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EP0533760B1 - Procede de fabrication d'un dispositif electrique - Google Patents

Procede de fabrication d'un dispositif electrique Download PDF

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Publication number
EP0533760B1
EP0533760B1 EP91910990A EP91910990A EP0533760B1 EP 0533760 B1 EP0533760 B1 EP 0533760B1 EP 91910990 A EP91910990 A EP 91910990A EP 91910990 A EP91910990 A EP 91910990A EP 0533760 B1 EP0533760 B1 EP 0533760B1
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EP
European Patent Office
Prior art keywords
mixture
polymer material
electrodes
electrically conductive
polymer
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
EP91910990A
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German (de)
English (en)
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EP0533760A1 (fr
Inventor
Tomas Hansson
Ulf Henriksson
Hakan Johansson
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ABB AB
Original Assignee
Asea Brown Boveri AB
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Publication date
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Publication of EP0533760A1 publication Critical patent/EP0533760A1/fr
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon

Definitions

  • the present invention relates to a method of manufacturing an electrical device, particularly an overcurrent protective device, comprising a body, provided with two parallel surfaces, of an electrically conductive polymer composition with a resistivity of at most 100 m ⁇ cm and two electrodes arranged in contact with the parallel surfaces, the polymer composition comprising a polymer material and an electrically conductive powdered material distributed in the polymer material.
  • PTC element Physical Temperature Coefficient
  • the resistance of a PTC element of the above kind is low, for example a few hundredths ⁇ , in the normal working range of the element which may extend to, for example, 80°C and increases slightly with the temperature. If the temperature of the element exceeds this value, for example because of overcurrent, the resistance increases more rapidly, and upon exceeding a certain critical temperature, the element suddenly changes from a low-resistance to a high-resistance state in which the resistance may amount to 10 k ⁇ and more.
  • thermal overload relay Another type of such an electrical device in the form of an overcurrent protective device is a thermal overload relay.
  • the used polymer material if it is a thermoplastic resin, for example polyethylene, is melted and mixed (compounded) with the conductive powdered material which normally consists of carbon in some form or of a metallic material or of a mixture of carbon and a metallic material.
  • the conductive powdered material which normally consists of carbon in some form or of a metallic material or of a mixture of carbon and a metallic material.
  • This technique involves a number of limitations.
  • the polymer material must have a relatively low viscosity and even if this is the case, it may be impossible to intermix the desired, sufficiently high contents of carbon.
  • the powerful processing during the compounding operation also entails a risk that the conductive material is crushed or otherwise influenced so as to undergo undesirable changes.
  • the produced mixture is subjected to a processing in connection with it being formed by extrusion, compression moulding, or in some other way, which entails a risk of an undesired anisotropy arising in the material in the formed product.
  • the processes described may lead to problems in achieving reproducible properties in the manufactured, finished body.
  • the body After the forming of the body of polymer composition, the body is provided with electrodes according to applied technique.
  • the electrodes usually consist of metal foils and are applied by being pressed onto the body while being heated.
  • the invention makes possible the use of polymer material with a considerably higher viscosity than what has previously been possible. It provides a considerably greater freedom of choice as regards types and contents of conductive materials.
  • the conductive material is not subjected to any processing with undesired consequences. No forming, entailing a risk of anisotropy, occurs.
  • the electrodes may be applied without having to carry out a separate operating step.
  • a particularly important advantage is that the method makes it possible to obtain devices with very low transition resistance between electrode and polymer composition.
