CN110358297A - Ionic rubber elastomer and preparation method thereof, from electronic type electronic skin - Google Patents
Ionic rubber elastomer and preparation method thereof, from electronic type electronic skin Download PDFInfo
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- CN110358297A CN110358297A CN201811637647.XA CN201811637647A CN110358297A CN 110358297 A CN110358297 A CN 110358297A CN 201811637647 A CN201811637647 A CN 201811637647A CN 110358297 A CN110358297 A CN 110358297A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- G01L1/14—Measuring force or stress, in general by measuring variations in capacitance or inductance of electrical elements, e.g. by measuring variations of frequency of electrical oscillators
- G01L1/142—Measuring force or stress, in general by measuring variations in capacitance or inductance of electrical elements, e.g. by measuring variations of frequency of electrical oscillators using capacitors
- G01L1/144—Measuring force or stress, in general by measuring variations in capacitance or inductance of electrical elements, e.g. by measuring variations of frequency of electrical oscillators using capacitors with associated circuitry
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L23/00—Devices or apparatus for measuring or indicating or recording rapid changes, such as oscillations, in the pressure of steam, gas, or liquid; Indicators for determining work or energy of steam, internal-combustion, or other fluid-pressure engines from the condition of the working fluid
- G01L23/08—Devices or apparatus for measuring or indicating or recording rapid changes, such as oscillations, in the pressure of steam, gas, or liquid; Indicators for determining work or energy of steam, internal-combustion, or other fluid-pressure engines from the condition of the working fluid operated electrically
- G01L23/12—Devices or apparatus for measuring or indicating or recording rapid changes, such as oscillations, in the pressure of steam, gas, or liquid; Indicators for determining work or energy of steam, internal-combustion, or other fluid-pressure engines from the condition of the working fluid operated electrically by changing capacitance or inductance
- G01L23/125—Devices or apparatus for measuring or indicating or recording rapid changes, such as oscillations, in the pressure of steam, gas, or liquid; Indicators for determining work or energy of steam, internal-combustion, or other fluid-pressure engines from the condition of the working fluid operated electrically by changing capacitance or inductance by changing capacitance
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L9/00—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means
- G01L9/12—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means by making use of variations in capacitance, i.e. electric circuits therefor
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/02—Copolymers with acrylonitrile
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- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2201/00—Specific properties of additives
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
Abstract
The present invention provides a kind of ionic rubber elastomers, are in terms of 100% by the total weight of the ionic rubber elastomer, comprising: rubber base material 10%~95%；Liquid ionic material 1%~80%；Nano-powder material 0.1%~50%；Additive 0%~30%.Ionic rubber elastomer provided by the invention is added with nano-powder material, and the nano-powder material has high-specific surface area characteristic, can be evenly dispersed in rubber base material；Simultaneously because hydroxyl is contained on the nano-powder material surface, polarity is strong, therefore there is preferable compatibility with liquid ionic material, the liquid ionic material can be coated on nano powder surface, and realize that liquid ionic material is evenly dispersed in rubber base material by the load of nano-powder material, so that it is compound to be originally difficult to mixed liquid ionic material and rubber base material functionality, macroion conduction and high unit-area capacitance are obtained.
Description
Technical field
The invention belongs to sensor technical fields more particularly to a kind of ionic rubber elastomer and preparation method thereof, and
One kind is from electronic type electronic skin.
Background technique
Skin serves as extremely important role during people and extraneous interaction.Percutaneous a variety of perception energy
Power, people can feel the shouting pain of needle point, can experience the stimulation of flame, ice cube, can also distinguish glass, fabric easily
With the surface of rubber.But or amputation personnel, the impression function of skin impaired for skin histology are destroyed, they
Quality of life will be greatly reduced.Existing mechanical artificial's artifucial limb can be very good to simulate the appearance of original limbs and a variety of machines
Tool function, and after to the perceptional function of mechanical prosthesis addition skin, it will be able to a variety of extraneous sensing capabilities for restoring artifucial limb are given
The life of user brings practical help.With the development of intelligent robot and artificial intelligence, in shape with human or animal's phase
As robot it is expected will accompany and attend in household services, companion, the development of the fields acquisition great-leap-forward such as pet is accompanied, public displaying,
Its relevant market also will gradually expand.It assigns the perceptional function of skin to intelligent robot, robot is allow to pass through skin sense
By signals such as extraneous pressure, vibrations, on the one hand action control can be carried out by tactile intelligent assistance robot, for example grab
It takes, pat, stroke；Imitate intelligent robot further the function of human or animal, robot can be with
It makes a response to extraneous stimulation, preferably service the mankind and protects oneself；Also provided is a kind of completely new human-computer interactions
Mode is added to tactile intelligence, makes one and robot on the basis of the existing Visual intelligent of intelligent robot, sense of hearing intelligence
Exchange more comprehensively it is convenient.In addition to this, have the flexible wearable sensors of the sensing capabilities such as pressure, pulling force, temperature
In recent years large development is also obtained.On heart rate, pulse, monitoring of respiration field and gesture, limb action identification field, intelligently may be used
Wearing electronics is quickly grown.The above application is built upon high-performance flexible pressure, vibration, pulling force, temperature sensor
On the basis of.Therefore, from theory, material, technique and this kind of sensor of the upper development of application, with obtain higher sensitivity, resolution ratio,
Response speed etc. and higher preparation efficiency, lower cost, more application scenarios will be that these applications is pushed to fall always
Real basis and the power for promoting related industry to develop.
