CN107389232A - A kind of asymmetric flexible force sensitive sensing material of bio-based and preparation method thereof - Google Patents

A kind of asymmetric flexible force sensitive sensing material of bio-based and preparation method thereof Download PDF

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Publication number
CN107389232A
CN107389232A CN201710450586.5A CN201710450586A CN107389232A CN 107389232 A CN107389232 A CN 107389232A CN 201710450586 A CN201710450586 A CN 201710450586A CN 107389232 A CN107389232 A CN 107389232A
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bio
sensing material
flexible force
sensitive sensing
force sensitive
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CN107389232B (en
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刘岚
陈松
刘书奇
董旭初
魏勇
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South China University of Technology SCUT
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South China University of Technology SCUT
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01LMEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L1/00Measuring force or stress, in general
    • G01L1/20Measuring force or stress, in general by measuring variations in ohmic resistance of solid materials or of electrically-conductive fluids; by making use of electrokinetic cells, i.e. liquid-containing cells wherein an electrical potential is produced or varied upon the application of stress
    • G01L1/22Measuring force or stress, in general by measuring variations in ohmic resistance of solid materials or of electrically-conductive fluids; by making use of electrokinetic cells, i.e. liquid-containing cells wherein an electrical potential is produced or varied upon the application of stress using resistance strain gauges

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Force Measurement Appropriate To Specific Purposes (AREA)
  • Measurement Of Length, Angles, Or The Like Using Electric Or Magnetic Means (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)

Abstract

The invention discloses asymmetric flexible force sensitive sensing material of a kind of bio-based and preparation method thereof, belong to the preparation field of advanced function material.This method comprises the following steps:(1)Zero dimension, one-dimensional or two-dimentional electrical-conductive nanometer material in the fiber surface load or assembling of fully biodegradable, are made the different conductive fibre fabric of two panels electric conductivity;(2)Positive and negative electrode is connected at the larger conductive fibre fabric both ends of resistance simultaneously;(3)By " face-to-face " fitting of the different conductive fibre fabric of two panels electric conductivity and encapsulate, obtain the asymmetric flexible force sensitive sensing material of bio-based.High-molecular bone frame material of the present invention is totally biodegradable natural macromolecular material, has the characteristics of environment-friendly;And sensitivity of the power sensitive sensing material of the present invention to pressure, Bending Deformation, twist distortion is superior to the current most of pressure resistance type flexible force sensitive sensing material reported, and show superpower stability and detectable limit and outstanding pliability.

