EP1050054B1 - Composition polymere - Google Patents

Composition polymere Download PDF

Info

Publication number
EP1050054B1
EP1050054B1 EP99901767A EP99901767A EP1050054B1 EP 1050054 B1 EP1050054 B1 EP 1050054B1 EP 99901767 A EP99901767 A EP 99901767A EP 99901767 A EP99901767 A EP 99901767A EP 1050054 B1 EP1050054 B1 EP 1050054B1
Authority
EP
European Patent Office
Prior art keywords
granules
polymer
composite
conductive
electrically conductive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99901767A
Other languages
German (de)
English (en)
Other versions
EP1050054A1 (fr
Inventor
David Lussey
Andrew Brian King
Christopher John Lussey
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Peratech Ltd
Original Assignee
Peratech Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/GB1998/000206 external-priority patent/WO1998033193A1/fr
Priority claimed from GBGB9806623.6A external-priority patent/GB9806623D0/en
Priority claimed from GBGB9814131.0A external-priority patent/GB9814131D0/en
Application filed by Peratech Ltd filed Critical Peratech Ltd
Publication of EP1050054A1 publication Critical patent/EP1050054A1/fr
Application granted granted Critical
Publication of EP1050054B1 publication Critical patent/EP1050054B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • 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

Definitions

  • This invention relates to a polymer composition including a finely divided electrical conductor, particularly comprising such a composition in an advantageous physical form.
  • hydrophobic flowable granules comprising hydrophilic inorganic powder and 0.03 to 15% w/w of hydrophobic polyorganosiloxan and a process of producing them by mixing the powder in a granulator with an aqueous emulsion of the polyorganosiloxan and drying the resulting product at elevated temperature.
  • powders listed are metals and alloys.
  • the granules are, however, for use in enamelling; there is no disclosure that they might form part of an electrical circuit or, further, that they could be electrically insulating when quiescent but conducting when subject to mechanical stress or electrostatic field.
  • US-A- 5106540 discloses a composition with a matrix polymer and a particulate conductive filler distributed therein, such as carbon black.
  • a composite filler is produced by melt-extruding and then comminuting the extrudate. The composite filler is then blended with polymer to form a resistive component.
  • granules comprising at least one substantially non-conductive polymer and at least one electrically conductive filler selected from powder-form metallic elements and alloys, electrically conductive oxides of said elements and alloys, and mixtures thereof, and said electrically conductive filler has a dendritic, filamentous or spiked structure whereby said granules are electrically insulating when quiescent but conductive when subjected to mechanical stress or electrostatic charge.
  • the invention further provides a process defined by the features of claim 5, a composite defined by the features of claim 7, a composite structure defined by the features of claim 8, a use defined by the features of claim 10 and an electromagnetic shield defined by the features of claim 11.
  • the granules are typically in the size range up to 1mm, especially 0.04 to 0.2mm. Thus the smaller granules behave as powders.
  • the ranges are based on measuring the greater diameter of the granules if not regularly spherical. To suit user's requirements, the granules may be for example in an approximate Poisson size distribution, or sieved to a skewed distribution or a narrow spread (for example, largest granules no greater than 2 x smallest) or classified so that small granules fill the spaces between larger granules.
  • the conductor: polymer volumetric ratio (tapped bulk: voidless solid) is suitably at least 3:1.
  • the ratio of conductive medium to polymer small changes will be required to account for differences in relative surface tensions of types and grades of polymer and the various surface energies of the different conductive oxides and other solids present. Changes of this ratio have an effect on the piezo-charge properties, the overall resistance range, the recovery hysteresis and the pressure sensitivity of the granules.
  • the conductive material can be one or more metals, other conductive or semiconductive elements and oxides or intrinsically conductive or semiconductive organic or inorganic polymers.
  • the conductive material is suitably selected from powdered forms of the metallic elements or their electrically conductive alloys or reduced oxides either on their own or together.
  • the conducting filler can be the basic element in the unoxidised state; or can be a layer on a carrier core of powder, grains, fibres or other shaped forms.
  • the oxides can be mixtures comprising sintered powders of an oxycompound.
  • the alloy may be for example titanium diboride.
  • the micro-structure of the conductor particles is of substantial importance.
  • dendritic, filamentous, and spiked forms of the conductive materials have been shown to be capable of producing particularly sensitive granules when coated with a polymer such as silicone.
  • the conductor particles are rough-surfaced with smaller and spikier powders producing more sensitive granules.
  • the particles comprise metal having at least one of these characteristics:
