EP0649150B1 - Verbundwerkstoff - Google Patents

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Publication number
EP0649150B1
EP0649150B1 EP94115003A EP94115003A EP0649150B1 EP 0649150 B1 EP0649150 B1 EP 0649150B1 EP 94115003 A EP94115003 A EP 94115003A EP 94115003 A EP94115003 A EP 94115003A EP 0649150 B1 EP0649150 B1 EP 0649150B1
Authority
EP
European Patent Office
Prior art keywords
resistor
filler
cores
particles
shells
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
EP94115003A
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German (de)
English (en)
French (fr)
Other versions
EP0649150A1 (de
Inventor
Felix Dr. Greuter
Ralf Dr. Strümpler
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.)
ABB Research Ltd Switzerland
ABB Research Ltd Sweden
Original Assignee
ABB Research Ltd Switzerland
ABB Research Ltd Sweden
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Publication date
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Publication of EP0649150A1 publication Critical patent/EP0649150A1/de
Application granted granted Critical
Publication of EP0649150B1 publication Critical patent/EP0649150B1/de
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
    • H01C7/10—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 voltage responsive, i.e. varistors
    • H01C7/12—Overvoltage protection resistors
    • 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
    • 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
    • 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
    • H01C7/10—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 voltage responsive, i.e. varistors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/901—Printed circuit
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/259—Silicic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

