A kind of flexible wearable formula strain transducer and preparation method thereof
Technical field
The present invention relates to flexible electronics and sensor technical field, particularly relate to a kind of flexible wearable formula strain transducer
And preparation method thereof.
Background technique
With the popularization of intelligent terminals, wearable electronic shows huge market prospects.Sensor is strong in human body
Health monitoring aspect plays vital effect, and flexible wearable electronic sensor is with light and portable, electric property is excellent
The features such as different and integrated level is high, and can be raw by human healths such as real-time monitoring pulse, heartbeat, body temperature, muscle group vibrations
Index is managed, feedback is made to healthy data variation, or even realize primary prevention and the diagnosis of disease in time, becomes most
One of concerned electric sensor.The a large amount of strain transducer with special design structure is developed, but this complexity
Design lead to the difficult grow exponentially in manufacturing technology, cause them extremely difficult in commercial applications.Therefore, do not having
In the case where having performance loss, the simplification of device architecture will be top-priority.Therefore the strain for designing a kind of suitable wearing passes
Sensor has portability, consistency and portability, can be bonded human body, accurately measures continuous human motion detection, raw
Reason measurement and medical diagnosis on disease, and long periods of wear is suitble to use, it is problem to be solved of the present invention.
With size, small, large specific surface area, porosity are high, the degree of orientation is good, tensile strength is big for electro-spun nanofiber yarn,
The advantages of being easy to secondary operation, the sensor being made of nano-fibre yams have a clear superiority and broad based growth prospect.Firstly,
Nanometer yarn is made of nanofiber, and yarn can keep the advantage of original nanofiber large specific surface area;Secondly, nanometer yarn
The weak disadvantage of conventional nanofibers film dynamic performance is overcome, is strongly significantly improved, and can further weave, is compound, function
Change, various structural materials, composite material, specific function material can be made, weaves the two dimension of different structure or the fabric of three-dimensional,
It realizes the transformation by nano materials such as random or oriented nanofibers to macroscopic material, material function stability can be improved,
And the service life of material prepared.The present invention passes through the conjugation electrostatic spun yarn technology being previously reported and prepares continuous nanometer
Fiber yarn, then fiber surface in-situ polymerization coats one layer of conducting polymer in yarn, by the conductive-nano-fibers yarn of acquisition
Line spiral winding will obtain spiral complex yarn and further integrate the obtained strain transducer of encapsulation, tool to the surface of elastic filament
There are high stitchability and integration.
Summary of the invention
The present invention proposes a kind of flexible wearable formula strain transducer and preparation method thereof, solves existing sensor function
Problem unstable, service life is short.
The technical scheme of the present invention is realized as follows:
A kind of flexible wearable formula strain transducer, the sensor include the spiral complex yarn of two intersections, every spiral
One end of complex yarn is stained with copper adhesive tape, and two copper adhesive tapes are connected with copper conductor respectively, on the spiral complex yarn of two intersections
Paste PDMS elastic membrane in lower two sides;The length of the sensor is not less than 35mm.
The spiral complex yarn is prepared continuously the preparation method comprises the following steps: nanofiber is passed through conjugation electrostatic spun yarn technology
Nano-fibre yams, then in yarn fiber surface in-situ polymerization coat strata pyrroles's conducting polymer, by leading for acquisition
Conducting nanofiber yarn spiral winding completes the preparation of spiral complex yarn to the surface of elastic filament.
The diameter of the nanofiber is the polyacrylonitrile fibre of 100-300nm, and the molecular weight of polyacrylonitrile is not less than
100000;The diameter of nano-fibre yams is 300-650 μm.
