EP0115191A1 - Elektrische Stromkreisunterbrechungsvorrichtung - Google Patents

Elektrische Stromkreisunterbrechungsvorrichtung Download PDF

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Publication number
EP0115191A1
EP0115191A1 EP83307922A EP83307922A EP0115191A1 EP 0115191 A1 EP0115191 A1 EP 0115191A1 EP 83307922 A EP83307922 A EP 83307922A EP 83307922 A EP83307922 A EP 83307922A EP 0115191 A1 EP0115191 A1 EP 0115191A1
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EP
European Patent Office
Prior art keywords
actuating element
conductive polymer
dopant
polymer
circuit
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.)
Withdrawn
Application number
EP83307922A
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English (en)
French (fr)
Inventor
Ian Paul Atkins
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.)
Raychem Ltd
Original Assignee
Raychem 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
Application filed by Raychem Ltd filed Critical Raychem Ltd
Publication of EP0115191A1 publication Critical patent/EP0115191A1/de
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H85/00—Protective devices in which the current flows through a part of fusible material and this current is interrupted by displacement of the fusible material when this current becomes excessive
    • H01H85/02—Details
    • H01H85/04—Fuses, i.e. expendable parts of the protective device, e.g. cartridges
    • H01H85/05—Component parts thereof
    • H01H85/055—Fusible members
    • H01H85/06—Fusible members characterised by the fusible material