Definitions

  • the invention is based on an electrical Resistance according to the preambles of claims 1, 6 and 11.
  • An electrical resistor of the aforementioned type is known from EP-A2-0 548 606.
  • This resistor contains a resistance body made of a composite material with a polymer as a matrix.
  • An electrically conductive powder such as carbon black, and a powdery varistor material, for example based on a spray granulate, are embedded in the polymer matrix as fillers.
  • the electrically conductive powder forms current paths through the resistor body in normal operation.
  • the resistance body heats up intensely above a certain value of the current.
  • the polymer matrix expands greatly and thus separates the particles of the electrically conductive filler that form the current path. The electricity is interrupted.
  • the particles of the varistor material form percolating paths above a predetermined limit value of the voltage locally or through the entire resistance body, which dissipate the undesirably high voltage.
  • two different fillers are required for the functions of current interruption and voltage limitation described above and caused by a non-linear behavior of the composite material with regard to the current or the applied voltage. This is undesirable for some applications and may lead to difficulties in the manufacture of the composite.
  • This resistance has one Resistor body made of a PTC composite material with a Polymer matrix and two powders embedded in the matrix, from which one is made of particles with an electrical Conductivity of at least 100 S / m, in particular carbon black, Silver, gold or nickel, and the other of particles with an electrical conductivity of at most 0.1 S / m and the best possible thermal conductivity, such as in particular Silicon, selenium or SiC is formed.
  • the invention lies based on the task of resistance of the aforementioned Specify which is easy to manufacture and by appropriate choice of filler and matrix with regard to its material properties easily to a given Requirements profile can be adjusted.
  • the resistance according to the invention is characterized in that that it is easy by appropriate selection of filler and matrix can be adapted to a specific requirement profile.
  • This requirement profile can already be used for the State-of-the-art PTC behavior, where the resistance is above a transition temperature increases its resistivity nonlinearly and in doing so limits a current carried by him, also a previous one existing varistor behavior after performing the PTC transition include.
  • Such an electrical resistance is then a Varistor with self-protection against excessive heating.
  • the requirement profile can be in addition to the aforementioned PTC transition include another PTC transition.
  • the resistance is then a PTC resistor in which the temperature of the Current is gradually limited.
  • the filler and / or the matrix can be compared to one external physical size due to a structural change, for example a phase transition from solid to liquid, react by a nonlinear change in a material property, for example the electrical conductivity, is caused.
  • a nonlinear change in one Material properties can also be influenced by the external physical quantities, for example an electrical one Field without causing structural changes.
  • a matrix is called active if it when one or more physical quantities act, one Undergoes structural change which leads to a nonlinear Change in a material property of the composite material leads.
  • a matrix is said to be passive if it Impact of one or more physical quantities none Undergoes structural change and therefore not a non-linear one Change in a material property of the composite material evokes.
  • a polymer for example a thermoplastic and / or thermoset and / or an elastomer, is generally provided as the matrix.
  • an inorganic material for example glass, ceramic, for example based on ZrO 2 , quartz, geopolymer and / or metal, can also be provided as the matrix.
  • the matrix is predominantly made up of solids, but may also be liquid if necessary.
  • the matrix can be passive, but is generally selected to actively respond to temperature changes (polyethylene), pressure (elastomers or thermoplastics filled with deformable particles such as hollow spheres, thermoplastics), or electric fields (piezoelectric polymers such as polyvinylidene fluoride) Structural changes responded.
  • the filler should have particles of core-shell structure or of granular structure with average particle sizes of typically contain up to some 100 ⁇ . If the filler a component with particles of granular structure However, the composite material should not have a filler component contain with electrically conductive particles whose electrical conductivity is higher than electrical conductivity the particles of granular structure upon exposure one to a nonlinear change in electrical Conductivity of the composite leading electrical Field.
  • the shells of the particles of core-shell structure are with Advantage from insulating material, whereas the core of this Particles preferably made of electrically conductive and / or exist electrically semiconducting material.