Under such society and industrial background, this concept of electronic skin is come into being.Electronic skin is the simulation mankind
The electronic device of skin contours and function, i.e., the stimulation such as the external pressure experienced bionics skin, vibration, passes through e-mail
Number mode transmitted and analyzed, so that it is determined that the information such as size, position of stimulation, are to obtain more and more concerns in recent years
Project.People experiences environmental stimuli, including temperature, pressure etc. by the sense organ cell in skin.The touch feeling of skin by
The mechanical sensitivity receptor being present in skin different-thickness layer provides, these mechanicalness receptors will provide ambient enviroment for the mankind
Pressure, roughness, hardness, the information such as vibration.Mechanicalness receptor can be divided into different classes of according to its structure and function: answer part
Power sensitivity is located at the Merkel's disk of skin surface；The Ruffini end-organ that signal is located at deep skin is generated to elongation strain；It is right
There is low frequency dynamic excitation source the Metz of uniform response sensitivity to receive corpusculum and to the selective response of high frequency stimulation and to being less than
The pole 10nm miniature deformation has the corpuscula lamellosa of hypersensitivity.Four kinds of receptors change the pressure received, vibration signal
For electric signal and by neurotransmission to brain, brain by analysis, obtains pressure, the position of vibration and size, to obtain
Including body form, lines, the information such as hardness.And electronic skin is exactly to be gone in simulation application on human skin by artificial electronic device
The function of various receptors.According to the difference of measuring principle, the pliable pressure sensor in electronic skin be broadly divided into pressure resistance type,
Parallel plate capacitor formula, piezoelectricity and friction electric-type, structure and principle are as shown in Figure 1.
It is a kind of novel pressure sensing technology based on interfacial electric double layer capacitance principle from electronic pressure sensor.It is this
Pressure sensor has used the material rich in the zwitterion that can move freely, such as the higher boiling solution of electrolyte, ionic liquid
Body, polyelectrolyte, ionic liquid gel etc..Apply voltage on this ionic material, at this moment the positive and negative ion in ionic material
Will be under the action of electric field rapidly to two polar motions, and form close charge layer on the surface of two electrodes respectively, i.e., double electricity
Layer.This electric double layer is a kind of nanoscale capacitance structure arranged and formed by ion, since the distance between negative ions are extremely short,
Its unit-area capacitance is 1000 times or more of Conventional parallel plate capacitor.For ionic material of the same race, interface capacitance is main
Contact area correlation between electrode and ionic material, and interface capacitance formula pressure sensor is then according to this
Point, under pressure, contact area increases between ionic material and electrode, and sensor capacitance is also increase accordingly, such as Fig. 2 institute
Show.Interface capacitance formula pressure sensing mechanism is that a kind of one kind different from existing resistance-type, condenser type and piezoelectric type sensing is complete
New sensor mechanism.Since the value of interface capacitance can reach several hundred nF even uF rank, compared to the parallel plate capacitor of tens pF
Formula sensor, sensitivity improves 1000 times or more, and has very strong anti-interference ability to human body and environmental capacitance noise.
Compared to piezoresistive pressure sensor, interface capacitance formula pressure sensor has preferable linear response within the scope of certain pressure
Degree can be prepared into the forms such as solution, ink, slurry compared to such as graphene, carbon nanotube conductive material, ionic material, can
More convenient is prepared into ionic material layer by a variety of processing methods such as dip-coating, blade coating, ink-jet, printing.Compared to such as piezoelectric type
With friction electric-type pressure sensor, interface capacitance formula pressure sensor, can while having quick mechanical response speed
To be detected to static pressure.Therefore, will there is more excellent performance using the electronic skin prepared from electronic type mechanism.
Summary of the invention
The purpose of the present invention is to provide a kind of ionic rubber elastomer and preparation method thereof, one kind containing ionic rubber bullet
Property body from electronic type electronic skin, it is intended to it is low and with mechanical structure poor compatibility to solve existing electronic skin sensitivity
Problem.
Another object of the present invention is to provide one kind from electronic type electronic skin, it is intended to solve existing electronic skin spirit
Sensitivity is low, structure is complicated, complex process and the problem of with mechanical structure poor compatibility.
For achieving the above object, The technical solution adopted by the invention is as follows:
First aspect present invention provides a kind of ionic rubber elastomer, and the total weight with the ionic rubber elastomer is
100% meter, the ionic rubber elastomer includes the following raw materials according component of following weight percentage:
Second aspect of the present invention provides a kind of ionic rubber method for producing elastomers, comprising the following steps:
Each component is weighed according to ionic rubber elastomer formulation of the present invention；
By rubber material presoma and its curing agent, liquid ionic material, solid nano material, additive mixed processing,
Obtain the persursor material of pulpous state；
The persursor material is deposited on substrate, curing process, obtains ionic rubber elastomer.
