CN108303200B - A kind of high resiliency active electronic skin forming method based on electrostatic spinning technique - Google Patents
A kind of high resiliency active electronic skin forming method based on electrostatic spinning technique Download PDFInfo
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- CN108303200B CN108303200B CN201810283447.2A CN201810283447A CN108303200B CN 108303200 B CN108303200 B CN 108303200B CN 201810283447 A CN201810283447 A CN 201810283447A CN 108303200 B CN108303200 B CN 108303200B
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 39
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- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
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- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims description 10
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- 239000012528 membrane Substances 0.000 claims description 6
- 238000013461 design Methods 0.000 claims description 5
- -1 glycol Ether compound Chemical class 0.000 claims description 5
- 239000013013 elastic material Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000002077 nanosphere Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 241000193935 Araneus diadematus Species 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 6
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- 238000005516 engineering process Methods 0.000 abstract description 3
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- 238000004519 manufacturing process Methods 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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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 1
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/16—Measuring force or stress, in general using properties of piezoelectric devices
Abstract
The invention belongs to electronic skins to prepare correlative technology field, and disclose a kind of high resiliency active electronic skin forming method based on electrostatic spinning technique, comprising: select the high-molecular copolymer material containing flexible blocks that crosslinking agent, synthesis of super branched polymer or crosslinking amorphous polymer is added；Into synthesized polymer, addition has power-electrotransformation feature functional material, and to be uniformly dispersed to obtain electrostatic spinning solution；So that solution is carried out electrostatic spinning using electrostatic spinning technique and collect film forming, thus directly obtains required electronic skin product.Through the invention, high quality, high efficiency electronic skin can be made without using flexible base board, and the product highly sensitive output signal while can significantly improve the characteristics such as surface area and aperture rate to realize the test of power in a manner of active voltage.
Description
Technical field
The invention belongs to electronic skins to prepare correlative technology field, be based on electrostatic spinning technique more particularly, to one kind
High resiliency active electronic skin forming method.
Background technique
Electronic skin can imitate the wearable flexible sensor of human skin exceptional function as one kind, robot,
The multiple fields such as artificial intelligence, artificial limb, health detection and biomedicine have great application value, thus world in recent years
Swift and violent development is obtained in range.Especially, for that can have for the electronic skin of high-acruracy survey contact pressure
Wide application prospect, and just becoming one of the technique direction that scientists are paid close attention to.
Mode currently used for preparing electronic skin is mainly the flexible substrates in for example PDMS (dimethyl silicone polymer)
It is upper to make electrode layer or pressure sensor etc. by technologies such as MEMS, spray printing or 3D printings, thus to obtain required electronic skin.
For example, CN201310507497.1 proposes a kind of electronic skin and preparation method thereof, it is disclosed that first in template surface
One layer of organic molecule layer is formed, then proceedes to be formed on sensitive layer and supporting layer, by the sensitive layer after heat treatment for solidification
It is removed with supporting layer from template, eventually forms upper electrode layer and lower electrode layer；For another example, CN201410770984.1 proposes one kind
Electronic skin and preparation method thereof, it is disclosed that being performed etching on the two-sided flexible base board for being covered with conductive material, depositing shape
At oxide thin film transistor, pressure sensor and temperature sensor etc..
