CN101198851A - Polymeric strain sensor - Google Patents
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- CN101198851A CN101198851A CNA2006800181301A CN200680018130A CN101198851A CN 101198851 A CN101198851 A CN 101198851A CN A2006800181301 A CNA2006800181301 A CN A2006800181301A CN 200680018130 A CN200680018130 A CN 200680018130A CN 101198851 A CN101198851 A CN 101198851A
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- Measurement Of Length, Angles, Or The Like Using Electric Or Magnetic Means (AREA)
Abstract
A strain sensor consisting of a non conducting polymer incorporating conductive nanoparticles below the percolation threshold and preferably less than 10 % v/v of the polymer. The polymer is a polyimide and the conducting nanoparticle is carbon black having an average particle size of 30-40 nm and an aggregate size of 100-200 nm. The sensor can sense strain in extension, compression and torsion.
Description
Technical field
The present invention relates to strain transducer, microstrain sensor particularly, it makes and is used to be in the continuous monitoring of the structure under the strained condition easily.
Background technology
The someone proposes the polymeric strain instrument.
United States Patent (USP) 5,989,700 disclose the preparation of pressure sensitive ink, and it can be used for the manufacturing of pressure transducer such as strainmeter, wherein resistance indication institute applied pressure.Described printing ink has the elastomeric polymer component, and semiconductor nanoparticle is dispersed in this polymer adhesive.
United States Patent (USP) 5,817,944 disclose the strain transducer that is used for xoncrete structure, and it contains conductive fiber.
United States Patent (USP) 6079277 discloses strain or the strain gauge of being made up of polymer composites and carbon filament matrix.
United States Patent (USP) 6276214 discloses the strain transducer of use conductive particle-polymer complexes.Carbon black dispersion forms the conducting polymer matrix in ethylene-vinyl acetate copolymer.
The manufacturing of all these polymer sensors all is by the preparation conductive particle, by solution or fusion method it is sneaked in the polymkeric substance then, and film forming is made then.Then this assembly is affixed on the stilt of insulation, and be embedded on the physical construction that to monitor.Electrical lead need be connected to described sensor.The polymeric strain instrument that relies on the conducting film resistance variations usually can not be satisfactory, and owing to hysteresis causes serviceable life not long.Common preferable alloy strainmeter.
The objective of the invention is to develop the Performance Characteristics with improvement and the polymeric strain sensor of low magnetic hysteresis.
Summary of the invention
For this reason, the invention provides the composition polymer strain transducer, it is made up of the mixed conductive nano-particles that is lower than percolation threshold of non-conductive polymkeric substance, and described conductive nano-particles is preferably less than 10% of polymer volume.
Compare with polymeric strain sensor of the prior art (being generally 30%v/v), described conductive particle load is low relatively, this means that the eka-gold attribute that reveals with sensor sheet of the prior art compares, and described compound is a semiconductive.
Described polymkeric substance generally is a polyimide material, and described conductive particle is the carbon of different shape, comprises graphite, carbon black and vitreous carbon, and it has the mean grain size of 30-70nm and the aggregate size of 100-200nm.This nano composite material strain sensor element can directly be printed or sticked on the matrix of test with conductive traces by various curtain coatings, printing or conventional attachment techniques, makes described element can be connected to external circuit.
Compare with polymeric strain sensor of the prior art (being generally 30%v/v), described conductive particle load is low relatively, this means that the metalloid characteristic that reveals with sensor sheet of the prior art compares, and described compound substance is a semiconductive.Compare with compound sensor of the prior art, the composition that is proposed is starkly lower than percolation threshold, and compound sensor of the prior art depends on the physics contact between the conductive particle that the seepage flow network is provided, and is subjected to the effect of micromechanics hysteresis displacement.Because the destruction of infiltration conducting path in the compound substance, the conductivity of prior art polymers sensor is measured and is reduced.Described low load makes described polymer composites because the micromechanics characteristic reduction that high volume load causes minimizes.
