CN106338351B - A kind of stretching-sensitive type sensor of negative resistance effect - Google Patents
A kind of stretching-sensitive type sensor of negative resistance effect Download PDFInfo
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- CN106338351B CN106338351B CN201510600916.5A CN201510600916A CN106338351B CN 106338351 B CN106338351 B CN 106338351B CN 201510600916 A CN201510600916 A CN 201510600916A CN 106338351 B CN106338351 B CN 106338351B
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Abstract
The invention discloses a kind of stretching-sensitive type sensors of negative resistance effect, including stretching-sensitive material and are produced on the metal electrode of the stretching-sensitive material surface.The stretching-sensitive material is that the resistivity that is combined of conducting particles is filled in rubber material between 1.0 × 103Ω .cm and 1.0 × 108A kind of conductive rubber between Ω .cm.Tension sensor structure in the present invention is simple, mechanical quantity amplitude of variation is big, and flexible, after 1000 repeated stretchings, resistance variations intensity will not decline.And conductive rubber of the present invention uses the production technology of General Purpose Rubber, has the advantages that high production efficiency, manufacturing cost are low, thus have broad application prospects in fields such as biomethanics detection, rehabilitation medical, intelligence wearing, intelligent robots.
Description
Technical field
The present invention relates to pulling force responsive type sensor field, in particular to the stretching-sensitive type sensor of a kind of negative resistance effect.
Background technique
1885, English physicist Kelvin had found that metal generates mechanical deformation in receiving pressure (pulling force or torsion) afterwards
While, due to being influenced by scantling (length, sectional area) change, characteristic variation is also had occurred in resistance value, that is, is strained
Electricresistance effect.People just obtain the feature and magnitude of material stress from the variation of resistance value, develop respectively pressure-sensitive and
The resistance strain sensor of pulling force responsive type.The pulling force responsive type resistance strain type sensor being widely used at present, abbreviation stretching-sensitive
Electric resistance sensor mainly has metal strain resistance-type, semiconductor strain resistance-type, alloy strain resistance type etc..But due to passing
Feel the limitation of material elasticity modulus itself, these strain type resistive sensing elements have the disadvantage in that one is a lack of flexible and bullet
Property, cannot be bent, thus be restricted in the application for needing the field for the complicated deformation such as being bent, stretching；Second is that mechanical quantity changes
Amplitude is smaller, thus cannot be used for the biggish field of deformation quantity；Third is that structure is complicated, manufacturing cost is high.Biomethanics detect,
During the labyrinth mechanical meaurement in the fields such as rehabilitation medical, intelligent robot, wearable device, it is desirable that sensor is not only wanted
Have good stress-resistance characteristic, and requires have outstanding flexible mechanical property.Therefore, metal type in these areas
Or the application of semiconductor-type resistance strain sensor just receives the limitation of natural resiliency modulus.It is, thus, sought for new is soft
The mechanics sensitive material of good-toughness manufactures strain type tension sensor flexible.
Summary of the invention
The purpose of the present invention is to provide a kind of stretching-sensitive type sensors of negative resistance effect, enhance the flexibility and bullet of sensor
Property, increase the amplitude of variation of mechanical quantity, reduces cost.
To achieve the goals above, the technical scheme is that a kind of stretching-sensitive type sensor of negative resistance effect, including
Stretching-sensitive material and the metal electrode for being produced on the stretching-sensitive material surface.The stretching-sensitive material is to fill to lead in rubber material
Resistivity made of electric filler is between 1.0 × 103Ω .cm and 1.0 × 108A kind of conductive rubber between Ω .cm, the metal
Electrode is selected from one of metal film, metal foil, sheet metal, passes through conductive glue bond, silver paste silk-screen printing, vacuum coating or machine
The mode of tool crimping is produced on stretching-sensitive material ends.Resistance is not under tensile force effect for the negative resistance effect stretching-sensitive type sensor
Disconnected decline, shows negative pulling force-electricresistance effect, can produce 5-500 times of resistance variations, and the drawing when deformation quantity is 30%
The amplitude of variation of the mechanical quantity of quick type sensor is big, and flexible and elasticity is fine, and after 1000 repeated stretchings, resistance variations are strong
Degree will not decline.It is converted into electric current, voltage or capacitance signal by the variation of detection resistance value, or by resistance signal, it can
The information of external forces suffered by sensor is obtained, it can be in biomethanics detection, rehabilitation medical, intelligence wearing, intelligence machine
The measurement of the fields such as people progress mechanical quantity.
