CN106943147A - Fibrous strain sensor with shape memory function and preparation method and application thereof - Google Patents
Fibrous strain sensor with shape memory function and preparation method and application thereof Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 20
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- 239000000758 substrate Substances 0.000 claims abstract description 15
- 238000004070 electrodeposition Methods 0.000 claims abstract description 14
- 229920002521 macromolecule Polymers 0.000 claims abstract description 6
- 229920000431 shape-memory polymer Polymers 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000005229 chemical vapour deposition Methods 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 229920000128 polypyrrole Polymers 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
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- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
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- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
- 230000037081 physical activity Effects 0.000 description 2
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/103—Detecting, measuring or recording devices for testing the shape, pattern, colour, size or movement of the body or parts thereof, for diagnostic purposes
- A61B5/11—Measuring movement of the entire body or parts thereof, e.g. head or hand tremor, mobility of a limb
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/08—Detecting, measuring or recording devices for evaluating the respiratory organs
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/68—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient
- A61B5/6801—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient specially adapted to be attached to or worn on the body surface
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Heart & Thoracic Surgery (AREA)
- Medical Informatics (AREA)
- Physics & Mathematics (AREA)
- Veterinary Medicine (AREA)
- Biophysics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Surgery (AREA)
- Animal Behavior & Ethology (AREA)
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- Oral & Maxillofacial Surgery (AREA)
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- Measurement Of Length, Angles, Or The Like Using Electric Or Magnetic Means (AREA)
Abstract
The invention relates to a fibrous strain sensor with a shape memory function and a preparation method thereof; the invention takes shape memory polymer fiber as a substrate, wraps an oriented carbon nanotube film as a conductive layer, and modifies conductive macromolecules by an electrochemical deposition method to form the carbon nanotube/conductive macromolecule composite film with a network structure. The invention utilizes polymer fiber with shape memory function to prepare the fiber-shaped strain sensor with the shape memory function, can be shaped into different curvatures and lengths by heating, and can return to the original shape when reaching the transition temperature. The fibrous strain sensor with the shape memory function can be attached to the skin or attached to clothes to realize detection of human joint movement, respiration and the like, and the unique shape memory function can be tightly matched with wearable accessories in any shapes, so that a new idea is provided for preparation of wearable devices.
Description
Technical field
The present invention relates to strain transducer field, and in particular to flexible wearable strain transducer field.
Background technology
In recent years, it is soft as a series of electronic equipments that Google's glasses, intelligent watch, bracelet etc. are representative enter market
Property wearable electronic obtained very big attention and fast development, increasing research work is directed to developing flexible sensing
The wearable microelectronic devices such as device, flexible actuator, man-made electronic's skin.
Traditional strain transducer is often prepared with rigid material, and extensibility and wearable property are all poor.Flourish recently
The field such as wearable electronic device, interactive bio-robot require sensor can detect big strain (>>5%), and
There is compatibility with organism, traditional sensor obviously can not meet above-mentioned requirements.Therefore, people exploring it is new can
The strain transducer of stretching.
CNT has quasi- one-dimensional and excellent electric conductivity, and natural the having of its macroscopical aggregation (film) can be drawn
Performance is stretched, is the ideal material for preparing stretchable function element.In addition, filamentary structure can realize it is soft on three-dimensional
Property, diversified product design is can adapt to, and the weaving of low cost can be passed through as traditional chemical fiber
Technology, is made wearable fabric of good performance, so as to effectively meet the hair of wearable device and various portable electric appts
Exhibition needs.
But common strain transducer only has single shape, it is difficult to meet various electronic function or various
Change the demand of practical application.In actual applications, different shapes usually needs to be fixed, such as by wearable electronic device
It is fixed on the different parts of body.Therefore, development one kind disclosure satisfy that a variety of demands, realize wearing for User Defined shape
Wear equipment and just seem and be even more important.
The content of the invention
Goal of the invention：A kind of fibrous strain transducer with shape memory function and preparation method thereof is provided.
Technical scheme：Fibrous strain transducer with shape memory function is using shape memory polymer fibers as base
Bottom, orientation carbon nanotube film is wrapped up as conductive layer with the method for Mechanical entanglement, then is led with the method modification of electrochemical deposition
Electric macromolecule, forms the carbon nano tube/conducting macromolecule laminated film with network structure, finally gives with shape memory work(
The fibrous strain transducer of energy.
