CN105602122A - Conducting rubber material for flexible sensor and preparation method and application of conducting rubber material - Google Patents

Conducting rubber material for flexible sensor and preparation method and application of conducting rubber material Download PDF

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Publication number
CN105602122A
CN105602122A CN201610061623.9A CN201610061623A CN105602122A CN 105602122 A CN105602122 A CN 105602122A CN 201610061623 A CN201610061623 A CN 201610061623A CN 105602122 A CN105602122 A CN 105602122A
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rubber
conductive
rubber material
strain
conductive rubber
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李大军
徐行涛
方斌
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SHENZHEN HUIRUI ELECTRONIC MATERIALS Co Ltd
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SHENZHEN HUIRUI ELECTRONIC MATERIALS Co Ltd
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    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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    • C08L83/00—Compositions 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; Compositions of derivatives of such polymers
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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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
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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
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    • C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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    • C08L2203/00—Applications
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention is applicable to the field of flexible sensors and provides a conducting rubber material for a flexible sensor and a preparation method and application of the conducting rubber material. The conducting rubber material is prepared from, by weight, 100 parts of rubber matrix, 5-90 parts of conducting filler and 0.1-15 parts of a bulking agent. The preparation method of the conducting rubber material comprises the steps of dispersing the conducting filler into a rubber material, and conducting electron beam or gamma-ray radiation crosslinking, so that the conducting rubber material is obtained.

Description

A kind of conductive rubber material for flexible sensor and its preparation method and application
Technical field
The invention belongs to flexible sensor field, relate in particular to a kind of conductive rubber material for flexible sensorMaterial and its preparation method and application.
Background technology
Strain ga(u)ge type sensor is that a kind of signal of telecommunication such as resistance or electric capacity that mechanical deformation information can be converted to is exportedA kind of device. English physicist Kelvin in 1885 finds that metal is bearing after pressure (pulling force or torsion)When producing mechanical deformation, resistance value is the variation of occurrence characteristics also, is called strain-resistance effect. Be subject to thisInspire, people draw from the variable quantity of resistance value feature and the value that material is stressed, thereby produce so-calledStrain transducer, mainly comprises pressure-strain sensor and tension strain sensor. At present, metal, metalAlloy and the semi-conducting material with piezoresistive effect become the main responsive material of strain ga(u)ge type sensor sensing unitMaterial, has obtained application very widely. Along with scientific and technological fast development, biomedical detection, rehabilitation medical,The mechanical meaurement of the field such as intelligent robot, wearable device labyrinth, not only requires sensor to possessGood strain-resistance characteristic, and to have outstanding flexility. Due to metal, metal alloy and partly leadThe springform quantitative limitation of body material own, there is following shortcoming in metal type or semiconductor-type resistance strain sensor:Flexibility is poor, mechanical quantity amplitude of variation is less, complex structure, and manufacturing cost is high. So traditional metal typeOr semiconductor-type resistance strain sensor is just restricted in the application in these fields, can not meets and work as previous convictionThe requirement of skill development. Therefore, develop strain ga(u)ge type sensor that a kind of new pliability is good to meet new neckTo sensor, flexible requirement becomes an urgent demand of current techniques and application development in territory.
Summary of the invention
The object of the present invention is to provide a kind of conductive rubber material for flexible sensor, be intended to solve existingThere is flexible poor, the baroque problem of metal mold, metal alloy type or semi-conductor type strain transducer.
Another object of the present invention is to provide a kind of preparation side of the conductive rubber material for flexible sensorMethod.
The present invention is achieved in that a kind of conductive rubber material for flexible sensor, comprises following weightThe following component of amount umber:
100 parts of rubber matrixs;
Conductive filler 5-90 part;
Bulking agent 0.1-15 part;
And described conductive rubber material is by being dispersed in electroconductive stuffing in elastomeric material, through electron beam or γX radiation x is crosslinked to be made.
Correspondingly, a kind of manufacture method of the conductive rubber material for flexible sensor, comprises the following steps:
Formula according to the above-mentioned conductive rubber material for flexible sensor takes each component;
Each component is carried out to mixing processing, obtain elastomeric compound;
Described elastomeric compound is carried out to forming processes;
Adopt the method for electron beam or gamma Rays to be cross-linked the sample through forming processes, obtain toolThere is the conductive rubber of strain-resistance effect.
And a kind of strain ga(u)ge type sensor, comprises sensing unit and the gold that is arranged on described sensing unit two endsBelong to electrode, described sensing unit is made up of the above-mentioned conductive rubber material for flexible sensor.
Conductive rubber material for flexible sensor provided by the invention, is dispersed in rubber by electroconductive stuffingIn material, make through electron beam or gamma Rays are crosslinked, with respect to adopting sulphur or organic peroxide to doThe chemical crosslink technique of crosslinking agent, have that production efficiency is high, environmental pollution is little, crosslink density is easily controlled andThe advantage that conductive rubber distribution of resistance is narrow.
Described conductive rubber material has good flexibility and elasticity, can produce higher mechanical deformation amount.Concrete, described conductive rubber material can produce more than 100% tensile deformation under pulling force effect,Under pressure-acting, can produce more than 50% compressive deformation. Further, conductive rubber material of the present inventionWhen material produces deformation under external force, its resistance value and electric capacity all change, and can produce simultaneouslyRaw strain-resistance effect and strain-capacity effect, and strain-resistance effect and strain-capacity effect trend phaseInstead. More specifically, conductive rubber material of the present invention under pulling force or pressure-acting its resistance along with stretchingDeformation increases constantly and declines, and presents negative resistance-strain effect, as its electricity in the time that the deformation quantity of sensor is 30%Resistance produces the variation of at least 5 times, and its variation even can be up to more than 100 times; Described conductive rubber materialUnder pulling force or pressure-acting, its capacitance increases along with deformation increases constantly, presents positive electric capacity-strain effect, asIn the time that the deformation quantity of sensor is 30%, its capacitance produces the variation of at least 10 times, and it changes even can be highReach more than 500 times. And conductive rubber material of the present invention has good signal sensitivity and stability,Its resistivity is between 5.0 × 102-1.0×1010Between Ω .cm, be specially adapted to as compliance sensor (asPulling force and pressure-strain type sensor) sensing unit material.
The preparation method of conductive rubber material of the present invention, adopts electron beam or gamma Rays to be cross-linked,Can be by controlling the degree of cross linking of the random regulation and control rubber of absorbed dose of radiation, and electron beam or gamma-rays can penetrateRubber glue-line, makes the rubber entirety degree of cross linking unanimously even; Described rubber conductive material is as sensor sensingWhen unit material, can realize the uniformity of the distribution of the resistance value of strain ga(u)ge type sensor, particularly resistance electricityThe performances such as the sensitivity of the signals of telecommunication such as appearance variation under external force, stability, recovery. In addition, originallyInventive method is simply controlled, is easy to realize industrialization.
Strain ga(u)ge type sensor provided by the invention, comprises and has strain-resistance effect and strain-electric capacity effect simultaneouslyThe sensing unit of answering and be arranged on the metal electrode at described sensing unit two ends. By detecting described strain typeSensor is being stretched or the variation of resistance value or capacitance when compressed, or converts resistance value to voltageOr current value, can carry out power in fields such as biomethanics, rehabilitation medical, intelligence wearing and artificial intelligenceMeasurement, be with a wide range of applications. In addition, described strain ga(u)ge type sensor is simple in structure, manufacturing costLow, easily install, easy to use.