Definitions

  • a known form of electrical circuit interruption device is the conventional metallic fuse which may be designed to operate at various current ratings but is generally unsatisfactory at low operating currents because it either takes a relatively long time to "blow” at moderate overloads or, if it is a "quick-blow” fuse, then its life-time at the rated current is relatively short - often a matter of only a few hours. This slowness of actuation is a particular problem in electronic equipment such as integrated circuits where moderate overload currents can be tolerated in operation for only very short intervals, and the short life-time of the "quick-blow” fuse is obviously inconvenient.
  • the present invention provides an electrical circuit interruption device having an actuating element comprising an inherently electrically conductive polymer.
  • conductive polymers Inherently electrically conductive polymers (hereinafter “conductive polymers”) can be selected which have a conductivity high enough to pass a substantial current, and can thus serve as the actuating element of the device according to the present invention.
  • conductive polymers are highly advantageous for use as the actuating element in circuit protection devices, such as fuses, especially at low operating currents, by which is meant less than 1 Amp, preferably less than 200mA, more preferably less than 100mA, and especially less that 50mA. It has been found that at moderate to low overload currents, the time taken for the conductive polymer actuating element to "blow” (that is, to interrupt the circuit) is considerably shorter than found in conventional fuses of comparable life-time at the rated current of the device.
  • the circuit interruption may be effected by reduction of the current to a negligible level e.g. by increasing the resistance of the actuating element, without physically destroying or breaking the actuating element.
  • physical breakage or destruction is preferred.
  • the conductive polymer is selected and-arranged so that the actuating element takes less than 60 seconds to interrupt the circuit when carrying twice the rated operating current, and is capable of continuously carrying its rated operating current for at least 24 hours.
  • a SOmA rated device according to the present invention has been found to "blow" in 2 to 3 seconds at a current of 100mA (i.e. twice the rated current) whereas a conventional metal 50mA rated fuse continued to pass a 100mA current for about 17 minutes before "blowinq".
  • Known electrically conductive polymers include polysulphur nitrides, polyanilines, polyphenylenes, polyacetylenes and polypyrroles.
  • polysulphur nitrides e.g. ((SN)x
  • polyanilines e.g.
  • polyphenylenes e.g. ((SN)x)
  • polyacetylenes require oxidation or reduction
  • polypyrroles require oxidation.
  • the process of oxidation (or reduction) is often called doping and a counter ion is required to associate itself with the (or reduced) polymer to balance the ionic charges therein. This counter-ion is often referred to as a dopant.
  • dopants examples include BF 4 - , p-toluene sulphonate, Br , perchlorate ions, picrate ions and positively charged ions such as alkyl ammonium ions and metal ions such as potassium ions.
  • Polyacetylenes may be prepared as described by H. Shirakawa et al, J. Polymer Sci., Polym. Chem. Ed., 12, 11 (1974); polyphenylenes may be prepared as described by J.K. Stille et al, J. Polymer Sci, Part D, 5, 385 (1971); polyanilines, polynaphthylamines and polythio- phenes may be prepared by methods analogous to the polypyrrole preparations described below.
  • the phrase "electrically conductive polymer” will be used herein to mean any polymer or oligomer inherently capable of electrical conductivity or semi-conductivity, (hereinafter both included in the terms “electrical conductivity” or “electrically conductive”), including those requiring oxidation/reduction of the polymer and/or the presence of a “dopant” to render them electrically conductive.
  • the aforesaid phrase includes inorganic polymers such as the polysulphur nitrides, and organic polymers such as the polypyrroles, all of which conduct electronically, electronic conduction being preferred for the present purposes.
  • doping and "de-doping” will be taken to mean the oxidation/reduction processes used to convert the polymers between their less conductive and more conductive states; the term “dopants” will refer to the aforementioned counter-ions and to the materials used to provide the counter-ions which stabilise the more conductive form of the polymers; and the terms “undoped”, “doped” and “de-doped” will be understood accordingly.
  • the preferred conductive polymers for use in the present invention are polypyrrole and its suitably conductive derivatives, e.g. poly(3,4-dimethylpyrrole). These polymers in their doped conductive state have the necessary resistance to degradation on.aging, and can be synthesised in suitable physical forms.
  • Polypyrrole and suitably substituted derivatives may be prepared from pyrroles as shown by the accompanying general formula (I) in Fig. 1 of the accompanying drawings, in which R 1 to R 5 , which may be the same or different, represent possible substituents, although sufficient positions must be left unsubstituted to permit polymeri-sation, Electrically conductive polymers are generally believed to operate by means of a conjugated pi-electron system and it is understood that some substituents or combinations of substituents may interfere with the conjugated system so as to detract from or destroy the desired electrical conductivity. Acceptable substituents can be readily determined by simply testing the conductivity of the resulting polymer.
  • Electrochemical methods of preparing electrically conductive polymers can be used as follows to produce the actuating element materials of the present invention.
  • an electrochemical cell is used, wherein two electrodes (made from, for example, stainless steel, platinum or indium oxide coated glass) are immersed in an electrolyte mixture, suspension or solution.
  • the electrolyte includes a material carrying groups which are ionisable into an appropriately charged ionic dopant species.
  • the solvent or mixture of solvents may be chosen from protic and aprotic solvents, for example acetonitrile, tetrahydrofuran, dimethyl formamide, water-, methanol.
