CN1149588C - polymer composition - Google Patents
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- CN1149588C CN1149588C CNB998031917A CN99803191A CN1149588C CN 1149588 C CN1149588 C CN 1149588C CN B998031917 A CNB998031917 A CN B998031917A CN 99803191 A CN99803191 A CN 99803191A CN 1149588 C CN1149588 C CN 1149588C
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- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
- H01C7/027—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient consisting of conducting or semi-conducting material dispersed in a non-conductive organic material
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Abstract
一种聚合物组合物包含至少一种基本不导电的聚合物和至少一种导电性填料并且是颗粒的形式，颗粒尺寸范围优选最大1mm并更优选0.04mm～0.2mm，导体对聚合物的体积比优选范围3∶1～15∶1。
A polymer composition comprises at least one substantially non-conductive polymer and at least one conductive filler and is in the form of particles, the particle size preferably ranging up to 1 mm and more preferably 0.04 mm to 0.2 mm, the volume ratio of conductor to polymer preferably ranging from 3:1 to 15:1.
Description
The present invention relates to a kind of polymer composition that comprises the fine-powdered conductor, particularly comprise this based composition of suitable physical form.
The existing device that is used to control or cut off electric current of this based composition, avoiding or to reduce such as the danger that produces transition effect and sparkover, this is that the standard machinery switch starting causes.
Especially, on January 23rd, 1998 is co-pending application PCT/GB98/00206 and follow-up open sequence number WO98/33193 thereof simultaneously, discloses this based composition and based on its switch.This application discloses the particulate composition that contains polymer and electroconductive stuffing for the first time.Present patent application relates to the polymer composition of this form and to its further improvement.
DE-A-4315382, be equivalent to US-A-5589222, the hydrophobicity flow particles is wherein disclosed, the hydrophobic organopolysiloxane that comprises hydrophilic inorganic powder and 0.03-15wt%, its production method is also disclosed, be by in granulator, powder being mixed with the aqueous emulsion of organopolysiloxane, and dry at elevated temperatures products therefrom.Metal and alloy are arranged in listed powder.But this particle can be used for enamelled wire; Do not have to disclose they can form circuit a part or, in addition, they are electric insulation when static state, and can conduct electricity when imposing mechanical stress or electrostatic charge.
According to the present invention, a kind of particle with the maximum 1mm of particle size range is provided, comprise at least a nonconducting substantially polymer and at least a electroconductive stuffing particle, wherein this filler is selected from the electroconductive oxide of granulated metal element and alloy, described element and alloy, it is characterized in that described electroconductive stuffing particle has structure dendroid, fibril or elongated, thereby described particle is electric insulation when being in static state, but can conduct electricity when imposing mechanical stress or electrostatic charge.
The typical size range of particle is maximum 1mm, preferably 0.04～0.2mm.Therefore smaller particles plays the effect of powder.If not the sphere of rule, this scope from the bigger diameter of particle after measured.For satisfying user's demand, particle be such as being approximate Poisson distribution of sizes, perhaps sieve into asymmetric distribution or narrow distribution (be no more than smallest particles 2 times) such as the largest particles thus or carry out classification granule be filled in the space between larger particles.
In granule interior, conductor: (deposit: volume ratio nonporous solid) was at least 3: 1 polymer aptly.For the ratio of conductive medium and polymer, need to do change slightly so that its relative surface tension of the polymer of all kinds and grade produces the difference that difference also has the surface energy of different electroconductive oxides and contained other solid.The change of this ratio is influential to piezoelectric property, overall impedance scope, magnetic hysteresis answer and the pressure sensibility of particle.
Usually, conductive material may be one or more metals, other conductivity or semiconductive element and oxide, or the organic or inorganic polymer of conductivity own or semiconductor property.Therefore be selected from metallic element or its conductivity alloy of powder type aptly or go back the ortho states oxide, independent or sharedly all can.More particularly it is one or more of titanium, tantalum, zirconium, vanadium, niobium, hafnium, aluminium, silicon, tin, chromium, molybdenum, tungsten, lead, magnesium, beryllium, iron, cobalt, nickel, platinum, palladium, osmium, iridium, rhenium, technetium, rhodium, ruthenium, gold, silver, cadmium, copper, zinc, germanium, arsenic, antimony, bismuth, boron, scandium and group of the lanthanides and actinide metals.Electroconductive stuffing can be the pure element of non-oxidation state; It perhaps may be a layer that is on powder, particle, fibril or other shape carrier core.Oxide may be the mixture that comprises the oxo-compound sintered powder.Alloy may be such as being titanium diboride.