Description

A kind of asymmetric flexible force sensitive sensing material of bio-based and preparation method thereof
Technical field
The present invention relates to the preparing technical field of advanced function material, and in particular to a kind of asymmetric flexible force of bio-based is quick Sensing material and preparation method thereof.
Background technology
With developing rapidly for electronic technology, there is an urgent need to can meet intelligent robot, electronic skin, wearable device etc. High performance flexible force sensitive sensing material.It is a kind of surface that can be attached at various irregular objects, can perceive material Surface reaction forces (compression, bending, stretching, distortion etc.), and the deformation signal in the external world is converted into electric signal and realizes the quick sensing of power Electronic functional material.It is by the preferable macromolecule matrix of pliability(Or flexible substrate, including rubber, plastic sheeting and fibre Dimensional fabric etc.)With conductive element(Conductive filler)It is combined by certain way, due to various irregular tables can be attached at On face, flexible, compression, frivolous, the advantages that being easy to carry, in wearable device, intelligent robot, biomethanics, medical treatment inspection The fields such as survey, flexible flat panel display device have a wide range of applications, and become the focus direction of Current electronic investigation of materials.
In recent years, with the development of science and technology, many high sensitivity, high stability, low detectable limit and can quickly ring The sensing arrangement answered has been devised and has been applied to flexible force sensitive sensing material.But these flexible force sensitive sensing materials are equal Design, i.e., pasted the completely the same conductive surface with certain roughness of two panels in a manner of " face-to-face " for symmetric form Close, connect electrode respectively on upper and lower two surfaces and encapsulate and complete;And the high score used in this kind of flexible force sensitive sensing material Subbase body is the nondegradable thermo-setting elastomers such as silicon rubber, natural rubber, butadiene-styrene rubber, cross-linked type polyurethane.Many institute's weeks Know, the renewal rate of Current electronic product is very fast, and this not biodegradable macromolecule matrix is obviously not suitable for current electricity The development trend of sub- material, it is therefore necessary to develop a kind of with excellent sensing capabilities and can be quick with biodegradable flexible force Sensing material.
The content of the invention
It is an object of the invention to provide a kind of flexible force sensitive sensing material and preparation method thereof, and in particular to a kind of biology Asymmetric flexible force sensitive sensing material of base and preparation method thereof, be advantageous to widen the Research connotation of current flexible force sensitive sensing material With scope, the inventive method is simple, efficient, has very wide application prospect.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of the asymmetric flexible force sensitive sensing material of bio-based, comprises the following steps:
(1)Zero dimension, one-dimensional or two-dimentional electrical-conductive nanometer material in the fiber surface load or assembling of fully biodegradable, system Obtain the different conductive fibre fabric of two panels electric conductivity;
(2)Positive and negative electrode is connected at the larger conductive fibre fabric both ends of resistance simultaneously;
(3)By " face-to-face " fitting of the different conductive fibre fabric of two panels electric conductivity and encapsulate, it is quick to obtain the asymmetric flexible force of bio-based Sensing material.
Preferably, described fiber is derived from the natural plants of the Nature or the natural fiber of animal or natural polymer Compound obtained textile fabric after chemical process spinning.
Preferably, described fully biodegradable natural fiber is derived from the natural plants or animal fibre of the Nature Dimension, can be pure natural cotton fiber, flaxen fiber, wool fiber, silk, spider silk etc. or by cellulose, marine alga The obtained weaving after chemical process spinning of the natural polymers such as acid, chitin, chitosan, starch, protein is fine Dimension.A diameter of 100 nm-100 μm of the dimension of the single fiber, length is 10 μm of -5 cm.
Preferably, the thickness of described conductive fibre fabric is 1-400 μm.
Preferably, described zero dimension, one-dimensional or two-dimentional electrical-conductive nanometer material can be metal nanoparticle (such as silver nanoparticles Particle, golden nanometer particle, copper nano-particle etc.), non pinetallic nano particle (such as acetylene carbon black), metal nanometer line (such as silver nanoparticle Line, nanowires of gold, copper nano-wire etc.), CNT, graphene, blended metal oxide (such as aluminium-doped zinc oxide nano-particle Or nano wire) in one or more.