Third aspect present invention provides a kind of from electronic type electronic skin, the flexible circuit including being provided with interdigital electrode
Plate, and be covered on the ionic rubber on the interdigital electrode surface of the flexible circuit board, wherein the ionic rubber includes and institute
The first surface of flexible printed circuit interdigital electrode fitting and the second surface away from the flexible printed circuit interdigital electrode are stated,
The first surface is rough surface, and the material of the ionic rubber is ionic rubber elastomer described in the embodiment of the present invention.
Ionic rubber elastomer provided by the invention is added with nano-powder material, the nano-powder material surface tool
Polarized group, such as hydroxyl, so that highly polar liquid ionic material is adsorbed on nano-powder material due to polarity similar reasons
Expect surface.It is supported on the liquid ionic material on the nano-powder material surface, by the high surface of the nano-powder material
Product is realized evenly dispersed inside rubber material.When the nano-powder material content is higher than percolation threshold, due to receiving
Contacting with each other between rice powder body material so that the liquid ionic material on nano-powder material surface also contacts with each other, formed from
Sub- conductive channel, so that whole rubber obtains macroion conduction.When without adding nano-powder material, due to liquid ion material
Polarity spectrum is larger between material and rubber matrix, liquid ionic material meeting split-phase, shape in rubber presoma in dispersion process
At lotion, independent emulsion particle is mutually not attached to, therefore can not form ion conductive channel, so that whole rubber ion conduction is very
Difference.Therefore, the addition of nano-powder material is so that be originally difficult to mixed liquid ionic material and rubber base material functionality
It is compound, macroion conduction is obtained, hundreds and thousands of times of unit-area capacitance of increase of rubber is shown as.
Ionic rubber method for producing elastomers provided by the invention need to only be provided according to ionic rubber elastomer formulation
Rubber material presoma and its curing agent, liquid ionic material, solid nano material, additive, after each raw material mixed processing
Curing process can be obtained on substrate, and operating method is simple and easy.
It is provided by the invention from electronic type electronic skin, on the one hand, based on the working mechanism from electronic type, using the present invention
The ionic rubber of ionic rubber elastomeric material has the sensitivity from electronic pressure sensor as functional structure
The advantages that height, fast response time, strong antijamming capability, response good linearity, detectable static pressure.On the other hand, using will be upper
The ionic rubber for stating ionic rubber elastomeric material is covered on interdigital electrode surface, since the height of ionic rubber is flexible,
It is described easily to stick on mechanical structure surface from electronic type electronic skin, improve the compatibility with mechanical structure.In addition,
It is provided by the invention from electronic type electronic skin, mature flexible printed circuit technology can be used, to prepare large area height
The big array electronic skin of density, and can be reliably connected with existing control, reading, power supply circuit.
Detailed description of the invention
Fig. 1 is the operation principle schematic diagram for the pliable pressure sensing that the prior art provides；
Fig. 2 is prior art offer from electronic flexible pressure sensing technology schematic illustration and its equivalent circuit；
Fig. 3 is provided in an embodiment of the present invention from electronic type electronic skin schematic diagram；
Fig. 4 is flexible electrode array schematic diagram provided in an embodiment of the present invention；
Fig. 5 is the transducer sensitivity test result figure that the embodiment of the present invention 1 provides.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
First aspect of the embodiment of the present invention provides a kind of ionic rubber elastomer, with the gross weight of the ionic rubber elastomer
Amount is 100% meter, and the ionic rubber elastomer includes the following raw materials according component of following weight percentage:
Ionic rubber elastomer provided in an embodiment of the present invention is added with nano-powder material, the nano-powder material
Surface has polar group, such as hydroxyl, so that highly polar liquid ionic material is adsorbed on nanometer due to polarity similar reasons
Powder body material surface.It is supported on the liquid ionic material on the nano-powder material surface, by the nano-powder material
High surface area, realize inside rubber material it is evenly dispersed (nano-powder material have high-specific surface area characteristic, energy
It is enough evenly dispersed in rubber base material).When the nano-powder material content is higher than percolation threshold, due to nano-powder
Contacting with each other between material forms ion conducting so that the liquid ionic material on nano-powder material surface also contacts with each other
Channel, so that whole rubber obtains macroion conduction.When without adding nano-powder material, due to liquid ionic material and rubber
Polarity spectrum is larger between matrix body, and liquid ionic material meeting split-phase in rubber presoma in dispersion process forms lotion,
Independent emulsion particle is mutually not attached to, therefore can not form ion conductive channel, so that whole rubber ion conduction is very poor.Cause
This, the addition of nano-powder material so as to be originally difficult to mixed liquid ionic material and rubber base material functionality compound,
Macroion conduction is obtained, hundreds and thousands of times of unit-area capacitance of increase of rubber is shown as.
Specifically, matrix component one of of the rubber base material as ionic rubber elastomer, in entire ion rubber
The matrix effect of structural support is served as in glue, and is provided high flexible.Preferably, the rubber base material is selected from thermosetting
Property rubber material.