The microstructure of electroconductive particle is quite important.Therefore proof tree conductive material dendritic, fibrous and elongated shape can produce responsive especially particle when applying with polymer such as organosilicon etc.Usually, the surface of electroconductive particle becomes coarse because forming the existence of the littler and elongated powder of sensitive particles more.Preferred particle comprises the metal that possesses one of these characteristics at least:
(i) elongated and/or dendritic surface pattern;
(ii) filament structure, the chain three-dimensional network that has elongated ball to constitute, the cross section of chain is that 2.5～3.5 μ m grow possibly above 15～20 μ m on average.
These characteristics generally be electroconductive particle with polymer mixed before possess, and to control mixed process so that keep it fully.
As further described below, preferred electroconductive particle comprises from carbonyl derives and next metallic nickel.Other example comprises dendroid copper.
The polymer composition of particle can be selected from very wide material scope, all is that mobile performance is enough to be fit to introduce the just passable of electroconductive particle as long as can guarantee resulting polymer or its precursor.Under an opposite extreme situations, can be the resin that solidifies wholly or in part, such as formaldehyde condensation products, epoxy resin, maleimide resin or three-dimensional olefin resin.Use more generally flexible polymer such as the line style thermoplastic.Very the suitable polymer blend composition is an elastomer.Because elastomer is preferred in some comprises the complex of particle, below can be further described with regard to it.
The invention provides a kind of by electroconductive particle mixes the method for making particle under the particle condition with liquid polymer becoming.Liquid polymer is such as being in the granulating subprocess or the precursor of polymerization or cross-linking reaction taking place afterwards.Liquid state refers to mobile performance to be enough to realize and the mixing of electroconductive particle.Polymer can be unusual thickness.May contain a kind of liquid to change the viscosity of polymer, as mixed aid.Such as can be by adding with polymer or electroconductive powder premixed.This liquid certainly must be with respect to conductor and polymer chemistry inertia.Preferably volatile, the boiling point under its atmospheric pressure is lower than 120 ℃ in other words, is convenient to remove after the mixed process neutralization.Hydro carbons such as petroleum distillate are very suitable.Before mixing or therebetween, can add a kind of water-repelling agent.It is believed that and can play from constituents of a mixture such as electroconductive particle, following solid additive, particularly aerosil, also may be the effect that replaces adsorbed water from the polymer that newly exposes and the new particle surface that forms.This reagent also plays the effect of lubricant, has reduced the friction to the mixer surface.Because it can be by forming as thin as a wafer, in addition monolayer and working, thereby institute's expense is just considerably less, such as the 10～1000ppm w/w that accounts for mixture.The example of this reagent be with group can promote liquid hydrocarbon and fluorocarbons to metallochemistry absorption.
The manufacture method of particle is, with a kind of controlled mixed form polymeric layer is coated on the electroconductive particle, constituents of a mixture only applied the additional force that is enough to finish the power of coating processes and avoids finding final polymer composition electrical property is diminished.Relation between filler, adhesive, mixed tensor, time, shear rate, temperature and pressure determines final particle grain size distribution and electromechanical performance.As if electroconductive particle also plays into the effect of granular core.Mixed process is preferably carried out under low-shearing force, so that electroconductive particle can keep the integrality of its structure.Can adopt pan-type pelletizer, blunger, coaxial circles cartridge type mixer (rotation fretting corrosion type) aptly.In the granulating process, total shearing force as if identical with the order of magnitude in the body composition manufacture process but when implementing intensity higher and the time is shorter.
Become the particle process preferably to accompany by polymer cross-linking reaction to a certain degree.The prescription of selective polymer is control mixing condition also, and is synchronous with the cross-linking reaction that is enough to form the required polymer of non-sticky state so that mixture is ground into particle.Suitable especially is to adopt the RTV organosilicon.If necessary, can control to make the precursor of particle technology, wherein polymer can be further through crosslinked to give its elasticity.The manufacturing that this type of precursor has more been widened in the organosilyl application of HTV.Very suitable is to shrink bigger organosilicon in the cross-linking process, such as 10～20%.This makes that improve conductor in the particle greatly becomes possibility to the volume ratio of polymer, and can not run into the trouble of height ratio when beginning to mix.
If the organosilicon content in the raising mixture, susceptibility descend and the aggravation clustering phenomena.Organosilicon content if desired is higher, organosilicon can be administered on the lower particle of previously prepared organosilicon content.In rotation fretting corrosion process, adjust pestle to the gap length of mortar and the pressure that pestle is executed, to reach required condition by mechanical means.Pressure is influential and be important to final size and each intergranular aggregation extent of coating layer thickness, particle to the time that reaches graininess and consume.Pressure is crossed the shearing force of damaging property of conference.