Brief description of the drawings
Fig. 1 is capacitance/resistance-tensile deformation curve map that the embodiment of the present invention 1 provides;
Fig. 2 is capacitance/resistance-tensile deformation curve map that the embodiment of the present invention 2 provides;
Fig. 3 is capacitance/resistance-tensile deformation curve map that the embodiment of the present invention 3 provides;
Fig. 4 is capacitance/resistance-tensile deformation curve map that the embodiment of the present invention 4 provides;
Fig. 5 is capacitance/resistance-tensile deformation curve map that the embodiment of the present invention 5 provides;
Fig. 6 is capacitance/resistance-compressive deformation curve map that the embodiment of the present invention 6 provides;
Fig. 7 is capacitance/resistance-compressive deformation curve map that the embodiment of the present invention 7 provides;
Fig. 8 is capacitance/resistance-compressive deformation curve map that the embodiment of the present invention 8 provides.
Detailed description of the invention
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, withUnder in conjunction with the embodiments, the present invention is further elaborated. Should be appreciated that described herein concreteEmbodiment only, in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of conductive rubber material for flexible sensor, comprises following weightThe following component of umber:
100 parts of rubber matrixs;
Conductive filler 5-90 part;
Bulking agent 0.1-15 part;
And described conductive rubber material is by being dispersed in electroconductive stuffing in elastomeric material, through electron beam or γX radiation x is crosslinked to be made.
In the embodiment of the present invention, described conductive filler in described rubber matrix by the shape that is in contact with one another of microcosmicBecome conductive path, in the time that material is subject to External Force Acting, the spacing of material internal adjacent conductive particle changes,The conductive path that causes relying on the contact of described conductive filler and form changes, and causes macroscopic view upper materialResistance changes. Because conductive rubber material described in the embodiment of the present invention has this advantage, therefore, energyEnough in a kind of ess-strain sensing material.
Concrete, in the embodiment of the present invention, described rubber matrix has excellent flexibility and elasticity, gives instituteState the good flexibility of conductive rubber material and elasticity, and larger mechanical quantity amplitude of variation, can overcome goldGenus formula or the semiconductor-type strain transducer deficiency aspect pliability and elasticity.
As preferred embodiment, described rubber matrix is made up of two kinds or above rubber blending, i.e. described rubberMatrix comprises the first rubber matrix and the second rubber matrix, and wherein, described the first rubber bodies is for having carbon-carbon bondThe carbochain type olefin rubber of structure macromolecular main chain, described the second rubber matrix is large for having silicon oxygen bond structureThe non-carbochain type silicon rubber of molecular backbone.
Described in the embodiment of the present invention, the olefin rubber of the first rubber matrix carbochain type has good Mechanics of MachineryPerformance, such as natural rubber its hot strength in the situation that there is no carbon black-filled reinforcement reaches20-30MPa, the hot strength after carbon black filled reinforcement can arrive 35MPa, and other olefin rubber is as fourthThe reinforcement after-drawing intensity of nitrile rubber, neoprene all can reach 25-30MPa. In addition described the first rubber,The tearing strength 30-150MPa of matrix. Described the second rubber matrix has silicon oxygen bond structural molecule chain, its pointBetween son, cohesion energy density is low, and the hot strength of its hot strength in the situation that there is no reinforcement is less than 1MPa,Adopt carbon black or white carbon reinforcement after-drawing intensity to increase to some extent, but still rest on 4-12MPa scope,This hot strength level is only 1/3 of olefin rubber hot strength. In addition tearing of described the second rubber matrix,Resistance to spalling is lower, is only 10-50MPa. Therefore, adopt merely described the second rubber matrix silicon rubber as rubberWhen matrix body, the described conductive rubber material obtaining obviously has the deficiency of mechanical mechanics property aspect, and this is notFoot will affect its use field and service life in sensor orientation. Although but described the second rubber-basedThere is the problem that mechanical strength is lower in body, but due to the bond energy (370kJ/mol) of silicon rubber main chain Si-O keyMore much bigger than the bond energy of C-C key (240kJ/mol), therefore there is very high heat endurance, main manifestations isThere is resistance to ozone and the weatherability of remarkable resistant of high or low temperature, excellence.
The embodiment of the present invention is used in combination described the first rubber matrix and described the second rubber matrix, as instituteState flexible sensor as the sensitive material of strain ga(u)ge type sensor, both can bring into play described the first rubber matrix alkeneThe advantage of class rubber aspect mechanical mechanics property, can bring into play again described the second rubber matrix silicon rubber resistance toThe advantage of hot, cold resistance, weatherability aspect, learns from other's strong points to offset one's weaknesses, thereby makes to be obtained by the embodiment of the present inventionDescribed conductive rubber material there is good mechanical property, heat endurance and resistance to old for flexible sensorVoltinism energy, thus the applied environment temperature range of sensor widened. In addition, due to described the second rubber matrixMolecular backbone Si-O key be the key of tool rotatory power in all kinds of polymer molecular chains, thereby can give instituteState the good submissive performance of conductive rubber material, and then make to use its sensor as sensitive material to havePliability preferably. The method by add softening agent, plasticiser in formula compared promotes conductive rubberPliability, the use of embodiment of the present invention compounded rubber matrix can be avoided stretching when raising is flexibleThe decline of intensity, ensures good mechanical property, meets sensor simultaneously and draws the pliable and tough and mechanical property of quick materialThe demand of energy.
As a concrete preferred embodiment, described the first rubber matrix is natural rubber, acrylonitrile-butadiene rubber, secondThe third rubber, butadiene-styrene rubber, polyisoprene rubber, butadiene rubber, neoprene, chlorinated polyethylene rubber,At least one in CSM, fluorubber, ACM. Specifically excellent as anotherSelect embodiment, described the second rubber matrix is high temperature vulcanizable silicone, preferably dimethyl silicone rubber, methylAt least one in vinylsiloxane rubber, methyl ethylene phenyl siloxane rubber, phenylene silicone rubber, fluorosioloxane rubberKind. Of course it is to be understood that herein, described the first rubber matrix and described the second rubber matrix can be anyBe used in conjunction with, described first rubber matrix of selection and the quantity of described the second rubber matrix is not strict limit alsoMake, can select one or more described the first rubber matrix and described the second rubber matrix simultaneously.
The specific embodiment of the invention, the described conductive rubber material for flexible sensor is with 100 parts of described rubbersMatrix body is that benchmark regulates, but not means described in the embodiment of the present invention that rubber matrix can only be 100Part.