However, further investigations have shown that, above-mentioned existing preparation method still has defect or deficiency below: firstly,
It is often inevitably needed in the prior art using to flexible base board, and relies primarily on flexibility and the draftability of substrate to mention
Supplied for electronic skin it is flexible, but for electrode layer or various kinds of sensors, the flexible draftability of their own is but very low,
To reduce the draw ratio of entire electronic skin and limit its scope of application, while the use of substrate also results in manufacture
Complex process, it is at high cost the problems such as.Secondly, for the whole process using same material manufacture electronic skin, manufacture
Technique improves the key factor of sensitivity and sensitivity in fact, although the modes such as spray printing in the prior art, 3D printing or MEMS
Also have various advantages, but discovery is typically difficult to be formed and has the thin of larger surface area and higher aperture rate in actual condition
Film.Although finally, also proposed using electrostatic spinning technique the scheme of electronic skin for preparing in the prior art, such as
CN201410016459.0 discloses a kind of scheme, CN201210196840.0 that micro-nano corrugated structure is prepared using electrostatic spinning
A kind of preparation method of flexible force sensitive sensor is disclosed, CN20141055404.2 discloses a kind of based on nano-piezoelectric fiber
Flexible energy capture device and preparation method thereof, however in these earlier patents there is still a need for process lower electrode, piezoelectric material,
Top electrode and substrate etc., therefore the technical problem more than equally existing.Correspondingly, this field needs to make this further
It improves, to conform better to the higher quality and efficiency requirements of modernization manufacture production.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of height based on electrostatic spinning technique
Elastic active electronic skin forming method, wherein nano high elastic material is combined into one with piezoelectric material by selectivity
Configure mixed solution, while the characteristics of specific aim combination electrostatic spinning technique, to be mixed solution directly quiet under given conditions
Electrospun and collect film forming, accordingly not only can in entire electronic skin forming process without using any flexible base board,
And obtained electronic skin product highly sensitive output signal can be shown simultaneously in a manner of active voltage with realizing the test of power
Work improves the characteristics such as surface area and aperture rate, is therefore particularly suitable for all kinds of needs high-precisions and high efficiency measures contact pressure
Electronic skin prepare occasion.
To achieve the above object, it is proposed, according to the invention, provide a kind of high resiliency active electric based on electrostatic spinning technique
Sub- skin forming method, which is characterized in that this method includes the following steps:
(a) synthesis of nano-elastic material
Select the high-molecular copolymer material containing flexible blocks that crosslinking agent is added, synthesis of super branched polymer or crosslinking are fixed
Shape polymer, and the polymer has the cross-linked network structure of nano particle, and good elasticity and restoring force is accordingly presented；
(b) configuration of electrostatic spinning solution
Addition has power-electrotransformation feature functional material, the function material in through polymer synthesized by step (a)
The structure of nanosphere is presented in material, and is dispersed among the polymer, thus to obtain required electrostatic spinning solution；
(c) electrostatic spinning and collect film forming
It will be injected in electrostatic spinning apparatus by step (b) electrostatic spinning solution obtained, and in positive and negative voltage design
For 100V~30kV, liquid inventory is designed as 0.01mL/h~10mL/h, receives the process conditions that distance is designed as 5cm~50cm
Under, so that its electrostatic spinning is collected film forming, accordingly directly obtains electronic skin product in the case where being not necessarily to flexible substrates.
By conceiving above, the feature of electrostatic spinning technique and stress sensitivity characteristic material respectively is sufficiently combined, initiative mentions
It configures nano compound film directly out to replace the use of flexible base board, is accordingly not only remarkably improved the effect of entire moulding process
Rate and cost is reduced, and effectively overcomes present in existing electronic skin flexible draftability is relatively low, draw ratio is insufficient etc.
Problem, at the same be dispersed in the piezoelectric material among membrane body can in a manner of active voltage output signal realize power survey
Examination；Further, since the mutual compound of Filamentous and chondritic nano material is formd during electrostatic spinning, it is corresponding made
The electronic skin obtained has bigger surface area and higher aperture rate compared with existing product, and then significantly improves material of the same race
The sensitivity of material manufacture electronic skin and sensitivity.
As it is further preferred that power-electrotransformation functional material accounts for polymer in electrostatic spinning solution in step (b)
Mass fraction configured by following range: 5%~95%.
As it is further preferred that in step (b), it is preferred to use mechanical stirring and the mode of ultrasonic vibration make described
Functional material is dispersed among the polymer.
As it is further preferred that the high-molecular copolymer material containing flexible blocks preferably include polytetrahydrofuran,
The polyether compound containing terminal hydroxy group or amino such as polyethylene glycol, polypropylene glycol；The crosslinking agent preferably include containing there are three and
The isocyanate ester compound or epoxy of three or more functional groups；The functional material of the power of the having-electrotransformation feature is preferred
Including the similar polymer such as polyvinylidene fluoride, polyvinyl chloride, polymethyl methacrylate, polypropylene.