The preparation method of shape memory fiber shape strain transducer of the present invention, is concretely comprised the following steps：
1. aligned carbon nanotube array can be spun by being prepared with chemical vapour deposition technique (CVD), aligned carbon nanotube battle array can spun
Orientation carbon nanotube film is pulled out on row；
2. shape memory fiber is fixed on two consistent motors of rotating speed, coordinate translation stage, by aligned carbon nanotube
Film is ridden on shape memory fiber relative to the fiber of horizontal direction with 70 ° of -80 ° of angles；Control the rotating speed and translation stage of motor
Speed remain a constant speed, make carbon nano-tube film uniform winding on shape memory fiber and keep angle constant, obtain CNT bags
The TPU conductive fibers wrapped up in；
3. the method for use electrochemical deposition modified conducting polyphosphazene polymer pyrroles on conductive fiber, being formed has network structure
Carbon nano tube/conducting macromolecule laminated film, obtain fibrous strain transducer.
The preparation method of wearable device of the present invention is：Obtained fibrous strain transducer is fixed on poly- two
In methylsiloxane (PDMS) flexible substrates, two termination copper cash apply elargol, are sealed after drying with epoxide-resin glue, obtain wearable
Device.
Prepared by aligned carbon nanotube arrays use chemo vapour deposition process of the present invention, comprise the concrete steps that：In Si/
SiO2Spraying plating a layer thickness 1nm Fe films, using chemical vapour deposition technique, carbon source are made with ethene as catalyst on substrate,
Using argon gas as carrier gas, in Si/SiO2Height-oriented carbon nano pipe array is synthesized on substrate；Wherein ethene flow is 30-
50sccm, argon flow amount is 100-200sccm, and 10min is grown at 750 DEG C in the tube furnace of the equipment inch quartz tube of diameter 1.
The method of electrochemical deposition polypyrrole of the present invention, is comprised the concrete steps that：Configure KCl containing 0.02M, 0.05M pyrroles
Monomer, 0.001M HCl solution are coughed up, with parcel CNT TPU fibers as working electrode, Ag/AgCl electrodes make reference electrode,
Platinum electrode is made to electrode, polymerize 500-2000s under 0.75V constant voltages.
Beneficial effect:
1st, the present invention prepares shape memory fiber shape using the high polymer fiber with shape-memory properties and answered
Become sensor, because carbon nano-tube film with 70 ° of -80 ° of angle uniform windings forms network structure on shape memory fiber, and
Polypyrrole layer can be used as protective layer again as conductive layer so that carbon nano-tube/poly pyrroles laminated film under big strain still
The integrality of right energy holding structure, thus sensor can keep higher sensitivity (0-10% in 0-50% range of strain
It within 10,10-50% strains be 3-5 to be within strain), and with relatively low test limit (0.1% strain), can guarantee that its work
Detection for strain transducer to all kinds of human motions.
2nd, this strain transducer also has shape memory function, can be shaped into different curvature and length, and up to
To that can return to original shape during transition temperature, obvious change does not occur for performance before and after deformation.It is this that there is shape memory
The fibrous strain transducer of function can realize human body joint motion, breathing, language by being directly affixed on skin or being attached to clothing
The detection of sound identification, and its unique shape memory function can realize tight fit with the wearable accessory of arbitrary shape, be
The preparation of wearable device provides new thinking.
Brief description of the drawings
Fig. 1 is can to spin the SEM photograph of aligned carbon nanotube array and carbon nano-tube film, wherein figure a is can to spin orientation carbon
Nano-tube array；It is orientation carbon nanotube film to scheme b；
Fig. 2 is the preparation process schematic diagram of shape memory fiber shape strain transducer；
Fig. 3 is the SEM shape appearance figures for the TPU fiber electrochemical deposition polypyrrole different times for wrapping up CNT, wherein figure a is not
Presedimentary SEM shape appearance figures, figure b, c, d are the SEM shape appearance figures for depositing 500s, 1000s, 2000s respectively；
Fig. 4 is the relatively electric of electrochemical deposition 0s, 500s, 1000s, 2000s shape memory fiber shape strain transducer
Resistive-strain curve；
Fig. 5 is the curve for testing shape memory fiber shape strain transducer test limit；
Fig. 6 is the detection that shape memory fiber shape strain transducer is applied to human finger arthrogryposis；
Fig. 7 is the detection that shape memory fiber shape strain transducer is applied to human body respiration；
Fig. 8 is that shape memory fiber shape strain transducer reaches transition temperature deformation and the procedure chart recovered；
Fig. 9 is that shape memory fiber shape strain transducer is woven into fabric, real by shape memory function and joint
The demonstration graph of existing tight fit.