The particle that obtains can be pulverized, to reach required scope.If necessary, can sieve to isolate the different aggregation of size.The sensitiveness that particle showed that size is different is also different; Separate each particle size and mix once more, to change the final sensitiveness of particulate composition by different proportion.Also find before forming agglomeration of particles/coating processes, to mix different conductive material and conductivity, semiconductive or insulating properties powder, thereby obtain required electric conductivity or other electric and mechanical performance with final particle form.
The present invention also provides a kind of complex that comprises particle.The application form of particle generally is, is included in the device, it can't be rolled but can import electric or mechanical pressure makes its activation.It can mix with other body or foamable polymer or apply thereon to form solid, half flexible or flexible complex structure.A kind of structure type is that particle can be extruded or be compressed into the form of lamellar body, pill or fiber or be cast into molded.Can carry out mastication or deep cooling in forming process pulverizes.But the energy that the polymer composition of its uncured state is granted in mixing and moulding process may influence the physics and the electric property of complex.
Second type complex is that particle links to each other with a kind of appearance carrier (containing means).It may be such as the fiber of polymer fiber film, plate or fabric or lamellar body and may have particle on the surface, one or both sides.The polymer lamellar body may contain or have such as examining the electroconductive particle described in the embodiment 7 that applies for jointly.Lamellar body can comprise or have the adhesive that is suitable for particle.
Form in the method for this type of complex at another, particle-precursors (above-mentioned) can be pressed on the one or more surfaces of still uncrosslinked carrier polymer and when it is crosslinked and for good and all be bonded on the carrier polymer.This can form a pressure-sensitive or EM screening layer on carrier polymer.
The complex of the third type is that particle links to each other with a kind of three dimensional matrix.Though matrix may be non-conductive, such as can constituting, such as examining described in application or the existing open source literature common by the polymer that wherein is dispersed with electroconductive particle.This type has several possible versions, such as:
The particle of the conduction respectively that (i) adds, non-conductive or mixed type;
(ii) different base matters with the particulate polymers degree of cross linking;
(iii) base matter can enter gap between particles or may be a packaging bag.
In a particular of the third type, wherein polymer composition may be the common body form described in the application or preferred with following particle form introducing of examining:
Be used to take place at one, in the middle of the complex structure of detection and deferred telegram subsignal, realized inner connection,, particularly be coated with the continuous web of metal, typically polyester-based such as layer of metal film or sheet etc. with the form of monolithic conductive parts.Effect by strain being played the hard fibre base wad and between the inherent low resistance of complex zone, form an electron bridge, thereby fabric has improved the tactile sensativity (relative supporting power, the reduction amplitude of resistance increases) of conductive polymer composition.Polymer composition can bond to or be molded on the conductive component.
Though complex may be a kind of simple Devices that is used to open when distortion, such as can in the layer of the fabric construction that is coated with metal, going out more complicated circuit by the group structure.Can metal be administered on the woven by evaporation deposition method, metallikon or similar approach, typically to produce the fabric that scribbles metal.
Similar with etching on common printed circuit board, the method for making circuit be, covers and etching is coated with the fabric of metal in advance or preferably covers target fabric at the point that is coated with metal with mask with mask.
In follow-up application examples, metal coating only is deposited on the position of mask permission and forms the circuit structure of conduction through technology thus.
The complex that comprises the circuit fabric shows real flexibility, be solid-state and can make its to touch or other active force quite responsive.Can be used for numeral and analog switch and control, can possess PTC load regulation or calorific capacity, and can carry basic current.
No matter from the angle of which kind of type complex, useful especiallyly then comprise particle and comprise and import the utensil that electric power and/or mechanical deformation make its activation.Therefore lamellar body or matrix may comprise the ohmic conductor that conductivity connects the particle assembly.
Particle also can match separately or with other powder, particle or other insulating properties, semiconductive or conductive material, as the conduction component of other conductivity and electromagnetic shielding material.
The surface of particulate is responsive especially to institute's applied pressure, along with the increase pressure sensitiveness of surperficial load-bearing also improves.Imposing 0.01～6N/cm
2During the power of scope, its resistance of the surface of particle itself and particulate has reduced to surpass 10
12Ω.
No matter what make is the complex of which kind of type, when group structure particle assembly, preferably contain a kind of above-mentioned water-repelling agent.
