EP0810612A1 - Oxide ceramic thermistor containing indium - Google Patents

Oxide ceramic thermistor containing indium Download PDF

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Publication number
EP0810612A1
EP0810612A1 EP97201533A EP97201533A EP0810612A1 EP 0810612 A1 EP0810612 A1 EP 0810612A1 EP 97201533 A EP97201533 A EP 97201533A EP 97201533 A EP97201533 A EP 97201533A EP 0810612 A1 EP0810612 A1 EP 0810612A1
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Prior art keywords
spinel
composition
thermistor
oxide
oxide ceramic
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German (de)
French (fr)
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EP0810612B1 (en
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Wilhelm Albert Dr. Groen
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Philips Intellectual Property and Standards GmbH
Koninklijke Philips NV
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Philips Patentverwaltung GmbH
Koninklijke Philips Electronics NV
Philips Electronics NV
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-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
    • H01C7/04Non-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 negative temperature coefficient
    • H01C7/042Non-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 negative temperature coefficient mainly consisting of inorganic non-metallic substances
    • H01C7/043Oxides or oxidic compounds

Definitions

  • the invention relates to a thermistor with a semiconductor ceramic with an oxide spinel.
  • Thermistors also called NTC resistors, have a negative temperature coefficient (NTC), their resistivity decreases almost exponentially with temperature.
  • Semiconducting oxide ceramics are usually used as resistance-determining materials. Ceramic thermistors are widely used as temperature sensors, e.g. B. in the food and plastics industry, in automotive electronics, in portable industrial measuring instruments and in medical technology, also as clinical thermometers. Some of the applications concern the temperature compensation of coils, the operating point stabilization of transistors and the overtemperature protection of electronic devices. Advantageous applications also arise in low-temperature measurement technology, as radiation receivers in pyrometers and as transmitters in flow anemometers.
  • oxide spinels An important group of ceramic materials for the manufacture of thermistors are the oxide spinels. These are ionic crystals with the composition AB 2 O 4 , the structure of which is determined by the cubic closest packing of the large negatively charged oxygen ions O 2- . The larger cations A occupy octahedral gaps in the anion lattice, the smaller cations B occupy the tetrahedral gaps in the anion lattice.
  • Today's thermistor components are based almost exclusively on mixed crystals with spinel structure, which are generally composed of 2 to 4 cations from the group manganese, nickel, cobalt, iron, copper and titanium.
  • One problem, however, is the thermal stability of these connections. In order to obtain uniform spinel phases, precise process control is necessary even in the manufacturing process. In addition, the working temperatures must not exceed certain upper limit values.
  • NTC resistors with the general formula Zn z Fe xz III Ni Mn 2-xz III Mn z IV O 4 with 0> z ⁇ x. These oxide spinels form a uniform spinel phase, they do not fall into separate oxide phases during production and can therefore be produced with a reproducible setting of the thermistor parameters.
  • the object is achieved by a thermistor with a semiconductor ceramic with an oxide spinel, which contains the elements manganese, nickel and indium.
  • a thermistor with a semiconductor ceramic with an oxide spinel which contains the elements manganese, nickel and indium, is thermodynamically very stable because indium only occurs in one oxidation state (+3) and therefore not with oxygen the atmosphere reacts. It is also characterized by high values for the specific resistance and the B value.
  • the oxide spinel has the composition Mn 2.33-x In x Ni 0.67 O 4 with 0.05 x x 0,7 0.75.
  • Spinels with this composition are particularly stable at high working temperatures because their crystal structure is monomorphic, ie they do not change at higher temperatures.
  • the spinel has the composition Mn 2.33-x In x Ni 0.67 O 4 with 0.5 ⁇ x ⁇ 0.66.
  • a thermistor with such a composition has a surprisingly high thermal stability of the resistance value in the long-term test.
  • Fig. 1 Specific resistance and B value as a function of the indium content x in Mn 2.33-x In x Ni 0.67 O 4 .
  • the thermistor according to the invention contains a semiconductor ceramic with an oxide spinel, which contains the elements manganese, nickel and indium, in particular those of the composition Mn 2.33-x In x Ni 0.67 O 4 with 0.05 x x 0,7 0.75 . Due to the low electron affinity and the high ionization potential of indium (+3), this oxide spinel is redox-stable and does not change through interaction with the atmosphere at elevated temperatures.
  • the composition of the spinel is preferably chosen so that it is close to the phase transition from the cubic to the tetragonal spinel structure and the composition Mn 2.33-x In x Ni 0.67 O 4 with 0.05 ⁇ x ⁇ 0 , 75 has. Surprisingly, it has been found that these compositions show minimal aging.
  • the thermistor is manufactured according to the usual ceramic manufacturing methods, with numerous variants being possible depending on the desired tolerances and the field of application.
  • oxides, hydroxides, carbonates, oxalates and the like. use. These are weighed in according to the desired composition, wet milled, dried and granulated.
  • the oxide mixture can then be calcined at 900 ° C to 1000 ° C to achieve pre-compression and chemical homogenization.
  • the calcined mixture is ground again and suspended with a binder composition. This is followed by the design.
  • the powder suspension can be cast into foils or screen printed onto a substrate for thick-film circuits.
  • the suspension can also be processed into granules, from which any shaped body can then be pressed.
  • the binder is burned out and then the final sintering, in which the spinel phase is formed.
  • the contacts are applied in a further process step.
  • Single-phase oxide spinels are formed, which contain the elements manganese, nickel and indium. This is confirmed by X-ray examinations.
  • the corresponding starting oxides are mixed in a stoichiometric mixing ratio and 16 Milled for hours with zircon grinding balls.
  • the premixed powder is granulated with a conventional binder preparation. Tablets with a diameter of 6 mm and a thickness of 1 mm are pressed from the granules. These tablets are sintered in the air for six hours at 1250 ° C. X-ray diffraction images show that the semiconductor ceramic obtained in this way is a single-phase material with a spinel structure.
  • the relative density of the mixed crystal oxides is greater than 97% of the theoretical density.
  • Fig. 1 shows that the main thermistor parameters, ie the specific resistance (R 25 ) and the B value increase with increasing indium content.
  • the aging tests were carried out at 150 ° C for 1800 h.
  • the thermistor parameters R 25 and the thermal constant B were measured at intervals. The tests showed that the aging is practically complete after 150 h.
  • the experiments further showed that the relative change in the resistance R / R 0 with time near the phase boundary between the cubic and tetragonal phase boundary has a minimum.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Thermistors And Varistors (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