Conducting particles to form conductive path by microcosmic contacting with each other in rubber matrix, thus when material is by the external world
Pressure or pulling force effect when, the spacing of material internal adjacent conductive particle changes, and results in relying on the contact of conducting particles
And the conductive path formed changes, and the resistance of macroscopically material is caused to change, therefore can be used as a kind of mechanics biography
Feel material.The excellent flexibility of rubber matrix itself and elasticity assign the stretching-sensitive type sensor excellent flexibility and elasticity, and
Biggish mechanical quantity amplitude of variation can overcome metal type or semiconductor-type resistance strain sensor in terms of flexibility and elasticity
Deficiency.
To realize above-mentioned technical proposal, the stretching-sensitive material is according to mass parts each component ratio are as follows: and 100 parts of rubber matrix,
0.1-3 parts of protection system, 1-15 parts of vulcanizing system, 20-100 parts of conductive filler.Wherein, mass parts are industrially for calculating side
Just the intuitive quality proportioning method of one used, the mass ratio of proportion substance required for number directly indicates.
Further, the rubber material is natural rubber, nitrile rubber, ethylene propylene diene rubber, butadiene-styrene rubber, poly- isoamyl
At least one of diene rubber, butadiene rubber.
Further, the protection system, including amines antioxidants and phenol antiager.
Further, the vulcanizing system, including vulcanizing agent, vulcanization accelerator and activating agent.
Further, the activating agent includes zinc oxide or stearic acid.
Further, the vulcanization accelerator includes thuriam acceserator, thiazole accelerator, guanidines or secondary
Sulfonamides promotor.
Further, the vulcanizing agent includes sulphur and organic peroxide.
Further, organic peroxide, including cumyl peroxide DCP, Isosorbide-5-Nitrae-dual-tert-butyl peroxy isopropyl base benzene,
The positive fourth of bis- (t-butyl peroxy) valeric acids of 1,1-bis(t-butylperoxy)cyclohexane, tert butyl isopropyl benzene peroxide, 4,4-
Ester.
Further, the conductive filler is carbon black, average grain diameter 20-120nm, oil factor 40cm3/100g-
200cm3/100g。
Further, the resistivity of the conductive rubber material is between 1.0 × 103Ω .cm and 1.0 × 108Between Ω .cm.
Further, the metal electrode is selected from one of metal foil, sheet metal, metal film, special-shaped metal component, leads to
The mode for crossing conductive glue bond, conductive silver paste silk-screen printing, vacuum coating or mechanical crimp is produced on stretching-sensitive material ends.It is described
Conductive silver paste is ultraviolet curing type.The method of the vacuum coating includes vacuum vapor plating, vacuum magnetron sputtering coating film, true
Empty ion film plating.
Further, the stretching-sensitive type sensor of the negative resistance effect, including stretching-sensitive material and production stretching-sensitive material surface
Metal electrode.
Further, the resistance value of stretching-sensitive type sensor is between 50k Ω and 50000k Ω.
Stretching-sensitive type sensor resistance value rapid decrease under tensile force effect, shows negative stretching-sensitive electricresistance effect, when
It can produce 5-500 times of resistance variations when stretching 30%.The variation of stretching-sensitive type electric resistance sensor resistance value before and after tensile deformation
Multiplying power can characterize the sensitivity of stretching-sensitive sensor.
The stretching-sensitive sensor is after under tension effect, and stretching-sensitive length of material increases, and sectional area becomes smaller and material
The variation in inner conductive particle gap leads to material conductive microstructure network change, so as to cause the variation of resistivity of material.Material
The comprehensive change of the factors such as length of material also simultaneously results in the capacitor between stretching-sensitive material ends electrode between resistivity, electrode
Value changes.
Further, the capacitance of stretching-sensitive type sensor of the invention increases as tensile deformation increases, and 30% stretches
The capacitance variation multiplying power of stretching-sensitive sensor is 5 to 500 times in deformation range.