In some embodiments, the rubber base material is selected from thermoset rubber material and is selected from thermosetting property nitrile rubber
Class, thermosetting property organic silicon rubber class, thermosetting property butadiene-styrene rubber class, thermosetting acrylate rubber, thermosetting property natural rubber class
At least one of.Preferred rubber base material good mechanical performance, and be under presoma room temperature or under appropriate heating state
Liquid or viscous state are easy to carry out homogeneous blend with nano-powder material and liquid ionic material.Further preferred rubber forerunner
The rubber base material that body is in a liquid state at normal temperature.
It is the weight of the rubber base material in terms of 100% by the total weight of ionic rubber elastomer in the embodiment of the present invention
Measuring percentage composition is 1%~95%, concretely 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%,
45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%.
In the embodiment of the present invention, the liquid ionic material assigns the ionic rubber elasticity as matrix functional material
The excellent ion conduction property of body, to provide function guarantor from electronic type electronic skin to prepare using ionic rubber elastomer
Barrier.In some embodiments, the liquid ionic material is in ionic liquid, ionic liquid solution, solid electrolyte solution
At least one, and the solvent in the ionic liquid solution, solid electrolyte solution is protected in the ionic rubber elastomer
It stays.
Specifically, the ionic liquid is the ionic compound being in a liquid state under the conditions of temperature is 10 DEG C~35 DEG C.One
In a little embodiments, the ionic liquid solution can be selected from glyoxaline ion liquid, ion liquid of quaternaries, pyridines ionic liquid
At least one of body, pyrrole ionic liquid, piperidines ionic liquid, pyrrolidines ionic liquid, it is certainly, without being limited thereto.
In a preferred embodiment, the ionic liquid solution is selected from the nontoxic lower toxicity ionic liquid for having high ionic conductivity at normal temperature
Body, such as pyrrolidines ionic liquid, ion liquid of quaternaries.
The ionic liquid dowtherm is that ion liquid dissolving is formed in the highly polar organic solvent of higher boiling
Solution, and the highly polar organic solvent of the higher boiling be boiling point not less than 200 DEG C and in molecular structure containing hydroxyl, amido,
The organic solvent of at least one of ester group, amide groups, carboxyl.At this point, the highly polar organic solvent boiling point of higher boiling is high, no
It is volatile, and since solvent polarity is larger, the biggish ionic compound of polarity itself effectively can be dissolved well.Some
In embodiment, in the ionic liquid solution, the ionic liquid be selected from glyoxaline ion liquid, ion liquid of quaternaries,
At least one of pyridine ionic liquid, pyrrole ionic liquid, piperidines ionic liquid, pyrrolidines ionic liquid；Institute
It states the highly polar organic solvent of higher boiling and is selected from dibutyl phthalate, tributyl citrate, N-methyl pyrrolidones, diformazan Asia
At least one of sulfone, glycerol, ethylene glycol.
The solid electrolyte dowtherm is under the conditions of temperature is 10 DEG C~35 DEG C in solid ionization
The solution that object is formed in the highly polar organic solvent of higher boiling is closed, and the highly polar organic solvent of the higher boiling is not less than for boiling point
Organic solvent containing at least one of hydroxyl, amido, ester group, amide groups, carboxyl in 200 DEG C and molecular structure.At this point,
The highly polar organic solvent boiling point of higher boiling is high, not volatile, and since solvent polarity is larger, can be well by pole itself
The biggish ionic compound of property effectively dissolves.In some embodiments, in the solid electrolyte solution, the ionic compound
Selected from least one of small molecule electrolyte, polymer dielectric；The highly polar organic solvent of higher boiling is selected from adjacent benzene two
At least one of formic acid dibutyl ester, tributyl citrate, N-methyl pyrrolidones, dimethyl sulfoxide, glycerol, ethylene glycol.
It is the weight of the liquid ionic material in terms of 100% by the total weight of ionic rubber elastomer in the embodiment of the present invention
Measuring percentage composition is 1%~80%, concretely 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%,
45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%.
In the embodiment of the present invention, the addition of the nano-powder material can promote to be difficult to mixed liquid ion originally
Material and rubber base material are realized functional compound.The nano-powder material surface has polar group, such as hydroxyl.?
Nano-powder material, liquid ionic material, rubber liquid precursor co-mixing system in, liquid ionic material is similar due to polarity
Reason can be adsorbed on nano-powder material surface, to cooperate with solid nano-powder material, during being dispersed with stirring uniformly
Be dispersed in inside rubber material.When nano-powder material content is higher than percolation threshold, due between nano-powder material
It contacts with each other, so that the liquid ionic material of powder surface also contacts with each other, forms ion conductive channel, so that whole rubber obtains
Obtain macroion conduction.Without add nano-powder material, due between liquid ionic material and rubber matrix polarity spectrum compared with
Greatly, liquid ionic material in dispersion process can in rubber presoma split-phase, form lotion, the mutual not phase of independent emulsion particle
Even, therefore ion conductive channel can not be formed, so that whole rubber ion conduction is very poor.
