cotton fabric to be 54.55-66.40 k omega.
And (3) repeatedly carrying out the step (3) for three times, wherein an electron microscope photograph of the surface of the finished carbon nanotube coated fabric is shown in fig. 5, and the resistance of the finished cotton fabric is measured to be 28.47-40.87 k omega.
And (3) repeating the step (3) five times, wherein the surface electron microscope photo of the finished carbon nanotube coated fabric is shown in fig. 6, and the resistance of the finished cotton fabric is 11.09-13.26 k omega. The resistance test data is an average value calculated after 5 measurements.
It can be seen from fig. 4, 5 and 6 that, when the number of times of coating is increased, the content of the carbon nanotubes attached to the surface of the fiber is increased, the distribution range on the fiber is widened, and the conductivity is improved.
The results of fig. 4, 5 and 6 show that the finishing steps with different repetition times can gradually increase the adsorption amount on the surface of the fiber and gradually decrease the fabric resistance, which is mutually verified with the results of fig. 1 to 3 and table 1.
Taking different fabric textures as variables, operating to the step (4) according to the method in the embodiment 1, carrying out electron microscope scanning detection on the surface of the carbon nanotube coated fabric finished by the method in the step (4) and measuring the resistance value:
the strain sensing curve of the plain-stitch-structure fabric obtained after finishing in the steps 3 and 4 in the embodiment 1 is shown in fig. 7, and the measured resistance of the finished cotton fabric is 29773.92-31001.48 omega.
The dynamic sensing curve of the 1+1 rib structure fabric obtained after finishing in the steps 3 and 4 in the embodiment 1 is shown in fig. 8, and the measured resistance of the finished cotton fabric is 61002.06-67133.29 omega.
The dynamic sensing curve of the 2+2 rib structure fabric obtained after finishing in the steps 3 and 4 in the embodiment 1 is shown in fig. 9, and the measured resistance of the finished cotton fabric is 40267.25-46862.18 omega.
It can be seen from fig. 7, 8 and 9 that, in the three fabric textures prepared under the same preparation condition, the plain stitch structure has the best conductivity, and the 2+2 rib coating knitted fabric has the best sensing performance.
The resistance test data is an average value calculated after 5 measurements.
The electrical resistance values of the CNTs coated sensing fabrics prepared in examples 1-4 and comparative examples 1-2 were measured 5 times for each sample, and the results are shown in Table 2:
TABLE 2 Effect of different preparation techniques on the resistance of fabrics
Group of Fabric resistance (omega/sq)
Example 1 129.5±6.7
Example 2 152.8±8.3
Example 3 115.8±3.9
Example 4 39.5±5.1
Comparative example 1 459.7±12.8
Comparative example 2 945.2±8.7
In the results shown in table 2, the comparison of the resistance data of examples 1 to 3 with example 4 shows that the adsorption capacity of the carbon nanotubes and the starch-based water-absorbent resin as a coating is increased (see fig. 1 to 6), and the comparison of the resistance data of comparative example 1 with example 3 shows that the starch-based water-absorbent resin forms a water-containing conductive medium with sodium dodecylbenzenesulfonate after absorbing moisture, the water-containing conductive medium is coated on the carbon nanotubes and the long carbon fibers (see fig. 1 to 3), the lap-joint conductivity between the carbon nanotubes is significantly higher than that of the natural lap-joint form between the carbon nanotubes, and the CNTs, CNTs grafted long carbon fibers and the conductive sealing film are further conducted to form a three-dimensional conductive network, so that the overall resistance of the coated fabric is significantly reduced. The addition of the starch-based water-absorbent resin and the sodium dodecyl benzene sulfonate is also beneficial to the dispersion of the carbon nano tube and the prevention of agglomeration. The starch-based water-absorbent resin also has a strong moisture storage capacity, and does not cause rapid moisture escape due to temperature and humidity changes of the use environment (see table 4).