These compound substances demonstrate the conductivity of enhancing by electronics jump (electron hopping) mechanism.The conductivity characteristic of this system (temperature dependence/deformation dependence/voltage dependence etc.) depends on the concentration and the grain spacing of carbon granule size, carbon nano-particle.When the concentration of carbon nano-particle increased to 8%v/v by 1%v/v, the conductivity of described composite structure was from 10
-7To 10
-2S/cm gradually changes.Thereby these composite membranes are semiconductives in their temperature characterisitic, and it is not used in strain sensing, but owing to the characteristic of their non-infiltration electron transport mechanism is used as extremely low magnetic hysteresis strain transducer film.In these films, utilized the electrical property of carbon-polyimide nano-composite material membrane to depend on the variation (it depends on the particle gap that occurs in the deformation process fatefully) of deformation to obtain the purposes of strain transducer as these films.
With the prior art polymers strain transducer (under zero strain, conductivity depends on the existence of the seepage flow network of conductive particle) difference, the conductivity key of these carbon polymer nanocomposite films depends on and is embedded in that the electronics between the nano particle in (being separated by grain spacing clearly) polymeric matrix jumps.The characteristic of semiconductor of these nano-complex films under zero strain also provides compensation mechanism for the temperature dependence of its resistance.
This makes strain sensor element of the present invention (SSE) to respond:
A) stretch (promptly stretching) deformation, enlarging the resistance that causes described film by grain spacing under tensile strain increases, and
B) compression set reduces the reduction of caused SSE film resistance by grain spacing under compressive load, and this strain transducer based on polymkeric substance with prior art is different, and it is because the existence of seepage flow network and insensitive to compressive load, and
C) torsional deformation relies on its response to tensile deformation and compression set.
This SSE can easily make with Any shape and size and use, and comprises thin or thick film or any solid shape, depends on the specific purposes and the requirement of sensitivity.
The special performance of these SSE makes Quantitative Monitoring become possibility, for example the Quantitative Monitoring of stretching and compression set and power, torsional deformation and power, vibration, impact and sinusoidal deformation.
Suitable polymers is the polyimide that is generally used in the microelectronic device.Polyimide has splendid micromechanics, chemistry and electrical property in-270 ℃ to 260 ℃ wide in range temperature range.
Preferred conductive nano-particles is the carbon black with aggregate size of the mean grain size of 30-70nm and 100-200nm.Preferred carbon content is about 1%v/v.
Description of drawings
Fig. 1 has illustrated employed preparation process in one embodiment of the invention;
Fig. 2 has illustrated in the variation of 20 ℃ of following conductivity with carbon content;
Fig. 3 has illustrated at stand alone type (free standing) film and the variation of the temperature-dependent resistance between the lining form has been arranged;
Fig. 4 has illustrated the electromagnetic hysteresis that is caused by thermal cycle;
Fig. 5 has illustrated and the general micromechanics behavior than sensor of the present invention of the polymer phase of not filling;
Fig. 6 has illustrated the general electromechanical behavior of sensor of the present invention;
Fig. 7 has illustrated that the strain resistor of sensor of the present invention changes and the coefficient of strain;
Fig. 8 is the synoptic diagram of carbon fibre composite paddle (rowing Oar), and the position that demonstrates SSE is to place along the axis of oar;
Fig. 9 is during the cyclic deformation of described oar, the figure of corresponding time of the resistance ratio of strain sensor element;
The resistance of Figure 10 strain sensor element is with the figure of the load change that applies;
Figure 11 is that strain sensor element SG1 is at the resistance variations figure in the cyclic loading experiment under two different temperatures;
Figure 12 is the figure of the corresponding time of the resistance variations of strain sensor element during cyclic loading of appointment;
Figure 13 is the figure of the resistance relative variation of SSE when being stretched with compression set;
Figure 14 strain sensor element that to be all place along the oar axle is tensile deformation and relative variation of resistance under the compression set, and described deformation produces by the power that applies 200N;
Figure 15 is the figure of corresponding time of resistance variations when applying torsional deformation periodically in a clockwise direction or counterclockwise on the oar axle;
The synoptic diagram of Figure 16 has provided and has been used to use the Instron testing machine to carry out the details of the location of the described carbon fibre reinforced pipe that torsional deformation measures;
Figure 17 demonstrates the variation that a) is applied to the moment of torsion on the described pipe when applying torsional deformation periodically on carbon fibre reinforced pipe, b) variation and the c of torsional deformation angle (degree)) resistance of SSE is over time.
