CN114739280A - Multi-element nano carbon fiber yarn strain sensor and preparation method thereof - Google Patents
Multi-element nano carbon fiber yarn strain sensor and preparation method thereof Download PDFInfo
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- CN114739280A CN114739280A CN202210296896.7A CN202210296896A CN114739280A CN 114739280 A CN114739280 A CN 114739280A CN 202210296896 A CN202210296896 A CN 202210296896A CN 114739280 A CN114739280 A CN 114739280A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
- G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
- G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
- G01B7/18—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge using change in resistance
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
Abstract
The invention discloses a multielement nanometer carbon fiber yarn strain sensor and a preparation method thereof. The preparation method is simple and reasonable, can prepare the conductive nano-fiber yarn with knitability and washability in a large scale, and the yarn can be directly used as a strain sensor. The yarn sensor can be directly woven or sewn into sports equipment such as clothes, wristbands and kneepads and other articles on human bodies, such as: the plaster is pasted on a human body and is used for detecting physiological information such as human body movement, respiration, heartbeat and the like.
Description
Technical Field
The invention belongs to the technical field of sensor materials, and particularly relates to a multielement nano carbon fiber yarn strain sensor and a preparation method thereof.
Background
The nanofiber yarn has the advantages of high length-diameter ratio, large surface area, small size and the like, and is widely applied to the fields of sensors, capacitors, generators and the like. These applications typically require good electrical conductivity of the nanofiber yarn. The method comprises the following steps: firstly, preparing polyurethane nanofiber yarn, and then spraying silver nanowire dispersion liquid on the surface of the yarn to prepare conductive composite nanofiber yarn; the method II comprises the following steps: firstly, dispersing graphene oxide in a spinning solution, preparing nano-fiber yarns by electrostatic spinning, and then sequentially soaking the yarns in ferric trichloride and pyrrole solution to obtain conductive nano-fiber yarns; the method comprises the following steps: graphene oxide was dispersed in the spinning solution and receiving bath of wet electrostatic spinning, respectively, and then reduced in hydrazine hydrate vapor to improve the conductivity of the nanofiber yarn. The above method generally requires more than two steps of processes and is complicated in operation, and the yarn itself is poor in uniformity and stability. Blending nanocarbon materials in a flexible matrix to build a stretchable conductive network is a common method for developing flexible strain sensors. For example: carbon black is dispersed in a rubber material, carbon nanotubes are dispersed in an organic silicon elastomer, graphene is dispersed in epoxy resin, and the like, so that the flexible sensor with resistance response to strain is prepared. Doping two structurally different nanocarbon materials, combining multiple processes, can improve the performance of flexible strain sensors, for example: the one-dimensional carbon nano tube and the two-dimensional graphene are compounded by two-step chemical vapor deposition, successive dip coating, vacuum extraction of the mixed dispersion liquid and other methods to construct a binary conductive network with a synergistic effect. However, the preparation process of the method is complex, the preparation process of the sensor is unstable, and the prepared sensor has no knittability and washability.
Therefore, the invention provides a multi-element nano carbon fiber yarn strain sensor and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a multielement nanometer carbon fiber yarn strain sensor and a preparation method thereof.
The invention adopts a technical scheme that:
a multi-component carbon nanofiber yarn strain sensor comprises nanofibers, wherein a multi-component conductive network formed by point-shaped carbon black, linear carbon nanotubes and flaky graphene in a mutually bridged mode is arranged inside the nanofibers, when the mass fraction of the carbon black is 0-35%, the mass fraction of the carbon nanotubes is 0-35%, the mass fraction of the graphene is 0-15%, the total mass fraction of the carbon black, the carbon nanotubes and the graphene is 15-35%, and the balance of components are thermoplastic polyurethane, the conductivity of the sensor is 3.59 multiplied by 10-60.212S/cm, the maximum detection strain is 93-439%, the sensitivity in the 100% strain range is 4.67-1258.3, the response time is less than 300ms, the response can be stably repeated for more than 5000 cycles, and the performance is kept unchanged after washing for more than 30 times.