The comparison result of the embodiment 3 and the comparison example 1 shows that the fabric prepared by blending the long carbon fiber main body with the yarn after the CNTs pre-grafting treatment is taken as the matrix can obviously reduce the overall resistance of the fabric and improve the electric conduction capability, mainly because the CNTs grafting structure formed on the surface of the long carbon fiber through chemical deposition can reduce the resistance generated by the natural lap joint of the CNTs and the carbon fiber main body, after the yarn is blended, the long carbon fiber can be taken as the framework of the electric conduction network, the deposited CNTs can be lap jointed with the adsorbed CNTs to form a branch electric conduction structure, and the branch electric conduction structure can be communicated with other long carbon fiber main bodies or electric conduction sealing films to form a three-dimensional electric conduction network.
The coated sensing fabric was prepared according to the method of example 2 with the moisture content of the fabric as a variable, and the conductive ability of the fabric was measured, and the results are shown in table 3.
TABLE 3 Effect of Fabric moisture content on Fabric resistance
Fabric moisture content (wt%) Fabric resistance (omega/sq)
1.0 335.4±9.4
1.5 310.7±8.1
2.0 262.8±5.6
2.5 211.3±4.9
3.0 174.4±6.7
3.5 148.7±6.1
4.0 126.2±3.8
4.5 121.2±2.7
5.0 118.6±6.4
5.5 116.7±7.7
6.0 119.2±5.6
The results in table 3 show that the resistance of the fabric decreases with the increase of the water content of the fabric, the resistance decreases significantly when the water content is 2-5 wt%, and the resistance of the fabric changes insignificantly when the water content is higher than 5 wt%. The main effect of the water-containing conductive medium is that the CNTs are lapped and communicated after water absorption and expansion to form a conductive network, and the conductivity mainly depends on the CNTs and carbon fibers, so that the influence of the water content on the conductivity is reduced after the network lapping is finished.
The CNTs coated sensing fabric prepared in example 3 and comparative example 3 was exposed to the same daily indoor environment, and the overall resistance of the fabric was measured every 2d for 20d, 5 times for each resistance measurement, and the results are shown in table 4:
TABLE 4 stability evaluation of conductive Capacity of coated Fabric
Figure BDA0002222344550000111
Figure BDA0002222344550000121
The results in table 4 show that the fabric resistance of the coated fabric prepared by the invention has little change under different temperature and humidity conditions, and the conductive capability is not influenced by the fluctuation of the ambient temperature and humidity, while the resistance of the conductive fabric prepared by the comparative example 3 is greatly influenced by the ambient temperature and humidity, the fluctuation is also large, and the conductive stability is obviously lower than that of the example 3. Mainly because the conduction and the construction of a three-dimensional conductive network are carried out by adopting a water-containing conductive medium, the water content of the fabric becomes an important index influencing the conductive capability, and how to keep the stability of the water content of the fabric unchanged becomes an important technical problem to be solved, because the temperature and the humidity in the daily use environment can be changed constantly, if no conductive sealing film exists, the water content in the fabric can be fluctuated constantly, and the change of the water content can obviously influence the conductive capability of the fabric according to the table 3, therefore, a flexible silicon rubber is needed to be adopted to prepare a sealing film on the surface layer of the fabric, the silicon rubber matrix of the conductive sealing film can isolate the inner layer and the outer layer of the fabric after being crosslinked, the stability of the water content of the starch-based water-absorbent resin can be kept, excessive water absorption expansion or drying and water loss are prevented, the water content of the conductive medium is kept stable, so that the stability of the conductive sensing performance is maintained, and the water content of the fabric is fixed, thereby stabilizing the conductive ability of the fabric in the use environment.