Detailed Description Of The Invention
As shown in Figure 1, described nano-composite material membrane is to prepare by the precursor of carbon black being sneaked into polyimide (being the polyamic acid of benzophenone tetracarboxylic dianhydride), and 4 in use n-methyl 2-Pyrrolidone (NMP) solvent, 4 '-amino-diphenylethers (BPDA-ODA) rice film forming.Described cast film is in the scope of 50-100 micron.Described carbon black has the mean grain size of 30-70nm and the aggregate size of 100-200nm.The load of carbon remains on below the 10%v/v, makes conductivity 10
-6To 10
-2Scm
-1Scope in and in semi-conductive scope, as shown in Figure 2.
Fig. 3 has shown that the carbon content of curtain coating on silicon substrate is the resistance-hygrogram of the nano-composite material membrane of 5%v/v.Resistance reduces with the rising of temperature, and this is typical characteristic of semiconductor.This figure also demonstrates the resistance hysteresis behavior that the circulation time that is heated reduces.
Fig. 4 has shown in stand alone type and has had that temperature-dependent resistance changes in the carbon-polyimide nano-composite material film of lining.The resistance variations difference of two kinds of films demonstrates the effect of matrix to the electricity behavior of polymer nanocomposites film.
The invention has the advantages that compare with the polymer film of particle load in the seepage flow scope, magnetic hysteresis is very low, as shown in Figure 3.Because relatively low load, the micromechanics character of described compound substance is similar to pure polyimide, as shown in Figure 5.The resistance vs. static strain of sensor of the present invention is shown in Fig. 6 and Fig. 7.Under stretch mode, the coefficient of strain of described free-standing strain transducer film is 8 (Fig. 6), and under beam mode, the coefficient of strain that is fixed on the strain transducer film on the silicon substrate is 12.When strain transducer is used on the different matrix, can obtain high to 25 the coefficient of strain.
May obtain 25 the coefficient of strain when using some matrix.The coefficient of strain that conventional metal strain instrument has usually＜5.
An illustration of the application of these special performances of this SSE material is its application in the micromechanics behavior of monitoring carbon fibre composite paddle.
Be by these strain sensor element being placed the embodiment that obtains in the paddle, having confirmed their potential application below.
Fig. 8 has shown the synoptic diagram of left hand oar (LO).Begin to measure to the distance of blade tie-point by oar axle and blade.The position is measured according to blade.Table 1 has provided the definite geometric position of SSE on oar in the experiment.
Table 1:SSE their resistance values separately under detail location on the oar and room temperature
| Strainmeter | Distance (mm) to blade | Position on oar | The angle that becomes with the oar axle | Resistance (K Ω) |
| Right hand oar (RO) | ||||
| |
300 | The front | 0° | 87.7 |
| SG2 | 500 | The front | 45° | 93.6 |
| SG3 | 600 | The front | 0° | 83.3 |
| SG4 | 900 | The front | 0° | 84.2 |
| SG5 | 800 | The bottom | 0° | 80.7 |
Experimental establishment
SSE used in this example bar long by 5mm, that 1mm is wide, about 0.06mm is thick is formed.The resistance of SSE uses the data acquisition system (DAS) of the computer control with multimeter to measure, and bent rowing is simulated with universal testing machine (INSTRON), described simulation by described INSTRON by flatly clamping oar and blade being faced down, fixedly the handle of oar is to shank portion, and the oar the tip of the axis upwards drawn realize.The handle of described paddle to sleeve part is fixed on the concrete work platform, can not occur moving or deformation in experimentation with this part of guaranteeing oar.Oar the tip of the axis (being the joint of oar axle and blade) passes through specially designed fixture attached on the described INSTRON.For the power of 300 N, the perpendicular displacement of the blade of Chan Shenging is about 130mm herein.It is the cyclic deformation of 1000mm per minute (in testing continuously is about 112 loading periods in 1450 seconds) that described oar is subjected to speed.