As it is further preferred that it is also preferable to include following steps after step (c):
(d) design and plating of circuit
On the two sides for being formed by fiber membrane by step (c), different circuits is plated respectively and forms longitude and latitude intersection
Line, thus stress size and location of positioning electronic skin.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, mainly have below
Technological merit:
1, it not only can be in entire electronic skin forming process without using any flexible base board, but also is obtained
Electronic skin product can highly sensitive output signal be in a manner of active voltage to realize the test of power, due to its low cost, high
Flexible and biocompatibility, thus it is with important application prospects in the energy conversion application between electric energy and machinery；
2, by electrostatic spinning solution as the material of key component component and in terms of set
It counts, more actual test shows that the characteristics such as the surface area of fiber membrane obtained and aperture rate can be significantly improved, thus
It is particularly suitable for the electronic skin preparation occasion of all kinds of needs high-precisions and high efficiency measurement contact pressure.
Detailed description of the invention
Fig. 1 is the technique of the high resiliency active electronic skin forming method according to the invention based on electrostatic spinning technique
Flow chart；
Fig. 2 is the electron-microscope scanning schematic diagram that present invention electronic skin structure obtained is shown as demonstration.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Fig. 1 is the technique of the high resiliency active electronic skin forming method according to the invention based on electrostatic spinning technique
Flow chart.As shown in fig. 1, this method mainly includes operating procedure below:
Firstly, being the synthesis step of nano-elastic material.
In this step, the high-molecular copolymer material containing flexible blocks may be selected, crosslinking agent is added, synthesis of super branched is poly-
Object or crosslinking amorphous polymer are closed, and the polymer has the cross-linked network structure of nano particle, accordingly presents good
Elasticity and restoring force.
More specifically, for example the polytetrahydrofuran of choosing multiple molecular weight distribution is as flexible blocks, to contain more officials
Can group compound be used as crosslinking agent, thus synthesis of super branched polymer or be crosslinked amorphous polymer, these high molecular polymerizations
Object, can since polymer crosslinking network structure supporting role makes it have very strong memory restoring force when stretching or pressing
It is promptly restored to original shape, makes it have good elasticity.
It then, is the configuration step of electrostatic spinning solution.
In this step, into synthesized polymer, addition has power-electrotransformation feature functional material, the function material
The structure of nanosphere is presented in material, and is dispersed among the polymer, thus to obtain required electrostatic spinning solution.
More specifically, can for example introduce polyvinylidene fluoride as functional material, by the uniform functional material of particle diameter distribution
Nanosphere is added by a certain percentage in high resiliency high molecular polymer, and mechanical stirring and ultrasonic vibration obtain evenly dispersed
Novel nano composite functional material.
Then, it is electrostatic spinning and collects film formation step.
By electrostatic spinning solution obtained inject electrostatic spinning apparatus in, and positive and negative voltage design be 100V~
30kV, liquid inventory are designed as 0.1mL/h~10mL/h, receive distance and are designed as under the process conditions of 5cm~50cm, keep its quiet
Electrospun and collect film forming, accordingly without directly obtaining electronic skin product in the case where flexible substrates.
Furthermore, it is alternatively that, it can also be formed by membrane body two sides, different electricity is for example plated using silver nanowires
Road forms longitude and latitude cross spider, carrys out the size and location of positioning electronic skin stress.As shown in Fig. 2, electronic skin obtained has
Effect overcomes the problems such as tough draftability is relatively low, draw ratio is insufficient, while being dispersed in the piezoelectric material among membrane body can
Output signal realizes the test of power in a manner of active voltage, while having bigger surface area and higher compared with existing product
Aperture rate.