  • preferred conductor particles comprise carbonyl-derived metallic nickel.
  • Other examples include dendritic copper.
  • the polymer constituent of the granules can be chosen from a wide range of materials, the only limitation being that the polymer or a precursor thereof should be available in a form sufficiently mobile to permit incorporation of conductor particles. In an extreme case it can be a fully or partly cured resin, such as a formaldehyde condensate, epoxy resin, maleimide resin or 3-dimensional olefin resin. Polymers having flexibility, such as linear thermoplasts, are of more general application. Very suitably the polymer constituent is an elastomer. Since elastomers are preferred in certain composites including the granules, they will be described further below.
  • the invention provides a method of making the granules by mixing conductor particles with liquid-form polymer in granule-forming conditions.
  • the liquid-form polymer may be, for example, a precursor subject to polymerization or to cross-linking during the granule-forming step or later.
  • Liquid-form means sufficiently flowable to undergo mixing with the conductor particles.
  • the polymer may be very viscous.
  • a liquid may be present to modify the viscosity of the polymer as an aid to mixing. It may be added, for example, by pre-mixing with the polymer or with the conductor powder.
  • the liquid should of course be chemically inert with respect to the conductor and polymer.
  • the agent is volatile, that is, has an atmospheric pressure boiling point under 120°C, to assist removal during and after mixing.
  • Hydrocarbons such as petroleum distillates
  • a hydrophobising agent Before or during mixing there may be added a hydrophobising agent. This is believed to act by displacing adsorbed water from the surfaces of the components of the mix, for example the conductor particles, solid additives such as those described below, especially fumed silica, and possibly of newly exposed polymer and newly formed granules.
  • the agent may also act as a lubricant limiting friction at mixer surfaces. Since it can act by formation of very thin, even unimolecular layers, the quantity to be used is very small, for example 10 - 1000 ppm w/w of the mix. Examples of the agent are liquid hydrocarbons carrying groups favouring chemisorption on metals, and fluorocarbons.
  • the granules are made by coating conductive particles with a layer of polymer in a controlled mixing regime that imparts only sufficient force to the components of the mix to achieve the coating process and avoids additional force which has been found to have a degrading effect on the electrical properties of the final polymer composition.
  • the relationship between filler, binder, mixing energy, time, rate of shear, temperature and pressure determine the particle size-distribution and electro-mechanical properties of the resulting granule. It appears likely that the conductor particles act as nuclei for granule formation.
  • Such mixing is preferably at a low level of shear, so that the conductor particles remain structurally intact.
  • a dish-granulator, blunger, coaxial cylinder mixer (rotary ablation) can be used.
  • the total shear can be of the same order as in the production of bulk composition but applied at greater intensity for a shorter time.
  • Granule formation is preferably accompanied by some cross-linking of the polymer.
  • the polymer formulation is chosen and the conditions of mixing are controlled so that breakage of the mixture into granules is synchronized with cross-linkage of the polymer sufficient for a non-sticky state. This is especially convenient using RTV silicone.
  • the process may if desired be controlled to produce a precursor of the granules in which the polymer may be subjected to further cross-linking to develop elastomerism.
  • Use of HTV silicone affords more scope in making such precursors.
  • the silicone very suitably is one subject to high shrinkage for example by 10 - 20% on cross-linking. This makes possible a relatively high conductor to polymer volume ratio in granules without an inconveniently high ratio at the start of mixing.
  • silicone content of the mix is increased, sensitivity is decreased and agglomeration increases.
  • silicone may be applied to previously made granules of lower silicone content.
  • This pressure affects the time taken to achieve the granulated state and is important to the coating thickness, the eventual size of the granule and the amount of agglomeration between individual granules. Too much pressure produces destructive shear forces.
  • the resulting granules can be comminuted to provide a desired range. They can be screened to separate the different sized agglomerations if required. Different sized granules show different sensitivities; granule sizes can be separated and remixed in different proportions to alter the final sensitivity of the granule composite. It has also been found possible to combine different conductive materials, conductive, semi-conductive or non-conductive powders, prior to the granule-forming agglomeration/coating process to obtain the required conduction or other electrical and mechanical properties in the final granule form.
  • the invention provides also a composite comprising the granules.
  • the granules can be used by containing them in a device which limits peripheral movement but allows the input of an electrical or mechanical pressure in order to activate it. They may be mixed with or coated onto other bulk or foamed polymers to form solid, semi-flexible or flexible composite structures.