Preferably, the nano-powder material is scale in 1000nm solid nanoparticles below.The nano-powder
Material particle size is smaller, and since specific surface area is bigger, theoretical percolation threshold is also lower, the weight ratio of the nano-powder of required addition
Also just smaller, the influence to rubber mechanical property is smaller.If the nano-powder material scale is more than 1000nm, to what is obtained
The Effect on Mechanical Properties of ionic rubber elastomer is larger.The nano-powder material can be solid nanoparticles, or
Solid nano line can also be solid nano pipe, two-dimension nano materials.Herein, when the nano-powder material is graininess,
Scale indicates grain diameter；When the nano-powder material is nanotube, scale is the caliber for indicating nanotube；When described
When nano-powder material is strands, scale is the diameter for indicating strands；When the nano-powder material is two-dimension nano materials,
Scale is the longest diagonal line for indicating two-dimension nano materials.Of course it is to be understood that the nano-powder material can choose one kind
The nano material of form also can choose the nano material of two or more form.
In some embodiments, the nano-powder material is selected from zero dimension nano SiO 2 particle, silica nanometer
Strands, Silica Nanotube, two-dimensional nano silica, titanium dioxide nano thread material, titania nanotube, two-dimensional nano
At least one of titanium dioxide, nano-calcium carbonate particles, nano alumina particles.Preferred nano-powder material and rubber-based
Body material, liquid ionic material compound tense, can significantly improve liquid ionic material being uniformly dispersed in rubber base material
Property, and it is low in cost.
It is the weight of the nano-powder material in terms of 100% by the total weight of ionic rubber elastomer in the embodiment of the present invention
Measuring percentage composition is 1%~50%, concretely 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%,
45%, 50%.
In the embodiment of the present invention, one or more additions can also be added in ionic rubber elastomer according to the actual situation
Agent, the performance of Lai Tigao ionic rubber elastomer.Specifically, the additive is in defoaming agent, levelling agent, rubber antiager
At least one, but not limited to this.Wherein, the defoaming agent, the levelling agent are used to improve the machinability in preparation process,
The rubber antiager is used to improve the anti-aging property of the ionic rubber elastomer, and then improves the ionic rubber elasticity
The service life of body.
It is the weight percent of the additive in terms of 100% by the total weight of ionic rubber elastomer in the embodiment of the present invention
Content is 0%~30%, concretely 0,1%, 5%, 10%, 15%, 20%, 25%, 30%.
Ionic rubber elastomer described in the embodiment of the present invention can be prepared by following methods.
Second aspect of the embodiment of the present invention provides a kind of ionic rubber method for producing elastomers, comprising the following steps:
S01. each component is weighed according to ionic rubber elastomer formulation of the present invention；
It S02. will be at rubber material presoma and its curing agent, liquid ionic material, solid nano material, additive mixing
Reason, obtains the persursor material of pulpous state；
S03. the persursor material is deposited on substrate, curing process, obtains ionic rubber elastomer.
Ionic rubber method for producing elastomers provided in an embodiment of the present invention, only need to matching according to ionic rubber elastomer
Side provides rubber material presoma and its curing agent, liquid ionic material, solid nano material, additive, and each raw material is mixed
Curing process can be obtained on substrate after processing, and operating method is simple and easy.
Specifically, in above-mentioned steps S01, the composition of raw materials and its preferred situation of the ionic rubber elastomer institute for example above
It states, in order to save length, details are not described herein again.Wherein, the rubber base material correspondence is converted to rubber material presoma
Content.
In above-mentioned steps S02, using conventional hybrid mode, by rubber material presoma and its curing agent, liquid ion
Material, solid nano material, additive mixed processing, obtain the persursor material of pulpous state.
In above-mentioned steps S03, the persursor material is deposited on substrate, can be carried out using conventional method, including
But it is not limited to pour, prints, is coated with, hot pressing.The substrate can be conventional substrate, or mold.Further, will
Post-depositional persursor material carries out curing process, obtains ionic rubber elastomer.
In some embodiments, in order to obtain the ionic rubber elastomer that surface has coarse structure, to meet difference
Use demand, using there is the substrate of default rough surface as the substrate for preparing ionic rubber elastomer, by the forerunner
Body material is deposited on the default rough surface of the substrate, curing process, obtains the ionic rubber with default rough surface
Elastomer.
As shown in figure 3, the third aspect of the embodiment of the present invention provides a kind of from electronic type electronic skin, including it is provided with interdigital
The flexible circuit board of electrode, and be covered on the ionic rubber on the interdigital electrode surface of the flexible circuit board, wherein it is described from
Sub- rubber include the first surface being bonded with the flexible printed circuit interdigital electrode and away from the flexible printed circuit it is interdigital
The second surface of electrode, the first surface is rough surface, and the material of the ionic rubber is ion rubber of the present invention
Glue elastomer.
It is provided in an embodiment of the present invention from electronic type electronic skin, on the one hand, based on the working mechanism from electronic type, use
The ionic rubber of ionic rubber elastomeric material of the embodiment of the present invention has and senses from electronic pressure as functional structure
The high sensitivity of device, strong antijamming capability, response good linearity, can detect the advantages that static pressure at fast response time.Another party
Face, since the height of ionic rubber is flexible, described easily to stick on mechanical structure table from electronic type electronic skin
The compatibility with mechanical structure is improved in face.In addition, it is provided in an embodiment of the present invention from electronic type electronic skin, it can be used into
Ripe flexible printed circuit technology, the big array electronic skin of large-area high-density, and can be with existing control, reading, confession
Circuit is reliably connected.