Preferably, it is described by electrical-conductive nanometer material load, be assembled in fiber cloth surface can be by growth in situ or By the way that electrical-conductive nanometer material is fixed on into fiber surface the methods of Physical interaction (such as hydrogen bond, hydrophobic bond).
Preferably, the diameter of the zero dimension electrical-conductive nanometer material is less than 100 nm, and the draw ratio of monodimension nanometer material is 10- 1000, the thickness of two-dimension nano materials is 0.3-100 nm, nm-100 μm of piece footpath 100.
Preferably, described electrical-conductive nanometer material is 10 nm-10 μm in the thickness of fiber surface, and length is with width 1 cm-10 cm。
Preferably, described electrode is the metal electrodes such as copper electrode, platinum electrode, aluminium electrode, and positive and negative electrode should be fixed on electricity Hinder larger fiber cloth both ends.
Preferably, the resistance of the larger conductive fibre fabric of resistance and the less fiber cloth of resistance in described conductive fibre fabric Ratio is 1:1 to 50000:1.The difference of two panels conductive fibre fabric resistance value obtains high sensitivity flexible force sensitive sensing material Key, on the premise of conductive stability is ensured, the resistance of the larger conductive fibre fabric of its resistance and the less fiber cloth of resistance Ratio it is bigger (>1) sensitivity of the flexible force sensitive sensing material, obtained is higher, detectable limit is lower, and the response time is also faster.
Compared with prior art, the present invention has advantages below:
1st, preparation method of the invention is simple, efficient, has very wide application prospect.
2nd, high-molecular bone frame material of the present invention is totally biodegradable natural macromolecular material, has environment The characteristics of friendly;
3rd, the sensitivity of power sensitive sensing material of the invention to pressure can reach 5-10 kPa-1, the sensitivity to Bending Deformation 0.5-2 Rad can be reached-1, the sensitivity to twist distortion can reach 0.05-0.1 and often spend, and be superior to what is reported at present Most of pressure resistance type flexible force sensitive sensing material, and show superpower stability (>10000 circulations) and detectable limit (<5 ) and outstanding pliability mg.
Brief description of the drawings
Fig. 1 is the structural representation of the asymmetric flexible force sensitive sensing material of bio-based.
Embodiment
The present invention is further described with reference to embodiment, but the implementation of the present invention is not limited to this.
The structural representation of the asymmetric flexible force sensitive sensing material of bio-based of the present invention is as shown in figure 1, the material includes Electrode 1, encapsulating material 2, small resistor conductive fibre fabric 3 and big resistance conductive fiber cloth 4, wherein, big resistance conductive fiber cloth two End is connected to electrode, and small resistor conductive fibre fabric " face-to-face " is fitted in big resistance conductive fiber cloth, will by encapsulating material Electrode, small resistor conductive fibre fabric and the encapsulation of big resistance conductive fiber cloth.
Embodiment 1
Size is immersed in 2min in 3mg/ml graphene oxide water solution for the cotton fiber cloth of 1cm × 4cm × 1 μm, 80 DEG C Lower dry 30min, make the graphene oxide that 20 nm are thick in cotton fiber cloth surface-assembled, then under 80 DEG C of environment, concentration is 5mg/cm3Hydrazine hydrate steam in reduction 1h obtain the cotton fiber cloth for the load graphene that resistance is 5000 Ω, and at its both ends Connect copper electrode;The absolute ethyl alcohol for the nanowires of gold that size is immersed in into 3mg/ml for the cotton fiber cloth of 1cm × 4cm × 1 μm is molten Taken out in liquid after 2min, 60 DEG C of dry 20min, make the nanowires of gold that thickness is 500 nm in cotton fiber cloth surface-assembled, obtain Resistance is the cotton fiber cloth of 0.1 Ω load gold nano line;The cotton fiber cloth of load gold nano line is fitted in load graphite again On the cotton fiber cloth of alkene, it is packaged as encapsulating material to obtain flexible force sensitive sensing material using 3M adhesive tapes.
Sensitivity of the flexible force sensitive sensing material manufactured in the present embodiment to pressure is 10 kPa-1, the spirit to Bending Deformation Sensitivity is 1.1 Rad-1, sensitivity to twist distortion often spends for 0.09, and the most of pressure resistance type for being superior to report at present is soft Property power sensitive sensing material, and show superpower stability (>10000 circulations) and detectable limit (<5 mg) and outstanding Pliability.