Compare with resulting body pressure-sensitive polymer composition in the follow-up careful jointly application, contain the particle of film or multiphase mixture form, together with the complex of other polymer and material, it is linear that the variation that demonstrates higher reliability, sensitiveness and impedance easily more becomes.Similar with body composition, particle recovers its quiet impedance state when active force is eliminated.
For particle and/or matrix (particularly conductivity type), optimum polymer composition is an elastomer, and its performance is generally especially:
I) surface energy is low, and typical range is 15～50dyne/cm, particularly 22～30dyne/cm;
Ii) having hardened elastomeric wetting surface can be than uncured liquid height;
Iii) energy of rotation low (approximate zero) is then flexible high;
Iv) filler grain and the electronic contact for the treatment of bonding complex are demonstrated excellent pressure sensitive adhesive-in other words, with time period at the same level bonding time (part second) in, have higher viscoelastic ratio;
V) the triboelectric series row are high, are positive charge carrier (on the contrary, not electronegative on the surface);
Vi) chemical inertness, fire prevention and can effectively prevent entering of block and air.
The organosilicone elastic body rubber is typically but is not unique polymer based on dimethyl silicone polymer, polysilazane and similar organosilicon skeleton, leaving group, crosslinking agent and curing system based on:
Leaving group crosslinking agent curing system
HOC (O) CH
3CH
3Si[OC (O) CH
3]
3Acetic acid
HOCH
3CH
3Si (OCH
3)
3Alcohol
HONC (CH
3) (C
2H
5) CH
3Si[ONC (CH
3) C
2H
5]
3Oxime
CH
3C (O) CH
3CH
3Si[CH
2C (O) CH
3]
3Acetone
Satisfy all above-mentioned performance index.Elastomer can be a mixture, comprises the curing elastomer that is selected from a kind of, two or more organosilicon components, a kind of, two or more germanium polymer and poly-phosphine piperazine component and at least a organosilicon reagent.In the middle of this base polymer mixture, the organosilicon component is more than other polymeric components.
Other additive is that organosilicon is desired, in order to improve physics uncured or cured polymer compositions and/or electric property.This class additive can comprise at least a modifier, is selected from the modifier of alkyl and hydroxy alkyl cellulose, carboxymethyl cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, polyacrylamide, polyethylene glycol, poly-(oxygen ethene), polyvinyl alcohol, PVP, starch and modifier, calcium carbonate, pyrogenic silica, silicon gel and silicone based material and at least a silica species or silicone based material.Pyrogenic silica is an example of modifier, is usually used in the elastomer industrial.For the present invention, account for 0.01～20wt% of final polymer composition, its role strengthens elastic filler exactly, in other words, it has improved the elasticity of polymer composition, accelerates composition and reply its static speed after removing any power of executing.The example manufacturing of a preferred organosilicon system is from high-strength cold curing (RTV) the type organosilicon polymer that is filled with pyrogenic silica.Another example adopts hot setting HTV type silicon rubber, thereby fill with pyrogenic silica and to give its calking type structure, usable intensity, pressure viscosity and long-life, the typical case but be not limited to peroxidating 2, take place down crosslinked in high temperature under the peroxide of 4-dichloro dibenzoyl or the existence of other catalyst.This class HTV goods can be with its uncured state long storage time before being processed into lamellar body, bar, foam, fiber, compression molding thing or other form.
Another kind of useful elastomer is natural or the synthetic method hydrocarbon rubbers.Particularly for basis material, this class rubber may be introduced with the form of latex.
Final complex may demonstrate piezoelectric effect and can both react and change its intrinsic resistance pressure and deformation force.The effective resistance scope is 10
12～10
-1Ω and complex have excellent current capacity; Typically, the complex sample that 2mm is thick on the radiator can be controlled 3A/cm
2Interchange or direct current.The complex sample of high impedance is pressed or during power, the result can generate electrostatic charge at first; Increase pressure or power can reduce the resistance of complex.Complex is flexible and can reinstatement when power of removing or pressure.Meanwhile, resistance increases and can bring out a large amount of electrostatic charges towards the direction of quiescent value.This electrostatic effect can play the effect of digital switch indication or be used for making voltage source.Changes in resistance can be used for simulating institute's applied pressure or power.In addition, can utilize changes in resistance to make digital switch, especially but always be not in its upper and lower limit.Generate and, the responsive type complex that is easy to conduct electricity can be changed system into the state of complete conducting by imposing typically greater than the electrostatic charge of 0.5kV by pressure electric spark maker.