The other technical scheme of the invention is as follows:
a preparation method of a multielement nanometer carbon fiber yarn strain sensor comprises the following steps:
(1) preparing a spinning solution: adding carbon black, carbon nano tubes, graphene and a dispersing agent with an anti-settling effect on nano carbon particles into a mixed solvent of dimethylformamide and tetrahydrofuran, stirring, performing ultrasonic dispersion, then adding thermoplastic polyurethane particles into a multi-element nano carbon dispersion liquid, stirring, and performing ultrasonic dispersion to obtain a spinning solution;
(2) preparing the nanofiber yarn: continuously preparing multi-element carbon nanofiber bundles from the spinning solution by using an electrostatic spinning device, and then combining, twisting and shaping the carbon nanofiber bundles to form multi-element carbon nanofiber yarns;
(3) preparing a sensor: intercepting the 3-10 cm multielement nanometer carbon fiber yarn, fixing two ends of the yarn between two pieces of 1cm multiplied by 2cm aluminum foil paper by conductive silver adhesive to form electrodes, waiting at normal temperature for the multielement nanometer carbon fiber yarn to be completely dried, packaging the aluminum foil electrodes by an insulating adhesive tape, and adjusting the length of the yarn used by the sensor according to a measuring range required to form the multielement nanometer carbon fiber yarn strain sensor.
Further, in the step (1), the dispersing agent is modified PVA or a nonionic surfactant containing an aromatic group.
Further, in the step (1), the stirring is carried out at a rotating speed of 200r/min for 12-24 hours at a temperature of 25 +/-5 ℃, the power of ultrasonic dispersion is 200-500W, and the time is 1-3 hours.
Further, in the step (1), the mass fraction of the tetrahydrofuran in the mixed solvent is 20% to 50%.
Further, in the step (1), the mass fraction of the thermoplastic polyurethane in the spinning solution is 8-12%.
Further, in the step (1), the total mass of the carbon black, the carbon nano tube and the graphene is 15-35% of the total mass of the solute, wherein the mass fraction of the carbon black is 0-35%, the mass fraction of the carbon nano tube is 0-35%, the mass fraction of the graphene is 0-15%, and the addition amount of the dispersant is 10-30% of the total mass of the carbon black, the carbon nano tube and the graphene.
Further, in the step (2), the feeding speed of the spinning solution is 2-10 ml/h, the working voltage is 26-40 kV, the auxiliary voltage is 20-34 kV, the distance between the tip of the spinning needle and the liquid level of the received bath solution is 20-30 cm, the collecting speed of the winding device is 80-160 m/h, the drying device is a normal-temperature air blower, and the relative humidity of the spinning environment is controlled to be below 35%.
Further, in the step (2), the number of the combined carbon nanofiber bundles in the multi-element carbon nanofiber yarn is 2-10, and the twist is 1000-3500 twist/m.
Further, in the step (2), the shaping method comprises the steps of placing boiling water in the lower layer of a double-layer vacuum oven, fixing the yarns on an iron plate, and then placing the yarns in the upper layer of the oven, wherein the shaping temperature is 120-150 ℃, and the shaping time is 0.5-2 hours.
The invention provides a multielement nanometer carbon fiber yarn strain sensor and a preparation method thereof, and the multielement nanometer carbon fiber yarn strain sensor has the advantages that: the preparation method is simple and reasonable, and the conductive nanofiber yarn with weavability and washability can be prepared in a large scale and can be directly used as a strain sensor. When the mass fractions of the carbon black, the carbon nanotube and the graphene are respectively 24%, 3% and 3%, the conductivity of the yarn sensor is 0.154S/cm, the maximum detection strain is 227%, the sensitivity in a 100% strain range is 17.7, the response time is 220ms, the yarn sensor can stably and repeatedly respond for more than 5000 cycles, and the performance is kept unchanged after washing for more than 30 times. The yarn sensor can be directly woven or sewn into sports equipment such as clothes, wristbands and knee pads and other articles on human bodies, such as: the plaster is pasted on a human body and is used for detecting physiological information such as human body movement, respiration, heartbeat and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive labor. Wherein the content of the first and second substances,
FIG. 1 is a schematic diagram of a spinning solution preparation process in a preparation method of a multi-component nano carbon fiber yarn strain sensor according to the invention;
FIG. 2 is a schematic diagram of a nanofiber yarn manufacturing process in the manufacturing method of a multi-component carbon nanofiber yarn strain sensor according to the present invention;
FIG. 3 is a schematic diagram of a sensor manufactured by the method for manufacturing a multi-component carbon nanofiber yarn strain sensor according to the present invention;