Fig. 9 has shown that in the end resistance over time in 10 cycles: place the SSE of diverse location to stand the strain of different amounts, this is reflected in during their resistance ratios separately change.Strainmeter SG3 (being positioned at apart from 600mm place, blade center) and strainmeter SG4 (being positioned at apart from 900mm place, blade center) have produced the approximate strain-responsive that is caused by load, illustrate that oar is similar in the deformation behavior of these two positions.These two SSE also demonstrate peaked response, illustrate that the deformation of oar axle is in these position maximums.Strainmeter SG1 (being positioned at the 300mm place) compares with SG4 with SG3 and demonstrates lower strain (2/3rds), demonstrates the lower deformation of oar axle in this position, and SG2 (being positioned at the 500mm place) demonstrates minimum stress.When oar was subjected to 300 newton's tensile loads, a strainmeter SG5 who is positioned at axle 800mm place, edge (tip position) demonstrated compression property.
Above-mentioned experiment confirm the abilities of these SSE in Quantitative Monitoring paddle deformation, this makes us can determine the minimum and maximum strain location on the oar.This experiment has also confirmed the ability of strain sensor element of the present invention response compression set, and shown in the behavior of strain sensor element SG5, SG5 places along the axis of oar axle, but is 90 ° with the position of other strain sensor element.
Figure 10 has shown the variation diagram of resistance with the load that is applied.Resistance is by 83 under the load-less condition, and 000ohms becomes 83 under 300 newton's load, 700ohms.Realized the linear change of resistance with the load that is applied.All this behaviors along the strain sensor element that axle is placed all are identical.When the temperature of described strain transducer kept constant, in all were in described strain sensor element under the cyclic load, this electrical response had the repeatability of height.
Because its characteristic of semiconductor, the resistance under the load-less condition varies with temperature.Yet the temperature variant rate of change of the resistance of described strain sensor element remains unchanged.For example, Figure 11 has shown the variation of the resistance of strain sensor element SG1 under two different temperatures with the load that applies.The effect of environment temperature is to make the curve of the load of resistance-apply moving along y-axis shift.But the loading factor of resistance (slope) remains unchanged.
The proof of strain sensor element perception compression set feature of the present invention.
In Fig. 8, place but be 90 ° strain sensor element SG5 along the oar axle and demonstrate resistance and increase with the load that is applied and reduce with other SSE.This is to be caused by the SG5 lateral compression assembly along the oar axis.
Use INSTRON, to oar axle imposed load, under this load configuration, be compressed now by whole strain sensor element of tensile deformation before making from relative direction.
When Figure 12 had shown on cyclic load puts on given strain sensor element, its resistance over time.During described strain sensor element tensile deformation, the maximum load that puts on the oar remains on 300N, and at the deformation experimental session, the maximum load that puts on the oar axle remains on 200N in the other direction.
Figure 12 has shown that strain sensor element is in the continuous variation of periodic forward and reversed load resistance of following time.On both direction, observed deformation is all proportional with load.
This can be by more being clear that among Figure 13, above data made resistance in Figure 13 and change variation diagram with stretching that is applied and compressive load relatively.
Figure 14 has shown that the resistance of the differently strained instrument that its axis is placed in oar axle upper edge changes relatively, and described strainmeter is subjected to be become by stretching and compressibility that 200 newton's load cause.The subtle change of the numerical value in each strainmeter may be owing to place the subtle change of SSE film in the experiment along the oar axle.