The present invention also provides a kind of manufacturing methods of the stretching-sensitive sensor of negative resistance effect, comprising the following steps:
Step A: according to certain quality proportioning by rubber matrix, anti-aging agent, conductive filler, vulcanizing agent, according to above-mentioned suitable
Sequence is added sequentially to two-roll mill or mixer is kneaded, and after mixing, thin pass-out piece was entirely kneaded each component
The temperature of journey is controlled at 80 DEG C or less.
Step B: conductive rubber sizing material will be kneaded and be put into mold, sulfidization molding, obtains under certain temperature and pressure
To conductive rubber plate.Specific curing parameter is determined according to different rubber matrixs.
Step C: by conductive rubber plate, cutting into the rubber batten of certain length and width, be bonded using conductive silver glue,
The method of high temperature hot pressing, silver paste silk-screen printing or vacuum coating makes metal electrode at batten both ends, can also be further at it
Upper connection plain conductor, to prepare the stretching-sensitive sensor of negative resistance effect.
The utility model has the advantages that the resistance value of the stretching-sensitive sensor of negative resistance effect provided by the invention is between 50k Ω and 50000k
Between Ω.Stretching-sensitive sensor structure of the present invention is simple, and manufacturing cost is low, constantly declines in tensile force effect lower sensor resistance,
Negative resistance effect is showed, while being increased as tensile deformation increases the capacitance between the metal electrode of sensor both ends, shape is worked as
Variable can produce 5-500 times of resistance and capacitance variations when being 30%, the amplitude of variation of sensor mechanical quantity is big, flexible and elasticity
Very well, and the sensor is after 1000 repeated stretchings, and resistance variations intensity will not decline.The excellent flexibility of rubber itself
It assigns the sensor excellent flexibility and elasticity, overcomes metal type and semiconductor strain sensor in elasticity and flexibility side
The deficiency in face.It is converted into electric current, voltage or capacitance signal by the variation of detection resistance value, or by resistance signal, can be obtained
The information of external forces suffered by sensor is obtained, therefore in biomethanics detection, instrument and meter, health medical treatment, artificial intelligence etc.
Field has broad application prospects.
Detailed description of the invention
Fig. 1-Fig. 7 is the resistance value (capacitance) of the stretching-sensitive sensor of negative resistance effect of the present invention with the variation of tensile deformation
Curve graph.
Specific embodiment
In order to be more clearly understood that technology contents of the invention, spy lifts following embodiment and makees specifically to the present invention
It is bright:
Embodiment 1
The stretching-sensitive sensor of the negative resistance effect of the present embodiment is using conductive rubber as stretching-sensitive material, and production method is such as
Under:
The proportioning components of conductive rubber and the production method is as follows:
In the following order by the natural rubber of 100 mass parts, the antioxidant D of 1 mass parts, the zinc oxide of 5 mass parts, 2
The stearic acid of mass parts, the captax of 1 mass parts, carbon black (Raven520U, partial size 58nm, the oil factor of 110 mass parts
120m2/ g, Columbian Chemical), the sulphur of 2.5 mass parts is added sequentially to two-roll mill and is kneaded, open mill temperature
Be set as 50 DEG C, each component after mixing, thin pass-out piece.The conductive natural rubber being kneaded is put into mold, 140
DEG C, vulcanize 15 minutes under 15MPa pressure, obtains the conductive natural rubber plate of 1mm thickness.
By conductive rubber plate, length 50mm is cut into, the batten of width 5mm is existed using the method that conductive silver glue is bonded
Batten both ends make metal foil electrode and connect metal copper conductor on it, and wherein metal foil is nickel plating copper foil, thickness
0.035mm, length 10mm, width 5mm；Copper lines diameter 0.4mm.
Conductive rubber material described in the present embodiment is as stretching-sensitive material of the invention, and resistivity is between 1.0 × 103Ω
.cm with 1.0 × 108Between Ω .cm.Stretching-sensitive sensor manufactured in the present embodiment resistance value under tensile force effect constantly declines,
Show negative resistance effect, and flexibility and elasticity is good, mechanical quantity amplitude of variation is big, and structure is simple, and manufacturing cost is low.
