CN105647030A - Conductive rubber material for flexible sensors and preparation method and application thereof - Google Patents
Conductive rubber material for flexible sensors and preparation method and application thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- 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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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
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- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- C08L7/00—Compositions of natural rubber
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- C08K2003/0862—Nickel
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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 suitable for the field of flexible sensors and provides a conductive rubber material for flexible sensors and a preparation method and application thereof. The conductive rubber material is prepared from, by weight, 100 parts of rubber matrixes and 5-200 parts of conductive filler. The conductive rubber material is prepared in the mode that the conductive filler is dispersed in a rubber material and subjected to radiation crosslinking of electron beams or gamma rays.
Description
Technical field
The invention belongs to flexible sensor field, particularly relate to a kind of conductive rubber material for flexible sensor and its preparation method and application.
Background technology
Strain ga(u)ge type sensor is a kind of a kind of device that mechanical deformation information can convert to the output of the signal of telecommunication such as resistance or electric capacity. English physicist Kelvin in 1885 finds that metal is bearing while pressure (pulling force or torsion) produces mechanical deformation afterwards, and the variation of resistance value also occurrence characteristics is called strain-resistance effect. Being inspired by this, people draw feature and the value of material stress from the variable quantity of resistance value, thus producing so-called strain transducer, mainly include pressure-strain sensor and tension strain sensor. At present, metal, metal alloy and there is the semi-conducting material of piezoresistive effect become the sensitive prime material of strain ga(u)ge type sensor sensing unit, obtain application widely. Along with the fast development of science and technology, the mechanical meaurement of the field labyrinths such as biomedical detection, rehabilitation medical, intelligent robot, wearable device, not only require that sensor to possess good strain-resistance characteristic, and to have outstanding flexility. Due to the own springform quantitative limitation of metal, metal alloy and semi-conducting material, metal type or semiconductor-type resistance strain sensor have the disadvantage in that flexibility is poor, mechanical quantity amplitude of variation is less, structure is complicated, and manufacturing cost is high. So traditional metal type or the application in these fields of the semiconductor-type resistance strain sensor are just restricted, it is impossible to meet the requirement of Present S & T Development. Therefore, develop the excellent strain ga(u)ge type sensor of a kind of new pliability becomes an urgent demand of current techniques and application development to meet new field to the flexible requirement of sensor.
Summary of the invention
It is an object of the invention to provide a kind of conductive rubber material for flexible sensor, it is intended to solve existing metal mold, metal alloy type or semi-conductor type strain transducer flexibility problem poor, baroque.
Another object of the present invention is to the preparation method that a kind of conductive rubber material for flexible sensor is provided.
The present invention is achieved in that a kind of conductive rubber material for flexible sensor, including the following component of following parts by weight:
Rubber matrix 100 parts;
Conductive filler 5-200 part;
And described conductive rubber material cross-links by being dispersed in elastomeric material by electroconductive stuffing, through electron beam or gamma Rays and makes.
Correspondingly, the manufacture method of a kind of conductive rubber material for flexible sensor, comprise the following steps:
Each component is weighed according to the above-mentioned formula for the conductive rubber material of flexible sensor;
Each component is carried out mixing process, obtains elastomeric compound;
It is shaped described elastomeric compound processing;
Sample through forming processes is cross-linked by the method adopting electron beam or gamma Rays, obtains the conductive rubber with strain-resistance effect.
And, a kind of strain ga(u)ge type sensor, including sensing unit and the metal electrode being arranged on described sensing unit two ends, 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, it is dispersed in elastomeric material by electroconductive stuffing to make through electron beam or gamma Rays crosslinking, relative to the chemical crosslink technique adopting sulfur or organic peroxide to make cross-linking agent, there is production efficiency height, environmental pollution is little, crosslink density is easily controlled and conductive rubber distribution of resistance is narrow advantage.
Described conductive rubber material has good flexibility and elasticity, it is possible to produce higher mechanical deformation amount. Concrete, described conductive rubber material can produce the tensile deformation of more than 100% under a stretching force, can produce the compressive deformation of more than 50% under pressure. Further, conductive rubber material of the present invention produces while deformation under external force, its resistance value and electric capacity all change, and namely can produce strain-resistance effect and strain-capacity effect simultaneously, and strain-resistance effect and strain-capacity effect trend contrary. More specifically, conductive rubber material of the present invention its resistance under pulling force or pressure effect constantly declines along with tensile deformation increases, presenting negative resistance-strain effect, as when the deformation quantity of sensor is 30%, its resistance value produces the change of at least 5 times, its change even may be up to more than 100 times; Under described conductive rubber material pulling force or pressure effect, its capacitance is continuously increased along with deformation increase, present positive electric capacity-strain effect, as when the deformation quantity of sensor is 30%, its capacitance produces the change of at least 10 times, its change even may be up to more than 500 times. And conductive rubber material of the present invention has good signal susceptiveness and stability, its resistivity is between 5.0 �� 102-1.0��1010Between �� .cm, it is particularly suitable for application as the sensing unit material of contingency sensor (such as pulling force and pressure-strain type sensor).
The preparation method of conductive rubber material of the present invention, electron beam or gamma Rays is adopted to cross-link, can pass through to control the degree of cross linking of the random regulation and control rubber of absorbed dose, and electron beam or gamma-rays can penetrate rubber glue-line so that the rubber entirety degree of cross linking is unanimously uniform; When described rubber conductive material is used as sensor sensing unit material, it is possible to achieve the performances such as the susceptiveness of the signals of telecommunication such as the concordance of the distribution of the resistance value of strain ga(u)ge type sensor, particularly resistance capacitance change under external force, stability, recovery. Additionally, the inventive method is simply controlled, it is easy to accomplish industrialization.