The preparation method of the flexible wearable formula strain transducer, steps are as follows:
(1) graphene oxide is dissolved in dimethyl formamide solution, strength ultrasonic treatment is carried out under air-proof condition, obtained uniformly
The graphene oxide solution of dispersion;
(2) dry polyacrylonitrile powder is added in the graphene oxide solution that step (1) obtains, is stirred at 40-80 DEG C
3-8h is mixed, spinning solution is obtained;
(3) spinning solution that step (2) obtains is added in syringe pump and continuous nano-fibre yams is prepared;
(4) nano-fibre yams that step (3) obtains are immersed in liquor ferri trichloridi, handle 30-100min, then soaks again
Bubble handles 1-5 h in chromium solution at 0 DEG C, is cleaned after taking-up with deionized water, is subsequently placed in 30-90 DEG C of vacuum drying oven
Middle drying obtains conductive-nano-fibers yarn;
(5) it will be wound on elastic filament through conductive-nano-fibers yarn spirals made from step (4), and obtain spiral composite yarn
Line;
(6) two spiral complex yarns are taken, by one end distinguish fixed copper adhesive tape, intersection be placed on two layers of PDMS elastic membrane it
Between, PDMS(dimethyl silicone polymer is stretched out after then copper conductor is connected with copper adhesive tape respectively) elastic membrane, completing flexibility can wear
Wear the preparation of formula strain transducer.
The mass ratio of polyacrylonitrile and graphene oxide is 1:(0-0.05 in the step (2));The spinning solution is poly-
The mass fraction of acrylonitrile is 8-15%.
The condition of electrostatic spinning in the step (3) are as follows: voltage is 15-25 kV, and spinning solution total flow is 0.5-0.9
ML/h, the number of syringe needle are 4, positive and negative syringe needle liquid inventory ratio 1:0.3-1, the distance 13-17.5 cm between positive and negative syringe needle.
The concentration of liquor ferri trichloridi and chromium solution is 50-80 mol/L in the step (4).
The beneficial effects of the present invention are:
(1) present invention prepares continuous nano-fibre yams by being conjugated electrostatic spun yarn technology, then the fiber surface in yarn
In-situ polymerization coats one layer of conducting polymer, obtains conductive-nano-fibers yarn.On this basis, by the conductive-nano-fibers of acquisition
Yarn spirals are wound into the surface of elastic filament, are further made in the compound gel mould with copper wire of spiral composite yarn surface
Flexible yarn strain transducer.The result shows that the flexible yarn strain transducer is monitored in limb motion, and expression shape change, human body
The application of the gas detections such as pulse and formaldehyde etc. has practicability, shows in terms of wearable sensor and electronic skin
Huge potentiality are shown.
(2) the conductive-nano-fibers yarn that the present invention uses is made of diameter for the nanofiber of 100-300 nm, by mixing
Miscellaneous GO significantly improves the electric conductivity of spinning solution, obtains thinner nanofiber more evenly, and nanofiber passes through in high-voltage electricity field force
Under the action of constantly break up and stretch high polymeric solution or melt and obtain, polymer is the polyacrylonitrile (GO- for mixing graphene oxide
Doped PAN);Electrostatic spinning technique is combined in situ chemical oxidative polymerization method, preparing, there is the conduction of nanostructure to receive
Rice fiber yarn, and it is applied to wearable electronic skin, improve the added value of traditional textile.
(3) present invention prepares strain transducer with preferable mechanics self-adaptability, and sensitivity is higher, it can be achieved that really
Wearable sensors in meaning, structure innovation, manufacturing process is simple, low in cost easy to operate.
Detailed description of the invention
Fig. 1 is electrostatic spinning apparatus schematic diagram, 1- syringe pump, 2- perfusion tube, 3- syringe needle, 4- metal loudspeaker, 5- motor, 6-
Winding device.
Fig. 2 is the pictorial diagram of strain sensing, 7- copper conductor, 8- spiral complex yarn, 9-PDMS elastic membrane, 10- copper glue
Band.
Fig. 3 is the electron microscopic picture of spiral complex yarn, conductive yarn and single fiber, and wherein A is spiral complex yarn, B
For conductive yarn, C, D are the electron microscopic picture of single fiber.
Sensitivity of the strain transducer under differently strained in Fig. 4 embodiment 1.
Fig. 5 is electron microscope of the single fiber under different amplification.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's every other embodiment obtained under that premise of not paying creative labor, belongs to this hair
The range of bright protection.