Embodiment
Embodiment 1：
1. aligned carbon nanotube array can be spun by being prepared with chemical vapour deposition technique (CVD)：In Si/SiO2Spraying plating one on substrate
Thickness 1nm Fe films, using chemical vapour deposition technique, carbon source are made with ethene as catalyst, using argon gas as carrier gas,
Si/SiO2Height-oriented carbon nano pipe array is synthesized on substrate；Wherein ethene flow is 30sccm, and argon flow amount is
100sccm, 10min is grown in the tube furnace of the equipment inch quartz tube of diameter 1 at 750 DEG C.
2. the TPU fibers of certain diameter are fixed on two motors of same rotational speed, carbon nano-pipe array can be spun one
Row are placed on translation stage, and then carbon nano-tube film is pulled out from array, ridden over 70 ° of angles on TPU fibers.Control motor
The speed of rotating speed and translation stage at the uniform velocity, keeps that angle is constant CNT is spirally wound on TPU fibers, so as to obtain CNT
The TPU electrically conductive elastic fibers of parcel.
3. in one layer of conducting polymer-polypyrrole of conductive fiber surfaces electrochemical deposition：Configure KCl containing 0.02M, 0.05M
The solution of pyrrole monomer, 0.001M HCl, with parcel CNT TPU fibers as working electrode, Ag/AgCl electrodes make reference electricity
Pole, platinum electrode is made to electrode, polymerize 500s under 0.75V constant voltages, obtains fibrous strain transducer.
Embodiment 2：
1. aligned carbon nanotube array can be spun by being prepared with chemical vapour deposition technique (CVD)：In Si/SiO2Spraying plating one on substrate
Thickness 1nm Fe films, using chemical vapour deposition technique, carbon source are made with ethene as catalyst, using argon gas as carrier gas,
Si/SiO2Height-oriented carbon nano pipe array is synthesized on substrate；Wherein ethene flow is 50sccm, and argon flow amount is
200sccm, 10min is grown in the tube furnace of the equipment inch quartz tube of diameter 1 at 750 DEG C.
2. the TPU fibers of certain diameter are fixed on two motors of same rotational speed, carbon nano-pipe array can be spun one
Row are placed on translation stage, and then carbon nano-tube film is pulled out from array, ridden over 75 ° of angles on TPU fibers.Control motor
The speed of rotating speed and translation stage at the uniform velocity, keeps that angle is constant CNT is spirally wound on TPU fibers, so as to obtain CNT
The TPU electrically conductive elastic fibers of parcel.
3. in one layer of conducting polymer-polypyrrole of conductive fiber surfaces electrochemical deposition：Configure KCl containing 0.02M, 0.05M
The solution of pyrrole monomer, 0.001M HCl, with parcel CNT TPU fibers as working electrode, Ag/AgCl electrodes make reference electricity
Pole, platinum electrode is made to electrode, polymerize 1000s under 0.75V constant voltages, obtains fibrous strain transducer.
Embodiment 3：
1. aligned carbon nanotube array can be spun by being prepared with chemical vapour deposition technique (CVD)：In Si/SiO2Spraying plating one on substrate
Thickness 1nm Fe films, using chemical vapour deposition technique, carbon source are made with ethene as catalyst, using argon gas as carrier gas,
Si/SiO2Height-oriented carbon nano pipe array is synthesized on substrate；Wherein ethene flow is 45sccm, and argon flow amount is
155sccm, 10min is grown in the tube furnace of the equipment inch quartz tube of diameter 1 at 750 DEG C.