Strain ga(u)ge type sensor provided by the invention, including having the sensing unit of strain-resistance effect and strain-capacity effect and being arranged on the metal electrode at described sensing unit two ends simultaneously. By detecting the change of resistance value or capacitance when being stretched or compressed of described strain ga(u)ge type sensor, or resistance value is converted to voltage or current value, the measurement of power can be carried out in fields such as biomechanics, rehabilitation medical, intelligence wearing and artificial intelligences, be with a wide range of applications. Additionally, described strain ga(u)ge type sensor simple in construction, low cost of manufacture, it is easy to install, convenient use.
Accompanying drawing explanation
Fig. 1 is capacitance/resistance-tensile deformation curve chart that the embodiment of the present invention 1 provides;
Fig. 2 is capacitance/resistance-tensile deformation curve chart that the embodiment of the present invention 2 provides;
Fig. 3 is capacitance/resistance-tensile deformation curve chart that the embodiment of the present invention 3 provides;
Fig. 4 is capacitance/resistance-tensile deformation curve chart that the embodiment of the present invention 4 provides;
Fig. 5 is capacitance/resistance-tensile deformation curve chart that the embodiment of the present invention 5 provides;
Fig. 6 is capacitance/resistance-tensile deformation curve chart that the embodiment of the present invention 6 provides;
Fig. 7 is capacitance/resistance-tensile deformation curve chart that the embodiment of the present invention 7 provides;
Fig. 8 is capacitance/resistance-compressive deformation curve chart that the embodiment of the present invention 8 provides;
Fig. 9 is capacitance/resistance-compressive deformation curve chart that the embodiment of the present invention 9 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 clearly understand, below in conjunction with embodiment, the present invention is further elaborated. Should be appreciated that specific embodiment described herein is only in order to explain the present invention, is not intended to limit the present invention.
Embodiments provide a kind of conductive rubber material for flexible sensor, including the following component of following parts by weight:
Rubber matrix 100 parts;
Conductive filler 5-200 part;
And described conductive rubber material cross-links by being dispersed in elastomeric material by electroconductive stuffing, through electron beam or gamma Rays and makes.
In the embodiment of the present invention, described conductive filler passes through the formation conductive path that contacts with each other of microcosmic in described rubber matrix, when material is subject to External Force Acting, the spacing of material internal adjacent conductive particle changes, the conductive path resulting in relying on the contact of described conductive filler and formed changes, and causes the resistance of macroscopically material to change. Owing to conductive rubber material described in the embodiment of the present invention has this advantage, therefore, it is possible to as a kind of ess-strain sensing material.
Concrete, in the embodiment of the present invention, described rubber matrix has flexibility and the elasticity of excellence, gives the excellent flexibility of described conductive rubber material and elasticity, and bigger mechanical quantity amplitude of variation, it is possible to overcome metal type or the semiconductor-type strain transducer deficiency in pliability and elasticity.
As the presently preferred embodiments, described rubber matrix is the hydrocarbon rubbers containing carbon hydrogen element, at least one in rubber containing hetero atom or functional group, and described hydrocarbon rubbers has high resiliency and good mechanical performance. Concrete, described rubber matrix is at least one in natural rubber, nitrile rubber, hydrogenated nitrile-butadiene rubber, EP rubbers, ethylene propylene diene rubber, butadiene-styrene rubber, isoprene rubber, butadiene rubber, neoprene, chlorinated polyethylene rubber, CSM, acrylate rubber, polyurethane rubber, silicone rubber, fluorubber, fluorosioloxane rubber.
The specific embodiment of the invention, the described conductive rubber material for flexible sensor is adjusted with 100 parts of described rubber matrixs for benchmark, but is not meant as rubber matrix described in the embodiment of the present invention and is only 100 parts.
In the embodiment of the present invention, described conductive filler, as the conductive component of described conductive rubber material, plays a significant role. As the presently preferred embodiments, described conductive filler is at least one in carbon conductive filler, me tallic conductive filler, conjugated polymer conductive filler. As a specific embodiment, carbon conductive filler includes conductive black, nano-graphite, carbon fiber, CNT.As another specific embodiment, described me tallic conductive filler includes metal, metal/metal composites, metal/non-metal complex, and more specifically, described metallic conductive fillers includes Powdered, flakey, fibrous gold, silver, copper, aluminum, nickel; Described metal/metal composites refers to compound filler that is silver-plated at metal or metal oxide particle surface chemistry and that make, it is preferable that include the copper powder of electroplate, nikel powder, aluminium powder, ferrite, zinc oxide, aluminium oxide; Described metal/non-metal complex, refer to the compound filler made at particles of inorganic material, polymer particle surface chemical silvering, it is preferable that include the Pulvis Talci of electroplate, mica powder, glass fibre, hollow glass micropearl, graphite powder, polystyrene microsphere. As another specific embodiment, described conjugated polymer conductive filler includes polyaniline, polypyrrole, polyacetylene. Above-mentioned preferred described conductive filler, not only conducts electricity very well, and can be dispersed in described rubber matrix, improves the conductive stability of elastomeric material; Furthermore it is preferred that described conductive filler be conducive to described conductive rubber material to keep the flexibility of described rubber matrix and elasticity.
Conductive filler described in the embodiment of the present invention can adopt a kind of conductive filler to be used alone, it is also possible to two kinds or the composite use of above conductive filler.