The thickness and resistance of the CNTs coated sensing fabric prepared in example 3 and comparative example 4 were measured, and the CNTs coated sensing fabric obtained from example 3 operating to step (4) was used as a blank control, and the results were as follows:
TABLE 5 Effect of conductive seal film on Fabric resistance
Group of Fabric thickness (mm) Fabric resistance (omega/sq)
Example 3 0.64 104.3±2.4
Comparative example 4 0.63 629.1±5.4
Blank control 0.39 284.8±8.7
In the above results, the fabric resistance of the blank control group is significantly smaller than that of the control example 4, while the fabric resistance of the example 3 is significantly lower than that of the blank control, because the whole thickness of the fabric is increased after the conductive sealing film is coated, and the silicone rubber is not conductive, if the CNTs are not added, the fabric resistance is inevitably increased, so that the CNTs-containing silicone rubber in a liquid state is used for preparing the conductive sealing film, the CNTs contained in the conductive sealing film can be conducted with the CNTs adsorbed in the fabric, and the CNTs grafted long carbon fibers in the yarns are combined to form a three-dimensional conductive network, thereby solving the problem of resistance increase caused by coating.
In conclusion, the flexible fabric sensor with better conductivity is prepared, the prepared coating fabric is thin and light, the conductivity effect is good, the thickness is controllable, the structure is adjustable, the requirement on the required experimental operation condition is simple, the energy consumption is low, expensive equipment is not needed, the production cost is low, and the flexible fabric sensor can be industrially produced on the traditional sizing or printing and dyeing equipment. The carbon nanotube coated fabric also has the characteristics of softness and comfort, and the defects of heavy weight and poor comfort of the traditional metal fiber fabric are avoided. The carbon nano tubes can be uniformly and densely adsorbed on the fabric by using a simple dipping-coating process, so that the conductive network on the surface of the fabric is dense, the surfaces of the CNTs, the CNTs grafted long carbon fibers and the cotton fibers are coated with the starch-based water-absorbent resin, after moisture absorption, the water-containing starch-based water-absorbent resin is used as a conductive medium, the CNTs grafted long carbon fibers and the conductive sealing film are further conducted to form a three-dimensional conductive network, and the overall resistance of the coated fabric is remarkably reduced. The CNTs graft structure formed on the surface of the long carbon fiber through chemical deposition can reduce the resistance generated by natural lapping of the CNTs and the main carbon fiber, after the CNTs and the main carbon fiber are blended into yarn, the long carbon fiber can be used as a framework of a conductive network, the deposited CNTs and the adsorbed CNTs can be lapped to form a branch conductive structure, and the branch conductive structure can be communicated with other main carbon fiber to form a three-dimensional conductive network; by increasing the times of adsorbing the coating, the conductivity of the fabric is continuously improved; the conductivity of the fabric is continuously improved by increasing the concentration of the carbon nano tubes in the dispersion liquid; in the three fabric tissues, the plain structure has the optimal conductivity, and the 2+2 rib coating knitted fabric has the optimal sensing performance. The inner layer and the outer layer of the fabric can be isolated after the silicon rubber matrix of the conductive sealing film is crosslinked, the stability of the water content of the starch-based water-absorbent resin can be kept, excessive water absorption expansion or drying water loss is prevented, the water content of a conductive medium is kept stable, the stability of the conductive sensing performance is maintained, meanwhile, the whole thickness of the fabric is increased after the conductive sealing film is coated, the silicon rubber is not conductive, if CNTs are not added, the resistance of the fabric is increased inevitably, therefore, the conductive sealing film is prepared from liquid CNTs-containing silicon rubber, the CNTs contained in the conductive sealing film can be conducted with the CNTs adsorbed in the fabric, a three-dimensional conductive network is formed by combining the CNTs grafted long carbon fibers in the yarn, and the problem of resistance increase caused by coating a film layer is solved.
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention cannot be limited thereby, and any modification made on the basis of the technical scheme according to the technical idea proposed by the present invention falls within the protection scope of the present invention; the technology not related to the invention can be realized by the prior art.