FIG. 4 is a test chart of the strain sensing performance of a ternary nano carbon fiber yarn strain sensor under monotonic stretching, which is prepared by the preparation method of the multielement nano carbon fiber yarn strain sensor;
FIG. 5 is a test chart of the strain sensing performance of a ternary carbon nanofiber yarn strain sensor under cyclic stretching, which is manufactured by the manufacturing method of the polynary carbon nanofiber yarn strain sensor;
FIG. 6 is a test chart of the static strain sensing performance and the response time of the multi-component nano carbon fiber yarn strain sensor according to the invention;
FIG. 7 is a test chart of the durability of a multi-component nano carbon fiber yarn strain sensor according to the present invention;
FIG. 8 is a test chart of washability of a multi-component nano carbon fiber yarn strain sensor according to the present invention;
FIG. 9 is a graph of a multi-component nano carbon fiber yarn strain sensor according to the present invention monitoring different joint movements;
FIG. 10 is a graph showing the monitoring of different motion amplitudes of the elbow joint by the multi-element nano carbon fiber yarn strain sensor according to the present invention;
FIG. 11 is a test chart of the strain sensing performance of a binary nano carbon fiber yarn strain sensor under monotonic tension prepared by the method for preparing the multi-element nano carbon fiber yarn strain sensor;
FIG. 12 is a test chart of the strain sensing performance of a binary nano carbon fiber yarn strain sensor under cyclic stretching prepared by the preparation method of the multi-element nano carbon fiber yarn strain sensor of the invention;
FIG. 13 is a test chart of the strain sensing performance of a single tensile lower unitary nano carbon fiber yarn strain sensor prepared by the method for preparing a multi-component nano carbon fiber yarn strain sensor according to the present invention;
fig. 14 is a test chart of the strain sensing performance of the unitary carbon nanofiber yarn strain sensor under cyclic stretching, which is prepared by the preparation method of the multi-component carbon nanofiber yarn strain sensor.
Detailed Description
The multielement nanometer carbon fiber yarn strain sensor provided by the invention is used for preparing high-conductivity nanometer fiber yarn by a one-step method, and can be directly used as a strain sensor to be applied to textiles, clothes and apparel and medical materials for detecting motion, physiological information and the like of a human body. It has the characteristics that: the inside of the nanofiber is provided with a multi-element conductive network formed by mutually bridging point-shaped carbon black, linear carbon nanotubes and flake graphene, and the sensor has the advantages of high conductivity, high strain, high stability, knittability, washability and the like. The performance of the sensor can be adjusted by the mass ratio of carbon black, carbon nanotubes and graphene. When the total mass fractions of the carbon black, the carbon nano tube and the graphene are respectively 15-35%, wherein the mass fraction of the carbon black is 0-35%, the mass fraction of the carbon nano tube is 0-35%, the mass fraction of the graphene is 0-15%, and the rest components are thermoplastic polyurethane, the conductivity of the sensor is 3.59 multiplied by 10 < -6 > to 0.212S/cm, the maximum detection strain is 93-439%, the sensitivity in a 100% strain range is 4.67-1258.3, the response time is less than 300ms, the sensor can stably and repeatedly respond for more than 5000 cycles, and the performance is kept unchanged after more than 30 times of washing. The yarn sensor can be directly woven or sewn into sports equipment such as clothes, wristbands, kneepads and the like and other objects on a human body to detect physiological information such as human body movement, respiration, heartbeat and the like.
The preparation method of the multielement nanometer carbon fiber yarn strain sensor comprises the following steps:
(1) preparing a spinning solution: adding carbon black, carbon nano tubes, graphene and any dispersing agent (such as modified PVA, non-ionic surfactant containing aromatic groups and the like) having an anti-settling effect on nano carbon particles into a mixed solvent of dimethylformamide and tetrahydrofuran, stirring at the temperature of 25 +/-5 ℃ and the rotating speed of 200r/min for 12-24 h, then performing ultrasonic dispersion with the power of 200-500W for 1-3 h, then adding thermoplastic polyurethane particles into a multi-element nano carbon dispersion liquid, stirring at the temperature of 25 +/-5 ℃ and the rotating speed of 200r/min for 12-24 h, then performing ultrasonic dispersion with the power of 200-500W for 1-3 h, wherein the mass fraction of tetrahydrofuran in the mixed solvent is 20-50%, the mass fraction of thermoplastic polyurethane in the spinning liquid is 8-12%, and the total mass fraction of nano carbon materials in the solute is 15-35%, wherein, the mass fraction of the carbon black is 0-35%, the mass fraction of the carbon nano tube is 0-35%, the mass fraction of the graphene is 0-15%, and the adding mass of the dispersing agent is 10-30% of the total mass of the carbon black, the carbon nano tube and the graphene.