As the specific embodiment of the invention, the parts by weight of described conductive filler are 5-200 part, it may include the concrete numbers such as 5 parts, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, 160 parts, 170 parts, 180 parts, 190 parts, 200 parts.
Conductive rubber matrix described in the embodiment of the present invention adopts radiation method to realize vulcanization crosslinking. Concrete, embodiment of the present invention crosslinking with radiation is that rubber macromolecule chain is cross-linked into network structure by the method adopting high energy electron beams or gamma Rays. Crosslinking with radiation described in the embodiment of the present invention belongs to the cross-linking reaction of free radical mechanism, and carbon-to-carbon (C-C) key of formation compares the sulfide linkage excessively using sulfur cross-linking to be formed, and has better heatproof air aging performance and chemical stability. General, adopt sulfur or organic peroxide, as cross-linking agent, rubber is carried out chemical crosslinking, owing to being subject to the impact of the various factors such as accurately the controlling of the accurate measurement of cross-linking agent and dispersion level, mould or oven temperature, response time and the extent of reaction, products thickness and heat-transfer effect, the degree of cross linking is difficult to accurately control. Compared with chemical crosslink technique, adopt irradiation technique that rubber is cross-linked, can pass through to control the degree of cross linking of the random regulation and control rubber of absorbed dose, and electron beam or gamma-rays can penetrate rubber glue-line, make the rubber entirety degree of cross linking unanimously uniform, the problem of the ectonexine degree of cross linking difference that glue-line causes due to the difference of heat-transfer effect inside and outside rubber when not havinging chemical method crosslinking. Controlled and the degree of cross linking uniformity of the conductive rubber material degree of cross linking described in the embodiment of the present invention, during as sensing unit material, the performances such as the susceptiveness of the signals of telecommunication such as the concordance of the distribution of the resistance value of strain ga(u)ge type sensor, particularly resistance capacitance change under external force, stability, recovery can be realized. It addition, radiation cross-linking process has the ability of the distribution of resistance of more convenient and effective control conductive rubber, the degree of cross linking and the crosslinking uniformity than chemical crosslink technique.In addition, owing to the formula system of rubber radiation cross-linking process does not contain the vulcanization accelerator that can produce nitrosamine (a kind of carcinogen), thus more environmental protection, it is possible to better it is applied to medical field, carries out signal measurement and the sensing of biomechanics aspect with direct body contact.
In the embodiment of the present invention, it is bigger that embodiment of the present invention electron beam or gamma Rays are cross-linked impact by irradiation dose, concrete, when irradiation dose is lower than 5Mrad, rubber cross degree is not enough, not only mechanical mechanics property difference and also resilience of vulcanizate is poor, thus causing that the resistance recovery capacity of strain transducer is poor; When dosage is higher than 30Mrad, the mechanical mechanics property of elastomeric material is deteriorated, flexible and flexibility decrease, also degradation reaction can be there is there is cross-linking reaction because rubber is exposed to radiation while, simply reaction rate is different, when dosage is lower than 30Mrad, based on cross-linking reaction, and when dosage is higher than 30Mrad, degradation reaction increases further and even becomes primary response, reduces flexibility and the elasticity of rubber. As the presently preferred embodiments, described high-power electron beam or gamma-ray irradiation dose 5-30 Megarad (Mrad), more preferably 5-25 Megarad. Selective dose 5-25 Megarad of the present invention ensure that conductive rubber not only has good mechanical property but also have good pliability and resistance recovery. Wherein, rad (rad) is the measurement unit of the emittance that per unit material mass accepts, 1Mrad=1 �� 106rad��
In the embodiment of the present invention, the resistivity of described conductive rubber material is 5.0 �� 102-1.0��1010�� .cm. The resistivity of described conductive rubber material is lower than 5.0 �� 102�� .cm, strain-resistance effect is more weak, and when resistivity of material is higher than 1.0 �� 1010�� .cm, conducting medium contact conductive mechanism when conductive rubber is by low-resistivity is transformed into contact conductive mechanism and tunnel-effect conductive mechanism and deposits, become tunnel-effect conductive mechanism even completely, and the conductive mechanism of tunnel-effect easily causes the resistance stability of conductive rubber, recovery is deteriorated, and the difficulty controlling the stability of resistance concentration degree and strain-resistance effect in conductive rubber manufacture process increases. Conductive rubber material described in the embodiment of the present invention has the resistivity of excellence, gives described conductive rubber material better application performance.
The conductive rubber material for flexible sensor that the embodiment of the present invention provides, it is dispersed in elastomeric material by electroconductive stuffing to make through electron beam or gamma Rays crosslinking, relative to the chemical crosslink technique adopting sulfur or organic peroxide to make cross-linking agent, there is production efficiency height, environmental pollution is little, crosslink density is easily controlled and conductive rubber distribution of resistance is narrow advantage.