Because the unique ability that the electroresponse stretching of described strain sensor element and compressibility become, by described SSE band is placed on the specific geometrical position of axle, it can be used for measuring the torsional deformation that material takes place in test.
In the experiment of the behavior that these carbon polymer nanocomposite films are described, the form SSE of described strip is 45 ° direction placement with length direction and axle.The oar axle is subjected to clockwise direction and anticlockwise torsional deformation then.Under this layout, SSE when a direction applies is subjected to drawing stress when twisting resistance, and when twisting resistance reverses stress by compression.Therefore, when distortion power applies with a direction, be the just variation of resistance, and when direction is reversed, change for negative from the electroresponse of SSE.Also relatively change quantitative changeization with torsional deformation.
As seen from Figure 15, counterclockwise twist this oar and on strain sensor element SG2, apply moment of torsion by reaching in a clockwise direction.SG2 is at direction stress and be subjected to tension stress in opposite direction by compression.The number of degrees of moment of torsion are depended in the variation of resistance value, therefore depend on the suffered rotation number of degrees, and the sign of variation depends on the direction of the moment of torsion that is applied.
The carbon fiber axle that is used for above-mentioned torsional deformation measurement is a hollow tube, reduced gradually by loom to its diameter of blade, so the quantitative measurement torsional deformation is complicated work.Use the INSTRON testing machine to carry out independent experiment to prove the performance of SSE quantitatively.The synoptic diagram of described experimental provision as shown in figure 16.
Used the hollow tube of making by even pore carbon fibre composite 11.Described device is by forming with the lower part: pipe 11, the one end device 14 that is fixed is clamped on the anchoring base 12, and the other end that is supported by bearing 15 is subjected to twisting resistance.Described pipe is of a size of: long 1500mm, internal diameter 44.7mm, external diameter 46.2mm.The length direction of the SSE17 of strip shape and tube's axis are 45 ° and are placed on apart from pipe strong point 100mm place.Then by using transfer arm 16 (lever) and INSTRON testing machine to apply the moment of torsion of 150 Nm in the clockwise direction, and the moment of torsion that applies 120 Nm in the counterclockwise direction makes and manages 11 and be subjected to torsional deformation.Described moment of torsion is applied to apart from strong point 1160mm and apart from sensing station 1060mm place.Reduce to minimumly for the influence of the bending that makes the oar that is caused by the moment of torsion that is applied, described moment of torsion is applied to apart from two fixedly between the ball bearing of 360mm.Under this structure, when twisting resistance applied in the clockwise direction, SSE17 was subjected to clean effectively drawing stress, and is subjected to clean effectively compression stress when twisting resistance applies in the counterclockwise direction.Therefore, when twisting resistance applied in the clockwise direction, the resistance variations of SSE17 had been for just, and when twisting resistance applies in the counterclockwise direction for negative.Also should relatively change quantitative changeization with the twisting resistance that is applied.
When applying periodically torsional deformation, a) putting on the variation of the moment of torsion on the pipe, b) variation and the c of torsional deformation angle (degree)) resistance of SSE illustrates in Figure 17 over time.
The number of degrees of moment of torsion are depended in the variation of resistance value, therefore depend on the suffered rotation number of degrees, and the sign of variation depends on the direction of the moment of torsion that is applied.
As from the foregoing, the invention provides the strainmeter that can be used to measure big and small strain.Described polymer film can easily cut and be combined in most of surface types and above the shape.
Those of skill in the art should be appreciated that the present invention can implement in the outer mode of these described embodiments, and does not break away from core teachings of the present invention.
Claims (10)
1. composition polymer strain transducer, it is made up of non-conductive polymer mixed conductive nano-particles, and described conductive nano-particles is lower than percolation threshold, and preferred less than 10% of described polymer volume.
2. each strain transducer in the aforementioned claim, wherein said polymkeric substance is a polyimide.
3. each strain transducer in the aforementioned claim, wherein said conductive nano-particles are the carbon blacks with aggregate size of the mean grain size of 30-70nm and 100-200nm.
