CN106052544A - Flexible wearable strain sensor and preparation method thereof - Google Patents
Flexible wearable strain sensor and preparation method thereof Download PDFInfo
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- CN106052544A CN106052544A CN201610327953.8A CN201610327953A CN106052544A CN 106052544 A CN106052544 A CN 106052544A CN 201610327953 A CN201610327953 A CN 201610327953A CN 106052544 A CN106052544 A CN 106052544A
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- flexible wearable
- conductive
- strain transducer
- insulating barrier
- conductive filler
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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
Abstract
The invention relates to the field of strain sensors and in particular to a flexible wearable strain sensor and a preparation method thereof. The invention provides a flexible wearable strain sensor and is characterized in that the flexible wearable strain sensor includes an upper insulating layer, a conductive layer and a lower insulating layer. The conductive layer is arranged between the upper insulating layer and the lower insulating layer. The upper insulating layer and the lower insulating layer are made from a flexible wearable high-molecule material. The conductive layer is a high-molecule fiber/conductive filler composite film having a conductive network structure. According to the invention, the strain sensor is advantaged by low cost of raw materials, excellent product properties, simple technology operations, wide range of strain testing (suitable to response under large strain), and high sensitivity.
Description
Technical field
The present invention relates to strain transducer field, be specifically related to strain transducer and the preparation thereof of a kind of flexible wearable
Method.
Background technology
Conductive polymer composite (CPCs) is prepared from polymer-based bluk recombination by conductive filler.CPCs is answering
Under the stimulation in the outfields such as power, temperature, gas, liquid, often showing abundant respondent behavior, the character of this uniqueness makes the CPCs can
It is used as preferable Sensitive Apparatus.Strain transducer stimulates the composite microstructure brought to change by stress field, it is achieved
The change of CPC resistance, electrical conductivity and electric capacity.The strain transducer changed based on stress field and cause composite material resistance to change is existing
It is widely used to the aspects such as healthy detection, motion detection and monitoring structural health conditions.At present, along with development and the people of science and technology
People's growth in the living standard, people are growing for the demand of wearable device, and the strain transducer of flexible wearable meets the tendency
And give birth to.
Traditional strain transducer typically utilizes rigid material to prepare, and has poor extensibility and the most wearable spy
Point.2008, (Pham G T, Park Y B, Liang Z, the et al.Processing and modeling of such as Pham
conductive thermoplastic/carbon nanotube films for strain sensing.Composites
Part B Engineering, 2008,39 (1): 209-216) prepare polymethyl methacrylate methyl ester (PMMA)/many walls carbon to receive
Mitron (MWCNT) composite, this material has reversible strain-responsive under the strain less than 1%, and shortcoming is that PMMA is flexible
The best, therefore strain transducer extensibility based on this composite is the most poor.2013, (Zhang R, the Deng such as Zhang
H,Valenca R,et al.Strain sensing behaviour of elastomeric composite films
containing carbon nanotubes under cyclic loading.Composites Science&
Technology, 2013,74 (4): 1-5) it is prepared for thermoplastic polyurethane (TPU)/multi-wall carbon nano-tube composite material, this multiple
Condensation material has good strain-responsive under the strain of 5%, but occurs acromion under bigger strain, and material does not possess should
Become the practical feature of sensor.2016, Amjadi etc. (Amjadi M, Kyung K, Park I, et al.Stretchable,
Skin-Mountable,and Wearable Strain Sensors and Their Potential Applications:A
Review.Advanced Functional Materials, 2016,26 (11): 1678-1698) reviewing flexible wearable should
Becoming the progress of sensor, this material is respectively provided with great in fields such as following intelligent robot, medical apparatus and instruments, health monitorings
Potential using value.And preparation has big strain, highly sensitive strain transducer has highly important science undoubtedly and answers
By value.
Summary of the invention
For drawbacks described above, the present invention provides the strain transducer of a kind of flexible wearable, and this strain transducer is applicable to
Big strain, and highly sensitive.