Embodiment 2
Size is immersed in 2min in 3mg/ml carbon nano-tube aqueous solutions for the fibroin fiber cloth of 1cm × 4cm × 400 μm After take out, 80 DEG C of dry 30min, make the thick technical grade CNT of 100 nm in fibroin fiber cloth surface-assembled, obtain The fiber cloth for the load CNT that resistance is 1500 Ω, and connect aluminium electrode at its both ends;By size be the cm of 2 cm × 3 × 400 μm of fibroin fiber cloth be immersed in the silver nitrate containing 20wt%, 5wt% PVP the aqueous solution in take out after 2min, Then under 80 DEG C of environment, concentration 5mg/cm3Hydrazine hydrate steam situ reduction 30min, so as in fibroin fiber Cloth area load a layer thickness is 400 nm Nano silver grain, obtains the fiber for the load Nano silver grain that resistance is 5 Ω Cloth;The fiber cloth for loading Nano silver grain is fitted in the fiber cloth of load CNT again, using 3M adhesive tapes as encapsulation Material is packaged to obtain flexible force sensitive sensing material.
Sensitivity of the flexible force sensitive sensing material manufactured in the present embodiment to pressure is 5 kPa-1, to the sensitive of Bending Deformation Spend for 0.8 Rad-1, sensitivity to twist distortion often spends for 0.06, and the most of pressure resistance type for being superior to report at present is flexible Power sensitive sensing material, and show superpower stability (>10000 circulations) and detectable limit (<5 mg) and remarkably soft Toughness.
Embodiment 3
Size is immersed in 3mg/ml carbon nano-tube aqueous solutions after 2min for the wool fiber cloth of 1cm × 4cm × 200 μm and taken Go out, 80 DEG C of dry 30min, make the technical grade acetylene carbon black that 500 nm are thick in fiber cloth surface-assembled, it is 2000 Ω to obtain resistance Load acetylene carbon black wool fiber cloth, and connect copper electrode at its both ends;It is cm × 200 μm of 3 cm × 3 by size Wool fiber cloth be immersed in the copper chloride containing 20wt%, 5wt% PVP the aqueous solution in take out after 1min, then in 80 DEG C of rings Under border, concentration 5mg/cm3Hydrazine hydrate steam situ reduction 30min, so as in the thickness of wool fiber cloth area load one The copper nano-particle spent for 1 μm obtains the wool fiber cloth for the load copper nano-particle that resistance is 10 Ω;Supported copper is received again The wool fiber cloth of rice corpuscles is fitted on the wool fiber cloth of load acetylene carbon black, is carried out using 3M adhesive tapes as encapsulating material Encapsulation obtains flexible force sensitive sensing material.
Sensitivity of the flexible force sensitive sensing material manufactured in the present embodiment to pressure is 5 kPa-1, to the sensitive of Bending Deformation Spend for 0.6 Rad-1, sensitivity to twist distortion often spends for 0.09, and the most of pressure resistance type for being superior to report at present is flexible Power sensitive sensing material, and show superpower stability (>10000 circulations) and detectable limit (<5 mg) and remarkably soft Toughness.
Embodiment 4
Size is immersed in 3mg/ml graphene oxide water solution after 2min for the cotton fiber cloth of 1cm × 4cm × 100 μm and taken Go out, 80 DEG C of dry 30min, make the graphene oxide that 20 nm are thick in fiber cloth surface-assembled, and in 5mg/cm3The hydration of concentration 1h is reduced in hydrazine steam and obtains conductive sodium alginate fiber cloth of the resistance for 1000 Ω, and copper electrode is connected at its both ends;By chi It is very little be the sodium alginate fiber cloth of cm × 100 μm of 4 cm × 4 be immersed in the silver nitrate containing 20wt%, 5wt% PVP it is water-soluble Taken out in liquid after 2min, then under 80 DEG C of environment, concentration 5mg/cm3Hydrazine hydrate steam situ reduction 30min, so as to In the Nano silver grain that sodium alginate fiber cloth area load a layer thickness is 400 nm, the load silver that resistance is 10 Ω is obtained The sodium alginate fiber cloth of nano-particle;The sodium alginate fiber cloth for loading Nano silver grain is fitted in load graphene again In conductive sodium alginate fiber cloth, it is packaged as encapsulating material to obtain flexible force sensitive sensing material using 3M adhesive tapes.
Sensitivity of the flexible force sensitive sensing material manufactured in the present embodiment to pressure is 8 kPa-1, to the sensitive of Bending Deformation Spend for 0.7 Rad-1, sensitivity to twist distortion often spends for 0.1, and the most of pressure resistance type for being superior to report at present is flexible Power sensitive sensing material, and show superpower stability (>10000 circulations) and detectable limit (<5 mg) and remarkably soft Toughness.