In the embodiment of the present invention, described conductive filler, as the conductive component of described conductive rubber material, is brought into playImportant function. As preferred embodiment, described conductive filler is in conductive black, CNT, silvering powderAt least one. As a specific embodiment, the preferred average grain diameter of described conductive black be 10-100nm,Oil factor is 40cm3/100g-400cm3/ 100g, specific area are 20-1500m2The conductive black of/g. ShouldPreferred conductive black has the advantages that particle is little, specific area is large, degree of structuration is high, thereby described conduction charcoalBlack easily dispersed in described rubber matrix, between particle, be easy to contact with each other formation conductive path, withLittle loading can obtain suitable resistance value, thereby makes conductive rubber material well keep rubberFlexibility and elasticity. As another specific embodiment, described CNT comprises SWCN and manyWall carbon nano tube. As another specific embodiment, described silvering powder is at metal particles or non-metallic particleThe powder of coated with silver on surface, preferred silver-plated nickel powder, silvered glass microballon powder, further, described silvering powderParticle diameter be 1-50 μ m. The silvering powder of preferable particle size, granularity is little, good conductivity, is easy to less fillingAmount obtains suitable resistance value, and keeps flexibility and the elasticity of rubber.
Described in the embodiment of the present invention, conductive filler can adopt a kind of conductive filler to use separately, also can two kindsOr the composite use of above conductive filler.
As the specific embodiment of the invention, the parts by weight of described conductive filler are 5-90 part, can comprise 5 parts,The concrete umbers such as 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts.
In the embodiment of the present invention, because described the first rubber matrix is that strand is the carbon of carbon-carbon bond (C-C)Chain olefin polymer, is the silicon rubber of silicon oxygen bond (Si-O) and described the second rubber matrix is strand,Between the molecular structure of two class rubber, there is larger difference. This two classes rubber matrix is mixed and the used time to knotThereby structure difference can cause larger interfacial tension to occur that phase structure separates, and affects described conductive rubber fillerPerformance. In order to obtain good combined effect, must be to described the first rubber matrix and described the second rubberModification is carried out at the interface of matrix body. In the embodiment of the present invention, add for the first rubber matrix described in modificationBulking agent with described the second rubber matrix interface performance. As preferred embodiment, described bulking agent is a kind ofThe olefin copolymer that contains polar functional group, specifically comprises block type copolymer, graft type copolymer. Enter oneStep, optimal ethylene-methyl acrylate copolymer (EMA), ethene-vinyl acetate copolymer (EVA),Ethylene-acrylic acid copolymer (EAA), polycthylene grafted silane (VMX), second the third glue grafted silane (EPMX),At least one in silicon rubber grafted maleic anhydride. This preferred bulking agent, can effectively reduce described firstInterfacial tension between rubber matrix and described the second rubber matrix, improves interface compatibility, promotes the two class utmost pointsRapid mixing and dispersion between the different rubber matrix of property and molecular structure, form stable phase structure.
In addition, described in the embodiment of the present invention, bulking agent can also promote described rubber matrix and described conductive fillerBetween coupling, promote the abundant dispersion of described conductive filler in described rubber matrix, improve described conductionInterface binding power between filler and described rubber matrix, prevents being separated between conductive phase and matrix phase,Make system more stable, be conducive to improve that the embodiment of the present invention provides for flexible sensor as strain sensingThe repeatability of the conductive rubber material of device and stability.
As the specific embodiment of the invention, the parts by weight of described bulking agent are 0.1-15 part, can comprise 0.1Part, 0.5 part, 1.0 parts, 2.0 parts, 3.0 parts, 4.0 parts, 5.0 parts, 6.0 parts, 7.0 parts, 8.0 parts, 9.0Part, the concrete umbers such as 10.0 parts, 11.0 parts, 12.0 parts, 13.0 parts, 14.0 parts, 15.0 parts.
In the embodiment of the present invention, in order to make the conductive rubber of crosslinking with radiation there is good mechanical mechanics property,Higher dose of radiation need to be provided, when there is cross-linking reaction but rubber is subject to radiation, also can occurDegradation reaction, higher dose of radiation can cause degradation reaction to increase, cause described conductive rubber material mechanicsPerformance and pliability, flexibility decrease. In order to improve the combination property of crosslinking with radiation rubber, overcome high amount of radiationThe degradation problem causing, conductive rubber material also comprises crosslinking sensitizer described in the embodiment of the present invention. Described friendshipThe use of connection sensitizer can, in the situation that reducing dose of radiation, obtain the higher degree of cross linking and machine simultaneouslyTool performance, thus make conductive rubber there is good pliability and elasticity simultaneously. As preferred embodiment, instituteStating crosslinking sensitizer is the molecular structure that contains the two keys of two or more C=C, and described crosslinking sensitizerContain at least one in following functional group: pi-allyl, methacrylate, acrylate, isocyanates.Concrete, in described crosslinking sensitizer molecule, can contain the two keys of two or more C=C, contain one withUpper other functional groups, preferably two monomers, more preferably trifunctional monomer. Described crosslinking sensitizer,The type of its functional group comprises pi-allyl, methacrylate, acrylate, isocyanates. Particularly,Described crosslinking sensitizer includes but not limited to triallyl isonitrile urate (TAIC), the acid of triallyl cyanogen ureaEster (TAC), trihydroxy methyl propane trimethyl acrylate (TMPT), tetramethylol methane tetrapropyleneAcid esters (A-TMMT), trimethylolpropane triacrylate (TMPTA), hexa-methylene two isocyanic acidsEster (UA101H), toluylene group diisocyanate (UA306T), dimethacrylate three second diester(TEGDMA). The embodiment of the present invention can be selected suitable multifunctional single group according to different rubber clonesBody is as crosslinking sensitizer.
As the specific embodiment of the invention, the parts by weight of described sensitization crosslinking agent are 0.1-15 part, can comprise0.1 part, 0.5 part, 1.0 parts, 2.0 parts, 3.0 parts, 4.0 parts, 5.0 parts, 6.0 parts, 7.0 parts, 8.0 parts,The concrete umbers such as 9.0 parts, 10.0 parts, 11.0 parts, 12.0 parts, 13.0 parts, 14.0 parts, 15.0 parts.
Described in the embodiment of the present invention, conductive rubber matrix adopting radiation method is realized vulcanization crosslinking. Concrete, thisBright embodiment crosslinking with radiation is to adopt the method for high-power electron beam radiation or gamma Rays by rubber macromolecule chainBe cross-linked into network structure. Described in the embodiment of the present invention, crosslinking with radiation belongs to the cross-linking reaction of free radical mechanism, shapeCarbon-to-carbon (C-C) key becoming is compared the sulfide linkage of crossing that uses sulfur cross-linking formation, has better heat oxygen aging resistancePerformance and chemical stability. General, adopt sulphur or organic peroxide as crosslinking agent, rubber to be enteredRow chemical crosslinking, due to be subject to the accurate measurement of crosslinking agent and dispersion level, mould or oven temperature accuratelyThe impact of the various factors such as control, reaction time and the extent of reaction, products thickness and heat-transfer effect, the degree of cross linkingBe difficult to accurately control. Compared with chemical crosslink technique, adopt irradiation technique to be cross-linked rubber, can pass throughControl the degree of cross linking of the random regulation and control rubber of absorbed dose of radiation, and electron beam or gamma-rays can penetrate rubber glue-line,Make the rubber entirety degree of cross linking unanimously even, while there will not be chemical method crosslinked, the inside and outside glue-line of rubber is due to heat transferThe problem of the ectonexine degree of cross linking difference that the difference of effect causes. Conductive rubber material described in the embodiment of the present inventionControlled and the degree of cross linking uniformity of the degree of cross linking, during as sensing unit material, can realize strain ga(u)ge type sensorThe spirit of the signal of telecommunication variation under external force such as uniformity, particularly resistance capacitance of distribution of resistance valueThe performances such as quick property, stability, recovery. In addition, crosslinking with radiation method has more convenient than chemical crosslink techniqueAbility with distribution of resistance, the degree of cross linking and the crosslinked uniformity of effective control conductive rubber. In addition, due toThe formula system of rubber crosslinking with radiation method does not contain the sulfuration promotion that can produce nitrosamine (a kind of carcinogen)Agent, thereby more environmental protection, can better be applied to medical field, directly contacts and carry out biomethanics with human bodyThe signal measurement of aspect and sensing.