Described conductive rubber material has good flexibility and elasticity, it is possible to produce higher mechanical deformation amount. Concrete, described conductive rubber material can produce the tensile deformation of more than 100% under a stretching force, can produce the compressive deformation of more than 50% under pressure. Further, conductive rubber material described in the embodiment of the present invention produces while deformation under external force, its resistance value and electric capacity all change, and namely can produce strain-resistance effect and strain-capacity effect simultaneously, and strain-resistance effect and strain-capacity effect trend contrary. More specifically, its resistance under pulling force or pressure effect of conductive rubber material described in the embodiment of the present invention constantly declines along with tensile deformation increases, present negative resistance-strain effect, as when the deformation quantity of sensor is 30%, its resistance value produces the change of at least 5 times, its change even may be up to more than 100 times;Under described conductive rubber material pulling force or pressure effect, its capacitance is continuously increased along with deformation increase, present positive electric capacity-strain effect, as when the deformation quantity of sensor is 30%, its capacitance produces the change of at least 10 times, its change even may be up to more than 500 times. And conductive rubber material described in the embodiment of the present invention has good signal susceptiveness and stability, its resistivity is between 5.0 �� 102-1.0��1010Between �� .cm, it is particularly suitable for application as the sensing unit material of contingency sensor (such as pulling force and pressure-strain type sensor).
Described in the embodiment of the present invention, the conductive rubber material for flexible sensor can be prepared by following method.
Correspondingly, the manufacture method of a kind of conductive rubber material for flexible sensor, comprise the following steps:
S01. each component is weighed according to the above-mentioned formula for the conductive rubber material of flexible sensor;
S02. each component is carried out mixing process, obtain elastomeric compound;
S03. it is shaped described elastomeric compound processing;
S04. adopt the method for electron beam or gamma Rays that the sample through forming processes is cross-linked, obtain the conductive rubber with strain-resistance effect.
Concrete, in above-mentioned steps S01, for the recipe ingredient of conductive rubber material of flexible sensor and preferred situation thereof as described above, in order to save length, repeat no more herein.
In above-mentioned steps S02, when each component is carried out mixing process, in order to improve melting effect, obtain finely dispersed elastomeric compound, described rubber matrix, homogenizing agent, softening agent, conductive filler are preferably joined and carry out mixing in mill or banbury by the embodiment of the present invention in order successively, obtain elastomeric compound.
In above-mentioned steps S03, described forming processes can be realized by rubber-moulding equipment, can obtain the sheet material with certain size by forming processes or be directly formed to specific shape by mould. Concrete, described former includes screw extruder, calender and vulcanizing press.
In above-mentioned steps S04, as the presently preferred embodiments, adopt the method for electron beam or gamma Rays to when the sample of forming processes cross-links, the dosage of described electron beam or gamma Rays is 5-25Mrad, concrete, when irradiation dose is lower than 5Mrad, rubber cross degree is not enough, not only mechanical mechanics property difference and also resilience of vulcanizate is poor, thus causing that the resistance recovery capacity of strain transducer is poor; When dosage is higher than 30Mrad, the mechanical mechanics property of elastomeric material is deteriorated, flexible and flexibility decrease, also degradation reaction can be there is there is cross-linking reaction because rubber is exposed to radiation while, simply reaction rate is different, when dosage is lower than 30Mrad, based on cross-linking reaction, and when dosage is higher than 30Mrad, degradation reaction increases further and even becomes primary response, reduces flexibility and the elasticity of rubber. As the presently preferred embodiments, described high-power electron beam or gamma-ray irradiation dose 5-30Mrad, more preferably 5-25 Megarad. Selective dose 5-25Mrad of the present invention ensure that conductive rubber not only has good mechanical property but also have good pliability and resistance recovery. Additionally, due to the existence of oxygen can cause oxidative degradation in the process of cross-linking radiation, therefore, the rubber sheet that S03 step obtains needs evacuation to pack.
Further, sheet material after crosslinking can be cut into the definite shape sensing unit as sensor, or the given shape directly obtained by mould molding in step S03 is as the sensing unit of sensor, sensing unit makes metal electrode, obtains tension type strain transducer or pressure-type strain transducer.
The preparation method of conductive rubber material described in the embodiment of the present invention, electron beam or gamma Rays is adopted to cross-link, can pass through to control the degree of cross linking of the random regulation and control rubber of absorbed dose, and electron beam or gamma-rays can penetrate rubber glue-line so that the rubber entirety degree of cross linking is unanimously uniform; When described rubber conductive material is used as sensor sensing unit material, it is possible to achieve the performances such as the susceptiveness of the signals of telecommunication such as the concordance of the distribution of the resistance value of strain ga(u)ge type sensor, particularly resistance capacitance change under external force, stability, recovery. Additionally, embodiment of the present invention method is simply controlled, it is easy to accomplish industrialization.
And, a kind of strain ga(u)ge type sensor, including sensing unit and the metal electrode being arranged on described sensing unit two ends, 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 passes through the formation conductive path that contacts with each other of microcosmic in rubber matrix, when material is subject to External Force Acting, the spacing of material internal adjacent conductive particle changes, the conductive path resulting in relying on the contact of conducting particles and formed changes, the resistance causing macroscopically conductive rubber material changes, making described conductive rubber material have power-electricresistance effect, the external force being applied on conductive rubber includes pulling force and pressure two kinds.