Claims (10)

1. a kind of preparation method of the asymmetric flexible force sensitive sensing material of bio-based, it is characterised in that comprise the following steps:
(1)Zero dimension, one-dimensional or two-dimentional electrical-conductive nanometer material in the fiber surface load or assembling of fully biodegradable, system Obtain the different conductive fibre fabric of two panels electric conductivity;
(2)Positive and negative electrode is connected at the larger conductive fibre fabric both ends of resistance;
(3)By " face-to-face " fitting of the different conductive fibre fabric of two panels electric conductivity and encapsulate, it is quick to obtain the asymmetric flexible force of bio-based Sensing material.
2. a kind of preparation method of the asymmetric flexible force sensitive sensing material of bio-based according to claim 1, its feature exist In step(1)Described fiber is derived from the natural plants of the Nature or the natural fiber of animal or natural polymer chemical combination Thing obtained textile fabric after chemical process spinning;Nm-100 μm of a diameter of the 100 of single fiber in the fiber, it is long Spend for 10 μm of -5 cm.
3. a kind of preparation method of the asymmetric flexible force sensitive sensing material of bio-based according to claim 2, its feature exist In the natural fiber is cotton fiber, flaxen fiber, wool fiber, silk or spider silk;The natural polymer is fibre Tie up element, alginic acid, chitin, chitosan, starch or protein.
4. a kind of preparation method of the asymmetric flexible force sensitive sensing material of bio-based according to claim 1, its feature exist In step(1)Described zero dimension, one-dimensional or two-dimentional electrical-conductive nanometer material are Nano silver grain, golden nanometer particle, copper nanoparticle Son, acetylene carbon black, nano silver wire, nanowires of gold, copper nano-wire, CNT, graphene, aluminium-doped zinc oxide nano-particle or One or more in nano wire.
5. a kind of preparation method of the asymmetric flexible force sensitive sensing material of bio-based according to claim 1, its feature exist In step(1)The diameter of the electrical-conductive nanometer material of the zero dimension is less than 100 nm;The draw ratio of one-dimensional electrical-conductive nanometer material is 10-1000;The thickness of the electrical-conductive nanometer material of two dimension be 0.3-100 nm, and piece footpath is 100 nm-100 μm.
6. a kind of preparation method of the asymmetric flexible force sensitive sensing material of bio-based according to claim 1, its feature exist In step(1)Described electrical-conductive nanometer material is 10 nm-10 μm in the thickness of fiber surface, and length and width are 1 cm- 10 cm;The thickness of described conductive fibre fabric is 1-400 μm.
7. a kind of preparation method of the asymmetric flexible force sensitive sensing material of bio-based according to claim 1, its feature exist In step(1)In be that electrical-conductive nanometer material is fixed on by fiber surface by the method for growth in situ or Physical interaction.
8. a kind of preparation method of the asymmetric flexible force sensitive sensing material of bio-based according to claim 1, its feature exist In step(2)Described electrode is copper electrode, platinum electrode or aluminium electrode.
9. a kind of preparation method of the asymmetric flexible force sensitive sensing material of bio-based according to claim 1, its feature exist In step(3)The resistance ratio of the larger conductive fibre fabric of resistance and the less fiber cloth of resistance in described conductive fibre fabric For 1:1-50000:1.
A kind of 10. asymmetric flexible force sensitive sensing material of bio-based as made from the method described in claim any one of 1-9.
CN201710450586.5A 2017-06-15 2017-06-15 Bio-based asymmetric flexible force-sensitive sensing material and preparation method thereof Active CN107389232B (en)