(2) Preparing nano fiber yarns: and continuously preparing the spinning solution into multi-element carbon nanofiber bundles by adopting an electrostatic spinning device, and then combining, twisting and shaping the nano carbon fiber bundles to form the multi-element carbon nanofiber yarn. The feeding speed of the spinning solution is 2-10 ml/h, the working voltage is 26-40 kV, the auxiliary voltage is 20-34 kV, the distance between the tip of a spinning needle and the liquid level of the received bath solution is 20-30 cm, the collecting speed of a winding device is 80-160 m/h, a drying device is a normal-temperature air blower, and the relative humidity of the spinning environment is controlled below 35%. The number of the combined nanofiber bundles in the nanofiber yarn is 2-10, the twist is 1000-3500 twists/m, the setting temperature is 120-150 ℃, and the setting time is 0.5-2 h. The sizing method comprises the steps of placing boiling water in the lower layer of a double-layer vacuum oven, fixing yarns on an iron plate, and then placing the yarns in the upper layer of the oven.
(3) Preparing a sensor: intercepting 3-10 cm of multi-element carbon nanofiber yarn, fixing two ends of the yarn between two pieces of 1 cm-2 cm aluminum foil paper by using conductive silver adhesive to form electrodes, and packaging the aluminum foil electrodes by using an insulating tape after the yarn is completely dried at normal temperature. The length of the yarn used by the sensor can be adjusted according to the range to be measured.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are further described below. The invention is not limited to the embodiments listed but also comprises any other known variations within the scope of the invention as claimed.
First, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The present invention is described in detail by using the schematic structural diagrams, etc., and for convenience of illustration, the schematic diagrams are not enlarged partially according to the general scale when describing the embodiments of the present invention, and the schematic diagrams are only examples, which should not limit the scope of the present invention. In addition, the actual fabrication process should include three-dimensional space of length, width and depth.
Example 1
A preparation method of a multielement nano carbon fiber yarn strain sensor comprises the following steps:
(1) preparation of ternary nanocarbon spinning solution
The process of preparing the spinning dope is shown in FIG. 1. Adding 0.686g of conductive carbon black, 0.086g of multi-walled carbon nanotube, 0.086g of single-layer graphene and 0.17g of dispersing agent into a mixed solvent containing 15.49g of dimethylformamide and 3.87g of tetrahydrofuran, fully stirring at room temperature by using a magnetic stirrer, then performing ultrasonic dispersion, then adding 2g of thermoplastic polyurethane particles into the dispersion liquid, stirring again until the particles are completely dissolved, and performing ultrasonic dispersion to obtain the uniform carbon black/carbon nanotube/graphene/polyurethane composite spinning liquid. The mass fraction of polyurethane in the spinning solution is 9%, the mass fraction of carbon black in the solute is 24%, the mass fraction of carbon nano tubes is 3%, and the mass fraction of graphene is 3%.
(2) Preparation of ternary carbon nanofiber yarn
See fig. 2 for a process of making nanofiber yarn. Preparing a carbon black/carbon nano tube/graphene/polyurethane composite nanofiber bundle by using an electrostatic spinning device, and preparing the carbon black/carbon nano tube/graphene/polyurethane composite nanofiber yarn through the processes of combination, twisting and shaping. Wherein the spinning flow rate is 3ml/h, the working voltage is 26kV, the auxiliary voltage is 20kV, the receiving distance is 20cm, the winding speed is 80m/h, the number of combined threads is 10, the twist number is 1000 twists/m, the setting temperature is 120 ℃, and the setting time is 0.5 h. When the mass fraction of the carbon black is 24%, the mass fraction of the carbon nano tube is 3% and the mass fraction of the graphene is 3%, the performances of the ternary carbon nanofiber yarn are shown in table 1, it can be known from the table that the conductivity of the yarn is far higher than the standard of the conductive fiber, and the mechanical properties meet the requirements of textile processing.
| Conductivity (S/cm) | strength/MPa | Elongation/% of |
| 0.154 | 60.86 | 233 |
TABLE 1
(3) Preparation of the sensor
Cutting four pieces of 1cm × 2cm aluminum-foil paper, coating conductive silver adhesive on two ends of the yarn, fixing the yarn between the two pieces of aluminum-foil paper, and completely drying at room temperature to form electrodes with a distance of 2cm, wherein the schematic diagram of the sensor is shown in fig. 3.
(4) Strain sensing performance of sensor
The results of the strain sensing performance of the sensor that was monotonically stretched to failure are shown in fig. 4, and the results of the strain sensing performance of the sensor that was prestretched and then cyclically stretched 10 times in the range of 30% strain are shown in fig. 5, and the maximum detectable strain of the sensor was 227%, and the coefficient of sensitivity in the range of 100% strain was 17.74.