In the embodiment of the present invention, irradiation dose is on embodiment of the present invention electron beam or the crosslinked impact of gamma RaysLarger, concrete, when irradiation dose is during lower than 5Mrad, rubber cross degree deficiency, not only mechanical mechanicsEnergy is poor and rubber resilience is poor, thereby causes the resistance recovery capacity of strain transducer poor; When dosage higher thanWhen 30Mrad, mechanical mechanics property variation, flexibility and the flexibility decrease of elastomeric material, because rubber is subject toRadiation and degradation reaction also can occur when there is cross-linking reaction, just reaction rate difference is low at dosageIn the time of 30Mrad, taking cross-linking reaction as main, and when dosage is during higher than 30Mrad, degradation reaction is furtherIncrease and even become main reaction, reduce flexibility and the elasticity of rubber. As preferred embodiment, described high energy electricitySon bundle or gamma-ray irradiation dose 5-30 Megarad (Mrad), more preferably 5-25 Megarad. The present inventionEmbodiment preferred dose 5-25 Megarad can ensure that conductive rubber not only has good mechanical property but also hasGood pliability and resistance recovery. Wherein, rad (rad) is the radiation that per unit material mass is acceptedThe measurement unit of energy, 1Mrad=1 × 106rad。
In the embodiment of the present invention, the resistivity of described conductive rubber material is 5.0 × 102-1.0×1010Ω.cm。The resistivity of described conductive rubber material is lower than 5.0 × 102Ω .cm, strain-resistance effect a little less than, and work as materialMaterial resistivity is higher than 1.0 × 1010Ω .cm, the conducting medium contact conduction machine of conductive rubber during by low-resistivitySystem is transformed into contact conductive mechanism and tunnel-effect conductive mechanism and deposits, and becomes tunnel-effect conduction even completelyMechanism, and the conductive mechanism of tunnel-effect easily causes resistance stability, the recovery variation of conductive rubber,And the difficulty of the stability of controlling resistance concentration degree and strain-resistance effect in conductive rubber manufacture processIncrease. Described in the embodiment of the present invention, conductive rubber material has excellent resistivity, gives described conductive rubberThe better application performance of material.
The conductive rubber material for flexible sensor that the embodiment of the present invention provides, is disperseed by electroconductive stuffingIn elastomeric material, make through electron beam or gamma Rays are crosslinked, with respect to adopting sulphur or organic peroxyCompound is made the chemical crosslink technique of crosslinking agent, has that production efficiency is high, environmental pollution is little, crosslink density is easily controlledSystem and the narrow advantage of conductive rubber distribution of resistance.
Described conductive rubber material has good flexibility and elasticity, can produce higher mechanical deformation amount.Concrete, described conductive rubber material can produce more than 100% tensile deformation under pulling force effect,Under pressure-acting, can produce more than 50% compressive deformation. Further, described in the embodiment of the present invention, conduct electricityWhen elastomeric material produces deformation under external force, its resistance value and electric capacity all change, and canProduce strain-resistance effect and strain-capacity effect, and strain-resistance effect and strain-capacity effect become simultaneouslyGesture is contrary. More specifically, conductive rubber material its electricity under pulling force or pressure-acting described in the embodiment of the present inventionResistance declines along with tensile deformation increases constantly, presents negative resistance-strain effect, as the deformation quantity when sensor is30% time, its resistance value produces the variation of at least 5 times, and its variation even can be up to more than 100 times; Described leadingUnder electricity elastomeric material pulling force or pressure-acting, its capacitance increases along with deformation increases constantly, present positive electric capacity-Strain effect, as its capacitance in the time that the deformation quantity of sensor is 30% produces the variation of at least 10 times, itsChanging even can be up to more than 500 times. And described in the embodiment of the present invention, conductive rubber material has good letterNumber sensitivity and stability, its resistivity is between 5.0 × 102-1.0×1010Between Ω .cm, be specially adapted to doFor the sensing unit material of compliance sensor (as pulling force and pressure-strain type sensor).
Conductive rubber material for flexible sensor described in the embodiment of the present invention can be prepared by following methodObtain.
Correspondingly, a kind of manufacture method of the conductive rubber material for flexible sensor, comprises the following steps:
S01. take each component according to the formula of the above-mentioned conductive rubber material for flexible sensor;
S02. each component is carried out to mixing processing, obtain elastomeric compound;
S03. described elastomeric compound is carried out to forming processes;
S04. adopt the method for electron beam or gamma Rays to be cross-linked the sample through forming processes,To the conductive rubber with strain-resistance effect.
Concrete, in above-mentioned steps S01, for the recipe ingredient of the conductive rubber material of flexible sensor andIts preferred situation as described above, in order to save length, repeats no more herein.
In above-mentioned steps S02, when each component is carried out to mixing processing, in order to improve melting effect, obtain pointLoose uniform elastomeric compound, the embodiment of the present invention preferably in order successively by described rubber matrix, bulking agent,Conductive filler joins and in mill or banbury, carries out mixingly, obtains elastomeric compound.
In above-mentioned steps S03, described forming processes can realize by rubber-moulding equipment, by moulding placeReason can obtain to be had the sheet material of certain size or is directly formed to specific shape by mould. Concrete,Described former comprises screw extruder, calender and vulcanizing press.
In above-mentioned steps S04, as preferred embodiment, adopt the method for electron beam or gamma Rays to warpWhen the sample of overmolding processing is cross-linked, the dosage of described electron beam or gamma Rays is 5-25MradConcrete, when irradiation dose is during lower than 5Mrad, rubber cross degree deficiency, not only mechanical mechanics property poor andAnd rubber resilience is poor, thereby cause the resistance recovery capacity of strain transducer poor; When dosage is higher than 30MradTime, mechanical mechanics property variation, flexibility and the flexibility decrease of elastomeric material, send out because rubber is subject to radiationWhen raw cross-linking reaction, also can there is degradation reaction, just reaction rate difference, at dosage lower than 30MradTime, taking cross-linking reaction as main, and when dosage is during higher than 30Mrad, degradation reaction further increases even and becomesBecome main reaction, reduce flexibility and the elasticity of rubber. As preferred embodiment, described high-power electron beam or γ penetrateThe irradiation dose 5-30 Megarad (Mrad) of line, more preferably 5-25 Megarad. The embodiment of the present invention is excellentSelect dosage 5-25 Megarad can ensure that conductive rubber had not only had good mechanical property but also had good softToughness and resistance recovery. In addition, because the existence of oxygen in the process of cross-linking radiation can cause oxidative degradation,Therefore the rubber sheet that, S03 step obtains need to vacuumize packaging.