Flexibility stretching-sensitive material of the present invention is that conductive rubber material made of conductive filler, institute are filled in rubber material
It states metal electrode and is selected from one of metal film, metal foil, sheet metal, special-shaped metal component, pass through conductive glue bond, Gao Wenre
Pressure, silver paste silk-screen printing or the mode of vacuum coating are produced on the surface of stretching-sensitive material ends.Negative pulling sensitive effect of the invention
Switching mode electric resistance sensor structure is simple, and manufacturing cost is low, constantly declines in tensile force effect lower sensor resistance, shows negative
Stretching-sensitive electricresistance effect can produce 5-500 times of resistance variations when deformation quantity is 30%, and the amplitude of variation of mechanical quantity is big, flexible
It is fine with elasticity, and the sensor, after 1000 repeated stretchings, resistance variations intensity will not decline.
Preferably, the stretching-sensitive material is according to mass parts each component component ratio are as follows: and 100 parts of rubber material, protection system
0.1 part, 2 parts of vulcanizing system, 20 parts of conductive filler.
Preferably, according to mass parts each component ratio are as follows: 100 parts of rubber material, 1.5 parts of protection system, vulcanizing system 7
Part, 70 parts of conductive filler.
Preferably, according to mass parts each component ratio are as follows: 100 parts of rubber material, 3 parts of protection system, 15 parts of vulcanizing system,
110 parts of conductive filler.
Preferably, the rubber material is natural rubber, nitrile rubber, ethylene propylene diene rubber, butadiene-styrene rubber, poly- isoamyl two
At least one of alkene rubber, butadiene rubber.
Preferably, protection system includes amines antioxidants and phenol antiager.
Preferably, the vulcanizing system includes vulcanizing agent, vulcanization accelerator and activating agent.
Preferably, the activating agent includes zinc oxide or stearic acid.
Preferably, the vulcanization accelerator includes thuriam acceserator, thiazole accelerator, guanidines or secondary sulphur
Amides promotor.
Preferably, the vulcanizing agent is sulphur and organic peroxide.
Preferably, the organic peroxide, including cumyl peroxide DCP, Isosorbide-5-Nitrae-dual-tert-butyl peroxy isopropyl base
Bis- (t-butyl peroxy) valeric acids of benzene, 1,1-bis(t-butylperoxy)cyclohexane, tert butyl isopropyl benzene peroxide, 4,4- are just
Butyl ester.
Preferably, the conductive filler is carbon black, and the average grain diameter of the carbon black is 20nm, oil factor 40cm3/100g。
Preferably, the conductive filler is carbon black, and the average grain diameter of the carbon black is 70nm, oil factor 120cm3/100g。
Preferably, the conductive filler is carbon black, and the average grain diameter of the carbon black is 120nm, oil factor 200cm3/
100g。
Preferably, the resistivity of the conductive rubber material is 1.0 × 103Ω.cm。
Preferably, the resistivity of the conductive rubber material is 1.0 × 105Ω.cm。
Preferably, the resistivity of the conductive rubber material is 1.0 × 108Ω.cm。
Preferably, the metal electrode is selected from one of metal foil, sheet metal, metal film, passes through conducting resinl haircuts net
The mode of printing or vacuum coating or mechanical crimp is produced on the surface of stretching-sensitive material ends.
Preferably, the resistance value of the stretching-sensitive sensor is 50k Ω.
Preferably, the resistance value of the stretching-sensitive sensor is 5000k Ω.
Preferably, the resistance value of the stretching-sensitive sensor is 50000k Ω.
Preferably, resistance value increases with deformation and declines the stretching-sensitive sensor under a stretching force, when shape becomes 30%
Resistance change multiplying power is 5 times.
Preferably, resistance value increases with deformation and declines the stretching-sensitive sensor under a stretching force, when shape becomes 30%
Resistance change multiplying power is 100 times.
Preferably, resistance value increases with deformation and declines the stretching-sensitive sensor under a stretching force, when shape becomes 30%
Resistance change multiplying power is 500 times.
Preferably, capacitance increases with deformation and increases the stretching-sensitive sensor under a stretching force, when shape becomes 30%
Capacitance variation multiplying power is 5 times.