Technical scheme:
First technical problem that the invention solves the problems that is to provide the strain transducer of a kind of flexible wearable, including upper absolutely
Edge layer, conductive layer and lower insulating barrier, conductive layer is positioned at insulating barrier and the centre of lower insulating barrier；Described upper insulating barrier and lower insulation
Layer is made up of the macromolecular material with flexible wearable characteristic；Described conductive layer is the macromolecule fibre with conductive network structure
Dimension/conductive filler composite membrane.
Preferably, there is the macromolecular material of flexible wearable characteristic selected from polydimethylsiloxane described in insulating barrier
(PDMS), the one in thermoplastic elastomer (TPE) (TPE), natural rubber or synthetic rubber；More preferably polydimethylsiloxane.
Preferably, described macromolecular fibre/conductive filler composite membrane is prepared by following method: by conductive filler and deionization
Water is mixed to prepare mass concentration 0.01～the conductive filler dispersion liquid of 5%, is then placed in dispersion liquid by macromolecular fibre film
Supersound process 1～100min so that conductive filler is uniformly attached on macromolecular fibre film, will modify high score by conductive filler
Subbundle film surface, dries the most in atmosphere；Thus prepare that to have the macromolecular fibre/conductive filler of conductive network structure multiple
Close film.
It is furthermore preferred that described macromolecular fibre film is the electrospun fiber membrane prepared by electrostatic spinning.
Preferably, macromolecular fibre described in conductive layer is selected from styrene butadiene styrene block copolymer (SBS) (SBS)
Fiber, thermoplastic polyurethane (TPU) fiber, poly butylene succinate (PBS) fiber, polyvinylidene fluoride (PVDF) fiber,
At least one in polycaprolactone (PCL) fiber, collagen fabric or fibroin fiber.
Preferably, in described conductive layer, conductive filler is selected from graphene nanometer sheet, CNT, carbon fiber, metal nano
At least one in line or white carbon black.
Preferably, described upper insulating barrier and lower insulating barrier are polydimethylsiloxane；Described macromolecular fibre/conduction is filled out
Material composite membrane is thermoplastic polyurethane fibers/graphite that graphene nanometer sheet modifies that thermoplastic polyurethane fibers film surface is formed
Alkene nanometer sheet composite membrane.
Further, the strain transducer of described flexible wearable also includes conductive attachment element and wire, described conductive layer
Two ends respectively connect a wire, and described wire is connected with measuring instrument, and wire is fixed on conductive layer by wire fixed cell.
Further, at least during described wire fixed cell is elargol, two component epoxy glue or inorganic material conducting resinl
Kind.
Second technical problem that the invention solves the problems that is to provide the preparation side of the strain transducer of above-mentioned flexible wearable
Method, comprises the steps:
1) on substrate, coating has the elastic polymer material mixing liquid of flexible wearable characteristic, be then dried to
The degree still with excellent adhering forms insulating barrier；
2) macromolecular fibre/conductive filler composite membrane with conductive network structure is placed in step 1) insulating barrier on shape
Become conductive layer, then pass through the wire fixed cell two ends lead-in conductor at conductive layer；
3) again in step 2) conductive layer on coating there is the elastic polymer material mixing liquid of flexible wearable characteristic, so
Rear the driest.
Preferably, step 1) in, the condition being dried is: be dried 1～60min at 50～150 DEG C.
Preferably, step 2) in, there is the macromolecular fibre/conductive filler composite membrane of conductive network structure by following method
Prepare: conductive filler and deionized water are mixed to prepare mass concentration 0.01～the conductive filler dispersion liquid of 5%, then by height
Molecular fiber film is placed in supersound process 1～100min in dispersion liquid so that conductive filler is uniformly attached on macromolecular fibre film,
Macromolecular fibre film surface will be modified by conductive filler, dry the most in atmosphere；Thus prepare and there is conductive network structure
Macromolecular fibre/conductive filler composite membrane.
Preferably, step 1) and step 3) in, the thickness of described insulating barrier is 10～400 μm.
Preferably, step 3) in, the condition being dried is: be dried 5～120min at 50～150 DEG C.