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CN109264709A (en) * 2018-09-03 2019-01-25 浙江理工大学 A kind of preparation method of the implantable biosensor of graphene oxide modification
CN109762186A (en) * 2019-01-04 2019-05-17 华南理工大学 A kind of fibre-reinforced high molecular basis material and the preparation method and application thereof based on interface response
CN110411627A (en) * 2018-04-28 2019-11-05 京东方科技集团股份有限公司 Pressure sensor and preparation method thereof, pressure detection method and device
CN111504520A (en) * 2020-04-20 2020-08-07 河北工业大学 Integrated flexible stretchable touch sensor based on super-capacitor sensing principle
CN111504519A (en) * 2020-04-20 2020-08-07 河北工业大学 Flexible cable type touch sensor
CN111750975A (en) * 2020-06-19 2020-10-09 电子科技大学 Flexible vibration sensor with piezoresistive effect and preparation method thereof
CN111829699A (en) * 2020-08-10 2020-10-27 深圳先进技术研究院 Resistance type pressure sensor and preparation method thereof
CN112393827A (en) * 2019-08-12 2021-02-23 南京理工大学 Preparation method of biodegradable piezoelectric force sensor
CN114112128A (en) * 2021-10-15 2022-03-01 中国人民解放军海军工程大学 Wide-range high-temperature-resistant high-pressure-resistant resistance type pressure sensor and preparation method thereof
CN114184307A (en) * 2021-12-15 2022-03-15 深圳先进技术研究院 Microstructure flexible pressure sensor and preparation method thereof
CN114323367A (en) * 2021-12-07 2022-04-12 华南理工大学 Flexible bridge type switch sensor

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CN108036714A (en) * 2018-01-08 2018-05-15 成都柔电云科科技有限公司 A kind of elastoresistance foil gauge and preparation method thereof
CN110411627A (en) * 2018-04-28 2019-11-05 京东方科技集团股份有限公司 Pressure sensor and preparation method thereof, pressure detection method and device
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CN109264709A (en) * 2018-09-03 2019-01-25 浙江理工大学 A kind of preparation method of the implantable biosensor of graphene oxide modification
CN109264709B (en) * 2018-09-03 2021-08-31 浙江理工大学 Preparation method of graphene oxide modified implantable biosensor
CN109762186A (en) * 2019-01-04 2019-05-17 华南理工大学 A kind of fibre-reinforced high molecular basis material and the preparation method and application thereof based on interface response
CN112393827A (en) * 2019-08-12 2021-02-23 南京理工大学 Preparation method of biodegradable piezoelectric force sensor
CN111504520A (en) * 2020-04-20 2020-08-07 河北工业大学 Integrated flexible stretchable touch sensor based on super-capacitor sensing principle
CN111504519A (en) * 2020-04-20 2020-08-07 河北工业大学 Flexible cable type touch sensor
CN111504520B (en) * 2020-04-20 2022-05-24 河北工业大学 Integrated flexible stretchable touch sensor based on super-capacitor sensing principle
CN111750975A (en) * 2020-06-19 2020-10-09 电子科技大学 Flexible vibration sensor with piezoresistive effect and preparation method thereof
CN111829699A (en) * 2020-08-10 2020-10-27 深圳先进技术研究院 Resistance type pressure sensor and preparation method thereof
CN114112128A (en) * 2021-10-15 2022-03-01 中国人民解放军海军工程大学 Wide-range high-temperature-resistant high-pressure-resistant resistance type pressure sensor and preparation method thereof
CN114112128B (en) * 2021-10-15 2024-01-23 中国人民解放军海军工程大学 Large-range high-temperature-resistant high-pressure-resistant resistance type pressure sensor and preparation method thereof
CN114323367A (en) * 2021-12-07 2022-04-12 华南理工大学 Flexible bridge type switch sensor
CN114323367B (en) * 2021-12-07 2023-08-22 华南理工大学 Flexible bridge type switch sensor
CN114184307A (en) * 2021-12-15 2022-03-15 深圳先进技术研究院 Microstructure flexible pressure sensor and preparation method thereof

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