Described sensing unit produces elongation strain and compression strain respectively under pulling force and pressure effect, increases with deformation, and sensing unit deformation increases the resistance value in direction and declines, and presents negative strain-resistance effect. Described strain ga(u)ge type sensor is after being subject to external tensile force or pressure effect, sensing unit is stretched along deformation direction or compresses, namely interelectrode distance increases or reduces, and the sectional area both perpendicular to the nyctitropic sensing unit of shape reduces accordingly or increases; Simultaneously, the deformation that sensing unit produces under external force causes that the change in sensitive material inner conductive particle gap causes material conductive microstructure network to change, thus causing the change of sensitive material resistivity, in turn resulting in material dielectric constant and changing with External Force Acting. Therefore, the factor such as resistivity of material, the dielectric constant of material, sensing unit interelectrode distance changes under external force with the capacitance ultimately resulted between sensor sensing unit two end electrodes that comprehensively changes of external force. Therefore, flexible strain ga(u)ge type sensor using conductive rubber as sensing unit of the present invention, when being subject to external tensile force or pressure effect, sensor not only produces the change of resistance value, also there is the change of capacitance simultaneously, and strain-resistance effect is negative strain-electricresistance effect, strain-capacity effect is normal strain-electricresistance effect. So, described in the embodiment of the present invention, flexible strain ga(u)ge type sensor can as strain-electric resistance sensor, it is also possible to 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 by filled conductive filler in rubber matrix, cross-link through electron beam or gamma-ray irradiation and make, concrete formula and each component situation thereof are stated hereinbefore in detail, no longer illustrate herein. Described metal electrode one in metal forming, sheet metal, metal film or profiled metal part.
The embodiment of the present invention can be bonded by conducting resinl, high temperature hot pressing, conductive silver paste silk screen printing, vacuum coating or mechanical crimp mode described metal electrode is produced on the surface of sensing unit. Wherein, described conductive silver paste is ultraviolet curing type; The method of described vacuum coating includes evaporation coating, magnetron sputtering plating, ion film plating.
The preparation method of contingency sensor described in the embodiment of the present invention, can cut into the definite shape sensing unit as sensor using the sheet material after crosslinking;Or the given shape directly obtained by mould molding in the above-mentioned steps S03 preparing described conductive rubber material is as the sensing unit of sensor, sensing unit makes metal electrode, obtains tension type strain transducer or pressure-type strain transducer.
The strain ga(u)ge type sensor that the embodiment of the present invention provides, including having the sensing unit of strain-resistance effect and strain-capacity effect and being arranged on the metal electrode at described sensing unit two ends simultaneously. By detecting the change of resistance value or capacitance when being stretched or compressed of described strain ga(u)ge type sensor, or resistance value is converted to voltage or current value, the measurement of power can be carried out in fields such as biomechanics, rehabilitation medical, intelligence wearing and artificial intelligences, be with a wide range of applications. Additionally, described strain ga(u)ge type sensor simple in construction, low cost of manufacture, it is easy to install, convenient use.
Below, in conjunction with being embodied as illustrating. In the embodiment of the present invention, it is the ethylene propylene diene rubber of J-3080 that described ethylene propylene diene rubber (EPDM) is selected from the Jilin chemical industry trade mark, and in this ethylene propylene diene rubber, the weight percentage of ethylene is 68.5-74.5%; The natural rubber of the trade mark SCR5 that described natural rubber (NR) produces selected from hainan rubber; Described nitrile rubber (NBR) is the nitrile rubber of 3305 selected from the Lanzhou Petrochemical trade mark, and wherein, the weight/mass percentage composition of acrylonitrile is 33%; Described neoprene (CR) is M-40 selected from the NEC chemistry trade mark; It is the methyl vinyl silicone rubber of 110-1 that described methyl vinyl silicone rubber (MVQ) is selected from the east rank of nobility organosilicon trade mark, and the weight/mass percentage composition of this methyl vinyl silicone rubber medium vinyl is 0.13-0.22%; The MA600 that described conductive black produces selected from Mitsubishi Chemical, its particle diameter is 20nm, oil factor is 131cm3/ 100g, specific surface area is 140m2/ g; Described CNT (CNT) is the CNT of VGCF-H selected from Showa electrician's trade mark, its diameter 150nm, length 6 ��m; Described nikel powder is selected from the carbonyl nickel powder T210 of Canada INCO, particle diameter 0.5-1.0 ��m; Described silver-plated polystyrene (PS) microsphere selects particle diameter 10-30 ��m, self-control; Described electrically conductive polyaniline, self-control.
Embodiment 1
A kind of conductive rubber material for flexible sensor, including each content component described in table 1 embodiment 1, and described conductive rubber material cross-links by being dispersed in elastomeric material by electroconductive stuffing, through electron beam or gamma Rays and makes.
And, the preparation method of the described conductive rubber material for flexible sensor, comprise the following steps:
S11. each component is weighed according to the above-mentioned formula for the conductive rubber material of flexible sensor;
S12. described rubber matrix, conductive filler are joined mill carries out mixing, mixing time 20min, after various filler mix homogeneously, thin pass-out sheet, obtains elastomeric compound;
S13. described elastomeric compound rubber plate vulcanization machine compression molding being obtained tablet-type gum, tablet-type gum is of a size of length 100mm �� width 100mm �� thickness 1mm;
S14. adopting the method for electron beam or gamma Rays that the sample through forming processes is cross-linked, obtain the conductive rubber with strain-resistance effect, wherein, the irradiation dose of described electron beam or gamma Rays is such as shown in table 1 embodiment 1.
A kind of strain ga(u)ge type sensor, the sensing unit made including the conductive rubber material with strain-resistance effect and the metal electrode being arranged on described sensing unit two ends, its concrete production method is: the rubber sheet after crosslinking is cut into the definite shape sensing unit as sensor, and sheet material cuts the strip being of a size of length 40mm �� width 5mm, electrode is installed at its two ends, remove the effective telescopable portion length 30mm after electrode, the line terminal lug that electrode selects material to be TC specification SC6-5, obtains tension type strain transducer.
Embodiment 2
A kind of conductive rubber material for flexible sensor, including each content component described in table 1 embodiment 2, and described conductive rubber material cross-links by being dispersed in elastomeric material by electroconductive stuffing, through electron beam or gamma Rays and makes.