The invention have benefit that:
The strain transducer of the present invention be conductive fiber network is implanted to flexibility polymeric substrates in be prepared into soft
Property wearable device.It has, and cost of material is low, properties of product are excellent, technological operation is simple, strain testing scope extensively (is applicable to
Response under big strain) and sensitivity advantages of higher.Additionally, it can be fixed on finger-joint, knee joint etc. for straining
Detection, has, in fields such as health monitoring and motion detections, the prospect that is extremely widely applied.
Accompanying drawing illustrates:
Fig. 1 is the axonometric chart of flexible wearable strain transducer structure of the present invention, including insulating barrier 1, conductive layer 2, insulation
Layer 5, wire 3 and wire fixed cell 4；Described insulating barrier 1 is upper insulating barrier, and insulating barrier 5 is lower insulating barrier；Described conduction
Layer 2 is placed in centre；Conductive layer 2 two ends are connected with wire 3 by wire fixed cell 4, and wire 3 connects extraneous measurement apparatus,
Wire fixed cell 4 is elargol.
Fig. 2 is the strain transducer of present invention time m-resistance curve of 200 circulations under 5% strain.
Fig. 3 is the strain transducer of present invention time m-resistance curve of 200 circulations under 200% strain.
Fig. 4 is the strain transducer of present invention time m-electricity of each 5 circulations under 1%, 2%, 3%, 4% and 5% strain
Resistance curve.
Fig. 5 be the present invention strain transducer 50%, 100%, 150% and 200% strain under each 5 circulation time
M-resistance curve.
Detailed description of the invention
The present invention provides the preparation method of a kind of strain transducer, and a kind of specific embodiment is: spin coating on substrate
Upper thickness is the PDMS of 10～400 μm, is placed in the baking oven of 50～150 DEG C 1～60min, after by conductive filler modified
Electrospun fiber membrane placed on it, then by wire fixed cell lead-in conductor, the most on top spin coating last layer thickness is
The PDMS of 10～400 μm, is placed in the baking oven of 50～150 DEG C so that it is be fully cured；Wherein, conductive filler modifies electricity
Method on spinning fiber film is: conductive filler and deionized water are mixed to prepare mass concentration 0.01～the conductive filler of 5%
Dispersion liquid, is then placed in electrospun fiber membrane supersound process 1～100min in dispersion liquid, is then placed in air and dries.
Using the thermoplastic polyurethane fibers film of electrospinning as the substrate of conductive layer in the present invention, conductive filler is dispersed in
The conductive layer with conductive network it is prefabricated on fibrous membrane；Owing to using the macromolecular material conduct with flexible wearable characteristic
Substrate, it is possible to show its good stretch performance largely, when pair of strain sensors is circulated extension test,
During stretching, along with the increase of elongation strain, conductive network gradually destroys, and resistance will become big；During replying,
Along with the reduction of strain, conductive network gradually recovers, and resistance will diminish；Equally just because of the existence of elastic matrix so that
This strain transducer can have response in very big range of strain.Additionally, strain transducer of the present invention has three-decker,
Have an advantage in that: first material nature is stable, and the conductive network that conductive filler can be protected to modify does not falls off, is not destroyed
And corrosion；Secondly material recovery during cyclic tension is good, will not produce big residual resisitance.
The preparation of embodiment 1 strain transducer
The method of preparation, specifically comprises the following steps that
TPU and graphene nanometer sheet are placed in the baking oven of 80 DEG C and are dried 8h, remove moisture therein；
(1) electrostatic spinning: the TPU of 5.8g drying is joined N,N-dimethylformamide and the tetrahydrochysene of 10ml of 10ml
In the mixed solvent of furan, mechanical agitation 2.5h under room temperature, it is allowed to fully dissolve, is prepared as uniform TPU spinning solution；
TPU spinning solution forms TPU electrospinning fibre through electrostatic spinning: electrospinning parameters: spinning nozzle and collection device it
Between distance be 15cm, spinning voltage is 21KV, and drum rotation speed is 1200r/min, and collection device is the rotation being enclosed with aluminium foil
Cylinder, when, after the surface tension more than solution of the electric field force produced by high pressure, spinning solution will form jet at spinning nozzle,
Being then passed through jet instability, stretching, solvent volatilization, finally under the stretching action rotating cylinder, fiber is carried out around cylinder
Deposition, thus form the electrospun fiber membrane of orientation.