Complex can be made of the particle that is contained in the matrix.In granule interior, the particle size distribution of electroconductive particle will reach a kind of structure closely, and filling is all wanted in the particle gap.Contained space is closely adjacent and be fixed up in solidification process with elastomer filling and conductive particle gradually in mixed process in the conductor powder body.In order to form this array of structures, elastomeric surface energy liquid its surface energy mutually low and more uncured than powder can be low than the surface of elastomer that solidifies.This polymer compositions may comprise organosilicon, germanium polymer and poly-phosphine piperazine.Under stress, deform, thereby average contained distance reduces between particle.For metallic, this is equivalent to improve conductivity, for the particle of other type, may produce other effect (variations of ferromagnetism, piezoelectricity, the ion guide general character etc.).
For being in not stressed filling to transition stage between stress for the composition of metal, body conductivity can be changed to the conductive particle that is mingled with from elastomeric value.Under certain degree of deformation, the number in grain-intergranular open circuit district can cause conductivity approaching to the body resistance value of metal.Because this effect finally relates to the distortion of body complex, and because thereby the elasticity of bulk material is very high and absorb energy, faint " metal " conduction only is applicable to weak part (width is less than 2mm) or the external stress that is applied, strain or the distortion condition with higher of complex material.Material recovers its original structure when removing external force, and the particle that is mingled with is come by separate in elastic insulated network whereby.
Surprisingly, the particle assembly can carry obvious electric current.The conductor of present 2 * 2cm can carry the continuous load of maximum 30A when being in compressive state.Explanation to this special performance is mainly to realize conducting by above-mentioned metal bridge during compressive state.Therefore will explain the conducting phenomenon, preferably state material as multiphase mixture, insulating properties glue envelope owner kills its electric property when wherein static; And in compressive state ((local electrical resistance is near the numerical value of conductor, is typically the state of 1～1000 μ Ω-cm) to be tending towards conducting bridge when typically this volume resistance is greater than 1M Ω-cm).Because glue envelope thing has the acting in opposition of holding back negative " electronics " electric charge (the desirable typically friction positive charge carrier of glue envelope thing), electronic conductivity further only limits to electroconductive stuffing.For certain composition, the statistical probability of Cheng Qiao is directly relevant with the thickness of complex.Therefore all with the reducing and increase of thickness, minimum thickness is by the distribution of sizes decision of filler for deformation sensitive and current capacity.With regard to following mixture, its filler size distributes typically thickness limits at＞10-40 μ m.
By in elastomer silicone, granule interior and/or between introduce zirconium particle (or other ion guide general character material), complex just might have electronics concurrently and in the presence of gaseous oxygen, the oxonium ion conduction.By the stress (such as introduce static state or external resonance stress grid in body composition) of control bulk material, the conduction of electronics and oxygen will show at the not ipsilateral or the different parts place of body construction.This class performance is a particular importance for the design of fuel cell system.Find that also the heating of inner face ohm can influence the internal structure of complex.Therefore such as in the middle of the assorted composition that has electroconductive stuffing nickel, RTV silicon rubber glue to seal thing and the agent of pyrogenic silica framework modification of bag, finding, the percentage that the coefficient of expansion differed of glue envelope thing and conductor is very big (typically, glue envelope thing expands fast 14 times than conductor) to such an extent as to be enough to cause ohm to generate heat in heavy current through out-of-date, the difference of the coefficient of expansion has changed the variation pattern of impedance with stress/strain.(typically less than 100 ℃) may take place in this phenomenon under the less situation of differential temperature.Can utilize this effect (positive temperature coefficient [PTC] of bringing out impedance in mutually at complex) to be used to regulate electric current easily.Can be by increasing or reduce mechanical pressure on the polymer composition to regulate and control PTC and whether occur.In addition, the composition of resistance lower (typically＜100 Ω) during for static state is by the PTC effect conversion ohm heating between conducting slightly or in the composition of not exerting pressure and state of insulation.This effect makes polymer composition can be used as switch or the fuse that can respond overcurrent and switch to high impedance status fast, so and because its this genus elasticity need not to cut off the power supply when electric current recovers rated value just can recover its conduction state.The PTC effect also can be used in the self-regulating heater element, and the method for wherein adjusting temperature is, applies mechanical pressure and makes polymer composition always near its PTC point under temperature required.By the PTC phase of coming in and going out repeatedly, polymer composition just can keep the temperature of quite stable.The temperature resistant capability of composition is strong and thermal conductivity good.
Nickel powder of the present invention is INCO 287 types, and its performance is as follows: the bead average cross-section is 2.5～3.5 μ m; Chain length is greater than 15～20 μ m.It is a fibrous powder, constitutes the surface area height by the three-dimensional chain-shaped network of elongated beads.Structure adapts therewith, and its bulk density is 0.75～0.95g/cm
3
Nearly all particle size preferably has 75%w/w at least in the scope of 4.7～53 μ m all less than 100 μ m.