  • the granules can be extruded or pressed into sheet, pellet or fibre form or can be cast into moulds. In the course of the shaping process they can be milled or cryogenically powdered. Energy imparted during mixing and moulding the polymer composition in the uncured state may, however, affect the physical and electrical performance of the composite.
  • the granules may be associated with a containing means.
  • a containing means may be a fibre or sheet, for example of polymer fibre film, plate or cloth and may carry granules on one or both faces.
  • the polymer sheet may already contain or carry conductor particles as described for example in Example 7 of the co-pending application.
  • the sheet may comprise or carry an adhesive for the granules.
  • precursor granules (as specified above) can be pressed into the surface or surfaces of the un-cross-linked carrier polymer and permanently bonded to the carrier polymer when it is cross-linked. This produces a pressure sensitive or EM screening layer on the carrier polymer.
  • the granules are associated with a three-dimensional matrix.
  • the matrix may be electrically non-conducting, but could be composed, for example, of polymer having conductor particles dispersed in it , such as described in the co-pending application or in prior-published documents.
  • Several variants of this type are possible, for example:
  • the polymer composition may be in bulk form as described in the co-pending application or, preferably, introduced in granule form as follows:
  • the composite may be a simple device for switching on when deformed, more complicated electrical circuits may be built into the layer, for example, of the metallised cloth structure.
  • the metal coated fabric is typically manufactured by application of metal by vapour deposition, sputtering or similar means to a woven polyester cloth.
  • Electrical circuits analogous to those etched onto a conventional printed circuit board, may be created by masking and etching the pre-metallised cloth or preferably by masking the target cloth at the point of metallisation.
  • the metal coating will only be deposited where the mask allows and by this process a conductive circuit layout can be produced.
  • Composites incorporating the circuit cloth show true flexibility, are solid state and may be made extremely sensitive to touch or other operating forces. They may be used for digital and analogue switching and control, may incorporate PTC load control or heat production capability and have the capacity to carry substantial electric currents.
  • a particularly useful one comprises the granules and includes means for the input of electrical and/or mechanical deformation to activate it.
  • the sheet or matrix would comprise ohmic conductor (s) connecting the granule assembly electrically.
  • the granules can also be used as a component of other conductive and electromagnetic shielding materials either alone or in combination with Other powders or granules or other non-conductive, semiconductive or conductive materials.
  • Granule-coated surfaces can be particularly sensitive to applied pressure, increasing in pressure sensitivity with increasing surface loading.
  • Granules on their own and granule-coated surfaces can show a drop in electrical resistance of more than 10 12 ohms with an applied force within the range 0.01 - 6 N/cm 2 .
  • Composites containing the granules as a film or heterogeneous mixture with other polymers and materials tend to show greater repeatability, sensitivity and linearity of resistance change than can be obtained with bulk pressure sensitive polymer compositions as in the co-pending application. Like the bulk composition, the granules return to a quiescent resistance state when the operating force is removed.
  • the polymer constituent is an elastomer, especially having the general properties:
  • Silicone elastomer rubbers are typically but not exclusively based on polydimethylsiloxane, polysilamine and allied silicone backbone polymers, with leaving groups, cross-linkers and cure systems based on: Leaving Group Cross Linker Cure System HOC (O) CH 3 CH 3 Si[OC(O)CH 3 ] 3 ACETIC ACID HOCH 3 CH 3 Si (OCH 3 ) 3 ALCOHOL HONC (CH 3 ) (C 2 H 5 ) CH 3 Si [ONC (CH 3 ) C 2 H 5 ] 3 OXIME CH 3 C (O) CH 3 CH 3 Si [CH 2 C (O) CH 3 ] 3 ACETONE HN (CH 3 ) C (O) C 6 H 5 CH 3 Si [N (CH 3 ) C (O) C 6 H 5 ] 3 BENZAMIDE meet all the above mentioned property criteria.
  • the elastomer can be mixtures comprising cured elastomers selected from the group comprising one, two or more component silicones, one, two or more component polygermanes and polyphosphazines and at least one silicone agent.
  • the silicone component exceeds other polymer components.
  • additives are included with the silicone for the purpose of modifying the physical and/or electrical properties of the uncured or cured polymer composition.
  • Such additives can include at least one property modifier from the group comprising: alkyl and hydroxyalkycellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyacrylamide, polyethylene glycol, poly (ethylene oxide), I polyvinyl alcohol, polyvinylpyrrolidone, starch and its modifications, calcium carbonate, fumed silica, silica gel and silicone analogues and at least one silica analogue or silicone analogue modifier. Fumed silica is an example of a modifier as commonly used in elastomer technology.