Embodiment 1
The preparation method of the flexible wearable formula strain transducer of the present embodiment, comprising the following steps:
(1) graphene oxide is dissolved in dimethylformamide (DMF) solution, strength ultrasonic treatment is carried out under air-proof condition, is obtained
To evenly dispersed graphene oxide solution;
(2) dry polyacrylonitrile powder is added in the solution of step (1), stirs 3h at 80 DEG C, obtains polyacrylonitrile
The spinning solution that mass fraction is 10%, the molecular weight of the polyacrylonitrile are 150000;Polyacrylonitrile and graphene oxide
Mass ratio is 1:0.01;
(3) 1 electrostatic spinning apparatus is built as illustrated, the spinning solution in step (2) is added in syringe pump and is prepared continuously
Nano-fibre yams, electrostatic spinning voltage is 20 kV, and spinning solution total flow is 0.8 mL/h, the distance between positive and negative syringe needle
15 cm, the number of syringe needle are 4, positive and negative syringe needle liquid inventory ratio 1:0.3, vertical range of the syringe needle apart from flared rim
4cm, winding speed 35mm/min;
(4) nano-fibre yams prepared in step (3) are immersed in the ferric trichloride (FeCl that concentration is 75 mol/L3) solution
In 30 min;
(5) nano-fibre yams in step (4) are immersed in pyrroles (Py) solution that concentration is 75 mol/L at 0 DEG C
2 h are managed, are cleaned after taking-up with deionized water, are subsequently placed in 60 DEG C of vacuum drying oven dry;
(6) by the conductive-nano-fibers yarn in step (5), on spiral winding to elastic filament, spiral complex yarn is obtained;
(7) two spiral complex yarns are taken, by one end distinguish fixed copper adhesive tape, intersection be placed on two layers of PDMS elastic membrane it
Between, PDMS(dimethyl silicone polymer is stretched out after then copper conductor is connected with copper adhesive tape respectively) elastic membrane, completing flexibility can wear
Wear the preparation of formula strain transducer.
Fig. 2 is the picture in kind of strain sensing.The surface of spiral complex yarn, conductive yarn, fibre bundle and single fiber
As shown in figure 3, as seen from Figure 3, the helical structure of spiral complex yarn is intensive and uniformly for the electromicroscopic photograph of morphosis, leads
Electric yarn orientation is good, and PPy is evenly coated in GO-doped PAN nanofiber surface.Fig. 4 is strain transducer in difference
Sensitivity under strain.As seen from Figure 4, the strain transducer of preparation show superelevation sensitivity and wider sensing model
It encloses,
Embodiment 2
The preparation method of the flexible wearable formula strain transducer of the present embodiment, comprising the following steps:
(1) graphene oxide is dissolved in dimethylformamide (DMF) solution, strength ultrasonic treatment is carried out under air-proof condition, is obtained
To evenly dispersed graphene oxide solution;
(2) dry polyacrylonitrile powder is added in the solution of step (1), stirs 6h at 50 DEG C, obtains polyacrylonitrile
The spinning solution that mass fraction is 8%, the molecular weight of the polyacrylonitrile are 100000, polyacrylonitrile and graphene oxide
Mass ratio is 1:0.03;
(3) 1 electrostatic spinning apparatus is built as illustrated, the spinning solution in step (2) is added in syringe pump and is prepared continuously
Nano-fibre yams, electrostatic spinning voltage is 17 kV, and spinning solution total flow is 0.5 mL/h, the distance between positive and negative syringe needle
17 cm, the number of syringe needle are 4, positive and negative syringe needle liquid inventory ratio 1:1, vertical range 5cm of the syringe needle apart from flared rim,
Winding speed 30mm/min;
(4) nano-fibre yams prepared in step (3) are immersed in the ferric trichloride (FeCl that concentration is 55 mol/L3) solution
In 50 min;
(5) nano-fibre yams in step (4) are immersed in pyrroles (Py) solution that concentration is 50 mol/L at 0 DEG C
3 h are managed, are cleaned after taking-up with deionized water, are subsequently placed in 60 DEG C of vacuum drying oven dry;
(6) by the conductive-nano-fibers yarn in step (5), on spiral winding to elastic filament, spiral complex yarn is obtained;
(7) two spiral complex yarns are taken, by one end distinguish fixed copper adhesive tape, intersection be placed on two layers of PDMS elastic membrane it
Between, PDMS(dimethyl silicone polymer is stretched out after then copper conductor is connected with copper adhesive tape respectively) elastic membrane, completing flexibility can wear
Wear the preparation of formula strain transducer.