Claims (8)

1. A preparation method of a CNTs coating sensing fabric based on different fabric textures is characterized by comprising the following steps:
(1) soaking cotton fabrics with different fabric textures in alkali liquor, performing water bath constant temperature treatment, washing to be neutral, and then drying; the cotton fabric is woven by blended yarns of CNTs grafted long carbon fibers and cotton fibers;
(2) preparing a carbon nano tube dispersion liquid: dissolving 0.2-1.0 g of anhydrous starch-based water-absorbent resin in 50 mLN-methyl pyrrolidone to obtain a coating solution, heating to 60 ℃, dispersing carbon nanotubes in the coating solution, adding a surfactant, wherein the final concentration ratio of the carbon nanotubes to the surfactant is 1: 1-3, and performing ultrasonic treatment to obtain a carbon nanotube dispersion solution;
(3) flatly paving the cotton fabric dried in the step (1) in a container containing the carbon nano tube dispersion liquid, then carrying out constant-temperature oscillation treatment on the cotton fabric for 5 hours, and taking out and drying the cotton fabric subjected to the oscillation impregnation treatment;
(4) after drying, under the conditions of constant temperature and constant humidity of 25 ℃ and 100% relative humidity, absorbing moisture for 1-10 hours until the water content is 1-5 wt%;
(5) uniformly coating CNTs-containing silicon rubber on the upper surface layer and the lower surface layer of the cotton fabric after moisture absorption to form a conductive sealing film, so as to obtain CNTs coating sensing fabrics with different fabric tissues;
the preparation method of the CNTs grafted long carbon fiber comprises the following steps:
(A) placing the PAN-based carbon fiber in a CVD furnace, and calcining for 1h at 450 ℃ under the protection of nitrogen to remove a surface sizing agent;
(B) modifying the surface of the desized carbon fiber by using an electrochemical anodic oxidation method: the electrolyte solution used was 5wt% NH4H2PO4The wire feeding speed of the aqueous solution is 40cm/min, the current is 0.3-0.5A, and the corresponding electrochemical treatment strength is 70-150C/g respectively;
(C) washing the electrochemically modified carbon fiber sample with deionized water for 5min, drying at 120 deg.C for 10min, and introducing Co (NO) with final concentration of 0.05M3)2· 6H2Soaking in O ethanol solution for 3min, guiding out, drying in a drying device at 80 deg.C for 10min, and collecting carbon fiber with catalyst coating by a filament collecting machine;
(D) putting the carbon fiber sample attached with the catalyst coating into an FRD-400-CVD deposition furnace, introducing 10L/min high-purity nitrogen, raising the furnace temperature to 450 ℃ at 10 ℃/min, and closing N2Introducing 10L/min hydrogen to reduce for 1h, heating the furnace temperature to 550 ℃ at the heating rate of 25 ℃/min, and introducing C2H2、H2And N2The mixed gas is subjected to vapor deposition for 10min at the introduction rate of C2H2/H2/N2=6/6/12L/min；
(E) After the deposition is finished, C is closed2H2And H2And cooling the furnace temperature to room temperature under the protection of high-purity nitrogen of 10L/min to obtain the CNTs grafted long carbon fiber, wherein the air pressure in the furnace is constant at 0.02MPa in the whole reaction process.