To sum up, initiative of the present invention is proposed multi-functional flexible expanded material and power electrotransformation functional material direct combination
At electrostatic spinning solution, power-electrotransformation functional material is evenly spread to the macromolecule of high resiliency and sizing setting phase-state change,
Using its pressure-sensitive character, mechanical force can be converted into electric energy by material, output signal realizes power in a manner of active voltage
Test.Meanwhile Filamentous and chondritic is formed using electrostatic spinning process, there is big surface area and high aperture rate film,
Improve sensitivity and the sensitivity of same material manufacture electronic skin.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (5)
1. a kind of high resiliency active electronic skin forming method based on electrostatic spinning technique, which is characterized in that this method packet
Include the following steps:
(a) synthesis of nano-elastic material
Select the high-molecular copolymer material containing flexible blocks that crosslinking agent is added, synthesis of super branched polymer or crosslinking setting are poly-
Object is closed, and the polymer has the cross-linked network structure of nano particle, good elasticity and restoring force is accordingly presented；
(b) configuration of electrostatic spinning solution
Addition has power-electrotransformation feature functional material in through polymer synthesized by step (a), which is in
The structure of existing nanosphere, and be dispersed among the polymer, thus to obtain required electrostatic spinning solution；
(c) electrostatic spinning and collect film forming
It will be injected in electrostatic spinning apparatus by step (b) electrostatic spinning solution obtained, and be in positive and negative voltage design
100V~30kV, liquid inventory are designed as 0.01mL/h~10mL/h, receive the process conditions that distance is designed as 5cm~50cm
Under, make its electrostatic spinning and collect film forming, accordingly directly obtains electronic skin product in the case where being not necessarily to flexible substrates.
2. high resiliency active electronic skin forming method as described in claim 1, which is characterized in that in step (b), institute
It states to have power-electrotransformation feature functional material and account for the mass fraction of polymer in electrostatic spinning solution and be matched by following range
It sets: 5%~95%.
3. high resiliency active electronic skin forming method as claimed in claim 1 or 2, which is characterized in that in step (b)
In, make described to have power-electrotransformation feature functional material and be dispersed in by the way of mechanical stirring and ultrasonic vibration
Among the polymer.
4. high resiliency active electronic skin forming method as claimed in claim 1 or 2, which is characterized in that described containing flexibility
The high-molecular copolymer material of block includes polytetrahydrofuran, polyethylene glycol, these are poly- containing terminal hydroxy group or amino for polypropylene glycol
Ether compound；The crosslinking agent include containing there are three and three or more functional groups isocyanate ester compound or epoxy；
The functional material of the power of the having-electrotransformation feature include polyvinylidene fluoride, polyvinyl chloride, polymethyl methacrylate or
Polypropylene.
5. high resiliency active electronic skin forming method as claimed in claim 1 or 2, which is characterized in that step (c) it
Afterwards, further comprising the steps of:
(d) design and plating of circuit
On the two sides for being formed by fiber membrane by step (c), different circuits is plated respectively and forms longitude and latitude cross spider, by
The stress size and location of this positioning electronic skin.
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| CN109163827B (en) * | 2018-07-23 | 2021-04-20 | 深圳大学 | Preparation method of pressure sensor |
| CN109431460B (en) * | 2018-09-10 | 2021-06-11 | 中原工学院 | Flexible high-flexibility nanofiber core-spun yarn stress sensor with fold structure and preparation method thereof |
| CN111361302B (en) * | 2020-04-04 | 2021-08-03 | 南开大学 | Preparation method of flexible film resistant to stress stretching |
| CN113285026A (en) * | 2021-04-29 | 2021-08-20 | 北京航空航天大学 | Full-flexible ultraviolet detector based on high polymer material and preparation and application thereof |
| CN113699697B (en) * | 2021-10-11 | 2022-07-29 | 南京大学 | Non-inductive multifunctional electro-spinning micro pyramid array film and preparation method thereof |
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| US9476026B2 (en) * | 2009-03-12 | 2016-10-25 | New Jersey Institute Of Technology | Method of tissue repair using a piezoelectric scaffold |
| CN102954848A (en) * | 2011-08-16 | 2013-03-06 | 中国科学技术大学 | Novel flexible mechanical sensor and preparation method thereof |
| CN102443870B (en) * | 2011-09-13 | 2013-07-24 | 青岛大学 | Method for preparing ordered coaxial structural micro and nano fibers |
| KR101730396B1 (en) * | 2015-07-15 | 2017-05-11 | 경희대학교 산학협력단 | Pressure sensor using pla piezoelectric material of nanofiber web type by electrospinning |
| CN107287684B (en) * | 2017-05-31 | 2019-08-20 | 华南理工大学 | It is a kind of high to stretch highly sensitive quick sensing fiber of flexible force and preparation method thereof |
| CN107478360B (en) * | 2017-08-18 | 2020-05-19 | 北京纳米能源与系统研究所 | Capacitive flexible pressure sensor and preparation method thereof |
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