Embodiment 3
The preparation method of the flexible wearable formula strain transducer of the present embodiment, comprising the following steps:
(1) dry polyacrylonitrile powder is added in dimethyl formamide solution, stirs 4h at 60 DEG C, obtain quality point
The polyacrylonitrile solution that number is 12% is 150000 as spinning solution, the molecular weight of the polyacrylonitrile;
(2) 1 electrostatic spinning apparatus is built as illustrated, the polyacrylonitrile solution in step (1) is added in syringe pump and is prepared
Continuous nano-fibre yams, electrostatic spinning voltage are 20 kV, and spinning solution total flow is 0.8 mL/h, between positive and negative syringe needle
15 cm of distance, the number of syringe needle are 4, positive and negative syringe needle liquid inventory ratio 1:0.7, syringe needle apart from flared rim it is vertical away from
From 4cm, winding speed 35mm/min;
(3) nano-fibre yams prepared in step (2) are immersed in the ferric trichloride (FeCl that concentration is 75 mol/L3) solution
In 30 min;
(4) nano-fibre yams in step (3) are immersed in pyrroles (Py) solution that concentration is 60 mol/L at 0 DEG C
2 h are managed, are cleaned after taking-up with deionized water, are subsequently placed in 60 DEG C of vacuum drying oven dry;
(5) by the conductive-nano-fibers yarn in step (4), on spiral winding to elastic filament, spiral complex yarn is obtained;
(6) two spiral complex yarns are taken, by one end distinguish fixed copper adhesive tape, intersection be placed on two layers of PDMS elastic membrane it
Between, PDMS(dimethyl silicone polymer is stretched out after then copper conductor is connected with copper adhesive tape respectively) elastic membrane, completing flexibility can wear
Wear the preparation of formula strain transducer.
Embodiment 4
The preparation method of the flexible wearable formula strain transducer of the present embodiment, comprising the following steps:
(1) dry polyacrylonitrile powder is added in dimethyl formamide solution, stirs 4h at 70 DEG C, obtain quality point
The polyacrylonitrile solution that number is 14%, the molecular weight of the polyacrylonitrile are 150000;
(2) 1 electrostatic spinning apparatus is built as illustrated, the polyacrylonitrile solution in step (1) is added in syringe pump and is prepared
Continuous nano-fibre yams, electrostatic spinning voltage are 22 kV, and spinning solution total flow is 0.5 mL/h, between positive and negative syringe needle
15 cm of distance, the number of syringe needle are 4, positive and negative syringe needle liquid inventory ratio 1:0.8, syringe needle apart from flared rim it is vertical away from
From 4cm, winding speed 35mm/min;
(3) nano-fibre yams prepared in step (2) are immersed in the ferric trichloride (FeCl that concentration is 65 mol/L3) solution
In 80 min;
(4) nano-fibre yams in step (3) are immersed in pyrroles (Py) solution that concentration is 65 mol/L at 0 DEG C
5 h are managed, are cleaned after taking-up with deionized water, are subsequently placed in 60 DEG C of vacuum drying oven dry;
(5) by the conductive-nano-fibers yarn in step (4), on spiral winding to elastic filament, spiral complex yarn is obtained;
(6) two spiral complex yarns are taken, by one end distinguish fixed copper adhesive tape, intersection be placed on two layers of PDMS elastic membrane it
Between, PDMS(dimethyl silicone polymer is stretched out after then copper conductor is connected with copper adhesive tape respectively) elastic membrane, completing flexibility can wear
Wear the preparation of formula strain transducer.