(2) preparation of graphene dispersing solution: the graphene nanometer sheet that 0.5g dodecyl sodium sulfate and 0.05g are dried is added
Entering in 100g deionized water, under the effect of supersonic cleaning machine, ultrasonic disperse processes 60min, and obtaining mass concentration is 0.05%
The uniform dispersion of graphene nanometer sheet.
(3) structure of conductive network: by step 1) gained TPU electrospun fiber membrane is placed in step 2) gained graphene dispersing solution
Middle supersound process 30min, makes graphene nanometer sheet uniformly be attached on electrospun fiber membrane；Then it is placed in air under room temperature
Dry, i.e. can obtain the network of fibers with conductive characteristic；The TPU electrospun fiber membrane that i.e. graphene nanometer sheet is modified.
(4) preparation of strain transducer: first by polydimethylsiloxane host and firming agent with the ratio of mass ratio 10:1
Example stirs 15 minutes, and then evacuation 20 minutes is to remove bubble, thus prepares uniform mixed liquor；Secondly revolve on substrate
Coat thickness mixed liquor about 80 μm, be placed on 10min in 80 DEG C of baking ovens so that it is be in semi-cured state；Then will
Step 3) the TPU electrospun fiber membrane of gained graphene nanometer sheet modified is placed in as conductive layer on polydimethylsiloxane, so
Pass through the wire fixed cell elargol two ends lead-in conductor at conductive layer afterwards；Again in the TPU electrospinning of graphene nanometer sheet modified
The upper spin coating last layer thickness of fibrous membrane (i.e. conductive layer) is the polydimethylsiloxane host about 80 μm and the mixing of firming agent
Liquid, is placed in baking oven so that it is be fully cured, finally it is peeled from substrate.
Fig. 1 is the axonometric chart of prepared flexible wearable strain transducer structure, the strain sensing of this flexible wearable
Device includes insulating barrier 1 and 5, conductive layer 2, wire 3 and wire fixed cell 4.It is mainly by the three-decker being similar to sandwich
Composition.Described insulating barrier 1 and 5 is respectively placed in upper and lower two-layer, and described conductive layer 2 is placed in centre；Conductive layer 2 two ends are passed through
Wire fixed cell 4 is connected with wire 3, and wire 3 connects extraneous measurement apparatus, and wire fixed cell 4 is elargol.
Performance test:
Being placed on stretching-machine by the conductive polymer composite of the gained in embodiment 1, two ends are drawn by wire, folder
On the electrode of circuit tester, with circuit tester in-situ monitoring and the change recording its resistance value, it is circulated the test of tensile property.
Fig. 2 is the time m-resistance of the conductive polymer composite of embodiment 1 gained 200 circulations under 5% strain
Curve；As can be seen from the figure after the circulation of certain number of times, relative changes delta R/R of resistance0(Δ R=Rt-R0, wherein
RtAnd R0It is respectively defined as the sample resistance in t and the initial resistance of sample) reach a platform, show the present invention
The resistance-strain respondent behavior of gained conductive polymer composite has been issued to the most stable in repeated loading.
Fig. 3 be under 200% elongation strain the 200 times circulations of embodiment 1 gained conductive polymer composite time m-
Resistance curve.Showing after a number of circulation, this sample can show reasonable stability and good in the circulating cycle
Good repeatability.Additionally, this sample has bigger responsiveness；Show this sample to can be used to detect big strain, can be used as
Big strain transducer.
Fig. 4 be embodiment 1 resulting materials under 1%, 2%, 3%, 4% and 5% elongation strain each 5 circulation time m-
The curve of resistance；Can be seen that this strain transducer presents reasonable respondent behavior under small strain.
Fig. 5 be embodiment 1 resulting materials under 50%, 100%, 150%, 200% elongation strain each 5 circulation time
Between resistance situation, it can be seen that this strain transducer has reasonable respondent behavior under big strain, and has big responsiveness.