And, the preparation method of the described conductive rubber material for flexible sensor, comprise the following steps:
S21. each component is weighed according to the above-mentioned formula for the conductive rubber material of flexible sensor;
S22. described rubber matrix, conductive filler are joined mill carries out mixing, mixing time 20min, after various filler mix homogeneously, thin pass-out sheet, obtains elastomeric compound;
S23. described elastomeric compound rubber plate vulcanization machine compression molding being obtained tablet-type gum, tablet-type gum is of a size of length 100mm �� width 100mm �� thickness 1mm;
S24. adopting the method for electron beam or gamma Rays that the sample through forming processes is cross-linked, obtain the conductive rubber with strain-resistance effect, wherein, the irradiation dose of described electron beam or gamma Rays is such as shown in table 1 embodiment 2.
A kind of strain ga(u)ge type sensor, the sensing unit made including the conductive rubber material with strain-resistance effect and the metal electrode being arranged on described sensing unit two ends, its concrete production method is: the rubber sheet after crosslinking is cut into the definite shape sensing unit as sensor, and sheet material cuts the strip being of a size of length 40mm �� width 5mm, electrode is installed at its two ends, remove the effective telescopable portion length 30mm after electrode, the line terminal lug that electrode selects material to be TC specification SC6-5, obtains tension type strain transducer.
Embodiment 3
A kind of conductive rubber material for flexible sensor, including each content component described in table 1 embodiment 3, and described conductive rubber material cross-links by being dispersed in elastomeric material by electroconductive stuffing, through electron beam or gamma Rays and makes.
And, the preparation method of the described conductive rubber material for flexible sensor, comprise the following steps:
S31. each component is weighed according to the above-mentioned formula for the conductive rubber material of flexible sensor;
S32. described rubber matrix, conductive filler are joined mill carries out mixing, mixing time 20min, after various filler mix homogeneously, thin pass-out sheet, obtains elastomeric compound;
S33. described elastomeric compound rubber plate vulcanization machine compression molding being obtained tablet-type gum, tablet-type gum is of a size of length 100mm �� width 100mm �� thickness 1mm;
S34. adopting the method for electron beam or gamma Rays that the sample through forming processes is cross-linked, obtain the conductive rubber with strain-resistance effect, wherein, the irradiation dose of described electron beam or gamma Rays is such as shown in table 1 embodiment 3.
A kind of strain ga(u)ge type sensor, the sensing unit made including the conductive rubber material with strain-resistance effect and the metal electrode being arranged on described sensing unit two ends, its concrete production method is: the rubber sheet after crosslinking is cut into the definite shape sensing unit as sensor, and sheet material cuts the strip being of a size of length 40mm �� width 5mm, electrode is installed at its two ends, remove the effective telescopable portion length 30mm after electrode, the line terminal lug that electrode selects material to be TC specification SC6-5, obtains tension type strain transducer.
Embodiment 4
A kind of conductive rubber material for flexible sensor, including each content component described in table 1 embodiment 4, and described conductive rubber material cross-links by being dispersed in elastomeric material by electroconductive stuffing, through electron beam or gamma Rays and makes.
And, the preparation method of the described conductive rubber material for flexible sensor, comprise the following steps:
S41. each component is weighed according to the above-mentioned formula for the conductive rubber material of flexible sensor;
S42. described rubber matrix, conductive filler are joined mill carries out mixing, mixing time 20min, after various filler mix homogeneously, thin pass-out sheet, obtains elastomeric compound;
S43. described elastomeric compound rubber plate vulcanization machine compression molding being obtained tablet-type gum, tablet-type gum is of a size of length 100mm �� width 100mm �� thickness 1mm;
S44. adopting the method for electron beam or gamma Rays that the sample through forming processes is cross-linked, obtain the conductive rubber with strain-resistance effect, wherein, the irradiation dose of described electron beam or gamma Rays is such as shown in table 1 embodiment 4.
A kind of strain ga(u)ge type sensor, the sensing unit made including the conductive rubber material with strain-resistance effect and the metal electrode being arranged on described sensing unit two ends, its concrete production method is: the rubber sheet after crosslinking is cut into the definite shape sensing unit as sensor, and sheet material cuts the strip being of a size of length 40mm �� width 5mm, electrode is installed at its two ends, remove the effective telescopable portion length 30mm after electrode, the line terminal lug that electrode selects material to be TC specification SC6-5, obtains tension type strain transducer.
Embodiment 5
A kind of conductive rubber material for flexible sensor, including each content component described in table 1 embodiment 5, and described conductive rubber material cross-links by being dispersed in elastomeric material by electroconductive stuffing, through electron beam or gamma Rays and makes.
And, the preparation method of the described conductive rubber material for flexible sensor, comprise the following steps:
S51. each component is weighed according to the above-mentioned formula for the conductive rubber material of flexible sensor;
S52. described rubber matrix, conductive filler are joined mill carries out mixing, mixing time 20min, after various filler mix homogeneously, thin pass-out sheet, obtains elastomeric compound;
S53. described elastomeric compound rubber plate vulcanization machine compression molding being obtained tablet-type gum, tablet-type gum is of a size of length 100mm �� width 100mm �� thickness 1mm;
S54. adopting the method for electron beam or gamma Rays that the sample through forming processes is cross-linked, obtain the conductive rubber with strain-resistance effect, wherein, the irradiation dose of described electron beam or gamma Rays is such as shown in table 1 embodiment 5.