A novel thermistor includes a semiconductor ceramic comprising an oxide spinel containing Mn, Ni and In. Preferably, the oxide spinel has the composition Mn2.33-xInxNi0.67O4, where x = 0.05 to 0.75, preferably 0.5 to 0.66, especially 0.58 plus or minus 0.02.

Description

Die Erfindung betrifft einen Thermistor mit einer Halbleiterkeramik mit einem Oxid-Spinell.The invention relates to a thermistor with a semiconductor ceramic with an oxide spinel.

Thermistoren, auch NTC-Widerstände genannt, haben einen negativen Temperaturkoeffizienten (NTC), ihr spezifischer Widerstand nimmt mit der Temperatur annähernd exponentiell ab. Als widerstandsbestimmende Materialien werden üblicherweise halbleitende Oxidkeramiken verwendet. Keramische Thermistoren sind als Temperatursensoren weitverbreitet, z. B. in der Lebensmittel- und Kunststoffindustrie, in der Kfz-Elektronik, in transportablen Betriebsmeßgeräten und in der medizinischen Technik, auch als Fieberthermometer. Ein Teil der Anwendungen betrifft die Temperaturkompensation von Spulen, die Arbeitspunktstabilisierung von Transistoren und die Übertemperatursicherung von elektronischen Geräten. Vorteilhafte Anwendungen ergeben sich auch in der Tieftemperatur-Meßtechnik, als Strahlungsempfänger in Pyrometern und als Geber in Strömungsanemometern.Thermistors, also called NTC resistors, have a negative temperature coefficient (NTC), their resistivity decreases almost exponentially with temperature. Semiconducting oxide ceramics are usually used as resistance-determining materials. Ceramic thermistors are widely used as temperature sensors, e.g. B. in the food and plastics industry, in automotive electronics, in portable industrial measuring instruments and in medical technology, also as clinical thermometers. Some of the applications concern the temperature compensation of coils, the operating point stabilization of transistors and the overtemperature protection of electronic devices. Advantageous applications also arise in low-temperature measurement technology, as radiation receivers in pyrometers and as transmitters in flow anemometers.