In sum, the strain transducer prepared by the present invention has good repeatability and stability；Properties of product
Excellent, technological operation is simple, strain testing scope is wide, responsiveness is high and sensitivity advantages of higher.The pliability of composite makes
It can use as flexible wearable equipment.
Claims (10)
1. the strain transducer of flexible wearable, it is characterised in that described strain transducer includes insulating barrier, conductive layer and under
Insulating barrier, conductive layer is positioned at insulating barrier and the centre of lower insulating barrier；Described upper insulating barrier and lower insulating barrier by there is flexibility can
The macromolecular material dressing characteristic is made；Described conductive layer is that to have the macromolecular fibre/conductive filler of conductive network structure multiple
Close film.
The strain transducer of flexible wearable the most according to claim 1, it is characterised in that described in there is flexible wearable
The macromolecular material of characteristic one in polydimethylsiloxane, thermoplastic elastomer (TPE), natural rubber or synthetic rubber.
The strain transducer of flexible wearable the most according to claim 1 and 2, it is characterised in that described macromolecular fibre/
Conductive filler composite membrane is prepared by following method: conductive filler and deionized water are mixed to prepare mass concentration 0.01～5%
Conductive filler dispersion liquid, then macromolecular fibre film is placed in supersound process 1～100min in dispersion liquid so that conductive filler
Uniformly it is attached on macromolecular fibre film, macromolecular fibre film surface will be modified by conductive filler, dry the most in atmosphere；
Thus prepare the macromolecular fibre/conductive filler composite membrane with conductive network structure.
4. according to the strain transducer of the flexible wearable described in any one of claims 1 to 3, it is characterised in that in conductive layer
Described macromolecular fibre is selected from styrene butadiene styrene block copolymer (SBS) fiber, thermoplastic polyurethane fibers, polybutadiene
In acid butanediol ester fiber, polyvinylidene fluoride fiber, polycaprolactone fiber, collagen fabric or fibroin fiber extremely
Few one.
5. according to the strain transducer of the flexible wearable described in any one of Claims 1 to 4, it is characterised in that described conduction
At least one in graphene nanometer sheet, CNT, carbon fiber, metal nanometer line or white carbon black of conductive filler in Ceng.
6. according to the strain transducer of the flexible wearable described in any one of Claims 1 to 5, it is characterised in that described upper absolutely
Edge layer and lower insulating barrier are polydimethylsiloxane；Described macromolecular fibre/conductive filler composite membrane is that graphene nanometer sheet is repaiied
Thermoplastic polyurethane fibers/graphene nanometer sheet composite membrane that decorations are formed to thermoplastic polyurethane fibers film surface.
7. according to the strain transducer of the flexible wearable described in any one of claim 1～6, it is characterised in that described flexibility
Wearable strain transducer also includes conductive attachment element and wire, and described conductive layer two ends respectively connect a wire, described
Wire is connected with measuring instrument, and wire is fixed on conductive layer by wire fixed cell；Further, described wire fixed cell
For at least one in elargol, two component epoxy glue or inorganic material conducting resinl.
8. the preparation method of the strain transducer of the flexible wearable described in any one of claim 1～7, it is characterised in that bag
Include following steps:
1) on substrate, coating has the macromolecular material mixed liquor of flexible wearable characteristic, is then dried to still having good
The degree of good viscosity forms insulating barrier；
2) macromolecular fibre/conductive filler composite membrane with conductive network structure is placed in step 1) insulating barrier on formed and lead
Electric layer, then passes through the wire fixed cell two ends lead-in conductor at conductive layer；
3) again in step 2) conductive layer on coating there is the macromolecular material mixed liquor of flexible wearable characteristic, the most dry
Dry.
The preparation method of the strain transducer of flexible wearable the most according to claim 8, it is characterised in that step 1)
In, the condition being dried is: be dried 1～60min at 50～150 DEG C；Step 3) in, the condition being dried is: at 50～150 DEG C
It is dried 5～120min.
The preparation method of the strain transducer of flexible wearable the most according to claim 8 or claim 9, it is characterised in that step
1) and step 3) in, the thickness of described insulating barrier is 10～400 μm.
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Application publication date: 20161026 |