A kind of strain ga(u)ge type sensor, the sensing unit made including the conductive rubber material with strain-resistance effect and the metal electrode being arranged on described sensing unit two ends, its concrete production method is: the rubber sheet after crosslinking is cut into the definite shape sensing unit as sensor, and sheet material cuts the strip being of a size of length 40mm �� width 5mm, electrode is installed at its two ends, remove the effective telescopable portion length 30mm after electrode, the line terminal lug that electrode selects material to be TC specification SC6-5, obtains tension type strain transducer.
Embodiment 6
A kind of conductive rubber material for flexible sensor, including each content component described in table 1 embodiment 6, and described conductive rubber material cross-links by being dispersed in elastomeric material by electroconductive stuffing, through electron beam or gamma Rays and makes.
And, the preparation method of the described conductive rubber material for flexible sensor, comprise the following steps:
S61. each component is weighed according to the above-mentioned formula for the conductive rubber material of flexible sensor;
S62. described rubber matrix, conductive filler are joined mill carries out mixing, mixing time 20min, after various filler mix homogeneously, thin pass-out sheet, obtains elastomeric compound;
S63. described elastomeric compound rubber plate vulcanization machine compression molding being obtained tablet-type gum, tablet-type gum is of a size of length 100mm �� width 100mm �� thickness 1mm;
S64. adopting the method for electron beam or gamma Rays that the sample through forming processes is cross-linked, obtain the conductive rubber with strain-resistance effect, wherein, the irradiation dose of described electron beam or gamma Rays is such as shown in table 1 embodiment 6.
A kind of strain ga(u)ge type sensor, the sensing unit made including the conductive rubber material with strain-resistance effect and the metal electrode being arranged on described sensing unit two ends, its concrete production method is: the rubber sheet after crosslinking is cut into the definite shape sensing unit as sensor, and sheet material cuts the strip being of a size of length 40mm �� width 5mm, electrode is installed at its two ends, remove the effective telescopable portion length 30mm after electrode, the line terminal lug that electrode selects material to be TC specification SC6-5, obtains tension type strain transducer.
Embodiment 7
A kind of conductive rubber material for flexible sensor, including each content component described in table 1 embodiment 7, and described conductive rubber material cross-links by being dispersed in elastomeric material by electroconductive stuffing, through electron beam or gamma Rays and makes.
And, the preparation method of the described conductive rubber material for flexible sensor, comprise the following steps:
S71. each component is weighed according to the above-mentioned formula for the conductive rubber material of flexible sensor;
S72. described rubber matrix, conductive filler are joined mill carries out mixing, mixing time 20min, after various filler mix homogeneously, thin pass-out sheet, obtains elastomeric compound;
S73. described elastomeric compound rubber plate vulcanization machine compression molding being obtained tablet-type gum, tablet-type gum is of a size of length 100mm �� width 100mm �� thickness 1mm;
S74. adopting the method for electron beam or gamma Rays that the sample through forming processes is cross-linked, obtain the conductive rubber with strain-resistance effect, wherein, the irradiation dose of described electron beam or gamma Rays is such as shown in table 1 embodiment 7.
A kind of strain ga(u)ge type sensor, the sensing unit made including the conductive rubber material with strain-resistance effect and the metal electrode being arranged on described sensing unit two ends, its concrete production method is: the rubber sheet after crosslinking is cut into the definite shape sensing unit as sensor, and sheet material cuts the strip being of a size of length 40mm �� width 5mm, electrode is installed at its two ends, remove the effective telescopable portion length 30mm after electrode, the line terminal lug that electrode selects material to be TC specification SC6-5, obtains tension type strain transducer.
Embodiment 8
A kind of conductive rubber material for flexible sensor, including each content component described in table 1 embodiment 8, and described conductive rubber material cross-links by being dispersed in elastomeric material by electroconductive stuffing, through electron beam or gamma Rays and makes.
And, the preparation method of the described conductive rubber material for flexible sensor, comprise the following steps:
S81. each component is weighed according to the above-mentioned formula for the conductive rubber material of flexible sensor;
S82. described rubber matrix, conductive filler are joined mill carries out mixing, mixing time 20min, after various filler mix homogeneously, thin pass-out sheet, obtains elastomeric compound;
S83. described elastomeric compound rubber plate vulcanization machine compression molding being obtained tablet-type gum, tablet-type gum is of a size of length 100mm �� width 100mm �� thickness 1mm;
S84. adopting the method for electron beam or gamma Rays that the sample through forming processes is cross-linked, obtain the conductive rubber with strain-resistance effect, wherein, the irradiation dose of described electron beam or gamma Rays is such as shown in table 1 embodiment 8.
A kind of strain ga(u)ge type sensor, the sensing unit made including the conductive rubber material with strain-resistance effect and the metal electrode being arranged on described sensing unit two ends, its concrete production method is: the rubber sheet after crosslinking is cut into the definite shape sensing unit as sensor, and sheet material cuts the square piece shape being of a size of length 10mm �� width 10mm, lower surface adopts conductive adhesive electrode thereon, the nickel plating Copper Foil that electrode selects thickness to be 35 ��m, obtains pressure-type strain transducer.
Embodiment 9
A kind of conductive rubber material for flexible sensor, including each content component described in table 1 embodiment 9, and described conductive rubber material cross-links by being dispersed in elastomeric material by electroconductive stuffing, through electron beam or gamma Rays and makes.