Es existiert eine Vielzahl von halbleitenden Oxidkeramiken mit NTC-Characteristik. Für die praktische Anwendbarkeit müssen neben der Temperaturabhängigkeit des Widerstandes weitere Bedingungen wie gute Sinterbarkeit, mechanische und chemische Stabilität erfüllt sein.There are a number of semiconducting oxide ceramics with NTC characteristics. For practical use, in addition to the temperature dependence of the resistance, other conditions such as good sinterability, mechanical and chemical stability must be met.

Eine wichtige Gruppe von keramischen Werkstoffen für die Herstellung von Thermistoren sind die Oxid-Spinelle. Dabei handelt es sich um Ionenkristalle der Zusammensetzung AB2O4, deren Aufbau durch die kubisch dichteste Kugelpackung der großen negativ geladenen Sauerstoffionen O2-, bestimmt wird. Die größeren Kationen A besetzen Oktaederlücken des Anionengitters, die Kleineren Kationen B die Tetraederlücken des Anionengitters. Heutige Thermistor-Bauelemente basieren fast ausschließlich auf Mischkristallen mit Spinellstruktur, die sich im allgemeinen aus 2 bis 4 Kationen der Gruppe Mangan, Nickel, Cobalt, Eisen, Kupfer und Titan zusammensetzen. Ein Problem ist jedoch die thermische Stabilität dieser Verbindungen. Um einheitliche Spinellphasen zu erhalten, ist schon beim Herstellungsverfahren eine genaue Prozeßführung notwendig. Außerdem dürfen die Arbeitstemperaturen bestimmte obere Grenzwerte nicht überschreiten.An important group of ceramic materials for the manufacture of thermistors are the oxide spinels. These are ionic crystals with the composition AB 2 O 4 , the structure of which is determined by the cubic closest packing of the large negatively charged oxygen ions O 2- . The larger cations A occupy octahedral gaps in the anion lattice, the smaller cations B occupy the tetrahedral gaps in the anion lattice. Today's thermistor components are based almost exclusively on mixed crystals with spinel structure, which are generally composed of 2 to 4 cations from the group manganese, nickel, cobalt, iron, copper and titanium. One problem, however, is the thermal stability of these connections. In order to obtain uniform spinel phases, precise process control is necessary even in the manufacturing process. In addition, the working temperatures must not exceed certain upper limit values.

Es ist in der DE 42 13 629 vorgeschlagen worden, NTC-Widerstände mit der allgemeinen Formel ZnzFex-z IIINi Mn2-x-z IIIMnz IVO4 mit 0 > z < x herzustellen. Diese Oxidspinelle bilden eine einheitliche Spinellphase, sie verfallen bei der Herstellung nicht in separate Oxidphasen und lassen sich daher mit reproduzierbarer Einstellung der Thermistorparameter herstellen.It has been proposed in DE 42 13 629 to produce NTC resistors with the general formula Zn z Fe xz III Ni Mn 2-xz III Mn z IV O 4 with 0> z <x. These oxide spinels form a uniform spinel phase, they do not fall into separate oxide phases during production and can therefore be produced with a reproducible setting of the thermistor parameters.