In certain embodiments, particle size distribution (the μ m of unit and represent with wt%) following (representing with circular %): 2.4-3%, 3.4-5%, 4.7-7%, 6.7-10%, 9.4-11%, 13.5-12%, 19-15%, 26.5-15%, 37.5-11%, 53-8%, 75-4%, 107-are lower than 1%.
Also make other useful nickel powder by carbonyl technology for the present invention:
123 bulk density 1.6-2.6g/cm
2Deng shape shaft, elongated irregular table
Type: face; Account for 96% below the 100 μ m;
210 apparent densities are less than 0.5g/cm
2The fibrous powder average grain diameter is
Type: 0.5-1.0 μ m;
255 bulk density 0.5-0.65g/cm
2Fibrous powder is by cross section
Type: the three-dimensional chain-shaped network that the elongated beads of 2-3 μ m constitutes; Chain length
20-25 μ m; 100 μ m account for 91%.
Above-mentioned data referencing is from the special pulverulent product specification of the INCO of LondonGB-SW1H OXB type.
Usually, the bulk density of electroconductive particle 1/3rd also little than its density of solid.
Composition may be useful aspect negative electrode that comprises vitochemical electrochemical cell based on lithium, manganese, nickel, cobalt, zinc, mercury, silver or other battery chemistries or the anode group structure.Single or two electrodes can both replace with polymer composition or through its coating, demonstrate following advantage:
(i) battery can be introduced self integral pressure switch, operates such as locating general required pressure in the battery pack lattice by battery.Can reduce or eliminate the self discharge or the short circuit phenomenon of battery whereby, battery then is in stressless stand-by state;
(ii) the integral pressure switch can be simplified circuit design and be convenient to start new purposes because need not outer switch;
(iii), might produce overall plastic electrochemical cell because polymer composition can manufacture not containing metal.
The pressure-sensitive polymer composition also can not participated in the chemical reaction of battery directly, but obtains on shell by composition being installed in electrode or the non-reacted surface to use.Just can start the polymer composition switch by adding mechanical pressure such as finger pressure or from the spring pressure of battery pack lattice inside.This just forms a switch in order to the control external circuit, comprises the battery pack checking circuit.
Other purposes of composition comprises:
Mechanical transducer, relatively and absolute type all can, in order to gaging pressure, load-bearing, displacement, distortion, elongation, quality and stereomutation, acceleration, flow, fluctuate and other variation that causes by machinery.
Current converter.
Electromagnetic transducer.
Heat converter.
Magnetostrictor.
Magnetoresistance device.
The magnetic resonance device.
Survey and quantize the local motion of body part and organ.
The detection of sound wave and generation.
Relay contact and joint.
The lead of microdevice and inductor.
Temperature control.
Electromagnetic wave shielding.
Electric current and voltage protector.
Switch.
Electric power control.
Fig. 1 (a) and 1 (b) are legends, represent that particle of the present invention is exert pressure shifting gears/dependence of impedance down.
The particle manufacturing from:
INCO nickel powder 287 28g
2000 type ALFAS already use RTV organic
Silicon 4g
Magma shape organosilicon is placed on the bottom of the electronic mixer of RETSCH RM100 type of being furnished with steel motor and pottery rotation pestle.Nickel powder be placed on organic silico briquette around.Through manual control pestle is transferred to the position of the distance mortar wall about 1mm in gap.Machine imposes the rotation fretting corrosion to mixture.Behind about 5min, organosilicon is coated on the nickel shot and through this step and separates into the following particle of particle size distribution %w/w, the μ m of unit:
Grain size grading %w/w
+152 32
152～75 33
75～45 32
-45 less than 3
Become the end of particle process to show from the change of mixture color and lines.In mixed process, organosilyl cross-linking reaction produces the acetic acid flavor; If necessary, can further prolong this process, but when particle forms already or stop immediately afterwards mixing, with the danger of avoiding shearing force that the particulate form nickel particles is damaged.
Particle when static be nonconducting but to exert pressure very responsive.
Repeat the step of embodiment 1, adopt:
The industrial RTV of 1000 type ALFAS is organic
Silicon 6g
INCO nickel powder 287 30g
Though this nickel: polymer ratio is lower than embodiment 1, and the degree that used organosilicon characteristic in cross-linking process is shunk finally provides is the particle with regard to the tool conductive capability of not exerting pressure.Why shrink seemingly because the cause that volatile components loses in cross-linking process.ALFAS 1000 contains 12% volatile materials.ALFAS 2000 contains 4% volatile materials.