And, the preparation method of the described conductive rubber material for flexible sensor, comprise the following steps:
S91. each component is weighed according to the above-mentioned formula for the conductive rubber material of flexible sensor;
S92. described rubber matrix, conductive filler are joined mill carries out mixing, mixing time 20min, after various filler mix homogeneously, thin pass-out sheet, obtains elastomeric compound;
S93. described elastomeric compound rubber plate vulcanization machine compression molding being obtained tablet-type gum, tablet-type gum is of a size of length 100mm �� width 100mm �� thickness 1mm;
S94. adopting the method for electron beam or gamma Rays that the sample through forming processes is cross-linked, obtain the conductive rubber with strain-resistance effect, wherein, the irradiation dose of described electron beam or gamma Rays is such as shown in table 1 embodiment 9.
A kind of strain ga(u)ge type sensor, the sensing unit made including the conductive rubber material with strain-resistance effect and the metal electrode being arranged on described sensing unit two ends, its concrete production method is: the rubber sheet after crosslinking is cut into the definite shape sensing unit as sensor, and sheet material cuts the square piece shape being of a size of length 10mm �� width 10mm, lower surface adopts conductive adhesive electrode thereon, the nickel plating Copper Foil that electrode selects thickness to be 35 ��m, obtains pressure-type strain transducer.
Performance test: using conductive rubber material described in embodiment 1-10 as sensing unit material, the sensor prepared carries out performance test, and method is as follows:
1, the test of tension type strain transducer: the test initial resistivity value of pulling force sensor and capacitance, and resistance value when sensor stretches 30% deformation and capacitance, and calculate the change multiplying power of resistance value and capacitance, data are listed in table 2. Draw the relation curve of the resistance value of sensor, capacitance and tensile deformation, as shown in figs. 1-7;
2, the test of pressure-type strain transducer: the test initial resistivity value of pressure transducer and capacitance, and resistance value when sensor compresses 30% deformation and capacitance, and calculate the change multiplying power of resistance value and capacitance, data are listed in table 2. Draw the relation curve of the resistance value of sensor, capacitance and compressive deformation, as Figure 8-9.
Test result is as shown in table 2 below.
Table 1
Table 2
From upper table 2, described in the embodiment of the present invention, conductive rubber filler has good resistivity, after the sensing unit of strain ga(u)ge type sensor, make described strain ga(u)ge type sensor have simultaneously good strain-resistance effect and, strain-capacity effect, and strain-resistance effect is negative strain-electricresistance effect, strain-capacity effect is normal strain-electricresistance effect.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. made within the spirit and principles in the present invention, should be included within protection scope of the present invention.
Claims (10)
1. the conductive rubber material for flexible sensor, it is characterised in that include the following component of following parts by weight:
Rubber matrix 100 parts;
Conductive filler 5-200 part;
And described conductive rubber material cross-links by being dispersed in elastomeric material by electroconductive stuffing, through electron beam or gamma Rays and makes.
2. the conductive rubber material for flexible sensor as claimed in claim 1, it is characterised in that described rubber matrix is the hydrocarbon rubbers containing carbon hydrogen element, at least one in rubber containing hetero atom or functional group.
3. the conductive rubber material for flexible sensor as claimed in claim 2, it is characterized in that, described rubber matrix is at least one in natural rubber, nitrile rubber, hydrogenated nitrile-butadiene rubber, EP rubbers, ethylene propylene diene rubber, butadiene-styrene rubber, isoprene rubber, butadiene rubber, neoprene, chlorinated polyethylene rubber, CSM, acrylate rubber, polyurethane rubber, silicone rubber, fluorubber, fluorosioloxane rubber.
4. the conductive rubber material for flexible sensor as described in as arbitrary in claim 1-3, it is characterised in that described conductive filler is at least one in carbon conductive filler, me tallic conductive filler, conjugated polymer conductive filler.
5. the conductive rubber material for flexible sensor as claimed in claim 4, it is characterised in that described carbon conductive filler includes conductive black, nano-graphite, carbon fiber, CNT; Described me tallic conductive filler includes metal, metal/metal composites, metal/non-metal complex; Described conjugated polymer conductive filler includes polyaniline, polypyrrole, polyacetylene.
6. the conductive rubber material for flexible sensor as claimed in claim 5, it is characterised in that described metallic conductive fillers includes Powdered, flakey, fibrous gold, silver, copper, aluminum, nickel; Described metal/metal composites includes the copper powder of electroplate, nikel powder, aluminium powder, ferrite, zinc oxide, aluminium oxide; Described metal/non-metal complex includes the Pulvis Talci of electroplate, mica powder, glass fibre, hollow glass micropearl, graphite powder, polystyrene microsphere.
7. the conductive rubber material for flexible sensor as described in as arbitrary in claim 1-3, it is characterised in that the resistivity of described conductive rubber material is 5.0 �� 102-1.0��1010��.cm��
8., for a manufacture method for the conductive rubber material of flexible sensor, comprise the following steps:
Each component is weighed according to the arbitrary described formula for the conductive rubber material of flexible sensor of claim 1-7;
Each component is carried out mixing process, obtains elastomeric compound;
It is shaped described elastomeric compound processing;
Sample through forming processes is cross-linked by the method adopting electron beam or gamma Rays, obtains the conductive rubber with strain-resistance effect.
9. the conductive rubber material for flexible sensor as claimed in claim 8, it is characterised in that the dosage of described electron beam or gamma Rays is 5-30Mrad.
10. a strain ga(u)ge type sensor, including sensing unit and the metal electrode being arranged on described sensing unit two ends, it is characterised in that described sensing unit is made up of the arbitrary described conductive rubber material for flexible sensor of claim 1-7.
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