Embodiment 5
The preparation method of the flexible wearable formula strain transducer of the present embodiment, comprising the following steps:
(1) graphene oxide is dissolved in dimethylformamide (DMF) solution, strength ultrasonic treatment is carried out under air-proof condition, is obtained
To evenly dispersed graphene oxide solution;
(2) dry polyacrylonitrile powder is added in the solution of step (1), stirs 3h at 80 DEG C, obtains polyacrylonitrile
The spinning solution that mass fraction is 10%, the molecular weight of the polyacrylonitrile are 150000;Polyacrylonitrile and graphene oxide
Mass ratio is 1:0.05;
(3) 1 electrostatic spinning apparatus is built as illustrated, the spinning solution in step (2) is added in syringe pump and is prepared continuously
Nano-fibre yams, electrostatic spinning voltage is 25 kV, and spinning solution total flow is 0.9 mL/h, the distance between positive and negative syringe needle
17.5 cm, syringe needle the vertical range 4cm apart from flared rim, winding speed 35mm/min;
(4) nano-fibre yams prepared in step (3) are immersed in the ferric trichloride (FeCl that concentration is 80 mol/L3) solution
In 100 min;
(5) nano-fibre yams in step (4) are immersed in pyrroles (Py) solution that concentration is 80 mol/L at 0 DEG C
5 h are managed, are cleaned after taking-up with deionized water, are subsequently placed in 90 DEG C of vacuum drying oven dry;
(6) by the conductive-nano-fibers yarn in step (5), on spiral winding to elastic filament, spiral complex yarn is obtained;
(7) two spiral complex yarns are taken, by one end distinguish fixed copper adhesive tape, intersection be placed on two layers of PDMS elastic membrane it
Between, PDMS(dimethyl silicone polymer is stretched out after then copper conductor is connected with copper adhesive tape respectively) elastic membrane, completing flexibility can wear
Wear the preparation of formula strain transducer.
Embodiment 6
The preparation method of the flexible wearable formula strain transducer of the present embodiment, comprising the following steps:
(1) graphene oxide is dissolved in dimethylformamide (DMF) solution, strength ultrasonic treatment is carried out under air-proof condition, is obtained
To evenly dispersed graphene oxide solution;
(2) dry polyacrylonitrile powder is added in the solution of step (1), stirs 3h at 80 DEG C, obtains polyacrylonitrile
The spinning solution that mass fraction is 8%, the molecular weight of the polyacrylonitrile are 150000;Polyacrylonitrile and graphene oxide
Mass ratio is 1:0.04;
(3) 1 electrostatic spinning apparatus is built as illustrated, the spinning solution in step (2) is added in syringe pump and is prepared continuously
Nano-fibre yams, electrostatic spinning voltage is 15 kV, and spinning solution total flow is 0.5 mL/h, the distance between positive and negative syringe needle
13 cm, the number of syringe needle are 4, positive and negative syringe needle liquid inventory ratio 1:0.4, vertical range of the syringe needle apart from flared rim
4cm, winding speed 35mm/min;
(4) nano-fibre yams prepared in step (3) are immersed in the ferric trichloride (FeCl that concentration is 80 mol/L3) solution
Middle 30min;
(5) nano-fibre yams in step (4) are immersed in pyrroles (Py) solution that concentration is 80 mol/L at 0 DEG C
1h is managed, is cleaned after taking-up with deionized water, is subsequently placed in 30 DEG C of vacuum drying oven dry;
(6) by the conductive-nano-fibers yarn in step (5), on spiral winding to elastic filament, spiral complex yarn is obtained;
(7) two spiral complex yarns are taken, by one end distinguish fixed copper adhesive tape, intersection be placed on two layers of PDMS elastic membrane it
Between, PDMS(dimethyl silicone polymer is stretched out after then copper conductor is connected with copper adhesive tape respectively) elastic membrane, completing flexibility can wear
Wear the preparation of formula strain transducer.
Therefore, flexible wearable formula strain transducer prepared by the present invention, based on the biggish specific surface area of nanofiber and
The excellent mechanical property feature of nano-fibre yams, when being stimulated by external force, sensor show superelevation sensitivity and
Wider sensing scope.It has been successfully applied to human motion detection, limb motion monitoring, expression shape change, human pulse, Yi Jijia
The gas detections such as aldehyde etc. using practicability with higher, shown in terms of wearable sensor and electronic skin huge
Big potentiality.In addition, its simplification of structure innovation of the invention, manufacturing process is simple, and controllable operating low in cost is conducive to big
Scale commercial direction is developed.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.