(5) Static strain sensing performance and response time of sensor
And performing quasi-transient step-by-step strain test on the sensor, wherein the tensile strain range is 0-100%, each strain level is kept for 10s, and the strain interval is 5%. The test results shown in fig. 6 indicate that: in the strain range below 60%, the resistance of the sensor decreases in the quiescent state after being stretched; when the strain is greater than 60%, the resistance of the sensor is almost unchanged in a static state; the response time of the sensor is 220 ms.
(6) Durability of sensor
The test results of the strain sensing performance of the sensor which is stretched in the 30% strain range for 5000 times in a circulating mode refer to fig. 7, and the results show that the sensor shows the same resistance response in 1000-1003 cycles and 4000-4003 cycles, and has excellent fatigue resistance, stability and repeatability.
(7) Washability of sensor
The sensor is washed 30 times in a sample dyeing machine at 40 ℃ by using a conventional cleaning agent, and the test result of the strain sensing performance of the sensor after being dried after each 10 times of washing is shown in figure 8, and the result shows that the strain sensing performance of the sensor is almost unchanged from that before being washed after 10, 20 and 30 times of washing, and the sensor has excellent washability.
(8) Sensor's programmability and monitoring human motion signal
The sensor is sewed into the plaster by an embroidery needle and is stuck on the skin surface of each joint of a human body to study the monitoring capability of the sensor on joint movement. The results of monitoring the movements of different joints by the sensor shown in fig. 9 and the movements of different amplitudes of elbow joints by the sensor shown in fig. 10 show that the sensor can be easily sewed into a plaster, shows excellent flexibility and knittability, can capture the deformation of human skin during the movement of joints, and has good stability and can accurately distinguish the movements of different joints and different movement amplitudes.
Example 2
A preparation method of a multielement nanometer carbon fiber yarn strain sensor comprises the following steps:
(1) preparation of ternary nanocarbon spinning solution
Adding 0.89g of conductive carbon black, 0.092g of multi-walled carbon nanotube, 0.092g of single-layer graphene and 0.32g of dispersing agent into a mixed solvent containing 17.54g of dimethylformamide and 4.38g of tetrahydrofuran, fully stirring at room temperature by using a magnetic stirrer, then performing ultrasonic dispersion, then adding 2g of thermoplastic polyurethane particles into the dispersion liquid, stirring again until the particles are completely dissolved, and performing ultrasonic dispersion to obtain the uniform carbon black/carbon nanotube/graphene/polyurethane composite spinning solution. The mass fraction of polyurethane in the spinning solution is 8%, the mass fraction of carbon black in the solute is 29%, the mass fraction of carbon nano tubes is 3%, and the mass fraction of graphene is 3%.
(2) Preparation of ternary carbon nanofiber yarn
Preparing a carbon black/graphene/polyurethane composite nanofiber bundle by using an electrostatic spinning device, and preparing the carbon black/graphene/polyurethane composite nanofiber yarn through the processes of merging, twisting and shaping. Wherein the spinning flow rate is 2ml/h, the working voltage is 38kV, the auxiliary voltage is 32kV, the receiving distance is 28cm, the winding speed is 100m/h, the number of combined yarns is 7, the twist number is 1500 twists/m, the setting temperature is 120 ℃, and the setting time is 2 h. When the mass fraction of the carbon black is 29%, the mass fraction of the carbon nanotubes is 3%, and the mass fraction of the graphene is 3%, the properties of the ternary carbon nanofiber yarn are shown in table 2, and it can be known from comparison between table 2 and table 1 that the conductivity of the yarn is improved and the mechanical properties are reduced when the total mass fraction of the nanocarbon is improved.
| Conductivity (S/cm) | strength/MPa | Elongation/percent |
| 0.446 | 47.6 | 185 |
TABLE 2
(3) Preparation of the sensor
The same as in example 1.
(4) Strain sensing performance of sensor
The maximum detectable strain of the sensor is 210% and the coefficient of sensitivity in the 100% strain range is 18.86.
Example 3
A preparation method of a multielement nanometer carbon fiber yarn strain sensor comprises the following steps:
(1) preparation of binary nanocarbon spinning solution
Adding 0.77g of conductive carbon black, 0.086g of single-layer graphene and 0.17g of dispersing agent into a mixed solvent containing 15.49g of dimethylformamide and 3.87g of tetrahydrofuran, fully stirring at room temperature by using a magnetic stirrer, then performing ultrasonic dispersion, adding 2g of thermoplastic polyurethane particles into the dispersion liquid, stirring again until the particles are completely dissolved, and performing ultrasonic dispersion to obtain the uniform carbon black/graphene/polyurethane composite spinning solution. The mass fraction of polyurethane in the spinning solution is 9%, the mass fraction of carbon black in the solute is 27%, and the mass fraction of graphene is 3%.