  • a silicone system is manufactured from high strength room temperature cured fumed silica loaded (RTV) silicone polymer.
  • RTV room temperature cured fumed silica loaded
  • Another example uses high temperature cured HTV silicone filled with fumed silica to provide interstitial structure, useful strength, pressure tack and life, cross-linked at an elevated temperature in the presence of a peroxide or other catalyst, that may typically but not exclusively be 2,4 dichloro dibenzoyl peroxide.
  • HTV products may be stored for prolonged periods in the uncured state prior to processing into sheet, rod, foam, fibre, press moulded or other forms.
  • Another usable class of elastomer is the natural or synthetic hydrocarbon rubbers. Especially for matrix material, such rubber may be introduced in latex form.
  • the resulting composites may display a piezo-charge affect and will change their inherent electrical resistance in response to both pressure and strain forces.
  • Working resistance is around the range 10 12 to 10 -1 ohms and the composites have excellent current carrying capability; typically a 2mm thick sample of the composite on a heat-sink can control AC or DC currents of 3A/cm 2 .
  • the initial application of pressure or force to a sample of the high-resistance composite results in the generation of an electrostatic charge; increasing the pressure or force decreases the electrical resistance of the composite.
  • the composites can be flexible and can reassert themselves when the force or pressure is removed. As this occurs the electrical resistance will increase towards a quiescent value and a pronounced electrostatic charge will develop.
  • the electrostatic effect can provide digital switching indications or provide a voltage source.
  • the electrical resistance change can provide an analogue of the applied pressure or force.
  • the resistance range can be used to provide digital switching especially but not essentially at its upper and lower limits.
  • Sensitive versions of composite which are close to conduction can be changed into a fully conducting state by applying an electrostatic charge, typically that generated by a piezoelectric spark generator and greater than 0.5kV.
  • the composite may consist of the granules held within a matrix.
  • the conductive particles are of such a size distribution as to provide for a close packed structure with interstitial particle infilling.
  • Voids present in the bulk conductor powder become infilled with elastomer during mixing and conductor particles become set in close proximity during curing.
  • the elastomer will have a low surface energy relative to the powder phase and uncured liquid surface energy less than cured elastomer surface energy.
  • Such polymer compositions will include silicones, polygermanes and polyphosphazines. In the stressed state the distortion takes place such that the average entrapped inter-particle distance decreases. For metal particles this corresponds to an increase in electrical conductivity, for other types of particle other effects may be generated (change in ferromagnetism, piezoelectricity, ionic conduction, etc.).
  • the assembly of granules is capable of carrying significant electrical current.
  • Up to 30 amps continuous load has been carried by a 2 x 2cm conductor to date when in a compressed state.
  • This unique property may be explained by the fact that in the compressed state conduction occurs principally through the metal bridges described above. So for the purpose of explaining conduction the materials are best described in terms of a heterogeneous mixture in which the insulative encapsulant dominates electrical property in the quiescent state; and tending towards that of the conductor bridges (having a local resistivity tending to that of the conductor typically 1 - 1000 microhm-cm), in the compressed state (typically having a bulk resistivity greater than 1 milliohm-cm).
  • Electron conduction is further confined to the conductor filler by the inability of the encapsulant to hold negative 'electron' charge (typically the encapsulant is the optimal positive triboelectric charge carrier).
  • the encapsulant is the optimal positive triboelectric charge carrier.
  • the statistical chance of bridge formation is directly related to composite thickness.
  • both the sensitivity to distortion and current carrying capability increase with reduction in thickness with the thinnest films limited by the filler size distribution.
  • the filler size distribution will typically limit thickness to >10 - 40 microns.
  • the composite By incorporation of zirconium particles (or other ionic conducting materials) into a silicone elastomer, within and/or between granules, the composite may be made to conduct both electrons and, in the presence of gaseous oxygen, oxygen ions.
  • control of bulk material stress for example by the incorporation of static or externally resonated 'stress grids' into the bulk composition
  • conduction of electrons and oxygen may be made to occur in different planes or different parts of the bulk structure.
  • Such properties may be of particular interest in the design of fuel cell systems. It has also been found that internal ohmic heating may affect the internal structure of the composite.
  • ohmic heating switches by virtue of the PTC effect between conducting and insulating states in a composition that is under little or no compressive force.