  • the shells of these particles consist of a chalcogenide, such as, in particular, an oxide or sulfide, a nitride, phosphide and / or sulfate, they should be dimensioned such that the electrical conductivity of the composite material is non-linear for a given value of an electrical field acting in the composite material changes. If the particles are then in a passive matrix formed by a thermoplastic or thermosetting polymer, the electrical conductivity of this composite material can change twice nonlinearly when an appropriate electric field is selected. A first of these nonlinear changes causes a voltage limitation, a second a current, power or energy limitation.
  • a chalcogenide such as, in particular, an oxide or sulfide, a nitride, phosphide and / or sulfate
  • the particles are in an active matrix formed by a thermoplastic or thermoset or elastomeric polymer, then a third non-linear change in the conductivity of the composite material can also be achieved, which serves the additional self-protection of the composite material against excessive power consumption and thus against overheating .
  • the cores can advantageously contain doped V 2 O 3 or doped BaTiO 3 and the insulating shells VO 2 , V 2 O 5 , TiO 2 , BaO, BaS or BaSO 4 .
  • the aforementioned advantageous effects can also be achieved with cores made of doped or undoped semiconducting material, such as in particular ZnO, SiC, Si, TiO 2 or SnO 2 .
  • the cores of the particles have electrically conductive material, such as in particular TiC, TiB 2 , BaTi, SrTi, V 2 O 3 , Al, Cu, Sn, Ti or Zn, and the shells of the particles are formed from a material with a high dielectric constant, which is non-linear depends on an external physical size, preferably a ferroelectric or an antiferroelectric, so there is a composite material which can be used as a dielectric.
  • electrically conductive material such as in particular TiC, TiB 2 , BaTi, SrTi, V 2 O 3 , Al, Cu, Sn, Ti or Zn
  • the shells of the particles are formed from a material with a high dielectric constant, which is non-linear depends on an external physical size, preferably a ferroelectric or an antiferroelectric, so there is a composite material which can be used as a dielectric.
  • the matrix is formed by an elastomeric and therefore pressure-active polymer
  • the shells contain a bismuthate such as, in particular, BaW 1/3 Bi 23 O 3 , a niobate such as, in particular, PbFe 0.5 Nb 0.5 0 3 , and a scandate such as in particular PbW 1/3 Sc 2/3 O 3 , a stannate such as in particular SrSnO 3 , a tantalate such as in particular PbFe 0.5 Ta 0.5 O 3 , a titanate such as in particular BaTiO 3 or SrTiO 3 , a zirconate such as in particular PbZrO 3 , a manganite such as in particular PbW 1/3 Mn 2/3 O 3 , a rhenite such as in particular BaMn 0.5 Re 0.5 O 3 , a tellurite such as in particular BaMn 0.5 Te 0.5 0 3 , a tungsten ( VI
  • the matrix in such a filler is formed by a piezoelectric polymer, in particular polyvinylidene fluoride, and the shells contain bismuth, niobate, scandate, stannate, tantalate, titanate, zirconate, manganite, rhenite, tellurite, tungsten (VI) oxide or gallium (VI ) oxide, alone or in a mixture, two nonlinear changes in the dielectric constant are produced in such a composite material when the electric field strength and the temperature change.
  • This composite material can therefore be used as a dielectric of a voltage and temperature-dependent capacitance.
  • a composite material with a corresponding filler but with a matrix formed by an active thermoplastic or thermosetting polymer.
  • the composite contains a filler in which both the cores and the shells of the particles of core-shell structure are formed from electrically conductive material, the cores and / or the shells undergoing a structural change when exposed to temperature, such composite material can be used as a PTC resistor.
  • the shells should have a thickness such that the reduced electrical conductivity of the cores when there is a change in structure causes an increase in the electrical resistance of the composite material, for example a doubling. In this way, a reduction in a current conducted through the PTC resistor, for example a halving, can be achieved very quickly when a limit temperature is reached. If an active matrix, for example a thermoplastic or thermosetting polymer, is additionally provided, then the slower heating of the polymer then further limits the already reduced current.
  • an active matrix for example a thermoplastic or thermosetting polymer
  • the particles of granular structure provided in the filler as an alternative or optionally together with the particles of core-shell structure are formed either by crushing a sintered ceramic or a polycrystalline semiconductor or by spray drying a suspension or solution and calcining or sintering the spray-dried particles.
  • These particles can be ferroelectric or antiferroelectric and are primarily bismuth, niobate, scandate, stannate, tantalate, titanate, zirconate, manganite, rhenite, tellurite, tungsten (VI) oxide or gallium (VI) oxide, alone or in a mixture and also doped or undoped.
  • the particles can also consist of doped metal oxide or carbide, such as SiC, TiO 2 or ZnO, and / or BaTiO 3 , SrTiO 3 , InSb, GaAs or Si.
  • doped metal oxide or carbide such as SiC, TiO 2 or ZnO, and / or BaTiO 3 , SrTiO 3 , InSb, GaAs or Si.
  • Such composites exhibit two non-linear, oppositely directed changes in the electrical conductivity when the temperature changes and can be used as a combined NTC and PTC resistance element. If the particles with a granular structure are embedded in an active matrix, two non-linear changes in the electrical conductivity occur, one of which has a voltage-limiting effect and the other has a current-, power- or energy-limiting effect.