(2) Preparation of binary carbon nanofiber yarn
Preparing a carbon black/graphene/polyurethane composite nanofiber bundle by using an electrostatic spinning device, and preparing the carbon black/graphene/polyurethane composite nanofiber yarn through the processes of merging, twisting and shaping. Wherein the spinning flow rate is 4ml/h, the working voltage is 32kV, the auxiliary voltage is 26kV, the receiving distance is 25cm, the winding speed is 140m/h, the number of combined yarns is 4, the twist number is 3000 twist/m, the setting temperature is 140 ℃, and the setting time is 1.5 h. When the mass fraction of the carbon black is 27% and the mass fraction of the graphene is 3%, the performance of the binary carbon nanofiber yarn is shown in table 3, and comparing table 3 with table 1, it can be known that the carbon nanotube can simultaneously improve the conductivity and mechanical properties of the yarn when the total mass fraction of the nanocarbon is unchanged.
| Conductivity (S/cm) | strength/MPa | Elongation/percent |
| 0.141 | 44.6 | 144 |
TABLE 3
(3) Preparation of the sensor
The same as in example 1.
(4) Strain sensing performance of sensor
The results of the strain sensing performance of the sensor that was monotonically stretched to failure are shown in fig. 11, and the results of the strain sensing performance of the sensor that was prestretched and then cyclically stretched 10 times in the 30% strain range are shown in fig. 12, resulting in a maximum detectable strain of the sensor of 148% and a coefficient of sensitivity of 26.75 in the 100% strain range.
Example 4
A preparation method of a multielement nanometer carbon fiber yarn strain sensor comprises the following steps:
(1) preparation of binary nanocarbon spinning solution
Adding 0.77g of conductive carbon black, 0.086g of multi-walled carbon nanotube and 0.09g of dispersing agent into a mixed solvent containing 11.05g of dimethylformamide and 2.76g of tetrahydrofuran, fully stirring at room temperature by using a magnetic stirrer, then performing ultrasonic dispersion for 1.5h, then adding 2g of thermoplastic polyurethane particles into the dispersion liquid, stirring again until the particles are completely dissolved, and then performing ultrasonic dispersion for 1.5h to prepare the uniform carbon black/graphene/polyurethane composite spinning solution. The mass fraction of polyurethane in the spinning solution is 12%, the mass fraction of carbon black in the solute is 27%, and the mass fraction of the carbon nano tube is 3%.
(2) Preparation of binary carbon nanofiber yarn
Preparing a carbon black/graphene/polyurethane composite nanofiber bundle by using an electrostatic spinning device, and preparing the carbon black/graphene/polyurethane composite nanofiber yarn through the processes of merging, twisting and shaping. Wherein the spinning flow rate is 8ml/h, the working voltage is 36kV, the auxiliary voltage is 30kV, the receiving distance is 22cm, the winding speed is 110m/h, the number of combined threads is 5, the twist number is 3200 twist/m, the setting temperature is 150 ℃, and the setting time is 0.5 h. When the mass fraction of the carbon black is 27% and the mass fraction of the carbon nanotubes is 3%, the performance of the binary carbon nanofiber yarn is as shown in table 4, and it can be seen by comparing table 4 with table 1 that when the total mass fraction of the nanocarbon is unchanged, the graphene can improve the conductivity of the yarn, but reduce the mechanical properties.
| Conductivity (S/cm) | strength/MPa | Elongation/percent |
| 0.115 | 75.5 | 322 |
TABLE 4
(3) Preparation of the sensor
The same as in example 1.
(4) Strain sensing performance of sensor
The maximum detectable strain of the sensor is 241% and the sensitivity coefficient in the 100% strain range is 8.
Example 5
A preparation method of a multielement nanometer carbon fiber yarn strain sensor comprises the following steps:
(1) preparation of a Mono-carbon Nanocarbon spinning solution
Adding 0.86g of conductive carbon black and 0.17g of dispersing agent into a mixed solvent containing 15.49g of dimethylformamide and 3.87g of tetrahydrofuran, fully stirring at room temperature by using a magnetic stirrer, then carrying out ultrasonic dispersion for 1 hour, adding 2g of thermoplastic polyurethane particles into the dispersion liquid, stirring again until the particles are completely dissolved, and then carrying out ultrasonic dispersion for 1 hour to prepare the uniform carbon black/polyurethane composite spinning solution. The mass fraction of polyurethane in the spinning solution is 9%, and the mass fraction of carbon black in the solute is 30%.