  • the favourable results are obtained by mixing the polymer material in thermoplastic state and in powdered form with a grain size of below 100 ⁇ m, and of below 40 ⁇ m in at least 50% of the material, in solid, dry state with the electrically conductive powdered material in a grain size of below 100 ⁇ m into a mixture in which the polymer material constitutes at least 30 per cent and the electrically conductive powdered material at least 20 per cent of the total volume of these materials and by subjecting the mixture together with the electrodes to a pressing and a heating to a temperature at which the polymer material melts at least on the surface of the grains while forming a permanently coherent body of the mixture and while fixing the electrodes to the coherent body.
  • the grains of the polymer material then entirely lose their identity.
  • the mixture of polymer material and electrically conductive powdered material is subjected to a pressing operation at room temperature or other temperature which is considerably lower than the temperature at which the polymer material melts while forming a preformed body, before the mixture in the form of the preformed body together with the electrodes is subjected to the pressing and the heating for forming the permanently coherent body and for fixing the electrodes.
  • Electrodes there are preferably used prefabricated plates of a powdered metallic material, which have a porous structure on the side facing the mixture and are impermeable to the polymer material so that they prevent penetration of the polymer material to the side facing away from the mixture.
  • the electrodes are effectively secured to the conductive polymer composition without the polymer material providing any insulating or any possibly slightly conductive coating on the outside of the electrodes.
  • the polymer material penetrates, in its thermoplastic state, into the pores of the electrodes without penetrating the electrodes. Plates which are completely porous from the beginning may be made impermeable to the penetration of polymer material by being provided on the outside with a metallic coating, for example electrolytically.
  • the electrode material in powdered state may be applied in the form of layers on the surfaces of the conductive polymer composition, before it is subjected to pressing and heating for forming the permanently coherent body and for fixing the electrodes. Also in such a case, measures are preferably taken for ensuring that the electrodes are tight against the penetration of polymer material, for example by providing them with a tight coating of metallic material on that side facing away from the mixture.
  • the metallic material in the electrodes may advantageously consist of nickel or copper but also other metallic materials in the form of pure metal or metal alloy with sufficient electric conductivity may be used.
  • a suitable grain size of the metallic material is 0.5 ⁇ m - 20 ⁇ m and a suitable thickness of an electrode 100-1000 ⁇ m.
  • the coating may advantageously consist of copper which provides a well scattered electrical conduction in the lateral direction within the electrode in question, irrespective of the material on which the electrode is otherwise based.
  • the tight surface layer on an otherwise porous electrode may advantageously have a thickness which amounts to 3-30% of the thickness of the entire electrode.
  • a crosslinkable linear polymer is used as polymer material in the manufacture of the device. If the crosslinking ability of the polymer material is utilized, the crosslinking is carried out after the mixture of the polymer material and the conductive material together with the electrodes has been subjected to the pressing and the heating for forming the permanently coherent body and for fixing the electrodes.
  • crosslinking polymer material By crosslinking polymer material, a greater mechanical and thermal stability of the manufactured device may be achieved.
  • the polymer material preferably consists of a polyolefin, such as polyethylene, polypropylene, polybutene, or a copolymer of ethylene and propylene.
  • a polyolefin such as polyethylene, polypropylene, polybutene, or a copolymer of ethylene and propylene.
  • Specially preferred is HD polyethylene.
  • liner polymers which may be made sufficiently fine-grained and be mixed in dry state with the conductive material and be transferred into thermoplastic state when the mixture is subjected to pressing and heating for forming a permanently coherent body of the polymer composition and for fixing the electrodes.
  • Examples of such other linear polymers are polyamide, polethylene terephthalate, polybutene terephthalate and polyoxymethylene.
  • the polymer material preferably has a crystallinity of at least 5%.
  • the grain size of the polymer material is preferably 5-100 ⁇ m, of which at least 50% of the material has a grain size smaller than 40 ⁇ m.