  • This effect allows these polymer compositions to be used as switches or fuses which switch sharply to a high resistance state in response to excess current and which, because of their elastomeric nature, will return to a conductive state without the removal of power when the current flow returns to a set value.
  • This PTC effect can also be used in self-regulating heating elements where heat levels can be set by applying mechanical pressure to keep the polymer composition close to its PTC point at the required temperature.
  • the polymer composition will maintain a relatively steady temperature by cycling in and out of the PTC phase.
  • the composition has wide temperature tolerance and good thermal conductivity.
  • a nickel powder used in the invention was INCO Type 287 which has the following properties: beads are on average 2.5 - 3.5 microns in cross-section; chains may be more than 15 - 20 microns in length. It is a filamentary powder with a three-dimensional chain-like network of spiky beads having a high surface area. Consistent with this structure its bulk density is 0.75 - 0.95 g/cm 2 .
  • the sizes of the particles are substantially all under 100 microns, preferably at least 75% w/w being in the range 4.7 to 53 microns.
  • the particle size distribution (in microns and by weight) is as follows (in rounded % figures): 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 - below 1%.
  • nickel powders also made by the carbonyl process usable in the invention are:
  • the conductor particles have a bulk density less than one third of their solid density.
  • the composition may be usefully employed in association with the anode or cathode construction of an electrochemical cell based on lithium, manganese, nickel, cobalt, zinc, mercury, silver or other battery chemistry including organic chemistry. Either or both the electrodes may be exchanged or coated with the polymer composition to give the following advantages:
  • Pressure sensitive polymer composition can also be used without direct involvement in the cell chemistry by positioning the composition on external casings or non-reacting surfaces of electrodes. Switching of the polymer composition could be initiated by externally applied mechanical pressure such as finger pressure or spring pressure from within a battery compartment. This could form a switch for controlling external circuits including battery check circuits.
  • compositions include:
  • Granules were prepared from: INCO nickel powder 287 28g ALFAS Industries RTV silicone type 2000 4g [This weight ratio corresponds approximately to a nickel : polymer volume ratio of 70 : 1 based on the tapped bulk volume of the nickel and the voidless volume of the silicone]
  • the silicone as a soft lump was placed in the bottom of a RETSCH RM100 motorized mixer having a steel mortar and a porcelain rotary pestle.
  • the nickel powder was placed around the lump of silicone.
  • the pestle was lowered under hand control with an approximate 1mm clearance from the wall of the mortar. This machine subjects the mixture to rotary ablation.
  • the silicone coated the nickel particles and in so doing became resolved into granules having the following size distribution % w/w in microns: Size fraction %w/w + 152 32 152 to 75 33 75 to 45 32 - 45 less than 3
  • the granules are non-conductive in the quiescent state but are very sensitive to applied pressure.
  • Example 1 The procedure of Example 1 was repeated using: ALFAS Industries RTV silicone type 1000 6g INCO nickel powder 287 30g corresponding to a nickel: polymer ingredient volume ratio of approximately 50 : 1. Although the ratio is lower than in Example 1, the characteristic shrinkage on cross-linking of the grade of silicone used, resulted in granules electrically conductive without applied pressure. The shrinkage seems to be a product of the loss of volatile components at cross-linking.
  • ALFAS 1000 contains 12% of volatile substances.
  • AFAS 2000 contains 4% of volatile substances).
  • Such granules are for example of especial value in conductive adhesives, EM screening and PTC devices.
  • Example 1 was repeated with the difference that the starting materials were: INCO nickel powder 287 30g Dow Corning HTV silicone (20 Shore) 6g under 50°C petroleum (lighter fuel) 2g 2,4-dichloro-dibenzoyl peroxide 200mg
  • Granules were formed at the end of about 5 minutes, during which the petroleum evaporated off and sufficient (but incomplete) cross-linking of the silicone took place. The granules were fully cross-linken by heating at 120°C for 20 minutes and were then tested as described in Examples 3 and 4.
  • Example 1 was repeated with the difference that, before being added to the mixer, the nickel powder was sprayed with an aerosol of the hydrophobising agent WD40 (RTM).
  • the granules were tested as in Examples 3 and 4 and found to be substantially more sensitive than those prepared without the WD40.
  • Granules made as in Example 1 were formulated as follows: 45 - 75 micron fraction 0.225g 75 - 152 micron fraction 0.225g 25% in water hexadecyl-trimethylammonium chloride 0.1g Natural rubber latex (60% w/w) 0.12g Water 0.15g
  • the latex was added and further mixed to form a gel.
  • the gel was split in two and applied through a stencil onto:
  • the resulting structure was dried at 80 - 90°C for 30 minutes, or until dry.

