EP0258139B1 - Elément chauffant autorégulant et son procédé de préparation - Google Patents

Elément chauffant autorégulant et son procédé de préparation Download PDF

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Publication number
EP0258139B1
EP0258139B1 EP87401902A EP87401902A EP0258139B1 EP 0258139 B1 EP0258139 B1 EP 0258139B1 EP 87401902 A EP87401902 A EP 87401902A EP 87401902 A EP87401902 A EP 87401902A EP 0258139 B1 EP0258139 B1 EP 0258139B1
Authority
EP
European Patent Office
Prior art keywords
copolymer
vinyl acetate
weight
carbon black
self
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
EP87401902A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0258139A1 (fr
Inventor
Bernard Michel Dalle
Claude Caillot
François Legros
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.)
Electricite de France SA
Original Assignee
Electricite de France SA
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 Electricite de France SA filed Critical Electricite de France SA
Priority to AT87401902T priority Critical patent/ATE73257T1/de
Publication of EP0258139A1 publication Critical patent/EP0258139A1/fr
Application granted granted Critical
Publication of EP0258139B1 publication Critical patent/EP0258139B1/fr
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
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/146—Conductive polymers, e.g. polyethylene, thermoplastics

Definitions

  • the invention relates to a self-regulating heating element.
  • self-regulating heating elements structures, in particular of the cable or strip type, established in a synthetic polymer material which is given, by incorporation of conductive fillers, in particular carbon black, a resistivity which increases from the ambient temperature - it then has a value called P amb - up to a so-called "switching" temperature from which it increases very quickly to a maximum value called P max.
  • the self-regulating heating elements in question are said to have a positive temperature coefficient, by abbreviation CTP.
  • the switching temperature is not very far from the melting temperature of the polymer and experience has shown that, for temperatures above the melting temperature, certain polymers have a negative temperature coefficient, by abbreviation CTN, corresponding to a rapid decrease in resistivity.
  • the properties of the self-regulating heating elements derive from the PTC and the switching temperature.
  • the calorific energy dissipated by Joule effect within the element will depend on the temperature at which this one is find and, in any case, decrease as this temperature increases; this decrease becomes faster when the switching temperature is exceeded.
  • the temperature of the heating element increases, by the Joule effect, up to a temperature from which very little electric current flows through the element; it cools, its resistivity decreases, more current flows, the temperature rises and so on.
  • the resistivity of the elements in question does not increase suddenly from a given temperature; it simply increases faster from a certain temperature range including the switching temperature.
  • Figures 1 and 2 of the drawing show respectively in plan and in section along II-II fig. 1, a heating element established in accordance with the invention.
  • the proportion of vinyl acetate is preferably from 9 to 2% and, in practice, from 9 to 5%.
  • the proportion with which these black carbo are not dispersed in the copolymer is preferably 23 to 27% by weight and in particular 25% by weight.
  • antioxidant based on 4,4'-thiobis- (6-tert.-butyl-3-methylphenol) known under the trademark SANTONOX is mentioned.
  • the intimate mixture once obtained is extruded in a manner known per se in the form of a cable or a ribbon in which are embedded in the longitudinal direction and substantially parallel to each other, two conductive wires for example made of copper, tinned copper or nickel-plated copper.
  • the ribbon is generally represented at 1 and the wires at 2a and 2b.
  • the two wires are connected to the terminals of an electrical outlet 3.
  • the copolymer constituting the ribbon once extruded and provided with its wires, is crosslinked by irradiation; the conductive charges distributed in the copolymer are shown in 1 b.
  • the irradiation can be carried out by electron bombardment ( ⁇ radiation) with a dose of 15 Mrads.
  • the ribbon 1 may be advantageous to cover the ribbon 1 with a sheath 4 in a polymer or mixture of polymers with a melting temperature higher than that of the constituent copolymer of the ribbon 1, the latter being 105 ° C., 102 ° C. and 98 ° C. for vinyl acetate proportions of 5%, 7.5% and 9% respectively.
  • the switching temperature Tc (which corresponds to the intersection of the segments (almost linear for the copolymers used in accordance with the invention) encountered on the ascending part of the curve (the first segment being that between ambient temperature and the switching temperature, while the second is that reflecting the - brutal increase in the case of the copolymers used according to the invention - of the resistivity above switching temperature)] is determined with an inaccuracy of only ⁇ 5 ° C.
  • the range within which the switching temperatures are for the copolymers having a proportion of 5 to 9% of vinyl acetate is from 61 to 80 ° C.
  • the value of the resistivity P max (expressed in ⁇ -cm) at the peak temperature being approximately 10 9 while it is 5.10 4 at room temperature in the case of the element according to the invention constituted with a copolymer comprising 9% by weight of vinyl acetate and in which 25% by weight of carbon black have been dispersed, the ratio is approximately 2.10 4 .
  • this ratio is greater than 10 4 for all the heating elements of the type in question in accordance with the invention, which reflects the frank and abrupt nature of the increase in resistivity above the switching temperature, frank character that the heating elements of the kind in question according to the prior art do not have.
  • the stability of the self-regulating heating elements according to the invention is remarkable; it is reported that the decrease in the peak ratio is very small after 100 cycles between 70 and 130 ° C.
  • the elements in question do not have a negative temperature coefficient between the melting temperature of the copolymer and 120 ° C.
  • constituent copolymer of the self-regulating heating elements in accordance with the invention does not flow according to the NFC 32020 standard.