(2) Preparation of unitary carbon nanofiber yarn
Preparing a carbon black/polyurethane composite nanofiber bundle by using a multi-needle water bath electrostatic spinning device, and preparing the carbon black/polyurethane composite nanofiber yarn through the processes of combination, twisting and heat setting. Wherein the spinning flow rate is 10ml/h, the working voltage is 40kV, the auxiliary voltage is 34kV, the receiving distance is 30cm, the winding speed is 160m/h, the number of combined fibers is 2, the twist number is 3500 twist/m, the setting temperature is 150 ℃, and the setting time is 2 h. When the mass fraction of the carbon black is 30%, the properties of the unitary carbon nanofiber yarn are shown in table 5, and it can be known from comparing table 5 with table 1 that when the total mass fraction of the nanocarbon is unchanged, the conductive performance can be increased while the mechanical properties of the yarn are maintained by adding the carbon nanotubes and the graphene.
| Conductivity (S/cm) | strength/MPa | Elongation/% of |
| 0.126 | 57.44 | 289 |
TABLE 5
(3) Preparation of the sensor
The same as in example 1.
(4) Strain sensing performance of sensor
The results of the strain sensing performance test in which the sensor was monotonically stretched to failure are shown in fig. 13, and the results of the strain sensing performance test in which the sensor was stretched 10 times in cycles within the range of 30% strain after pre-stretching are shown in fig. 14, whereby the maximum detectable strain of the sensor was 234%, and the sensitivity coefficient was 9.11 within the range of 100% strain.
Example 6
A multi-element nanometer carbon fiber yarn strain sensor and a preparation method thereof are disclosed, which comprises the following steps:
(1) preparation of a Mono-carbon Nanocarbon spinning solution
Adding 0.35g of single-layer graphene and 0.04g of dispersing agent into a mixed solvent containing 14.12g of dimethylformamide and 3.53g of tetrahydrofuran, fully stirring at room temperature by using a magnetic stirrer, then carrying out ultrasonic dispersion for 3 hours, then adding 2g of thermoplastic polyurethane particles into the dispersion liquid, stirring again until the particles are completely dissolved, and then carrying out ultrasonic dispersion for 3 hours to obtain the uniform carbon black/polyurethane composite spinning liquid. The mass fraction of polyurethane in the spinning solution is 10%, and the mass fraction of graphene in the solute is 15%.
(2) Preparation of unitary carbon nanofiber yarn
Preparing carbon black/polyurethane composite nanofiber bundles by using a multi-needle water bath electrostatic spinning device, and preparing the carbon black/polyurethane composite nanofiber yarn through the processes of merging, twisting and heat setting. Wherein the spinning flow rate is 6ml/h, the working voltage is 27kV, the auxiliary voltage is 21kV, the receiving distance is 22cm, the winding speed is 150m/h, the number of combined threads is 10, the twist number is 1500 twists/m, the setting temperature is 120 ℃, and the setting time is 1.5 h. When the mass fraction of graphene is 15%, the properties of the unitary carbon nanofiber yarn are shown in table 6, and it is known that when the total mass fraction of nanocarbon is low, both the electrical conductivity and the mechanical properties of the yarn are poor.
| Conductivity (S/cm) | strength/MPa | Elongation/percent |
| 0.002 | 25.32 | 74 |
TABLE 6
(3) Preparation of the sensor
The same as in example 1.
(4) Strain sensing performance of sensor
The maximum detectable strain of the sensor is 74% and the coefficient of sensitivity in the 50% strain range is 1397.12.
In summary, the multielement nano carbon fiber yarn strain sensor and the preparation method thereof provided by the invention adopt a single electrostatic spinning process to prepare multielement nano carbon fiber yarn with carbon black/carbon nano tube/graphene doped inside, and tin foil paper and conductive silver adhesive are used to prepare electrodes at two ends of the yarn, so that the multielement nano carbon fiber yarn strain sensor with high conductivity, high strain, high stability, weavability and washability is developed.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A multi-element nanometer carbon fiber yarn strain sensor is characterized in that: the sensor comprises a nanofiber, wherein a multi-element conductive network formed by mutually bridging dot-shaped carbon black, linear carbon nano tubes and flaky graphene is arranged in the nanofiber, when the mass fraction of the carbon black is 0-35%, the mass fraction of the carbon nano tubes is 0-35%, the mass fraction of the graphene is 0-15%, the total mass fraction of the carbon black, the carbon nano tubes and the graphene is 15-35%, and the rest components are thermoplastic polyurethane, the conductivity of the sensor is 3.59 multiplied by 10-60.212S/cm, maximum detection strain 93% 439%, sensitivity in 100% strain range of 4.67-1258.3, response time less than 300 ms.