Preferably, capacitance increases with deformation and increases the stretching-sensitive sensor under a stretching force, when shape becomes 30%
Capacitance variation multiplying power is 100 times.
Preferably, capacitance increases with deformation and increases the stretching-sensitive sensor under a stretching force, when shape becomes 30%
Capacitance variation multiplying power is 500 times.
The stretching-sensitive characteristic of the negative resistance effect stretching-sensitive sensor of the present embodiment is tested according to following test method:
(a) test stretching-sensitive sensor draws electricity with the changing rule of increase its resistance value and capacitance of tensile deformation
The relation curve of resistance value and capacitance and tensile deformation, as shown in Figure 1.
(b) the repeatability energy and stability of test stretching-sensitive sensor resistance variations in the case where stretching deformation surely: setting stretches
Deformation 30% sets sample and is being stretched to the retention time for determining elongation as 5 seconds, and the turnaround time of sample is 30 after unloading pulling force
Second, the number of repeated stretching is 1000 times, records resistance before stretching every time and resistance value when being stretched to tensile deformation 30%, number
According to being listed in Table 2 below.
Embodiment 2
In conjunction with Fig. 2, according to the stretching-sensitive sensor with 1 same procedure of embodiment manufacture negative resistance effect, but 90 mass parts
Carbon black (Raven520U, partial size 58nm, oil factor 120m2/ g, Columbian Chemical) charcoal of 110 mass parts in alternate embodiment 1
Black (Raven520U, partial size 58nm, oil factor 120m2/ g, Columbian Chemical).According to identical side described in embodiment 1
Formula tests the properties of stretching-sensitive sensor, and the results are shown in Table 2.
Embodiment 3
In conjunction with Fig. 3, according to the stretching-sensitive sensor with 1 same procedure of embodiment manufacture negative resistance effect, but with 80 mass parts
Carbon black (Raven520U, partial size 58nm, oil factor 120m2/ g, Columbian Chemical) 110 mass parts in alternate embodiment 1
Carbon black (Raven520U, partial size 58nm, oil factor 120m2/ g, Columbian Chemical).According to identical with described in embodiment 1
Mode tests the properties of stretching-sensitive sensor, and the results are shown in Table 2.
Embodiment 4
In conjunction with Fig. 4, according to the stretching-sensitive sensor with 1 same procedure of embodiment manufacture negative resistance effect, but with 70 mass parts
Carbon black (Raven520U, partial size 58nm, oil factor 120m2/ g, Columbian Chemical) 110 mass parts in alternate embodiment 1
Carbon black (Raven520U, partial size 58nm, oil factor 120m2/ g, Columbian Chemical).According to identical with described in embodiment 1
Mode tests the properties of stretching-sensitive sensor, and the results are shown in Table 2.
Embodiment 5
In conjunction with Fig. 5, according to the stretching-sensitive sensor with 1 same procedure of embodiment manufacture negative resistance effect, but with 50 mass parts
Carbon black (Raven520U, partial size 58nm, oil factor 120m2/ g, Columbian Chemical) 110 mass parts in alternate embodiment 1
Carbon black (Raven520U, partial size 58nm, oil factor 120m2/ g, Columbian Chemical).According to identical with described in embodiment 1
Mode tests the properties of stretching-sensitive sensor, and the results are shown in Table 2.
Embodiment 6
In conjunction with Fig. 6, according to the stretching-sensitive sensor with 1 same procedure of embodiment manufacture negative resistance effect, but nitrile rubber is used
Instead of the natural rubber in embodiment 1, with carbon black (VXC72, partial size 30nm, oil factor 174m of 30 mass parts2/ g, Cabot)
Carbon black (Raven520U, partial size 58nm, oil factor 120m of 110 mass parts in alternate embodiment 12/ g, Columbian Chemical),
With the antioxidant D of 1 mass parts in the antioxidant D alternate embodiment 1 of 0.5 mass parts.According to identical side described in embodiment 1
Formula tests the properties of stretching-sensitive sensor, and the results are shown in Table 2.