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Ceramic Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Dispersion Chemistry (AREA)
  • Resistance Heating (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Apparatuses And Processes For Manufacturing Resistors (AREA)
  • Thermistors And Varistors (AREA)
  • Surface Heating Bodies (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Formation Of Insulating Films (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
EP87401902A 1986-08-21 1987-08-19 Elément chauffant autorégulant et son procédé de préparation Expired - Lifetime EP0258139B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87401902T ATE73257T1 (de) 1986-08-21 1987-08-19 Selbst regulierendes heizelement und verfahren zu seiner herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8611945A FR2603133B1 (fr) 1986-08-21 1986-08-21 Element chauffant autoregulant et son procede de preparation
FR8611945 1986-08-21

Publications (2)

Publication Number Publication Date
EP0258139A1 EP0258139A1 (fr) 1988-03-02
EP0258139B1 true EP0258139B1 (fr) 1992-03-04

Family

ID=9338434

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87401902A Expired - Lifetime EP0258139B1 (fr) 1986-08-21 1987-08-19 Elément chauffant autorégulant et son procédé de préparation

Country Status (10)

Country Link
US (1) US4908156A (enrdf_load_stackoverflow)
EP (1) EP0258139B1 (enrdf_load_stackoverflow)
JP (1) JPS63126203A (enrdf_load_stackoverflow)
AT (1) ATE73257T1 (enrdf_load_stackoverflow)
AU (1) AU610514B2 (enrdf_load_stackoverflow)
CA (1) CA1332280C (enrdf_load_stackoverflow)
DE (1) DE3777016D1 (enrdf_load_stackoverflow)
ES (1) ES2029280T3 (enrdf_load_stackoverflow)
FR (1) FR2603133B1 (enrdf_load_stackoverflow)
GR (1) GR3003975T3 (enrdf_load_stackoverflow)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0344734B1 (en) * 1988-06-01 1995-01-11 Matsushita Electric Industrial Co., Ltd. Temperature self-controlling heating composition
US5122641A (en) * 1990-05-23 1992-06-16 Furon Company Self-regulating heating cable compositions therefor, and method
US5113058A (en) * 1990-06-01 1992-05-12 Specialty Cable Corp. PCT heater cable composition and method for making same
US5517003A (en) * 1993-06-29 1996-05-14 Metagal Industria E Comercio Ltd. Self-regulating heater including a polymeric semiconductor substrate containing porous conductive lampblack
FR2733637B1 (fr) * 1995-04-26 1997-05-30 Gec Alsthom T & D Sa Appareillage isole a l'hexafluorure de soufre
US6036829A (en) * 1997-02-10 2000-03-14 Denso Corporation Oxygen sensor
DE102014005093A1 (de) * 2014-01-08 2015-07-09 Voss Automotive Gmbh Konfektionierte beheizbare Medienleitung sowie Verfahren zu deren Herstellung
DE102014005094A1 (de) * 2014-01-08 2015-07-09 Voss Automotive Gmbh Beheizbare Medienleitung, Verfahren zu deren Herstellung und Schaltungsanordnung für eine beheizbare Medienleitung

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3849333A (en) * 1972-09-26 1974-11-19 Union Carbide Corp Semi-conducting polymer system comprising a copolymer of ethylene-ethylarcralate or vinyl acetate,ethylene-propylene-termonomer and carbon black
JPS5123543A (ja) * 1974-08-22 1976-02-25 Dainippon Printing Co Ltd Dodenseikobunshizairyo
GB1597007A (en) * 1976-12-16 1981-09-03 Raychem Corp Conductive polymer compositions and devices
US4388607A (en) * 1976-12-16 1983-06-14 Raychem Corporation Conductive polymer compositions, and to devices comprising such compositions
US4150193A (en) * 1977-12-19 1979-04-17 Union Carbide Corporation Insulated electrical conductors
US4200973A (en) * 1978-08-10 1980-05-06 Samuel Moore And Company Method of making self-temperature regulating electrical heating cable
SE433999B (sv) * 1982-11-12 1984-06-25 Wolfgang Bronnvall Sjelvbegrensande elektrisk uppvermningsanordning och elektriskt motstandsmaterial
JPS6092340A (ja) * 1983-10-27 1985-05-23 Mitsubishi Petrochem Co Ltd 半導電性樹脂組成物
JPS61187119A (ja) * 1985-02-14 1986-08-20 Denki Kagaku Kogyo Kk 磁気記録媒体

Also Published As

Publication number Publication date
JPS63126203A (ja) 1988-05-30
ES2029280T3 (es) 1992-08-01
FR2603133B1 (fr) 1990-04-06
DE3777016D1 (de) 1992-04-09
AU610514B2 (en) 1991-05-23
ATE73257T1 (de) 1992-03-15
GR3003975T3 (enrdf_load_stackoverflow) 1993-03-16
AU7731487A (en) 1988-02-25
US4908156A (en) 1990-03-13
EP0258139A1 (fr) 1988-03-02
CA1332280C (en) 1994-10-11
FR2603133A1 (fr) 1988-02-26

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