4. each strain transducer in the aforementioned claim, wherein conductivity is 10
-6To 10
-2Scm
-1In the scope.
5. each strain transducer in the aforementioned claim, wherein deposit conductive traces on described composition polymer strain transducer can be connected described device with external circuit.
6. the method for preparing polymeric strain sensor, it may further comprise the steps: the conductive nano-particles of capacity is dispersed in the polymer solution, this polymer film of curtain coating comes film forming subsequently, exists in the amount of conductive nano-particles described in this film with the percolation threshold that is lower than described polymkeric substance.
7. prepare the method for polymeric strain sensor in the claim 6, wherein said polymkeric substance is a polyimide, and described conductive nano-particles is the carbon black with aggregate size of the mean grain size of 30-70nm and 100-200nm.
8. the method for preparing polymeric strain sensor in the claim 6 or 7, wherein said conductive nano-particles exists with 10% amount less than described polymer volume.
9. the method for preparing polymeric strain sensor in the claim 6 or 7, wherein said conductive nano-particles is can provide described polymer composites with 10
-6To 10
-2Scm
-1The amount of the conductivity in the scope exists.
10. the strain sensor element of being made by each polymer composites among the claim 1-5, it can detect the strain in stretching, compression and the distortion.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2005902662A AU2005902662A0 (en) | 2005-05-25 | Polymeric Strain Sensor | |
| AU2005902662 | 2005-05-25 | ||
| AU2005905029 | 2005-09-13 | ||
| PCT/AU2006/000680 WO2006125253A1 (en) | 2005-05-25 | 2006-05-24 | Polymeric strain sensor |
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| Publication Number | Publication Date |
|---|---|
| CN101198851A true CN101198851A (en) | 2008-06-11 |
| CN101198851B CN101198851B (en) | 2010-04-14 |
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| CN102183201A (en) * | 2011-02-20 | 2011-09-14 | 汪小知 | Low-dimensional nano material-based sensor for measuring mechanical deformation |
| CN102320556A (en) * | 2011-07-22 | 2012-01-18 | 北京科技大学 | Method for constructing netty nano ZnO material strain transducer |
| CN106415196A (en) * | 2014-04-04 | 2017-02-15 | 加州大学评议会 | Plasmonic nanoparticle-based colorimetric stress memory sensor |
| CN106671386A (en) * | 2016-12-27 | 2017-05-17 | 四川大学 | Conductive polymer tube with controllable axial conductivity and radial conductivity, and preparation method thereof |
| CN107209071A (en) * | 2014-09-17 | 2017-09-26 | 森斯埃布尔科技有限责任公司 | Sensing system comprising sensing structure |
| CN110763737A (en) * | 2018-11-22 | 2020-02-07 | 上海因士环保科技有限公司 | Nano conductive material/polymer composite gas sensor and preparation method thereof |
| CN111399682A (en) * | 2016-07-12 | 2020-07-10 | 新度技术有限公司 | Nano composite force sensing material |
| CN113984844A (en) * | 2014-03-25 | 2022-01-28 | 宝洁公司 | Apparatus for sensing strain of material |
| CN114858046A (en) * | 2022-05-08 | 2022-08-05 | 四川大学 | Method for improving sensitivity of polymer-based flexible strain sensor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6079277A (en) * | 1997-12-12 | 2000-06-27 | The Research Foundation Of State University Of New York | Methods and sensors for detecting strain and stress |
| US6276214B1 (en) * | 1997-12-26 | 2001-08-21 | Toyoaki Kimura | Strain sensor functioned with conductive particle-polymer composites |
| EP1135667A1 (en) * | 1998-08-26 | 2001-09-26 | The Board Of Governors For Higher Education State Of Rhode Island And Providence Plantations | Thin film strain sensors based on interferometric optical measurements |
| JP2004527880A (en) * | 2001-01-23 | 2004-09-09 | クァンタム ポリマー テクノロジーズ インコーポレイテッド | Conductive polymer materials and methods of making and using them |
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2006
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