In the embodiment of the present invention, the flexible circuit board for being provided with interdigital electrode can be obtained using conventional method preparation
?.It is common, flexibility is formed using conventional photoetching corrosion method or by the method preparation interdigital electrode of printed conductive material
Circuit board.In some embodiments, the flexible circuit board is the flexible circuit board that single side has interdigital electrode.In some implementations
In example, the flexible circuit board is the two-sided flexible circuit board with interdigital electrode.In some embodiments, the flexible circuit
Plate is the flexible circuit board with multilayer interdigital electrode.
Described from electronic type electronic skin further includes being covered on the ion rubber on the interdigital electrode surface of the flexible circuit board
Glue, and the material of the ionic rubber is ionic rubber elastomer described in the embodiment of the present invention.Specifically, the ionic rubber packet
Include the first surface being bonded with the flexible printed circuit interdigital electrode and away from the of the flexible printed circuit interdigital electrode
Two surfaces, the first surface are rough surface.When pressure acts on ionic rubber, due to the coarse table of ionic rubber
Face, the contact area between ionic rubber and interdigital electrode can be increase accordingly, due to the interface capacitance and ionic material of sensor
Contact area correlation between cell electrodes, integral capacitor detected by sensor (or other are by capacitor
Electrical parameter of influence, such as partial pressure, electric current, impedance, phase angle, resonance frequency etc.) it can increase accordingly, so that counter release pressure
Size.By be arranged rough surface so that it is described under pressure from electronic type electronic skin, ionic rubber and interdigital electrode
Between contact area increase, to increase the size of interfacial electric double layer capacitor.Further, the both ends connection of interdigital electrode
To capacitor, voltage, current detecting system, and the change of interfacial electric double layer capacitance size caused by pressure, it will system is arrived in reflection
The value of testing capacitor, voltage or electric current, and pressure size and the value of detection capacitor, voltage or electric current are one-to-one relationships,
It therefore can be by current testing capacitor, voltage or current value is counter pushes away pressure size.
Single-point type can be set into from electronic type electronic skin from electronic type electronic skin described in the embodiment of the present invention, it can also
Be arranged to multipoint mode from electronic type electronic skin, can also be arranged in an array formula from electronic type electronic skin.Such as Fig. 4 institute
It is shown as the flexible electrode array of the electronic skin of 256 points of per square centimeter, it is similar with single-point type electronic skin structure,
The ionic rubber of area needed for the covering of array-type flexible electrod-array surface is upper, can be obtained the big array of large-area high-density from electricity
Minor electronic skin.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method from electronic type electronic skin, comprising the following steps:
The preparation of ionic rubber elastomer: by Sylgard 184PDMS elastomer silicone presoma and curing agent according to 10:
The addition of 1 mass ratio, is added the O-phthalic with the bis trifluoromethyl sulfimide lithium of elastomer silicone forerunner body mass ratio 1:1
Dioctyl phthalate solution, wherein bis trifluoromethyl sulfimide lithium, which is dissolved in advance in dioctyl phthalate, forms 5% mass
Specific surface area 300m is added in the solution of score2The gas phase nano silica of/g, quality account for elastomer silicone presoma
10%, be added and account for the levelling agent of elastomer silicone presoma 0.1%, 0.3% defoaming agent, using mechanical stirring 500 turns/
Stirring 1 hour, is pre-mixed all components under minute, and 5 points are then stirred under 5000 revs/min using centrifugal blender
Clock is sufficiently mixed institute's component, obtains ionic rubber precursor pulp.100 1000 polyester fiber cloths are fitted in glass
Ionic rubber presoma is uniformly applied to fiber cloth surface by glass substrate surface, is then covered another piece of glass plate, is made fiber cloth
Distance is maintained at 0.5mm between glass plate.It is heated 30 minutes for 80 DEG C in baking oven, by cured ionic rubber from fiber after taking-up
It is stripped down on cloth, obtains the ionic rubber elastomer thin film that one side has coarse structure.
Electrode preparation: preparing interdigitated electrode structure using traditional lithography corrosion process on polyimide copper clad lamination,
Wherein interdigital electrode line width and line spacing are 250 microns, and 3 millimeters of electrode diameter.
Sensor preparation: ionic rubber elastomer is cut into 3 mm dias, and is placed on interdigital electrode on one side for coarse
Surface, and by way of hot pressing, by electrode and ionic rubber overall package among two panels thermoplastic polyurethane film, and cut
Cut packaged polyurethane film.
The sensor prepared with capacitance meter measurement embodiment 1, measures the capacitance of different pressure lower sensors, test three
It is secondary, it is averaged.As a result as shown in figure 5, its sensitivity is about 0.03nF/kPa.