2. A preparation method of a multielement nanometer carbon fiber yarn strain sensor is characterized by comprising the following steps:
(1) preparing a spinning solution: adding carbon black, carbon nano tubes, graphene and a dispersing agent with an anti-settling effect on nano carbon particles into a mixed solvent of dimethylformamide and tetrahydrofuran, stirring, performing ultrasonic dispersion, then adding thermoplastic polyurethane particles into a multi-element nano carbon dispersion liquid, stirring, and performing ultrasonic dispersion to obtain a spinning solution;
(2) preparing nano fiber yarns: continuously preparing multi-element carbon nanofiber bundles from the spinning solution by using an electrostatic spinning device, and then combining, twisting and shaping the carbon nanofiber bundles to form multi-element carbon nanofiber yarns;
(3) preparing a sensor: intercepting the 3-10 cm multielement nanometer carbon fiber yarn, fixing two ends of the yarn between two pieces of 1cm multiplied by 2cm aluminum foil paper by conductive silver adhesive to form electrodes, waiting at normal temperature for the multielement nanometer carbon fiber yarn to be completely dried, packaging the aluminum foil electrodes by an insulating adhesive tape, and adjusting the length of the yarn used by the sensor according to a measuring range required to form the multielement nanometer carbon fiber yarn strain sensor.
3. The method for preparing a multi-component nano carbon fiber yarn strain sensor according to claim 2, wherein the strain sensor comprises: in the step (1), the dispersing agent is modified PVA or a nonionic surfactant containing an aromatic group.
4. The method for preparing a multi-component nano carbon fiber yarn strain sensor according to claim 2, wherein the strain sensor comprises: in the step (1), stirring is carried out for 12-24 hours at a rotating speed of 200r/min under the condition that the temperature is 25 +/-5 ℃, the power of ultrasonic dispersion is 200-500W, and the time is 1-3 hours.
5. The method for preparing a multi-component nano carbon fiber yarn strain sensor according to claim 2, wherein the strain sensor comprises: in the step (1), the mass fraction of the tetrahydrofuran in the mixed solvent is 20-50%.
6. The method for preparing a multi-component nano carbon fiber yarn strain sensor according to claim 2, wherein the strain sensor comprises: in the step (1), the mass fraction of the thermoplastic polyurethane in the spinning solution is 8-12%.
7. The method for preparing a multi-component nano carbon fiber yarn strain sensor according to claim 2, wherein the strain sensor comprises: in the step (1), the total mass of the carbon black, the carbon nano tubes and the graphene is 15% -35% of the total mass of the solute, wherein the mass fraction of the carbon black is 0-35%, the mass fraction of the carbon nano tubes is 0-35%, the mass fraction of the graphene is 0-15%, and the addition amount of the dispersing agent is 10% -30% of the total mass of the carbon black, the carbon nano tubes and the graphene.
8. The method for preparing a multi-component nano carbon fiber yarn strain sensor according to claim 2, wherein the strain sensor comprises: in the step (2), the feeding speed of the spinning solution is 2-10 ml/h, the working voltage is 26-40 kV, the auxiliary voltage is 20-34 kV, the distance between the tip of the spinning needle and the liquid level of the received bath solution is 20-30 cm, the collecting speed of a winding device is 80-160 m/h, a drying device is a normal-temperature air blower, and the relative humidity of the spinning environment is controlled below 35%.
9. The method for preparing a multi-component nano carbon fiber yarn strain sensor according to claim 2, wherein the strain sensor comprises: in the step (2), the number of the carbon nanofiber bundles in the multi-element carbon nanofiber yarn is 2-10, and the twist is 1000-3500 twists/m.
10. The method for preparing a multi-component nano carbon fiber yarn strain sensor according to claim 2, wherein the strain sensor comprises: in the step (2), the shaping method comprises the steps of placing boiling water in the lower layer of a double-layer vacuum oven, fixing yarns on an iron plate, and then placing the yarns in the upper layer of the oven, wherein the shaping temperature is 120-150 ℃, and the shaping time is 0.5-2 hours.
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