Further, can cut into the sensing unit of definite shape as sensor by the sheet material after crosslinked, orPerson is the sensing unit using the given shape that in step S03, mould molding obtains as sensor directly, in sensitivityOn unit, make metal electrode, obtain tension type strain transducer or pressure-type strain transducer.
The preparation method of conductive rubber material described in the embodiment of the present invention, adopts electron beam or gamma Rays to enterRow is crosslinked, can pass through to control the degree of cross linking of the random regulation and control rubber of absorbed dose of radiation, and electron beam or gamma-raysCan penetrate rubber glue-line, make the rubber entirety degree of cross linking unanimously even; Described rubber conductive material is as passingWhen sensor sensing unit material, can realize the uniformity of the distribution of the resistance value of strain ga(u)ge type sensor, specialThe performances such as the sensitivity, stability, recovery of the variation under external force of the signals of telecommunication such as resistance capacitance.In addition, embodiment of the present invention method is simply controlled, is easy to realize industrialization.
And a kind of strain ga(u)ge type sensor, comprises sensing unit and the gold that is arranged on described sensing unit two endsBelong to electrode, described sensing unit is made up of the above-mentioned conductive rubber material for flexible sensor.
In the embodiment of the present invention, in described conductive rubber material conductive filler in rubber matrix by microcosmicBe in contact with one another formation conductive path, in the time that material is subject to External Force Acting, between material internal adjacent conductive particleApart from changing, cause relying on the contact of conducting particles and the conductive path that forms changes, cause macroscopic viewThe resistance of upper conductive rubber material changes, and makes described conductive rubber material have power-electricresistance effect, executesBe added in external force on conductive rubber and comprise two kinds of pulling force and pressure.
Described sensing unit produces respectively elongation strain and compression strain under pulling force and pressure-acting, with deformationIncrease, the resistance value that sensing unit deformation increases direction declines, and presents negative strain-resistance effect. DescribedStrain ga(u)ge type sensor is after being subject to external tensile force or pressure-acting, and sensing unit is stretched along deformation directionOr compression, interelectrode distance increases or reduces, simultaneously cutting perpendicular to the nyctitropic sensing unit of shapeArea reduces accordingly or increases; Meanwhile, the deformation that sensing unit produces under external force causes sensitive materialThe variation in inner conductive particle gap causes that material conductive microstructure network changes, thereby causes sensitive materialThe variation of resistivity, and then cause material dielectric constant to change with External Force Acting. Therefore, material resistanceThe factor such as dielectric constant, sensing unit interelectrode distance of rate, material finally causes with the comprehensive variation of external forceCapacitance between sensor sensing unit two end electrodes change under external force. Therefore, thisThe bright described flexible strain ga(u)ge type sensor using conductive rubber as sensing unit, is being subject to external tensile force or pressureDo the used time, sensor is the variation of the value of having a resistance not only, and the variation of capacitance also occurs simultaneously, and strain-Electricresistance effect is negative strain-electricresistance effect, and strain-capacity effect is normal strain-electricresistance effect. So, thisDescribed in bright embodiment, flexible strain ga(u)ge type sensor can be used as strain-electric resistance sensor, also can be used as strain-Capacitance sensor.
Concrete, in described strain ga(u)ge type sensor, the material of described sensing unit is above-mentioned conductive rubber material,Described conductive rubber material is by filled conductive filler in rubber matrix, through electron beam or gamma-ray irradiation friendshipJoin and make, concrete formula and each component situation thereof be statement in detail hereinbefore, no longer explanation herein.Described metal electrode is selected from the one in metal forming, sheet metal, metal film or profiled metal part.
The embodiment of the present invention can be by bonding, the high temperature hot pressing of conducting resinl, conductive silver paste serigraphy, vacuumThe mode of plated film or mechanical crimping is produced on described metal electrode on the surface of sensing unit. Wherein, described inConductive silver paste is ultraviolet curing type; The method of described vacuum coating comprise evaporation coating, magnetron sputtering plating,Ion film plating.
The preparation method of compliance sensor described in the embodiment of the present invention, can cut into one by the sheet material after crosslinkedSetting shape is as the sensing unit of sensor; Or directly by the above-mentioned steps of the described conductive rubber material of preparationThe given shape that in S03, mould molding obtains, as the sensing unit of sensor, is made gold on sensing unitBelong to electrode, obtain tension type strain transducer or pressure-type strain transducer.
The strain ga(u)ge type sensor that the embodiment of the present invention provides, comprise thering is strain-resistance effect and strain-simultaneouslyThe sensing unit of capacity effect and be arranged on the metal electrode at described sensing unit two ends. Described in detectingStrain ga(u)ge type sensor is being stretched or the variation of resistance value or capacitance when compressed, or resistance value is changedBecome voltage or current value, can be in fields such as biomethanics, rehabilitation medical, intelligence wearing and artificial intelligenceCarry out force measurement, be with a wide range of applications. In addition, described strain ga(u)ge type sensor is simple in structure, systemCause lowly, easily install, easy to use.
Below, describe in conjunction with specifically having implemented. In the embodiment of the present invention, described ethylene propylene diene rubber(EPDM) can be selected from the ethylene propylene diene rubber that the Jilin chemical industry trade mark is J-3080, in this ethylene propylene diene rubberThe weight percentage of ethene is 68.5-74.5%; Described natural rubber (NR) can be selected from the hainan rubber trade markFor SCR5; Described ACM (ACM) can be selected from Japanese synthetic rubber AR1100, and its Mooney is stickyDegree is 40; Described fluorubber (FPM) can be selected from the fluorubber that the rising sun whistle trade mark is Aflas100S, this fluorineRubber fluorine content 57%; Described methyl vinyl silicone rubber (MVQ) can be selected from the eastern rank of nobility organosilicon trade markThe methyl vinyl silicone rubber of 110-1, the quality percentage composition of this methyl vinyl silicone rubber medium vinyl is0.13-0.22%; Described fluorosioloxane rubber (FMVQ) can be selected from Shanghai three and like rich FE2801; Described conduction charcoalBlackly be selected from the conductive black that the Cabot trade mark is BP280, the particle diameter of described conductive black is 41nm, suctionOil value is 121cm3/ 100g, specific area are 42m2/ g; Described CNT (CNT) can be selected from clear andElectrician's trade mark is the CNT of VGCF-H, this CNT diameter 150nm, length 6 μ m; DescribedEMA resin can be selected from Du Pont's trade markEMA resin, this EMA resinSoftening point is 48 DEG C.
Embodiment 1
For a conductive rubber material for flexible sensor, comprise each content group described in table 1 embodiment 1Point, and described conductive rubber material is by being dispersed in electroconductive stuffing in elastomeric material, through electron beam or γX radiation x is crosslinked to be made.
And the preparation method of the described conductive rubber material for flexible sensor, comprises the following steps:
S11. take each component according to the formula of the above-mentioned conductive rubber material for flexible sensor;
S12. successively described rubber matrix, bulking agent, conductive filler are joined in mill, carry out mixing,Mixing time 20min, various fillers mix rear thin-pass slice, obtain elastomeric compound;
S13. described elastomeric compound is obtained to sheet sizing material with rubber plate vulcanization machine compression molding, sheet sizing material chiVery little is length 100mm × width 100mm × thickness 1mm;
S14. adopt the method for electron beam or gamma Rays to be cross-linked the sample through forming processes,To the conductive rubber with strain-resistance effect, wherein, the irradiation dose of described electron beam or gamma RaysAs shown in table 1 embodiment 1.