2. the TPU fibers of certain diameter are fixed on two motors of same rotational speed, orientation carbon nanometer can be spun one
Pipe array is placed on translation stage, and then orientation carbon nanotube film is pulled out from array, is ridden over 80 ° of angles on TPU fibers.Control
The rotating speed of motor processed and the speed of translation stage at the uniform velocity, keep that angle is constant CNT is spirally wound on TPU fibers, so that
Obtain the TPU electrically conductive elastic fibers of CNT parcels.
3. in one layer of conducting polymer-polypyrrole of conductive fiber surfaces electrochemical deposition：Configure KCl containing 0.02M, 0.05M
The solution of pyrrole monomer, 0.001M HCl, with parcel CNT TPU fibers as working electrode, Ag/AgCl electrodes make reference electricity
Pole, platinum electrode is made to electrode, polymerize 2000s under 0.75V constant voltages, obtains fibrous strain transducer.
The SEM photograph that aligned carbon nanotube array and orientation carbon nanotube film can be spun in embodiment 1-3 is shown in accompanying drawing 1.
The preparation process of shape memory fiber shape strain transducer is shown in accompanying drawing 2 in embodiment 1-3.
The polypyrrole shape appearance figure for implementing the different electrochemical deposition times in row 1-3 is shown in accompanying drawing 3.
Strain is applied to the shape memory fiber shape strain transducer in embodiment 1-3, test its relative resistance change (see
Accompanying drawing 4), test result shows that the effect that electrochemical deposition 2000s fiber is obtained is best：Can in 50% range of strain,
Keep higher sensitivity (be within 0-10% strains within 10,10-50% is strained be 3-5).
In order to test the low test limit of shape memory fiber shape strain transducer, to the shape memory fiber in embodiment 3
Shape strain transducer applies 2%-0.1% strain (see accompanying drawing 5) of successively decreasing, and test result shows that lowest detection is limited to 0.1% and answered
Become, be conducive to detecting small physical activity.
The fibrous strain transducer that embodiment 3 is obtained is fixed in PDMS flexible substrates, and two termination copper cash apply elargol,
Sealed after drying with epoxide-resin glue, can obtain wearable device, be easy to the monitoring of follow-up physical activity.Human finger is monitored to close
Bent-segment is shown in accompanying drawing 6, and monitoring human body respiration is shown in accompanying drawing 7.
Another important feature of the fibrous strain transducer is shape memory function, and fiber is heated into transition temperature can
To be shaped into desired shape, transition temperature resilient again is reached again, and process is shown in accompanying drawing 8.
In addition, plurality of fibers, which is woven together, can be made wearable fabric, the fabric can pass through shape memory work(
The tight fit with joint can be realized (see accompanying drawing 9), it is adaptable to which the object of a variety of nonplanar structures, is the preparation of wearable device
There is provided new thinking.
Claims (6)
1. a kind of shape memory fiber shape strain transducer, it is characterised in that its structure composition is as follows：With shape-memory polymer
Fiber is substrate, and parcel orientation carbon nanotube film modifies one layer conductive high as conductive layer, then with the method for electrochemical deposition
Molecule polypyrrole formation laminated film.
2. shape memory fiber shape strain transducer according to claim 1, it is characterised in that shape-memory polymer is fine
Tie up and be：Thermoplastic polyurethane fibers.
3. the preparation method of the shape memory fiber shape strain transducer described in claim 1, it is characterised in that specific steps are such as
Under：
(1) prepared by chemical vapour deposition technique can spin aligned carbon nanotube array, be taken that can spin to pull out on aligned carbon nanotube array
To carbon nano-tube film；
(2) shape memory fiber is fixed on two consistent motors of rotating speed, coordinates translation stage, by orientation carbon nanotube film
Fiber relative to horizontal direction is ridden on shape memory fiber with 70 ° -80 ° of angle, controls the rotating speed and translation stage of motor
Speed remain a constant speed, make carbon nano-tube film uniform winding on shape memory fiber and keep angle constant, obtain CNT bags
The TPU conductive fibers wrapped up in；
(3) method of use electrochemical deposition modified conducting polyphosphazene polymer pyrroles on conductive fiber, forms with network structure
Carbon nano tube/conducting macromolecule laminated film, obtains fibrous strain transducer.