This class particle is such as being specially adapted to conductive adhesive, EM shielding and PTC device.
Conductor example based on particle:
The manufacturing of conductor sample is, the particulate samples of embodiment 1 preparation is packed in the test cell, and it is by a diameter 12mm, thick 3mm and have the silicone sponge packing ring in a diameter 6mm hole to constitute, and is placed on the conductive surface as low position electrode.The conductivity pole plate is placed on the packing ring top and goes up to form high potential electrode.Electrode is connected on Picoscope ADC100 signal processor and the recorder via the 10V power supply of a constant current and the high impedance buffer amplifier of a 20M Ω.For the power that makes test is applied on the test cell, place it on the platform of load test equipment, promptly being furnished with range is the Lloyd Instruments LRX of the power analyzer of 100N.Slowly rising is applied to the pressure on the battery and writes down impedance and demonstrate image with signal processor.Test by two current gears:
Fig. 1 (a) 10mA (impedance Ω * 10
2) and Fig. 1 (b) 1mA (impedance Ω * 10
6).
These figure wherein map to the time with load-bearing and impedance, show the increase along with pressure, and the impedance of particle reduces and electrical potential difference (PD) is changed along battery in the battery.
The non-ohmic conductor example:
The test cell of embodiment 3 compresses with the static load-bearing of about 3N, and flowing through the electric current of 10mA in the test cell and calculating its impedance from potential difference (PD) is 100K Ω.Sustaining voltage and the pressure of being executed are constant, and electric current increases to 100mA.The PD that record this moment shows that the impedance of battery has been reduced to 50K Ω.
INCO nickel powder 287 30g
Dow Corning HTV organosilicon (20 Xiao
You) 6g
Oil below 50 ℃ (light fuel oil) 2g
Become the particle process to finish behind the 5min, this process PetroChina Company Limited. evaporate fully and organosilicon fully (but not exclusively) crosslinked.By make particle fully crosslinked and at 120 ℃ of heating 20min subsequently by embodiment 3 and 4 described tests.
The particle of embodiment 1 preparation is performed as follows preparation:
45-75 μ m level part 0.225g
75-152 μ m level part 0.225g
25% water of hexadecyltrimethylammonium chloride
Solution 0.1g
Natural rubber latex (60%w/w) 0.12g
Water 0.15g
The composition of mixing except that latex is to form lotion.Add latex and further the mixing to form gel.Gel is divided into two parts also to be administered to through an ornamental engraving plate:
(a) be coated with copper the polyimides printed circuit and
(b) be coated with on the polyester textile printed circuit of nickel.
The structure that obtains is in 80-90 ℃ of dry 30min, perhaps until drying.
Adopt dodecyl benzene sulfonate to replace hexadecyltrimethylammonium chloride to obtain similar result.
Claims (11)
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/GB1998/000206 WO1998033193A1 (en) | 1997-01-25 | 1998-01-23 | Polymer composition |
| GBPCT/GB98/00206 | 1998-01-23 | ||
| GB9806623.6 | 1998-03-28 | ||
| GBGB9806623.6A GB9806623D0 (en) | 1998-03-28 | 1998-03-28 | Conductive structures within conductive polymerse |
| GBGB9814131.0A GB9814131D0 (en) | 1998-06-30 | 1998-06-30 | Polymeric sensing materials |
| GB9814131.0 | 1998-06-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1291338A CN1291338A (en) | 2001-04-11 |
| CN1149588C true CN1149588C (en) | 2004-05-12 |
Family
ID=27269164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998031917A Expired - Lifetime CN1149588C (en) | 1998-01-23 | 1999-01-21 | polymer composition |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1050054B1 (en) |
| JP (1) | JP2002501949A (en) |
| CN (1) | CN1149588C (en) |
| AU (1) | AU2176899A (en) |
| CA (1) | CA2318742A1 (en) |
| WO (1) | WO1999038173A1 (en) |
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| TWI576588B (en) * | 2011-11-29 | 2017-04-01 | 佛姆費克特股份有限公司 | Hybrid electrical contactor |
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| EP2649439B1 (en) | 2010-12-08 | 2019-09-11 | Condalign AS | Method for assembling conductive particles into conductive pathways |