A kind of strain ga(u)ge type sensor, comprises and has the sensing list that the conductive rubber material of strain-resistance effect is madeUnit and the metal electrode that is arranged on described sensing unit two ends, its concrete production method is: by the rubber after crosslinkedFilm material cuts into the sensing unit of definite shape as sensor, and sheet material cut be of a size of length 40mm ×The strip of width 5mm, in its two ends installing electrodes, removes the effective scalable partial-length after electrode30mm, it is the line terminal lug of TC specification SC6-5 that electrode is selected material, obtains tension type strain sensingDevice.
Embodiment 2
For a conductive rubber material for flexible sensor, comprise each content group described in table 1 embodiment 2Point, and described conductive rubber material is by being dispersed in electroconductive stuffing in elastomeric material, through electron beam or γX radiation x is crosslinked to be made.
And the preparation method of the described conductive rubber material for flexible sensor, comprises the following steps:
S21. take each component according to the formula of the above-mentioned conductive rubber material for flexible sensor;
S22. successively described rubber matrix, bulking agent, conductive filler are joined in mill, carry out mixing,Mixing time 20min, various fillers mix rear thin-pass slice, obtain elastomeric compound;
S23. described elastomeric compound is obtained to sheet sizing material with rubber plate vulcanization machine compression molding, sheet sizing material chiVery little is length 100mm × width 100mm × thickness 1mm;
S24. adopt the method for electron beam or gamma Rays to be cross-linked the sample through forming processes,To the conductive rubber with strain-resistance effect, wherein, the irradiation dose of described electron beam or gamma RaysAs shown in table 1 embodiment 2.
A kind of strain ga(u)ge type sensor, comprises and has the sensing list that the conductive rubber material of strain-resistance effect is madeUnit and the metal electrode that is arranged on described sensing unit two ends, its concrete production method is: by the rubber after crosslinkedFilm material cuts into the sensing unit of definite shape as sensor, and sheet material cut be of a size of length 40mm ×The strip of width 5mm, in its two ends installing electrodes, removes the effective scalable partial-length after electrode30mm, it is the line terminal lug of TC specification SC6-5 that electrode is selected material, obtains tension type strain sensingDevice.
Embodiment 3
For a conductive rubber material for flexible sensor, comprise each content group described in table 1 embodiment 3Point, and described conductive rubber material is by being dispersed in electroconductive stuffing in elastomeric material, through electron beam or γX radiation x is crosslinked to be made.
And the preparation method of the described conductive rubber material for flexible sensor, comprises the following steps:
S31. take each component according to the formula of the above-mentioned conductive rubber material for flexible sensor;
S32. successively described rubber matrix, bulking agent, conductive filler are joined in mill, carry out mixing,Mixing time 20min, various fillers mix rear thin-pass slice, obtain elastomeric compound;
S33. described elastomeric compound is obtained to sheet sizing material with rubber plate vulcanization machine compression molding, sheet sizing material chiVery little is length 100mm × width 100mm × thickness 1mm;
S34. adopt the method for electron beam or gamma Rays to be cross-linked the sample through forming processes,To the conductive rubber with strain-resistance effect, wherein, the irradiation dose of described electron beam or gamma RaysAs shown in table 1 embodiment 3.
A kind of strain ga(u)ge type sensor, comprises and has the sensing list that the conductive rubber material of strain-resistance effect is madeUnit and the metal electrode that is arranged on described sensing unit two ends, its concrete production method is: by the rubber after crosslinkedFilm material cuts into the sensing unit of definite shape as sensor, and sheet material cut be of a size of length 40mm ×The strip of width 5mm, in its two ends installing electrodes, removes the effective scalable partial-length after electrode30mm, it is the line terminal lug of TC specification SC6-5 that electrode is selected material, obtains tension type strain sensingDevice.
Embodiment 4
For a conductive rubber material for flexible sensor, comprise each content group described in table 1 embodiment 4Point, and described conductive rubber material is by being dispersed in electroconductive stuffing in elastomeric material, through electron beam or γX radiation x is crosslinked to be made.
And the preparation method of the described conductive rubber material for flexible sensor, comprises the following steps:
S41. take each component according to the formula of the above-mentioned conductive rubber material for flexible sensor;
S42. successively described rubber matrix, bulking agent, conductive filler are joined in mill, carry out mixing,Mixing time 20min, various fillers mix rear thin-pass slice, obtain elastomeric compound;
S43. described elastomeric compound is obtained to sheet sizing material with rubber plate vulcanization machine compression molding, sheet sizing material chiVery little is length 100mm × width 100mm × thickness 1mm;
S44. adopt the method for electron beam or gamma Rays to be cross-linked the sample through forming processes,To the conductive rubber with strain-resistance effect, wherein, the irradiation dose of described electron beam or gamma RaysAs shown in table 1 embodiment 4.
A kind of strain ga(u)ge type sensor, comprises and has the sensing list that the conductive rubber material of strain-resistance effect is madeUnit and the metal electrode that is arranged on described sensing unit two ends, its concrete production method is: by the rubber after crosslinkedFilm material cuts into the sensing unit of definite shape as sensor, and sheet material cut be of a size of length 40mm ×The strip of width 5mm, in its two ends installing electrodes, removes the effective scalable partial-length after electrode30mm, it is the line terminal lug of TC specification SC6-5 that electrode is selected material, obtains tension type strain sensingDevice.
Embodiment 5
For a conductive rubber material for flexible sensor, comprise each content group described in table 1 embodiment 5Point, and described conductive rubber material is by being dispersed in electroconductive stuffing in elastomeric material, through electron beam or γX radiation x is crosslinked to be made.
And the preparation method of the described conductive rubber material for flexible sensor, comprises the following steps:
S51. take each component according to the formula of the above-mentioned conductive rubber material for flexible sensor;
S52. successively described rubber matrix, bulking agent, conductive filler are joined in mill, carry out mixing,Mixing time 20min, various fillers mix rear thin-pass slice, obtain elastomeric compound;
S53. described elastomeric compound is obtained to sheet sizing material with rubber plate vulcanization machine compression molding, sheet sizing material chiVery little is length 100mm × width 100mm × thickness 1mm;
S54. adopt the method for electron beam or gamma Rays to be cross-linked the sample through forming processes,To the conductive rubber with strain-resistance effect, wherein, the irradiation dose of described electron beam or gamma RaysAs shown in table 1 embodiment 5.
A kind of strain ga(u)ge type sensor, comprises and has the sensing list that the conductive rubber material of strain-resistance effect is madeUnit and the metal electrode that is arranged on described sensing unit two ends, its concrete production method is: by the rubber after crosslinkedFilm material cuts into the sensing unit of definite shape as sensor, and sheet material cut be of a size of length 40mm ×The strip of width 5mm, in its two ends installing electrodes, removes the effective scalable partial-length after electrode30mm, it is the line terminal lug of TC specification SC6-5 that electrode is selected material, obtains tension type strain sensingDevice.