Im Gebrauch verändert sich jedoch in diesen Spinellphasen durch Wechselwirkung mit der Atmosphäre die Oxidationsstufen des Eisens und damit auch die Themistorparameter. Außerdem lassen sich so nur Spinelle mit bestimmten Thermistorparameterbereichen herstellen.In use, however, the oxidation levels of iron and thus also the themistor parameters change in these spinel phases through interaction with the atmosphere. In addition, only spinels with certain thermistor parameter ranges can be produced in this way.

Es ist daher eine Aufgabe der vorliegenden Erfindung, einen Thermistor mit einer Halbleiterkeramik mit einem Oxid-Spinell zu schaffen, der thermisch stabil ist und hohe Thermistorparameter aufweist.It is therefore an object of the present invention to provide a thermistor with a semiconductor ceramic with an oxide spinel, which is thermally stable and has high thermistor parameters.

Erfindungsgemäß wird die Aufgabe gelöst durch einen Thermistor mit einer Halbleiterkeramik mit einem Oxid-Spinell, der die Elemente Mangan, Nickel und Indium enthält.According to the invention, the object is achieved by a thermistor with a semiconductor ceramic with an oxide spinel, which contains the elements manganese, nickel and indium.

Ein Thermistor mit einer Halbleiterkeramik mit einem Oxid-Spinell, der die Elemente Mangan, Nickel und Indium enthält, ist thermodynamisch sehr stabil, weil Indium nur in einer Oxidatonsstufe (+3) auftritt und daher nicht mit dem Sauerstoff der Atmospäre reagiert. Er zeichnet sich weiterhin durch hohe Werte für den spezifischen Widerstand und den B-Wert aus.A thermistor with a semiconductor ceramic with an oxide spinel, which contains the elements manganese, nickel and indium, is thermodynamically very stable because indium only occurs in one oxidation state (+3) and therefore not with oxygen the atmosphere reacts. It is also characterized by high values for the specific resistance and the B value.

Es ist im Rahmen der vorliegenden Erfindung besonders bevorzugt, daß der Oxid-Spinell die Zusammensetzung Mn2,33-xInxNi0,67O4 mit 0,05 ≤ x ≤ 0,75 hat. Spinelle mit dieser Zusammensetzung zeichnen sich durch eine besondere Stabilität bei hohen Arbeitstemperaturen aus, weil ihre Kristallstruktur monomorph ist, d.h. sie verändert sich nicht bei höheren Temperaturen.It is particularly preferred in the context of the present invention that the oxide spinel has the composition Mn 2.33-x In x Ni 0.67 O 4 with 0.05 x x 0,7 0.75. Spinels with this composition are particularly stable at high working temperatures because their crystal structure is monomorphic, ie they do not change at higher temperatures.

Es ist bevorzugt, daß der Spinell die Zusammensetzung Mn2,33-xInxNi0,67O4 mit 0,5 ≤ x ≤ 0,66 hat.It is preferred that the spinel has the composition Mn 2.33-x In x Ni 0.67 O 4 with 0.5 ≤ x ≤ 0.66.

Es ist besonders bevorzugt, daß der Spinell die Zusammensetzung Mn2,33-xInxNi0,67O4 mit x =0.58 ± 0,02 hat. Ein Thermistor mit einer derartigen Zusammensetzung hat eine überraschend hohe thermische Stabilität des Widerstandswertes im Langzeittest.It is particularly preferred that the spinel has the composition Mn 2.33-x In x Ni 0.67 O 4 with x = 0.58 ± 0.02. A thermistor with such a composition has a surprisingly high thermal stability of the resistance value in the long-term test.

Nachfolgend wird die Erfindung anhand von Beispielen und einer Zeichnung weiter erläutert.The invention is explained in more detail below with the aid of examples and a drawing.

Fig. 1: Spezifischer Widerstand und B-Wert als Funktion des Indium-Gehaltes x in Mn2.33-xInxNi0.67O4. Fig. 1: Specific resistance and B value as a function of the indium content x in Mn 2.33-x In x Ni 0.67 O 4 .