  • To the electrolyte mixture is added the monomer species that is to be polymerised to form the desired electrically conductive polymer.
  • Stirring of the resulting mixture may be required to achieve a homogeneous mixture.
  • an electrically conducting film is formed on the appropriate electrode.
  • positively charged polymers such as polypyrroles
  • the film is formed on the anode and is partially oxidised and contains a negatively charged dopant to provide charge neutrality to the film.
  • Chemical preparative methods can also be used, in which the monomer and the dopant are mixed with an oxidising agent in a suitable liquid vehicle.
  • the electrolytic cell was powered by a D.C. power supply. Electrolysis of the electrolyte mixture was carried out by applying to the cell an electrical potential of 5V for a period of one hour, during which time the current density was lmAcm -2 .
  • a brittle black film was deposited on the anode and was removed with difficulty to give a free-standing film, which could not be creased or folded in two like paper without fracturing.
  • a flexible film of polypyrrole doped with perchlorate ions and incorporating polyethylene glycol was produced, the polyethylene glycol acting as a "fuel” for destructive oxidation (detonation) by the perchlorate ions under conditions of use described hereinafter.
  • Self-supporting, preferably flexible, films of the conductive polymer may be advantageously used as the actuating element, although rigid films and films supported on suitable carriers are not excluded.
  • Preferred polypyrrole derivatives and dopants include polypyrrole doped with chloride, fluoroborate, perchlorate, or p-toluene sulphonate ions, the last of these dopants tending to produce more flexible films.
  • the invention also provides a method of protecting an electrical circuit comprising incorporating in the circuit a circuit interruption device of the present kind.
  • Devices according to the present invention may be conveniently incorporated into electrical circuitry, for example in printed circuit boards, if desired in combination with other protective devices.
  • the actuating element of the present invention may be enclosed in suitable preservative environments for example in vacuum or nitrogen gas or in a "potting" compound or electrically insulating oils if necessary, e.g. to minimise oxidation.
  • suitable preservative environments for example in vacuum or nitrogen gas or in a "potting" compound or electrically insulating oils if necessary, e.g. to minimise oxidation.
  • Mode 1 When the overload current is relatively small, e.g. twice the rated current, the resistivity of the polymer increases in an area (3) towards the middle of the actuating element. Hence the current passing through the actuating element is substantially reduced and so the electrical equipment is protected.
  • Mode 2 At a higher initial level of overload current, "blowing" occurs by actual physical destruction of the actuating element.
  • Mode 2 may occur after Mode 1 if the applied voltage is increased to a sufficiently high level.
  • Fig. 3 of the accompanying drawings A specific shape and arrangement of a device according to the invention are shown in Fig. 3 of the accompanying drawings. It will be appreciated that the dimensions and configuration of the conductive polymer actuating element may be selected to suit the inherent electrical resistivity of the polymer in order to produce a circuit interruption device of desired rating and overload performance. The dimensions and shape of the actuating element are thus not critical in themselves, but dimensions substantially as shown in Fig.3, with the conductivity of the polymer in the range from 10 to 500 ohms -1 cm -1 , have been found convenient in practice.
  • a fuse as shown in Fig. 3 rated at 50 - 60 mA was prepared with an actuating element (1) comprising a strip of electrochemically prepared (see Preparation 2) polypyrrole doped with p-toluenesulphonate ions and having the dimensions indicated in Fig. 3, and a conductivity of 100 ohms cm
  • a fuse was prepared as in Example 1 using BF 4 - doped polypyrrole prepared as in Preparation 1, having a conductivity of 11 ohm -1 cm -1 . At a current of 120 mA, the fuse "blew” by reducing the current to a negligible level in 225 milliseconds.
  • the actuating element may carry materials which react chemically to enhance its circuit breaking function under overload currents. Materials which act to speed up the degradation or destruction of the actuating element"under overload currents are especially useful, for example small amounts of substances which oxidise very rapidly on heating or passage of overload electric current through the conductive polymer actuating element so as to destroy it and break the circuit more rapidly.
  • the oxidising substance could be carried simply as a coating in a restricted area on the actuating element for oxidation on heating thereof, but it is possible in accordance with the present invention for doped systems to carry an explosive dopant, such as picrate ions, or a rapidly oxidising dopant such as perchlorate ions, preferably in the presence of a suitable "fuel" as described in Preparation 3 and 4 above capable of explosive reaction with the dopant, thus conveniently combining the functions of doping and oxidation.
  • a suitable fuel for the perchlorate dopant could be any readily oxidisable material which can be suitably associated with the perchlorate ions in or on the conductive polymer to produce the desired effect. Conveniently, the film itself may provide adequate fuel for the oxidation.
  • the circuit interruption device of this invention may be used as an electrical initiator or primer for explosive devices, e.g. a so-called "bridge wire", in which the relatively fast response of the present device at low overload currents may provide better control of detonation.
  • a fuse was prepared as in Example 1 using per- chlorate/polyethylene glycol doped polypyrrole prepared as in Preparation 3, having a conductivity of 200 ohm -1 cm -1 . At a current of 120mA the fuse "blew" by detonation in 150 milliseconds.
  • Example 1 was repeated using picrate-doped polypyrrole prepared as in Preparation 4, having a conductivity of 11 ohm -1 cm -1 . At a current of 120 mA the fuse "blew" by detonation in 1.1 seconds.