  • suitable electrically conductive materials in the polymer composition may be mentioned carbon in the form of conductive carbon powders such as carbon black, metallic materials such as, for example, nickel, tungsten, molybdenum, cobalt, copper, silver, aluminium and brass, borides such as, for example, ZrB 2 and TiB 2 , nitrides such as, for example, ZrN and TiN, oxides such as, for example, V 2 O 3 and TiO, carbides such as, for example, TaC, WC and ZrC, as well as mixtures of two or more of the exemplified materials such as, for example, a mixture of soot and nickel.
  • metallic materials such as, for example, nickel, tungsten, molybdenum, cobalt, copper, silver, aluminium and brass
  • borides such as, for example, ZrB 2 and TiB 2
  • nitrides such as, for example, ZrN and TiN
  • oxides such as, for example, V 2 O 3 and Ti
  • the grain size of the conductive carbon powders such as carbon black is usually 0.01-0.10 ⁇ m, the grain size of metallic material preferably 0.5-100 ⁇ m and the grain size of borides, nitrides, oxides, and carbides preferably 0.01-100 ⁇ m.
  • at least part of the electrically conductive powdered material has a grain size which is smaller than the cross section of the pores of the electrode, so that at least that part of the powdered material can accompany the polymer material when it penetrates into the pores of the electrode.
  • the polymer material suitably constitutes 30-80 per cent and the electrically conductive powdered material 20-70 per cent of the total volume of these materials in the polymer composition built up of the mixture.
  • the electrically conductive material consists of a mixture of carbon and metallic material, there are preferred a content of polymer material of 65-80 per cent and a content of electrically conductive powdered material of 20-35 per cent of the total volume of these materials in devices with a pronounced PTC effect.
  • the carbon preferably constitutes 5-75 per cent by volume and the metallic material 25-95 per cent by volume.
  • HD polyethylene 75 parts by volume HD polyethylene (NB 6081 from PLAST-LABOR S.A., Bulle, Switzerland) with a melting index (MI 190/2) of 40 g/10 min, a density of 0.960 g/cm 3 and a grain size of 5-90 ⁇ m, thereof a grain size of 24-36 ⁇ m in more than 50% of the material, is mixed with 13 parts by volume nickel powder with a grain size of less than 7 ⁇ m and with 12 parts by volume carbon black of type N550 (ASTM) with a grain size of 0.040-0.048 ⁇ m into a mixture in the form of a polymer composition.
  • the mixture is pressed at room temperature and a pressure of 70 MPa in a forming tool with a cylindrical cavity and one or two movable cylindrical dies into a preformed round plate with a diameter of 25 mm and a height of 1.5 mm.
  • each plate is electrolytically provided on one side with a 20 ⁇ m thick layer of copper which, for one thing, eliminates the presence of through-going pores by the layer being tight, and, for another, provides a radially scattered surface layer of high conductivity.
  • the plate of the polymer composition with one of the nickel electrode plates on each flat side is again placed in the forming tool with the copper layers facing outwards, whereupon the stack of the three plates is first pressed at room temperature and a pressure of 70 MPa and then at 150°C without changing the pressure.
  • the polymer composition then forms a permanently coherent body, to which the electrodes are mechanically secured in an effective manner with a low transition resistance between electrode and polymer composition by the polymer composition having penetrated into the pores of the electrodes or at least the polymer material and the part of the electrically conductive powdered material having a grain size which is smaller than the pores of the electrode.
  • the polymer composition has a resistivity of less than 50 m ⁇ cm. The manufactured device is excellently suited for use as PTC element.
  • a device is manufactured in the manner stated in Example 1 with the difference that the copper layers on the outside of the electrodes are not applied until the stack of the plates of the polymer composition and of the nickel electrodes has been pressed at room temperature into a coherent body. After application of the copper layers on the outside of the electrodes, the coherent body is subjected to a pressing at a pressure of 70 MPa and a temperature of 150°C.
  • a device is manufactured in the manner described in Example 1 with the difference that the electrode plates pressed at room temperature, instead of being provided with tight copper layers on the outside, are subjected to a sintering in hydrogen gas atmosphere at about 400°C for four hours followed by a grinding of the side facing away from the polymer composition using 320 mesh wet grinding paper.
  • the grinding entails a deformation of the surface layer so that this becomes tight.