Embodiment 6
For a conductive rubber material for flexible sensor, comprise each content group described in table 1 embodiment 6Point, and described conductive rubber material is by being dispersed in electroconductive stuffing in elastomeric material, through electron beam or γX radiation x is crosslinked to be made.
And the preparation method of the described conductive rubber material for flexible sensor, comprises the following steps:
S61. take each component according to the formula of the above-mentioned conductive rubber material for flexible sensor;
S62. successively described rubber matrix, bulking agent, conductive filler are joined in mill, carry out mixing,Mixing time 20min, various fillers mix rear thin-pass slice, obtain elastomeric compound;
S63. described elastomeric compound is obtained to sheet sizing material with rubber plate vulcanization machine compression molding, sheet sizing material chiVery little is length 100mm × width 100mm × thickness 1mm;
S64. adopt the method for electron beam or gamma Rays to be cross-linked the sample through forming processes,To the conductive rubber with strain-resistance effect, wherein, the irradiation dose of described electron beam or gamma RaysAs shown in table 1 embodiment 6.
A kind of strain ga(u)ge type sensor, comprises and has the sensing list that the conductive rubber material of strain-resistance effect is madeUnit and the metal electrode that is arranged on described sensing unit two ends, its concrete production method is: by the rubber after crosslinkedFilm material cuts into the sensing unit of definite shape as sensor, and sheet material cut be of a size of length 10mm ×The square piece shape of width 10mm, lower surface adopts conductive adhesive electrode thereon, and electrode selects thickness to beThe nickel plating Copper Foil of 35 μ m, obtains pressure-type strain transducer.
Embodiment 7
For a conductive rubber material for flexible sensor, comprise each content group described in table 1 embodiment 7Point, and described conductive rubber material is by being dispersed in electroconductive stuffing in elastomeric material, through electron beam or γX radiation x is crosslinked to be made.
And the preparation method of the described conductive rubber material for flexible sensor, comprises the following steps:
S71. take each component according to the formula of the above-mentioned conductive rubber material for flexible sensor;
S72. successively described rubber matrix, bulking agent, conductive filler are joined in mill, carry out mixing,Mixing time 20min, various fillers mix rear thin-pass slice, obtain elastomeric compound;
S73. described elastomeric compound is obtained to sheet sizing material with rubber plate vulcanization machine compression molding, sheet sizing material chiVery little is length 100mm × width 100mm × thickness 1mm;
S74. adopt the method for electron beam or gamma Rays to be cross-linked the sample through forming processes,To the conductive rubber with strain-resistance effect, wherein, the irradiation dose of described electron beam or gamma RaysAs shown in table 1 embodiment 7.
A kind of strain ga(u)ge type sensor, comprises and has the sensing list that the conductive rubber material of strain-resistance effect is madeUnit and the metal electrode that is arranged on described sensing unit two ends, its concrete production method is: by the rubber after crosslinkedFilm material cuts into the sensing unit of definite shape as sensor, and sheet material cut be of a size of length 10mm ×The square piece shape of width 10mm, lower surface adopts conductive adhesive electrode thereon, and electrode selects thickness to beThe nickel plating Copper Foil of 35 μ m, obtains pressure-type strain transducer.
Embodiment 8
For a conductive rubber material for flexible sensor, comprise each content group described in table 1 embodiment 8Point, and described conductive rubber material is by being dispersed in electroconductive stuffing in elastomeric material, through electron beam or γX radiation x is crosslinked to be made.
And the preparation method of the described conductive rubber material for flexible sensor, comprises the following steps:
S81. take each component according to the formula of the above-mentioned conductive rubber material for flexible sensor;
S82. successively described rubber matrix, bulking agent, conductive filler are joined in mill, carry out mixing,Mixing time 20min, various fillers mix rear thin-pass slice, obtain elastomeric compound;
S83. described elastomeric compound is obtained to sheet sizing material with rubber plate vulcanization machine compression molding, sheet sizing material chiVery little is length 100mm × width 100mm × thickness 1mm;
S84. adopt the method for electron beam or gamma Rays to be cross-linked the sample through forming processes,To the conductive rubber with strain-resistance effect, wherein, the irradiation dose of described electron beam or gamma RaysAs shown in table 1 embodiment 8.
A kind of strain ga(u)ge type sensor, comprises and has the sensing list that the conductive rubber material of strain-resistance effect is madeUnit and the metal electrode that is arranged on described sensing unit two ends, its concrete production method is: by the rubber after crosslinkedFilm material cuts into the sensing unit of definite shape as sensor, and sheet material cut be of a size of length 10mm ×The square piece shape of width 10mm, lower surface adopts conductive adhesive electrode thereon, and electrode selects thickness to beThe nickel plating Copper Foil of 35 μ m, obtains pressure-type strain transducer.
Performance test: using conductive rubber material described in embodiment 1-8 as sensing unit material, prepareSensor carry out performance test, method is as follows:
1, the test of tension type strain transducer: initial resistivity value and the capacitance of test pulling force sensor, withAnd resistance value and the capacitance of sensor while stretching 30% deformation, and the variation of calculated resistance value and capacitance doublyRate, data are listed in table 2. Draw the relation curve of resistance value, capacitance and the tensile deformation of sensor, asShown in Fig. 1-5;
2, the test of pressure-type strain transducer: the initial resistivity value of test pressure sensor and capacitance, withAnd resistance value and the capacitance of sensor while compressing 30% deformation, and the variation of calculated resistance value and capacitance doublyRate, data are listed in table 2. Draw the relation curve of resistance value, capacitance and the compressive deformation of sensor, asShown in Fig. 6-8.
Test result is as shown in table 2 below.
Table 1
Table 2
From upper table 2, conductive rubber filler has good resistivity described in the embodiment of the present invention, forAfter the sensing unit of strain ga(u)ge type sensor, make described strain ga(u)ge type sensor there is good strain-resistance simultaneouslyEffect and, strain-capacity effect, and strain-resistance effect is negative strain-electricresistance effect, strain-capacity effectFor normal strain-electricresistance effect.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, not all at thisAny amendment of doing within bright spirit and principle, be equal to and replace and improvement etc., all should be included in the present inventionProtection domain within.

Claims (10)

1. for a conductive rubber material for flexible sensor, it is characterized in that, comprise following parts by weightFollowing component:
100 parts of rubber matrixs;
Conductive filler 5-90 part;
Bulking agent 0.1-15 part;
And described conductive rubber material is by being dispersed in electroconductive stuffing in elastomeric material, through electron beam or γX radiation x is crosslinked to be made.
2. the conductive rubber material for flexible sensor as claimed in claim 1, is characterized in that, instituteState rubber matrix and comprise the first rubber matrix and the second rubber matrix, wherein, described the first rubber bodies is for havingThe carbochain type olefin rubber of carbon-carbon bond structure macromolecular main chain, described the second rubber matrix is for having silicon oxygen bondThe non-carbochain type silicon rubber of structure macromolecular main chain.