| GB201105025D0 (en) | 2011-03-25 | 2011-05-11 | Peratech Ltd | Electrically responsive composite material |
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| ES2485617B1 (en) * | 2013-09-16 | 2015-04-06 | Sensing Tex, S.L. | Piezo-resistive textile sensor and heart and / or respiratory rhythm detection system |
| US10935445B2 (en) | 2017-01-04 | 2021-03-02 | Mas Innovation (Private) Limited | Wearable touch button assembly |
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| CN110894359B (en) * | 2019-12-05 | 2022-02-18 | 中国电子科技集团公司第三十三研究所 | Sponge type directional conductive rubber and preparation method thereof |
| DE102020213275A1 (en) * | 2020-10-21 | 2022-04-21 | Robert Bosch Gesellschaft mit beschränkter Haftung | Process for the production of an electrically conductive composite material, use of an electrically conductive composite material for the production of a heating element, heating element |
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| JPS565840A (en) * | 1979-06-28 | 1981-01-21 | Shin Etsu Polymer Co Ltd | Anisotropic pressure electrically-conductive elastomer molded article |
| JPS5998164A (en) * | 1982-11-26 | 1984-06-06 | Toshiba Silicone Co Ltd | Pressure-sensitive electrically conductive silicone rubber composition |
| ATE103095T1 (en) * | 1986-01-14 | 1994-04-15 | Raychem Corp | CONDUCTIVE POLYMER COMPOSITION. |
| JPS63215745A (en) * | 1987-03-04 | 1988-09-08 | Toshiba Silicone Co Ltd | Pressure-sensitive electroconductive elastomer composition |
| JPH01213362A (en) * | 1987-05-25 | 1989-08-28 | Shin Etsu Chem Co Ltd | Silicone rubber composition |
| JPH0581924A (en) * | 1991-09-20 | 1993-04-02 | Asahi Chem Ind Co Ltd | Electric conductive rubber |
| IT1254974B (en) * | 1992-06-18 | 1995-10-11 | Bayer Italia Spa | COMPOSITE, SLIDING, HYDROPHOBIC GRANULATES, A PROCEDURE FOR THEIR PREPARATION AND THEIR USE |
| US5591382A (en) * | 1993-03-31 | 1997-01-07 | Hyperion Catalysis International Inc. | High strength conductive polymers |
-
1999
- 1999-01-21 CN CNB998031917A patent/CN1149588C/en not_active Expired - Lifetime
- 1999-01-21 WO PCT/GB1999/000205 patent/WO1999038173A1/en not_active Ceased
- 1999-01-21 CA CA002318742A patent/CA2318742A1/en not_active Abandoned
- 1999-01-21 EP EP99901767A patent/EP1050054B1/en not_active Expired - Lifetime
- 1999-01-21 JP JP2000528985A patent/JP2002501949A/en active Pending
- 1999-01-21 AU AU21768/99A patent/AU2176899A/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI576588B (en) * | 2011-11-29 | 2017-04-01 | 佛姆費克特股份有限公司 | Hybrid electrical contactor |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1999038173A1 (en) | 1999-07-29 |
| AU2176899A (en) | 1999-08-09 |
| JP2002501949A (en) | 2002-01-22 |
| CA2318742A1 (en) | 1999-07-29 |
| EP1050054A1 (en) | 2000-11-08 |
| EP1050054B1 (en) | 2007-03-07 |
| CN1291338A (en) | 2001-04-11 |
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| GR01 | Patent grant | ||
| CI01 | Publication of corrected invention patent application |
Correction item: Priority Correct: 1998.01.23 GB PCT/GB98/00206|1998.03.28 GB 9806623.6|1998.06.30 GB 9814131.0 False: 1998.01.23 GB PCT/GB98/00206 Number: 19 Page: 490 Volume: 20 |
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| CI03 | Correction of invention patent |
Correction item: Priority Correct: 1998.01.23 GB PCT/GB98/00206|1998.03.28 GB 9806623.6|1998.06.30 GB 9814131.0 False: 1998.01.23 GB PCT/GB98/00206 Number: 19 Page: The title page Volume: 20 |
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Free format text: CORRECT: PRIORITY; FROM: 1998.1.23 GB PCT/GB98/00206 TO: 1998.1.23 GB PCT/GB98/00206 1998.3.28 GB 9806623.6 1998.6.30 GB 9814131.0 |
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Free format text: CORRECT: PRIORITY; FROM: 1998.1.23 GB PCT/GB98/00206 TO: 1998.1.23 GB PCT/GB98/00206 1998.3.28 GB 9806623.6 1998.6.30 GB 9814131.0 |
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| C41 | Transfer of patent application or patent right or utility model | ||
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Effective date of registration: 20160311 Address after: Richmond City, England Patentee after: Pera Taco Holdings Ltd Address before: British Darlington Patentee before: Peratech Ltd. |
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| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20040512 |