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Thermistors And Varistors (AREA)

Claims (11)

  1. Granules comprenant au moins un polymère sensiblement non conducteur et au moins une charge électriquement conductrice sélectionnée parmi des éléments métalliques sous forme de poudre et des alliages, des oxydes électriquement conducteurs desdits éléments et alliages, et leurs mélanges caractérisés en ce que ladite charge électriquement conductrice a une structure dendritique filamentaire ou en épi, ce par quoi lesdits granules sont électriquement isolants quand ils sont au repos, mais conducteurs quand ils sont soumis à un effort mécanique ou une charge électrique statique.
  2. Granules selon la revendication 1 dans lequel le rapport volumétrique charge conductrice: polymère est d'au moins 3:1.
  3. Granules selon la revendication 1 ou la revendication 2 dans lesquels la charge comprend du nickel métallique dérivé de carbonyle.
  4. Granules selon l'une quelconque des revendications précédentes dans lesquels le polymère est un caoutchouc de silicone et il contient une charge améliorant la récupération.
  5. Procédé de production de granules comprenant le mélange de particules d'au moins une charge électriquement conductrice sélectionnée parmi des éléments et alliages métalliques en forme de poudre, des oxydes électriquement conducteurs desdits éléments et alliages, et leurs mélanges et ayant une structure dendritique, filamentaire ou en épi, avec un polymère sous forme liquide qui est sensiblement non conducteur dans des conditions de formation de granules à un faible niveau de cisaillement, ce par quoi les particules de charge conductrice restent sensiblement structurellement intactes.
  6. Procédé selon la revendication 5 dans lequel un tel mélange et une telle formation de granules est accompagné par une réticulation du polymère, et la formulation du polymère est choisie et les conditions de mélange sont contrôlées de façon qu'une rupture du mélange en granules soit synchronisée avec une réticulation du polymère suffisante pour un état non-collant.
  7. Composite comprenant des granules selon l'une quelconque des revendications 1 à 4 en association avec un matériau de matrice polymérique:
  8. Structure composite pour la production, la détection, et le relais de signaux électriques où une conductivité interne est obtenue sous la forme d'un élément électriquement conducteur intégré, la structure comprenant un composite selon la revendication 7.
  9. Composite selon la revendication 7 pour réguler l'écoulement de courant, ledit composite étant un composite de PTC et ayant des moyens le contenant, et ayant des moyens pour l'entrée d'une déformation électrique et/ou mécanique pour activer l'effet PTC du composite.
  10. Utilisation d'un composite selon la revendication 9 pour réguler l'écoulement de courant.
  11. Blindage électromagnétique comprenant des granules selon l'une quelconque des revendications 1 à 4 ou un composite selon la revendication 7.
EP99901767A 1998-01-23 1999-01-21 Composition polymere Expired - Lifetime EP1050054B1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
PCT/GB1998/000206 WO1998033193A1 (fr) 1997-01-25 1998-01-23 Composition polymere
WOPCT/GB98/00206 1998-01-23
GB9806623 1998-03-28
GBGB9806623.6A GB9806623D0 (en) 1998-03-28 1998-03-28 Conductive structures within conductive polymerse
GB9814131 1998-06-30
GBGB9814131.0A GB9814131D0 (en) 1998-06-30 1998-06-30 Polymeric sensing materials
PCT/GB1999/000205 WO1999038173A1 (fr) 1998-01-23 1999-01-21 Composition polymere

Publications (2)

Publication Number Publication Date
EP1050054A1 EP1050054A1 (fr) 2000-11-08
EP1050054B1 true EP1050054B1 (fr) 2007-03-07

Family

ID=27269164

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99901767A Expired - Lifetime EP1050054B1 (fr) 1998-01-23 1999-01-21 Composition polymere

Country Status (6)

Country Link
EP (1) EP1050054B1 (fr)
JP (1) JP2002501949A (fr)
CN (1) CN1149588C (fr)
AU (1) AU2176899A (fr)
CA (1) CA2318742A1 (fr)
WO (1) WO1999038173A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10923776B2 (en) 2007-12-31 2021-02-16 Apple Inc. Systems and methods for monitoring and responding to forces influencing a battery