4. the preparation method of shape memory fiber shape strain transducer according to claim 3, it is characterised in that step
(1) aligned carbon nanotube preparation method described in is：Spraying plating a layer thickness 1nm Fe films are as urging on Si/SiO2 substrates
Agent, using chemical vapour deposition technique, carbon source is done with ethene, using argon gas as carrier gas, and synthesis height takes on Si/SiO2 substrates
To carbon nano pipe array；Wherein ethene flow is 30-50sccm, and argon flow amount is 100-200sccm, in the equipment English of diameter 1
In the tube furnace of very little quartz ampoule 10min is grown at 750 DEG C.
5. the preparation method of shape memory fiber shape strain transducer according to claim 1, it is characterised in that step
(3) method of electrochemical deposition polypyrrole is in：KCl containing 0.02m, 0.05m pyrrole monomers, 0.001m HCl solution are configured,
Make working electrode with parcel CNT TPU fibers, Ag/AgCl electrodes make reference electrode, and platinum electrode is made to electrode, in the permanent electricity of 0.75V
Pressure polymerization 500-2000s.
6. the application of shape memory fiber shape strain transducer, it is characterised in that applied to wearable device, the fibre that will be obtained
Dimension shape strain transducer is placed in flexible dimethyl silicone polymer (PDMS) substrate, and two termination copper cash apply elargol, and use epoxy
Resin glue is sealed, and obtains wearable device.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108294747A (en) * | 2018-01-16 | 2018-07-20 | 中国科学院半导体研究所 | Aligned carbon nanotube adheres to dry electrode and its preparation process certainly |
| WO2018182532A1 (en) * | 2017-03-30 | 2018-10-04 | Nanyang Technological University | Strain sensor, method of forming and operating the same |
| CN108742636A (en) * | 2018-03-30 | 2018-11-06 | 南京工业大学 | Method for monitoring walking posture based on conductive leather |
| CN109524423A (en) * | 2018-09-29 | 2019-03-26 | 中国科学院半导体研究所 | It can pretend deformable intelligent visible light near infrared detector and preparation method thereof |
| CN112185607A (en) * | 2020-10-16 | 2021-01-05 | 郑州大学 | Flexible sensor with integrated electrode and preparation method and application thereof |
| CN113865475A (en) * | 2021-09-23 | 2021-12-31 | 浙江大学 | Preparation method and application of bionic self-adaptive winding wearable sensor for monitoring diameter micro-change of plant stem |
| CN114519953A (en) * | 2022-02-21 | 2022-05-20 | 北京工业大学 | Bionic insect |
| CN115844386A (en) * | 2022-11-16 | 2023-03-28 | 哈尔滨工业大学（深圳） | Flexible sensor and preparation method and application thereof |
| CN115901028A (en) * | 2022-09-02 | 2023-04-04 | 河北工业大学 | Flexible touch sensor with adhesive property and air permeability and preparation method thereof |
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| CN102509635A (en) * | 2011-10-31 | 2012-06-20 | 华中科技大学 | Preparation method of flexible super capacitor based on carbon cloth |
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| CN108294747A (en) * | 2018-01-16 | 2018-07-20 | 中国科学院半导体研究所 | Aligned carbon nanotube adheres to dry electrode and its preparation process certainly |
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| CN109524423A (en) * | 2018-09-29 | 2019-03-26 | 中国科学院半导体研究所 | It can pretend deformable intelligent visible light near infrared detector and preparation method thereof |
| CN112185607A (en) * | 2020-10-16 | 2021-01-05 | 郑州大学 | Flexible sensor with integrated electrode and preparation method and application thereof |
| CN112185607B (en) * | 2020-10-16 | 2022-02-22 | 郑州大学 | Flexible sensor with integrated electrode and preparation method and application thereof |
| CN113865475A (en) * | 2021-09-23 | 2021-12-31 | 浙江大学 | Preparation method and application of bionic self-adaptive winding wearable sensor for monitoring diameter micro-change of plant stem |
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| CN115901028A (en) * | 2022-09-02 | 2023-04-04 | 河北工业大学 | Flexible touch sensor with adhesive property and air permeability and preparation method thereof |
| CN115844386A (en) * | 2022-11-16 | 2023-03-28 | 哈尔滨工业大学（深圳） | Flexible sensor and preparation method and application thereof |
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