Der erfindungsgemäße Thermistor enthält eine Halbleiterkeramik mit einem Oxid-Spinell, der die Elemente Mangan, Nickel und Indium enthält, insbesondere solche der Zusammensetzung Mn2,33-xInxNi0,67O4 mit 0,05 ≤ x ≤ 0,75. Durch die geringe Elektronenaffinität und das hohe Ionisationspotential des Indiums(+3) ist dieser Oxid-Spinell redoxstabil und verändert sich nicht durch Wechselwirkung mit der Atmosphäre bei erhöhten Temperaturen.The thermistor according to the invention contains a semiconductor ceramic with an oxide spinel, which contains the elements manganese, nickel and indium, in particular those of the composition Mn 2.33-x In x Ni 0.67 O 4 with 0.05 x x 0,7 0.75 . Due to the low electron affinity and the high ionization potential of indium (+3), this oxide spinel is redox-stable and does not change through interaction with the atmosphere at elevated temperatures.

Die Zusammensetzung des Spinell wird bevorzugt so gewählt, daß sie in der Nähe des Phasenüberganges von der kubischen zur tetragonalen Spinell-Struktur liegt und die Zusammensetzung Mn2,33-xInxNi0,67O4 mit 0,05 ≤ x ≤ 0,75 hat. Überraschenderweise wurde gefunden, daß diese Zusammensetzungen minimale Alterung zeigen.The composition of the spinel is preferably chosen so that it is close to the phase transition from the cubic to the tetragonal spinel structure and the composition Mn 2.33-x In x Ni 0.67 O 4 with 0.05 ≤ x ≤ 0 , 75 has. Surprisingly, it has been found that these compositions show minimal aging.

Die Herstellung des Thermistors erfolgt nach den üblichen keramischen Fertigungsmethoden, wobei je nach den angestrebten Toleranzen und dem Anwendungsgebiet zahlreiche Varianten möglich sind. Als Ausgangsverbindungen kann man von Oxiden, Hydroxiden, Carbonaten, Oxalaten u. ä. verwenden. Diese werden gemäß der gewünschten Zusammensetzung eingewogen, naß gemahlen, getrocknet und granuliert. Anschließend kann man das Oxid- Gemisch bei 900°C bis 1000°C kalzinieren, um eine Vorverdichtung und chemische Homogenisierung zu erreichen. Die kalzinierte Mischung wird erneut gemahlen und mit einer Bindemittelzusammensetzung suspendiert. Daran schließt sich die Formgebung an. Die Pulversuspension kann zu Folien gegossen werden oder für Schaltungen in Dickschichttechnik auf ein Substrat siebgedruckt werden. Die Suspension kann auch zu Granulat verarbeitet werden, aus dem dann beliebige Formkörper gepreßt werden können. Anschließend erfolgt zunächst der Binderausbrand und dann die abschließende Sinterung, bei dem die Spinellphase gebildet wird. In einem weiteren Verfahrensschritt werden die Kontakte aufgebracht.The thermistor is manufactured according to the usual ceramic manufacturing methods, with numerous variants being possible depending on the desired tolerances and the field of application. As starting compounds, oxides, hydroxides, carbonates, oxalates and the like. use. These are weighed in according to the desired composition, wet milled, dried and granulated. The oxide mixture can then be calcined at 900 ° C to 1000 ° C to achieve pre-compression and chemical homogenization. The calcined mixture is ground again and suspended with a binder composition. This is followed by the design. The powder suspension can be cast into foils or screen printed onto a substrate for thick-film circuits. The suspension can also be processed into granules, from which any shaped body can then be pressed. Then the binder is burned out and then the final sintering, in which the spinel phase is formed. The contacts are applied in a further process step.

Es bilden sich einphasige Oxid-Spinelle, die die Elemente Mangan, Nickel und Indium enthalten. Dies wird durch röntgenographische Untersuchungen bestätigt.Single-phase oxide spinels are formed, which contain the elements manganese, nickel and indium. This is confirmed by X-ray examinations.