Families Citing this family (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6358436B2 (en) * 1999-07-23 2002-03-19 Ngk Insulators, Ltd. Inorganic-metal composite body exhibiting reliable PTC behavior
GB0011829D0 (en) * 2000-05-18 2000-07-05 Lussey David Flexible switching devices
GB0113905D0 (en) * 2001-06-07 2001-08-01 Peratech Ltd Analytical device
GB0322057D0 (en) * 2003-09-20 2003-10-22 Lussey David Variable conductance materials
US7093499B2 (en) 2004-12-21 2006-08-22 Delphi Technologies, Inc. Force sensor, strain sensor and methods for measuring same
US7857202B2 (en) 2006-08-11 2010-12-28 Mastercard International, Inc. Method and apparatus for a contactless smartcard incorporating a pressure sensitive switch
US7900843B2 (en) 2006-08-11 2011-03-08 Mastercard International, Inc. Proximity payment card with user-actuated switch and methods of making the card
US7997498B2 (en) 2006-09-08 2011-08-16 Mastercard International, Inc. Identification of installable card
GB2441733A (en) * 2006-09-18 2008-03-19 Powered Triangle Ltd Footwear display comprising a display
FR2907019B1 (fr) 2006-10-13 2009-04-03 Masters Internat Sarl Comp Dispositif de signalisation de touches pour la pratique de l'escrime sans fil
US7861931B2 (en) 2006-11-06 2011-01-04 Mastercard International, Inc. Method, apparatus, assembly and kit for identification token
US8730012B2 (en) 2007-01-05 2014-05-20 Mastercard International Incorporated Enabling identification token for a timed period
GB0708702D0 (en) 2007-05-04 2007-06-13 Peratech Ltd Polymer composition
US7837123B2 (en) 2007-09-10 2010-11-23 Mastercard International, Inc. Identification token and method of making identification token
US7992779B2 (en) 2007-09-10 2011-08-09 Mastercard International, Inc. Method for use in association with identification token and apparatus including identification token
US8230600B2 (en) 2007-09-17 2012-07-31 The Gillette Company Cartridge detachment sensor
US10783514B2 (en) 2007-10-10 2020-09-22 Mastercard International Incorporated Method and apparatus for use in personalizing identification token
US8226013B2 (en) 2007-10-26 2012-07-24 Mastercard International, Inc. Method and apparatus for use in providing an identification token
US8286862B2 (en) 2007-12-28 2012-10-16 Mastercard International, Inc. Methods and apparatus for use in association with security parameter
US8991695B2 (en) 2007-12-28 2015-03-31 Mastercard International Incorporated Methods and apparatus for use in docking
US8794532B2 (en) 2008-12-29 2014-08-05 Mastercard International Incorporated Methods and apparatus for use in association with identification token
GB0815724D0 (en) * 2008-08-29 2008-10-08 Peratech Ltd Pressure sensitive composition
US8812402B2 (en) 2009-01-05 2014-08-19 Mastercard International Incorporated Methods, apparatus and articles for use in association with token
US8684261B2 (en) 2009-01-20 2014-04-01 Mastercard International Incorporated Methods, apparatus, computer program products and articles for use in providing human understandable indication of account balance
JP5805974B2 (ja) 2010-03-31 2015-11-10 ティーケー ホールディングス，インコーポレーテッド ステアリングホイールセンサ
US8587422B2 (en) 2010-03-31 2013-11-19 Tk Holdings, Inc. Occupant sensing system
DE102011006649B4 (de) 2010-04-02 2018-05-03 Tk Holdings Inc. Lenkrad mit Handsensoren
US8983732B2 (en) 2010-04-02 2015-03-17 Tk Holdings Inc. Steering wheel with hand pressure sensing
EP3598122B1 (fr) 2010-12-08 2022-10-12 Condalign AS Capteurs avec des sentiers conducteurs formés de particules conductrices
GB201105025D0 (en) 2011-03-25 2011-05-11 Peratech Ltd Electrically responsive composite material
DE102011076717A1 (de) * 2011-05-30 2012-12-06 Siemens Aktiengesellschaft Hochfrequenzantenneneinheit, eine Magnetresonanzvorrichtung mit einer Hochfrequenzantenneneinheit, sowie ein Herstellungsverfahren für eine Hochfrequenzantenneneinheit
US9229029B2 (en) * 2011-11-29 2016-01-05 Formfactor, Inc. Hybrid electrical contactor
WO2013154720A1 (fr) 2012-04-13 2013-10-17 Tk Holdings Inc. Capteur de pression comprenant un matériau sensible à la pression à utiliser avec des systèmes de commande et ses procédés d'utilisation
DE112013004512T5 (de) 2012-09-17 2015-06-03 Tk Holdings Inc. Einzelschicht-Kraftsensor
DE102013202375A1 (de) * 2013-02-14 2014-08-14 Zumtobel Lighting Gmbh Schaltelement mit triboelektrischem Element
ES2485617B1 (es) * 2013-09-16 2015-04-06 Sensing Tex, S.L. Sensor textil piezo-resistivo y sistema de detección del ritmo cardiaco y/o respiratorio
US10935445B2 (en) 2017-01-04 2021-03-02 Mas Innovation (Private) Limited Wearable touch button assembly
GB2561609B (en) * 2017-04-21 2019-12-18 Peratech Holdco Ltd Method of producing agglomerates for inclusion in a composite material
CN110894359B (zh) * 2019-12-05 2022-02-18 中国电子科技集团公司第三十三研究所 一种海绵型定向导电橡胶及其制备方法
DE102020213275A1 (de) * 2020-10-21 2022-04-21 Robert Bosch Gesellschaft mit beschränkter Haftung Verfahren zur Herstellung eines elektrisch leitfähigen Verbundwerkstoffs, Verwendung eines elektrisch leitfähigen Verbundwerkstoffs zur Herstellung eines Heizelements, Heizelement