Embodiment 2
A kind of preparation method from electronic type electronic skin, comprising the following steps:
The preparation of ionic rubber elastomer: bis- (the trifluoro methylsulphurs of 1- butyl -1- crassitude are added in powder nitrile rubber
Acyl) imines, and the mass ratio of nitrile rubber and bis- (trifluoro methylsulfonyl) imines of 1- butyl -1- crassitude is 2:1；Grain is added
Diameter is the active nano-calcium carbonate of 50nm, and quality accounts for the 20% of powder nitrile rubber, and addition accounts for powder nitrile rubber 0.1%
Levelling agent, 0.3% defoaming agent are stirred 1 hour under conditions of 60 revs/min, 150 DEG C using mechanical stirring, make all groups
Divide premixing, the cumyl peroxide for accounting for 1.5% mass ratio of powder nitrile rubber is then added as vulcanizing agent, uses three rollers
Machine is uniformly mixed all materials.Use 500 mesh sand-blasting stainless steel plates as template, and use vulcanizing press, at 180 DEG C
Under the conditions of vulcanize 4 hours, nitrile rubber is removed from Stainless Molding Board after the completion of vulcanization, obtaining one side has coarse structure
Ionic rubber elastomer thin film.
Electrode preparation: preparing interdigitated electrode structure using traditional lithography corrosion process on polyimide copper clad lamination,
Wherein interdigital electrode line width and line spacing are 250 microns, and 3 millimeters of electrode diameter.
Sensor preparation: being cut into 3 mm dia disks for ionic rubber elastomer, and by it is coarse be placed on one side it is interdigital
Electrode surface, and by way of hot pressing, by electrode and ionic rubber overall package among two panels thermoplastic polyurethane film,
And cut packaged polyurethane film.
Embodiment 3
A kind of preparation method from electronic type electronic skin, comprising the following steps:
The preparation of ionic rubber elastomer: being in mass ratio the ratio of 1:1, and 1- ethyl -3- methyl is added in natural rubber
The nano-titanium dioxide powder of partial size 50nm, the quality of nano-titanium dioxide powder is added in bis- (trifluoro methylsulfonyl) imines of imidazoles
The 15% of natural rubber is accounted for, the levelling agent for accounting for natural rubber quality 0.1% is added, 0.3% defoaming agent is existed using mechanical stirring
It is stirred 1 hour under conditions of 60 revs/min, 150 DEG C, is pre-mixed all components, be then added and account for 1.5% matter of natural rubber latex
The sulphur of ratio is measured as vulcanizing agent, is uniformly mixed all materials using three-roller.Use 500 mesh sand-blasting stainless steel plates as mould
Plate, and vulcanizing press is used, vulcanize 4 hours under conditions of 140 DEG C, by natural rubber from Stainless Molding Board after the completion of vulcanization
Upper removing obtains the ionic rubber elastomer thin film that one side has coarse structure.
Electrode preparation: preparing interdigitated electrode structure using traditional lithography corrosion process on polyimide copper clad lamination,
Wherein interdigital electrode line width and line spacing are 250 microns, and 3 millimeters of electrode diameter.
Sensor preparation: being cut into 3 mm dia disks for ionic rubber elastomer, and by it is coarse be placed on one side it is interdigital
Electrode surface, and by way of hot pressing, by electrode and ionic rubber overall package among two panels thermoplastic polyurethane film,
And cut packaged polyurethane film.
Comparative example
A kind of preparation method from electronic type electronic skin, comprising the following steps:
The preparation of ionic rubber elastomer: by Sylgard 184PDMS elastomer silicone presoma and curing agent according to 10:
The addition of 1 mass ratio, is added the O-phthalic with the bis trifluoromethyl sulfimide lithium of elastomer silicone forerunner body mass ratio 1:1
Dioctyl phthalate solution, wherein bis trifluoromethyl sulfimide lithium, which is dissolved in advance in dioctyl phthalate, forms 5% mass
The solution of score, is added without nano-powder material.It is added and accounts for the levelling agent of elastomer silicone presoma 0.1%, 0.3% disappears
Infusion is stirred 1 hour under 500 revs/min using mechanical stirring, is pre-mixed all components, and centrifugal stirring is then used
Machine stirs 5 minutes under 5000 revs/min, is sufficiently mixed institute's component, obtains ionic rubber precursor pulp.By 100
1000 polyester fiber cloths are fitted in glass substrate surface, ionic rubber presoma are uniformly applied to fiber cloth surface, so
After cover another piece of glass plate, so that distance between fiber cloth and glass plate is maintained at 0.5mm.It is heated 30 minutes for 80 DEG C in baking oven,
Cured ionic rubber is stripped down from fiber cloth after taking-up, obtains the ionic rubber elastomer that one side has coarse structure
Film.
Electrode preparation: preparing interdigitated electrode structure using traditional lithography corrosion process on polyimide copper clad lamination,
Wherein interdigital electrode line width and line spacing are 250 microns, and 3 millimeters of electrode diameter.
Sensor preparation: ionic rubber elastomer is cut into 3 mm dias, and is placed on interdigital electrode on one side for coarse
Surface, and by way of hot pressing, by electrode and ionic rubber overall package among two panels thermoplastic polyurethane film, and cut
Cut packaged polyurethane film.