  • This resuls in electrode plates with a porous surface structure on the side facing the polymer composition but without through-going pores. They will therefore become impermeable to polymer material during the hot pressing.
  • a device is manufactured in the manner described in Example 1 with the difference that the porous electrodes, instead of being provided on the outside with a copper layer, are made tight there by melting down the surface layer to a depth of about 50 ⁇ m and causing it to solidify by the use of laser.
  • the device is excellently suited for use as PTC element.
  • a device is manufactured in any of the ways described in Examples 1-4. After the last pressing with heat treatment, the polymer composition is subjected to a crosslinking by electron-irradiating the device in its entirety until the crosslinking degree of the polymer material amounts to 80%.
  • the polymer composition has a resistivity of less than 50 m ⁇ cm. The device is excellently suited for use as PTC element.
  • Electrodes are manufacturd in a manner described in Example 1, Example 3 or Example 4.
  • the electrodes are placed together with the polymer composition described in Example 1 in the form of a powder, that is, without preforming, in the cavity of a forming tool of the kind described in Example 1 with the electrodes on either side of the polymer composition and with the tight layers (Examples 1 and 4) facing outwards.
  • the polymer composition and the electrodes are subjected to a pressing with a pressure of 70 MPa at a temperature of 150°C.
  • the polymer composition has a resistivity of less than 50 m ⁇ cm.
  • the device is excellently suited for use as PTC element.
  • a device is manufactured in any of the ways described in Examples 1-6 but with the difference that, instead of polyethylene mentioned there, there is used an LD polyethylene (HX 1681 from PLAST-LABOR S.A.) with a melting index of 70 g/10 min, a density of 0.916 g/cm 3 and a grain size of 5-35 ⁇ m, thereof a grain size of 10-14 ⁇ m in more than 50% of the material.
  • the polymer composition has a resistivity of less than 50 m ⁇ cm.
  • the produced device is excellently suited for use as a PTC element.
  • a device is manufactured in any of the ways described in Example 1, 2, 3, 4 or 6, with the difference that instead of polyethylene mentioned there, there is used polypropylene (PB 0580 from PLAST-LABOR S.A.) with a melting index (MI 230/5) of 100 g/10 min, a density of 0.905 g/cm 3 , and a grain size of 5-90 ⁇ m, thereof a grain size of 24-36 ⁇ m in more than 50% of the material and the difference that the hot pressing is carried out at 170°C.
  • PB 0580 from PLAST-LABOR S.A.
  • a device is manufactured in any of the ways described in Examples 1-8, with the difference that instead of the electrically conductive powdered materials in the form of 13 parts by volume nickel powder and 12 parts by volume carbon black mentioned there, there are used 50 parts by volume ZrN with a grain size of less than 45 ⁇ m.
  • the polymer composition has a resistivity of less than 50 m ⁇ cm.
  • a device is manufactured in the manner described in Example 9, with the difference that instead of ZrN there is used TiN with a grain size of less than 6-10 ⁇ m.
  • the polymer composition has a resistivity of less than 35 m ⁇ cm.
  • a device is manufactured in any of the ways described in Examples 1-8, with the difference that instead of the electrically conductive powdered materials in the form of 13 parts by volume nickel powder and 12 parts by volume carbon black mentioned there, there are used 13 parts by volume of the same carbon black and 52 parts by volume TiN with a grain size of 6-10 ⁇ m.
  • the polymer composition has a resistivity of less than 35m ⁇ cm.
  • a device is manufactured in the manner described in Example 10, with the difference that instead of TiN there is used ZrB 2 with a grain size of less than 45 ⁇ m.
  • the polymer composition has a resistivity of less than 30 m ⁇ cm.
  • a device is manufactured in the manner described in Example 9, with the difference that instead of ZrN there is used TiB 2 with a grain size of less than 45 ⁇ m.
  • a device is manufactured in any of the ways described in Examples 1-8, but with the difference that instead of the electrically conductive powdered materials mentioned there in the form of 13 parts by volume nickel powder and 12 parts by volume carbon black, there is used 120 parts by volume soot of the same kind as in Example 1.
  • a device is manufactured in any of the ways described in Examples 1-8, with the difference that instead of the electrically conductive powdered materials mentioned there in the form of 13 parts by volume nickel powder and 12 parts by volume carbon black, there is used 60 parts by volume nickel powder of the same kind as in Example 1.