  • a first embodiment of the resistor according to the Invention was - as known from the manufacture of varistors is - initially from a suspension or a solution of zinc oxide and dopants based on several elements, such as Bi, Sb, Mn, Co, Al, ..., by spray drying a granulate with particle diameters generated between 3 and 300 microns.
  • the granules was sintered into a powder at temperatures of approx. 1200 ° C.
  • the powder particles are essentially spherical trained and each consist of a variety of Grains, which are in the manner of the casing sections of a football casing adjoin.
  • Each of the grains of a powder particle consists of ZnO, which is known to contain Bi, Sb, Mn, and / or further elements and electrical current leads well. Are between adjacent grains electrically insulating grain boundaries, which when a Voltage of about 3 volts become electrically conductive. Depending on Leave selection of dopants and type of manufacturing process powder particles are thus produced, which are present when Voltages between 3 and 200 volts electrically conductive and are electrically non-conductive below this voltage.
  • the Powder particles therefore have an external electrical Field nonlinear, primarily due to the grain boundaries certain behavior. Instead of spherical shape, the Powder particles also have a needle or plate shape and can be compact or hollow depending on the manufacturing conditions be trained.
  • a varistor containing 25 parts by volume of doped ZnO has the current-voltage characteristic I shown in FIG. 1.
  • the varistor behaves essentially like a conventional varistor based on a sintered ceramic and has a highly non-linear dependence of the current I it carries on the applied voltage E.
  • the current is conducted in percolating paths formed by powder particles.
  • the critical current I c the polymer matrix is heated to temperatures higher than the melting temperature of polyethylene. The polymer matrix expands and breaks the current-carrying paths.
  • the varistor now goes back to a high-resistance state and blocks the current.
  • a varistor with the previously Composite described as an NTC or PTC element can be used. When heated, it decreases at temperatures T between 20 and 80 ° C the specific Resistance R of the composite is nonlinear to Temperatures between 110 and 130 ° C non-linear again increase.
  • the first change in resistance by the semi-conductive zinc oxide of the filler and the second Resistance change due to the active at approx. 110 to 130 ° C Polymer matrix can be used.
  • particles of shell-core structure are used as fillers.
  • One of these fillers contains cores made of conductive material, such as in particular V 2 O 3 , and shells made of an oxide, such as especially VO 2 or V 2 O 5 . If such fillers with a volume fraction of typically 20 to 50 percent by volume are embedded in a passive matrix, for example a thermoset based on epoxy, then such a composite material can advantageously be used as a resistance body of a varistor.
  • the current-voltage characteristic of a varistor with a resistance body based on an epoxy matrix and a core made of filler containing V 2 O 3 and shells made of VO 2 is shown in FIG. 1 and identified by the reference symbol II.
  • the filler contains cores made of doped BaTiO 3 instead of the cores made of V 2 O 3 .
  • the shells are advantageously formed from BaO, BaS, BaSO 4 , V 2 O 3 , VO 2 or TiO 2 . Since BaTiO 3 at a predetermined limit temperature due to a change in structure a substantially stronger PTC effect such a varistor causes as V 2 O 3, limits the performance significantly stronger than the varistor described above. This can be seen from its characteristic curve from FIG. 1, designated by the reference symbol III.
  • the composite material is used as a resistance body of a PTC resistor.
  • the composite material contains an active polymer, such as preferably polyethylene, and a filler with a core-shell structure. Both the cores and the shells are made of electrically conductive material. The material is selected in such a way that the cores and / or the shells undergo a structural change when one or more physical variables are involved.
  • the shells are preferably made of a material with good electrical conductivity, such as TiB 2 , TiC or a metal.
  • the cores preferably contain V 2 O 3 or BaTiO 3 , each in doped form.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Ceramic Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Thermistors And Varistors (AREA)
EP94115003A 1993-10-15 1994-09-23 Verbundwerkstoff Expired - Lifetime EP0649150B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH3124/93 1993-10-15
CH312493 1993-10-15

Publications (2)

Publication Number Publication Date
EP0649150A1 EP0649150A1 (de) 1995-04-19
EP0649150B1 true EP0649150B1 (de) 1998-06-24

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US (1) US5858533A (ja)
EP (1) EP0649150B1 (ja)
JP (1) JP3628049B2 (ja)
DE (1) DE59406312D1 (ja)

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US7843308B2 (en) 2002-04-08 2010-11-30 Littlefuse, Inc. Direct application voltage variable material
US8574358B2 (en) 2005-12-06 2013-11-05 James Hardie Technology Limited Geopolymeric particles, fibers, shaped articles and methods of manufacture

Also Published As

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DE59406312D1 (de) 1998-07-30
JPH07169607A (ja) 1995-07-04
US5858533A (en) 1999-01-12
EP0649150A1 (de) 1995-04-19
JP3628049B2 (ja) 2005-03-09

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