It is measured under different pressure using condition same as Example 1 with the sensor of capacitance meter measurement comparative example preparation
The capacitance of sensor, sensitivity are about 0.023pF/kPa.Compared with the embodiment 1 that nano silica is added, comparative example
Sensitivity be less than the former 1/1000.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (11)
1. a kind of ionic rubber elastomer, which is characterized in that by the total weight of the ionic rubber elastomer be 100% in terms of, institute
State the following raw materials according component that ionic rubber elastomer includes following weight percentage:
2. ionic rubber elastomer as described in claim 1, which is characterized in that the rubber base material is selected from thermosetting property rubber
Glue material.
3. ionic rubber elastomer as claimed in claim 2, which is characterized in that the rubber base material is selected from thermosetting property fourth
Nitrile rubber class, thermosetting property organic silicon rubber class, thermosetting property butadiene-styrene rubber class, thermosetting acrylate rubber, thermosetting property are natural
At least one of rubber.
4. ionic rubber elastomer as described in claim 1, which is characterized in that the nano-powder material is that scale exists
1000nm solid nano material below.
5. ionic rubber elastomer as claimed in claim 4, which is characterized in that the nano-powder material is selected from zero dimension dioxy
SiClx nano particle, nanometer silica line material, Silica Nanotube, two-dimensional nano silica, titanium dioxide nano thread
At least one of material, titania nanotube, two-dimensional nano titanium dioxide, nano-calcium carbonate particles, nano alumina particles.
6. such as ionic rubber elastomer described in any one of claim 1 to 5, which is characterized in that the liquid ionic material choosing
From at least one of ionic liquid, ionic liquid dowtherm, solid electrolyte dowtherm, wherein
The ionic liquid is the ionic compound being in a liquid state under the conditions of temperature is 10 DEG C~35 DEG C；
The ionic liquid dowtherm forms in the highly polar organic solvent of higher boiling molten for ion liquid dissolving
Liquid, and the highly polar organic solvent of the higher boiling is that boiling point contains hydroxyl, amido, ester not less than 200 DEG C and in molecular structure
The organic solvent of at least one of base, amide groups, carboxyl；
The solid electrolyte dowtherm is under the conditions of temperature is 10 DEG C~35 DEG C in solid ionic compound
The solution formed in the highly polar organic solvent of higher boiling, and the highly polar organic solvent of the higher boiling is that boiling point is not less than 200
DEG C and molecular structure in the organic solvent containing at least one of hydroxyl, amido, ester group, amide groups, carboxyl.
7. ionic rubber elastomer as claimed in claim 6, which is characterized in that the ionic liquid is selected from imidazole-like ionic liquid
Body, ion liquid of quaternaries, pyridine ionic liquid, pyrrole ionic liquid, piperidines ionic liquid, pyrrolidines ion
At least one of liquid；And/or
In the ionic liquid solution, the ionic liquid is selected from glyoxaline ion liquid, ion liquid of quaternaries, pyridines
At least one of ionic liquid, pyrrole ionic liquid, piperidines ionic liquid, pyrrolidines ionic liquid；It is described high boiling
The highly polar organic solvent of point is selected from dibutyl phthalate, tributyl citrate, N-methyl pyrrolidones, dimethyl sulfoxide, sweet
At least one of oil, ethylene glycol；And/or
In the solid electrolyte solution, the ionic compound is selected from trifluoromethanesulfonic acid lithium, lithium hexafluoro phosphate, polyphenyl sodium sulfonate
At least one of；The highly polar organic solvent of higher boiling is selected from dibutyl phthalate, tributyl citrate, N-methyl
At least one of pyrrolidones, dimethyl sulfoxide, glycerol, ethylene glycol.
8. such as claim to 1 to 5 described in any item ionic rubber elastomers, which is characterized in that the additive, which is selected from, to disappear
At least one of infusion, levelling agent, rubber antiager.
9. a kind of ionic rubber method for producing elastomers, which comprises the following steps:
Each component is weighed according to any one of claim 1 to the 8 ionic rubber elastomer formulation；
By rubber material presoma and its curing agent, liquid ionic material, solid nano material, additive mixed processing, obtain
The persursor material of pulpous state；
The persursor material is deposited on substrate, curing process, obtains ionic rubber elastomer.
10. the ionic rubber method for producing elastomers as described in claim to 9, which is characterized in that the substrate be with
The substrate of default rough surface, and the persursor material is deposited in the step on substrate, the persursor material is sunk
Product is on the default rough surface of the substrate, curing process, obtains the ionic rubber elastomer with default rough surface.
11. a kind of from electronic type electronic skin, which is characterized in that including being provided with the flexible circuit board of interdigital electrode, and cover
Cover the ionic rubber on the interdigital electrode surface of the flexible circuit board, wherein the ionic rubber includes and the flexibility prints
The first surface that circuit interdigital electrode processed is bonded and the second surface away from the flexible printed circuit interdigital electrode, described first
Surface is rough surface, and the material of the ionic rubber is any one of claim 1 to 8 ionic rubber elastomer.
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