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS565840A (en) * 1979-06-28 1981-01-21 Shin Etsu Polymer Co Ltd Anisotropic pressure electrically-conductive elastomer molded article
EP0231068B1 (fr) * 1986-01-14 1994-03-16 RAYCHEM CORPORATION (a Delaware corporation) Composition polymère conductrice
IT1254974B (it) * 1992-06-18 1995-10-11 Bayer Italia Spa Granulati compositi, scorrevoli,idrofobi,un procedimento per la loro preparazione nonche' loro impiego
US5591382A (en) * 1993-03-31 1997-01-07 Hyperion Catalysis International Inc. High strength conductive polymers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10923776B2 (en) 2007-12-31 2021-02-16 Apple Inc. Systems and methods for monitoring and responding to forces influencing a battery

Also Published As

Publication number Publication date
JP2002501949A (ja) 2002-01-22
CN1291338A (zh) 2001-04-11
AU2176899A (en) 1999-08-09
EP1050054A1 (fr) 2000-11-08
CN1149588C (zh) 2004-05-12
WO1999038173A1 (fr) 1999-07-29
CA2318742A1 (fr) 1999-07-29

Similar Documents

Publication Publication Date Title
EP1050054B1 (fr) Composition polymere
US6495069B1 (en) Polymer composition
EP0956565B1 (fr) Composition polymere
WO1998033193A9 (fr) Composition polymere
AU629592B2 (en) Electrical overstress pulse protection
US6646540B1 (en) Conductive structures
Stru Mpler et al. Feature article conducting polymer composites
US5476714A (en) Electrical overstress pulse protection
Ruschau et al. Critical volume fractions in conductive composites
JP5411227B2 (ja) 櫛歯状の力スイッチ及びセンサー
JPH02503049A (ja) 非線形材料及びそれを用いる過電圧保護素子
GB2465077A (en) Polymer composition with electrically-conductive filler
GB2054277A (en) Pressure-sensitive electroconductive bodies
US20060075629A1 (en) Method of fabricating a current control device
EP0277362B1 (fr) Procédé de fabrication de résistances électriques à grande gamme des valeurs de résistance spécifique
US6652968B1 (en) Pressure activated electrically conductive material
WO2005029514A1 (fr) Materiaux a conductance variable
RU2222065C2 (ru) Полимерная композиция
RU2234156C2 (ru) Полимерная композиция
JP3907431B2 (ja) 感圧センサ用抵抗体およびそれを用いた感圧センサ
JPH0787123B2 (ja) スイッチ素子として用いる感圧抵抗変化型導電性塗膜形成性組成物
DE69935416T2 (de) Polymerzusammensetzung
JP7478763B2 (ja) 複合材
JP3541264B2 (ja) 正温度特性素子
McCluskey et al. Nanocomposite materials offer higher conductivity and flexibility [conducting polymers]

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20000731

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI NL PT SE

17Q First examination report despatched

Effective date: 20011108

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69935416

Country of ref document: DE

Date of ref document: 20070419

Kind code of ref document: P

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070607

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070618

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070807

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

26N No opposition filed

Effective date: 20071210

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070608

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080121

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20150604 AND 20150610

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

Owner name: PERATECH HOLDCO LIMITED, GB

Effective date: 20151105

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 18

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 69935416

Country of ref document: DE

Representative=s name: JANY, PETER, DIPL.-PHYS. DR.RER.NAT., DE

Ref country code: DE

Ref legal event code: R081

Ref document number: 69935416

Country of ref document: DE

Owner name: PERATECH HOLDCO LIMITED, GB

Free format text: FORMER OWNER: PERATECH LTD., DARLINGTON, DURHAM, GB

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 19

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20171218

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20171213

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20180105

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69935416

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20190120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20190120