Embodiment 7
In conjunction with Fig. 7, according to the stretching-sensitive sensor with 1 same procedure of embodiment manufacture negative resistance effect, but EPDM is used
Rubber replaces the natural rubber in embodiment 1, with carbon black (Raven430, partial size 82nm, oil factor 75m of 100 mass parts2/ g,
Columbian Chemical) carbon black (Raven520U, partial size 58nm, oil factor 120m of 110 mass parts in alternate embodiment 12/ g, brother
The sub- chemistry of rival), with the antioxidant D of 1 mass parts in the antioxidant D alternate embodiment 1 of 2 mass parts.According to institute in embodiment 1
The properties that identical mode tests stretching-sensitive sensor are stated, the results are shown in Table 2.
Table 1
Note: material forms unit: mass parts
Initial resistance and resistivity are average value
Table 2
By the resistance or capacitor of the stretching-sensitive sensor of the negative resistance effect of embodiment 1 in Fig. 1 to Fig. 7 to embodiment 7 with
The relation curve of tensile deformation can be seen that stretching-sensitive sensor provided by the invention, resistance value with tensile deformation increase
Constantly decline, capacitance are continuously increased with tensile deformation increase.
Pass through the data in table 2, it can be seen that the stretching-sensitive type sensor of negative resistance effect of the invention has electricity well
Repeatability and pulling sensitive effect Repeatability are hindered, stretching-sensitive type resistor still has excellent stretching-sensitive after stretching by 1000 times
Effect.
The stretching-sensitive type sensor structure of negative resistance effect provided by the invention is simple, and manufacturing cost is low, in tensile force effect
Lower sensor resistance constantly declines, and shows negative resistance effect, while as tensile deformation increases sensor both ends metal electrode
Between capacitance increase, can produce 5-500 times of resistance and capacitance variations, stretching-sensitive biography of the invention when deformation quantity is 30%
The amplitude of variation of sensor mechanical quantity is big, and flexible and elasticity is fine, and the sensor is after 1000 repeated stretchings, resistance variations
Multiplying power will not decline.By detect drawing process sensor resistance variation, or by the resistance signal of variation be converted into voltage,
Electric current or capacitance signal can carry out the survey of power in fields such as biomethanics, rehabilitation medical, intelligence wearing and artificial intelligence
Amount, has broad application prospects.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (5)
1. a kind of stretching-sensitive type sensor of negative resistance effect, it is characterised in that: including stretching-sensitive material and be produced on the stretching-sensitive
The metal electrode of material surface；The stretching-sensitive resistance material be conducting particles be dispersed in rubber material manufactured resistivity between
1.0×103Ω .cm and 1.0 × 108A kind of conductive rubber material between Ω .cm, each component mass parts ratio are as follows: rubber matrix
100 parts, 0.1-5 parts of protection system, 1-15 parts of vulcanizing system, 20-100 parts of conducting particles；The stretching-sensitive type sensor is stretching
Increase resistance value decline with tensile deformation under power effect, resistance variations multiplying power is 5-500 times when tensile deformation 30%；The stretching-sensitive
Type sensor increases capacitance with tensile deformation under tensile force effect and increases, and capacitance variation multiplying power is when tensile deformation 30%
5-500 times；
The rubber material is selected from natural rubber, nitrile rubber, ethylene propylene diene rubber, butadiene-styrene rubber, neoprene, poly- isoamyl two
At least one of alkene rubber, butadiene rubber.
2. the stretching-sensitive type sensor of negative resistance effect as described in claim 1, it is characterised in that: the conducting particles is selected from charcoal
It is black, average grain diameter 20-120nm, oil factor 40cm3/100g - 200cm3/100g。
3. the stretching-sensitive type sensor of negative resistance effect as described in claim 1, which is characterized in that the conductive rubber material is
Vulcanization crosslinking is carried out using sulphur or organic peroxide.
4. the stretching-sensitive type sensor of negative resistance effect as described in claim 1, it is characterised in that: the metal electrode is selected from gold
Belong to one of film, metal foil, sheet metal or profiled metal part.
5. the stretching-sensitive type sensor of negative resistance effect as described in claim 1, it is characterised in that: the stretching-sensitive type sensor
Resistance value is between 50k Ω and 50000k Ω.
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