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  • Fuses (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
EP83307922A 1982-12-23 1983-12-22 Elektrische Stromkreisunterbrechungsvorrichtung Withdrawn EP0115191A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8236696 1982-12-23
GB8236696 1982-12-23

Publications (1)

Publication Number Publication Date
EP0115191A1 true EP0115191A1 (de) 1984-08-08

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Family Applications (1)

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EP83307922A Withdrawn EP0115191A1 (de) 1982-12-23 1983-12-22 Elektrische Stromkreisunterbrechungsvorrichtung

Country Status (2)

Country Link
EP (1) EP0115191A1 (de)
JP (1) JPS59134523A (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2626396A1 (fr) * 1988-01-22 1989-07-28 Oge Josette Systeme permettant l'acquisition de reflexes instantanes du controle des retroviseurs par l'eleve
FR2648078A1 (fr) * 1989-06-09 1990-12-14 Boulet D Auria Terlizzi Element d'electro-soudage en matiere plastique conductrice et raccord d'electro-soudage pour elements en matiere plastique realise a l'aide de celui-ci
US6440834B2 (en) 1999-06-04 2002-08-27 International Business Machines Corporation Method and structure for a semiconductor fuse
US6528815B1 (en) 1996-02-16 2003-03-04 Koninkl Philips Electronics Nv Write-once read-many electrical memory element of a conjugated polymer or oligomer
KR101278733B1 (ko) * 2010-06-28 2013-06-25 후란스 벳도 가부시키가이샤 삼륜 자전거의 요동 장치

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62161488U (de) * 1985-12-27 1987-10-14

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4293836A (en) * 1979-07-11 1981-10-06 San-O Industrial Co., Ltd. Electrical fuse with an improved fusible element
EP0054420A2 (de) * 1980-12-12 1982-06-23 Matsushita Electric Industrial Co., Ltd. Elektrisches Bauelement
EP0059342A1 (de) * 1981-02-18 1982-09-08 BASF Aktiengesellschaft Verfahren zur Herstellung von stabilen elektrisch leitfähigen Polymeren und deren Verwendung

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4293836A (en) * 1979-07-11 1981-10-06 San-O Industrial Co., Ltd. Electrical fuse with an improved fusible element
EP0054420A2 (de) * 1980-12-12 1982-06-23 Matsushita Electric Industrial Co., Ltd. Elektrisches Bauelement
EP0059342A1 (de) * 1981-02-18 1982-09-08 BASF Aktiengesellschaft Verfahren zur Herstellung von stabilen elektrisch leitfähigen Polymeren und deren Verwendung

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2626396A1 (fr) * 1988-01-22 1989-07-28 Oge Josette Systeme permettant l'acquisition de reflexes instantanes du controle des retroviseurs par l'eleve
FR2648078A1 (fr) * 1989-06-09 1990-12-14 Boulet D Auria Terlizzi Element d'electro-soudage en matiere plastique conductrice et raccord d'electro-soudage pour elements en matiere plastique realise a l'aide de celui-ci
US5229581A (en) * 1989-06-09 1993-07-20 Boulet D'auria, Terlizzi Et Cie Electro-welding element of conductive plastic and an electro-welding coupling including said element for interconnecting pieces made of plastic
EP0402200A3 (de) * 1989-06-09 1993-10-06 Boulet-D'auria, Terlizzi & Cie Elektro-Schweiss-Element aus leitendem Kunststoff und damit ausgestattete Elektro-Schweissmuffe zum Verbinden von Kunststoffgegenständen
US6528815B1 (en) 1996-02-16 2003-03-04 Koninkl Philips Electronics Nv Write-once read-many electrical memory element of a conjugated polymer or oligomer
US6440834B2 (en) 1999-06-04 2002-08-27 International Business Machines Corporation Method and structure for a semiconductor fuse
KR101278733B1 (ko) * 2010-06-28 2013-06-25 후란스 벳도 가부시키가이샤 삼륜 자전거의 요동 장치

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Publication number Publication date
JPS59134523A (ja) 1984-08-02

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Inventor name: ATKINS, IAN PAUL