3. the conductive rubber material for flexible sensor as claimed in claim 1, is characterized in that, instituteStating the first rubber matrix is natural rubber, acrylonitrile-butadiene rubber, EP rubbers, butadiene-styrene rubber, polyisoprene rubberGlue, butadiene rubber, neoprene, chlorinated polyethylene rubber, CSM, fluorubber, thirdAt least one in olefin(e) acid ester rubber; And/or
Described the second rubber matrix is dimethyl silicone rubber, methyl vinyl silicone rubber, methyl ethylene phenylAt least one in silicon rubber, phenylene silicone rubber, fluorosioloxane rubber.
4. the conductive rubber material for flexible sensor as described in as arbitrary in claim 1-3, its feature existsIn, also comprise crosslinking sensitizer.
5. the conductive rubber material for flexible sensor as claimed in claim 4, is characterized in that, instituteStating crosslinking sensitizer is the molecular structure that contains the two keys of two or more C=C, and described crosslinking sensitizerContain at least one in following functional group: pi-allyl, methacrylate, acrylate, isocyanates.
6. the conductive rubber material for flexible sensor as described in as arbitrary in claim 1-3, its feature existsIn, described conductive filler is at least one in conductive black, CNT, silvering powder; And/or
Described bulking agent is ethylene-methyl acrylate copolymer, ethene-vinyl acetate copolymer, ethylene-propyleneOne in acid copolymer, polycthylene grafted silane, second the third glue grafted silane, silicon rubber grafted maleic anhydride.
7. the conductive rubber material for flexible sensor as described in as arbitrary in claim 1-3, its feature existsIn, the resistivity of described conductive rubber material is 5.0 × 102-1.0×1010Ω.cm。
8. for a manufacture method for the conductive rubber material of flexible sensor, comprise the following steps:
Formula according to the arbitrary described conductive rubber material for flexible sensor of claim 1-7 takes respectivelyComponent;
Each component is carried out to mixing processing, obtain elastomeric compound;
Described elastomeric compound is carried out to forming processes;
Adopt the method for electron beam or gamma Rays to be cross-linked the sample through forming processes, obtain toolThere is the conductive rubber of strain-resistance effect.
9. the conductive rubber material for flexible sensor as claimed in claim 8, is characterized in that, instituteThe dosage of stating electron beam or gamma Rays is 5-30Mrad.
10. a strain ga(u)ge type sensor, comprises sensing unit and the metal that is arranged on described sensing unit two endsElectrode, is characterized in that, described sensing unit is arbitrary described for flexible sensor by claim 1-7Conductive rubber material is made.
CN201610061623.9A 2016-01-28 2016-01-28 Conducting rubber material for flexible sensor and preparation method and application of conducting rubber material Pending CN105602122A (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106009677A (en) * 2016-07-18 2016-10-12 深圳市尚智工程技术咨询有限公司 Nanometer conductive rubber sensing unit and method for preparing same
CN106589967A (en) * 2017-01-25 2017-04-26 林建光 Electric conduction rubber and preparation method thereof
CN107541072A (en) * 2017-08-22 2018-01-05 华南理工大学 High temperature circulation tensile force causes silicon rubber composite material of electric conductivity enhancing and preparation method thereof
CN109851872A (en) * 2018-12-27 2019-06-07 广州弗西林橡塑有限公司 A kind of high resiliency conductive rubber and preparation method thereof
CN110006465A (en) * 2018-05-31 2019-07-12 常州允能新材料有限公司 A kind of flexible resistive type sensor based on starch material
CN110157192A (en) * 2019-04-10 2019-08-23 中国科学院深圳先进技术研究院 A kind of flexible polymer film and its manufacturing method can be used for sound intensity detection
CN111363076A (en) * 2020-04-24 2020-07-03 四川道弘科技有限公司 Ternary peroxide fluororubber and preparation method thereof, and intelligent wearing material and preparation method thereof
CN111795764A (en) * 2019-04-09 2020-10-20 绍兴文理学院元培学院 Sandwich type large-area high-density flexible array sensor and preparation method thereof
CN112608533A (en) * 2020-12-01 2021-04-06 世目特种防护用品科技（江苏）有限公司 Conductive latex and preparation method and application thereof
CN115073696A (en) * 2022-06-16 2022-09-20 沈阳化工大学 Preparation method of fluorine-containing flexible sensor
CN115679697A (en) * 2022-11-04 2023-02-03 无锡腾华电缆材料科技有限公司 Production process of high-temperature-resistant petroleum conductive belt

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1470559A (en) * 2003-06-20 2004-01-28 山东大学 Silicon rubber/conductive ethylene propylene terpolymer and its preparing method
CN105157891A (en) * 2015-07-15 2015-12-16 深圳市慧瑞电子材料有限公司 Negative-resistance-effect tension-sensitive sensor and manufacturing method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1470559A (en) * 2003-06-20 2004-01-28 山东大学 Silicon rubber/conductive ethylene propylene terpolymer and its preparing method
CN105157891A (en) * 2015-07-15 2015-12-16 深圳市慧瑞电子材料有限公司 Negative-resistance-effect tension-sensitive sensor and manufacturing method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
中国大百科全书出版社编辑部编: "《中国大百科全书 化学I》", 28 February 1989, 中国大百科全书出版社 *
曹锡章 主编: "《英汉化学词典》", 30 November 2015, 清华大学出版社 *
翟茂林 等: "《高分子材料辐射加工技术及进展》", 31 May 2004, 化学工业出版社 材料科学与工程出版中心 *
邓本诚 等: "《橡胶并用与橡塑共混技术——性能、工艺与配方》", 30 June 1998, 化学工业出版社 *

Cited By (14)

* Cited by examiner, † Cited by third party
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CN106589967A (en) * 2017-01-25 2017-04-26 林建光 Electric conduction rubber and preparation method thereof
CN107541072A (en) * 2017-08-22 2018-01-05 华南理工大学 High temperature circulation tensile force causes silicon rubber composite material of electric conductivity enhancing and preparation method thereof
CN110006465A (en) * 2018-05-31 2019-07-12 常州允能新材料有限公司 A kind of flexible resistive type sensor based on starch material
CN109851872B (en) * 2018-12-27 2021-07-09 广州弗西林橡塑有限公司 High-elasticity conductive rubber and preparation method thereof
CN109851872A (en) * 2018-12-27 2019-06-07 广州弗西林橡塑有限公司 A kind of high resiliency conductive rubber and preparation method thereof
CN111795764A (en) * 2019-04-09 2020-10-20 绍兴文理学院元培学院 Sandwich type large-area high-density flexible array sensor and preparation method thereof
CN111795764B (en) * 2019-04-09 2021-11-09 绍兴文理学院元培学院 Sandwich type large-area high-density flexible array sensor and preparation method thereof
CN110157192A (en) * 2019-04-10 2019-08-23 中国科学院深圳先进技术研究院 A kind of flexible polymer film and its manufacturing method can be used for sound intensity detection
CN110157192B (en) * 2019-04-10 2021-10-01 中国科学院深圳先进技术研究院 Flexible polymer film for sound intensity detection and manufacturing method thereof
CN111363076A (en) * 2020-04-24 2020-07-03 四川道弘科技有限公司 Ternary peroxide fluororubber and preparation method thereof, and intelligent wearing material and preparation method thereof
CN112608533A (en) * 2020-12-01 2021-04-06 世目特种防护用品科技（江苏）有限公司 Conductive latex and preparation method and application thereof
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Application publication date: 20160525