2. The method for preparing the CNTs coating sensing fabric based on different fabric textures as the claim 1 is characterized in that: the preparation method of the conductive sealing film comprises the following steps:
(a) weighing 300mg of carbon nanotube, adding the carbon nanotube into 30m of 1 toluene solvent, stirring for 5min on a magnetic stirrer, then ultrasonically dispersing for 30min in an ultrasonic cleaning machine, then adding 10g of component A of Dow Corning Sylgard184PDMS silicone elastomer, magnetically stirring for 5min, ultrasonically dispersing for 30min, then adding 1g of component B of silicone rubber curing agent according to the mass ratio of 10:1, magnetically stirring for 5min, ultrasonically dispersing for 30min, and standing for 10min to obtain the silicone rubber containing CNTs;
(b) uniformly coating the CNTs-containing silicon rubber on the upper surface layer and the lower surface layer of the cotton fabric after moisture absorption, horizontally placing the cotton fabric in a vacuum oven with the relative vacuum degree of 0.05Mpa and the temperature of 40 ℃, taking out the cotton fabric after 40min, horizontally placing the cotton fabric in a fume hood for 12h to thoroughly volatilize toluene, and finally horizontally placing the cotton fabric in a constant-temperature blast drying oven with the temperature of 35 ℃ to cure for 4h to obtain a smooth and flat conductive sealing film without bubbles on the surface of the cotton fabric.
3. The method for preparing the CNTs coating sensing fabric based on different fabric textures as the claim 1 or 2, is characterized in that the different fabric textures are plain needle, 1+1 rib and 2+2 rib respectively; the alkali liquor is NaOH solution, and the concentration of the NaOH solution is 10 g/L; the water bath constant temperature treatment temperature in the step (1) is 60-70 ℃; the drying temperature in the step (1) is 60-80 ℃.
4. The method for preparing the CNTs coating sensing fabric based on different fabric textures as claimed in claim 3, wherein the surfactant in the step (2) is sodium dodecyl benzene sulfonate; the final concentration of the carbon nano-tubes in the step (2) is 3-11 mg/mL, the final concentration of the surfactant is 3-22 mg/mL, the ultrasonic treatment time is 30-90 min, and the ultrasonic treatment temperature is 30-60 ℃.
5. The method for preparing the CNTs coating sensing fabric based on different fabric textures as claimed in claim 4, wherein the bath ratio of the cotton fabric soaked in the carbon nanotube dispersion liquid in the step (3) is 1: 30-1: 40.
6. The method for preparing the CNTs coating sensing fabric based on different fabric textures as claimed in claim 1, wherein the temperature of the oscillatory immersion in the step (3) is 30-60 ℃ and the time is 30 min.
7. The method for preparing the CNTs coating sensing fabric based on different fabric textures as claimed in claim 1, wherein the drying temperature in the step (3) is 60-80 ℃, and the drying time is 1.5-2 h.
8. The method for preparing the CNTs coating sensing fabric based on different fabric textures as claimed in claim 1, further comprising the step of repeating step (3) circularly and then performing step (4).
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CN112376274B (en) * 2020-11-05 2022-11-25 武汉纺织大学 Strain sensing fabric and preparation method thereof
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102226089A (en) * 2011-04-14 2011-10-26 陕西杰邦铜接地科技有限公司 Soil improvement agent suitable for grounding works in high soil resistivity environments
CN104684975A (en) * 2012-09-28 2015-06-03 东丽株式会社 Prepreg and carbon fiber reinforced composite material
CN107988787A (en) * 2017-12-19 2018-05-04 安徽工程大学 A kind of preparation method for inhaling wave mode Electromagnetically shielding fabrics
CN109208333A (en) * 2018-09-05 2019-01-15 安徽工程大学 A method of it constructs and inhales wave mode Electromagnetism Shield Composite Coating fabric

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102226089A (en) * 2011-04-14 2011-10-26 陕西杰邦铜接地科技有限公司 Soil improvement agent suitable for grounding works in high soil resistivity environments
CN104684975A (en) * 2012-09-28 2015-06-03 东丽株式会社 Prepreg and carbon fiber reinforced composite material
CN107988787A (en) * 2017-12-19 2018-05-04 安徽工程大学 A kind of preparation method for inhaling wave mode Electromagnetically shielding fabrics
CN109208333A (en) * 2018-09-05 2019-01-15 安徽工程大学 A method of it constructs and inhales wave mode Electromagnetism Shield Composite Coating fabric

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