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  • Engineering & Computer Science (AREA)
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Claims (16)

  1. Procédé de fabrication d'un dispositif électrique, notamment d'un dispositif de protection vis-à-vis de surintensité comprenant un corps ayant deux surfaces parallèles en une composition polymère conductrice de l'électricité ayant une résistivité d'au plus 100 mOhm.cm et deux électrodes disposées au contact des surfaces parallèles, la composition polymère comprenant une matière polymère et une matière pulvérulente conductrice de l'électricité répartie dans la matière polymère
       caractérisé en ce que
    la matière polymère à l'état thermoplastique est sous forme pulvérulente ayant une granulométrie inférieure à 100 µm et de moins de 40 µm dans au moins 50 % de la matière,
    est mélangée à l'état solide sec à la matière pulvérulente conductrice de l'électricité ayant une granulométrie inférieure à 100 µm en un mélange,
    dans lequel la matière polymère constitue au moins 30 % et la matière pulvérulente conductrice de l'électricité au moins 20 % du volume total de ces matières,
    et en ce que le mélange ensemble avec les électrodes est soumis à un pressage et à un chauffage à une température à laquelle la matière polymère fond au moins à la surface des grains de manière à former un corps cohérent d'une manière permanente en le mélange dans lequel les grains de la matière polymère ont perdu entièrement leur identité et à fixer les électrodes au corps cohérent.
  2. Procédé suivant la revendication 1, caractérisé en ce qu'il consiste à soumettre le mélange à un pressage à la température ambiante ou à une autre température qui est considérablement inférieure à la température à laquelle la matière polymère fond, tout en formant un corps préformé avant que le mélange sous la forme du corps préformé ensemble avec les électrodes soit soumis au pressage et au chauffage pour former le corps cohérent de manière permanente et pour fixer les électrodes.
  3. Procédé suivant la revendication 1 ou 2, caractérisé en ce qu'il consiste à utiliser comme électrodes des plaques préfabriquées d'une matière métallique pulvérulente qui ont une structure poreuse sur la face regardant le mélange et qui sont étanches vis-à-vis de la pénétration de la matière polymère vers la face éloignée du mélange.
  4. Procédé suivant la revendication 3, caractérisé en ce que les plaques sont étanches sur la face éloignée du mélange en étant munies sur cette face d'un revêtement étanche en une matière métallique.
  5. Procédé suivant la revendication 3, caractérisé en ce que les plaques sont étanches sur la face éloignée du mélange en étant munies sur cette face d'une couche superficielle fondue et solidifiée de la matière métallique pulvérulente des plaques.
  6. Procédé suivant la revendication 3, caractérisé en ce que les plaques sont imperméables à la pénétration de la matière polymère par l'élimination de pores traversants par frittage des plaques et par un traitement mécanique subséquent de la face éloignée du mélange.
  7. Procédé suivant l'une quelconque des revendications 1 à 6, caractérisé en ce que l'on utilise comme matière polymère un polymère linéaire pouvant être réticulé et en ce que la matière polymère est réticulée après que le mélange ensemble avec les électrodes a été soumis au pressage et au chauffage pour former le corps cohérent de manière permanente et pour fixer les électrodes.
  8. Procédé suivant l'une quelconque des revendications 1 à 7, caractérisé en ce qu'il consiste à utiliser comme matière polymère une polyoléfine.
  9. Procédé suivant la revendication 8, caractérisé en ce qu'il consiste à utiliser comme matière polymère du polyéthylène.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que la matière polymère constitue de 30 à 80 % et la matière pulvérulente conductrice de l'électricité de 20 à 70 % du volume total de ces matières dans le mélange.
  11. Procédé suivant l'une quelconque des revendications 1 à 10, caractérisé en ce que la matière polymère constitue de 65 à 80 % et la matière pulvérulente conductrice de l'électricité de 20 à 35 % du volume total de ces matières dans le mélange.
  12. Procédé suivant l'une quelconque des revendications 1 à 11, caractérisé en ce qu'il consiste à utiliser comme matière pulvérulente conductrice de l'électricité du carbone sous la forme de noir de carbone.
  13. Procédé suivant l'une quelconque des revendications 1 à 11, caractérisé en ce qu'il consiste à utiliser comme matière pulvérulente conductrice de l'électricité dans le mélange une matière métallique.
  14. Procédé suivant l'une quelconque des revendications 1 à 11, caractérisé en ce qu'il consiste à utiliser comme matière pulvérulente conductrice de l'électricité dans le mélange un mélange de carbone sous la forme de noir de carbone et de matière métallique.
  15. Procédé suivant l'une quelconque des revendications 13 et 14, caractérisé en ce que la matière métallique consiste en nickel.
  16. Procédé suivant la revendication 14, caractérisé en ce que le carbone représente de 5 à 75 % et la matière métallique de 25 à 95 % du volume total de ces matières dans leur mélange.
EP91910990A 1990-06-05 1991-05-28 Procede de fabrication d'un dispositif electrique Expired - Lifetime EP0533760B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SE9001990A SE468026B (sv) 1990-06-05 1990-06-05 Saett att framstaella en elektrisk anordning
SE9001990 1990-06-05
PCT/SE1991/000375 WO1991019297A1 (fr) 1990-06-05 1991-05-28 Procede de fabrication d'un dispositif electrique

Publications (2)

Publication Number Publication Date
EP0533760A1 EP0533760A1 (fr) 1993-03-31
EP0533760B1 true EP0533760B1 (fr) 1999-11-17

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EP (1) EP0533760B1 (fr)
JP (1) JP2836959B2 (fr)
AT (1) ATE186793T1 (fr)
DE (1) DE69131787T2 (fr)
SE (1) SE468026B (fr)
WO (1) WO1991019297A1 (fr)

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FR3038710B1 (fr) 2015-07-10 2021-05-28 Cpc Tech Capteur d'une caracteristique physique, comportant de preference une structure multicouches
CN107230511B (zh) * 2016-03-24 2019-09-03 上海利韬电子有限公司 导电聚合物组合物、电气器件及其制备方法

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Publication number Publication date
SE468026B (sv) 1992-10-19
JPH05508055A (ja) 1993-11-11
EP0533760A1 (fr) 1993-03-31
ATE186793T1 (de) 1999-12-15
JP2836959B2 (ja) 1998-12-14
WO1991019297A1 (fr) 1991-12-12
SE9001990L (sv) 1991-12-06
DE69131787D1 (de) 1999-12-23
SE9001990D0 (sv) 1990-06-05
DE69131787T2 (de) 2000-06-21

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