AusführungsbeispielEmbodiment

Es werden Halbleiterkeramiken mit Oxidspinellen hergestellt, die Zusammensetzung Mn2,33-xInxNi0,67O4 mit x= 1/12, 1/6,1/3 und 2/3 haben . Die entsprechenden Ausgangsoxide werden im stöchiometrischen Mischungsverhältnis gemischt und 16 Stunden mit Zirkon-Mahlkugeln gemahlen. Das vorgemischte Pulver wird mit einer konventionellen Bindemittelzubereitung granuliert. Aus dem Granulat werden Tabletten mit einem Durchmesser von 6mm und einer Dicke von 1mm gepreßt. Diese Tabletten werden sechs Stunden bei 1250°C an der Luft gesintert. Röntgenbeugungsaufnahmen zeigen, daß die so erhaltene Halbleiterkeramik ein einphasiges Material mit Spinell - Struktur ist. Die relative Dichte der Mischkristalloxide ist größer als 97 % der theoretischen Dichte.Semiconductor ceramics with oxide spinels are produced, which have the composition Mn 2.33-x In x Ni 0.67 O 4 with x = 1/12, 1 / 6.1 / 3 and 2/3. The corresponding starting oxides are mixed in a stoichiometric mixing ratio and 16 Milled for hours with zircon grinding balls. The premixed powder is granulated with a conventional binder preparation. Tablets with a diameter of 6 mm and a thickness of 1 mm are pressed from the granules. These tablets are sintered in the air for six hours at 1250 ° C. X-ray diffraction images show that the semiconductor ceramic obtained in this way is a single-phase material with a spinel structure. The relative density of the mixed crystal oxides is greater than 97% of the theoretical density.

TestergebnisseTest results

Fig. 1 zeigt, daß wichtigsten Thermistorparameter, d.h. der spezifische Widerstand (R25) und der B-Wert mit wachsendem Indium-Gehalt zunehmen.Fig. 1 shows that the main thermistor parameters, ie the specific resistance (R 25 ) and the B value increase with increasing indium content.

Die Alterungsversuche wurden bei 150°C über 1800 h durchgeführt. Dabei wurden in Abständen die Thermistorparameter R25 und die thermische Konstante B gemessen. Die Versuche ergaben, daß die Alterung nach 150 h praktisch abgeschlossen ist. Die Versuche ergaben weiterhin, daß die relative Änderung des Widerstandes R/R0 mit der Zeit in der Nähe der Phasengrenze zwischen kubischer und tetragonaler Phasengrenze ein Minimum hat.The aging tests were carried out at 150 ° C for 1800 h. The thermistor parameters R 25 and the thermal constant B were measured at intervals. The tests showed that the aging is practically complete after 150 h. The experiments further showed that the relative change in the resistance R / R 0 with time near the phase boundary between the cubic and tetragonal phase boundary has a minimum.

Claims (4)

Thermistor mit einer Halbleiterkeramik mit einem Oxid-Spinell, der die Elemente Mangan, Nickel und Indium enthält.Thermistor with a semiconductor ceramic with an oxide spinel, which contains the elements manganese, nickel and indium. Thermistor nach Anspruch 1,
dadurch gekennzeichnet,
daß der Oxid- Spinell die Zusammensetzung Mn2,33-xInxNi0,67O4 mit 0,05 ≤ x ≤ 0,75 hat.
Thermistor according to claim 1,
characterized by
that the oxide spinel has the composition Mn 2.33-x In x Ni 0.67 O 4 with 0.05 ≤ x ≤ 0.75.
Thermistor nach Anspruch 1,
dadurch gekennzeichnet,
daß der Oxid- Spinell die Zusammensetzung Mn2,33-xInxNi0,67O4 mit 0,5 ≤ x ≤ 0,66 hat.
Thermistor according to claim 1,
characterized by
that the oxide spinel has the composition Mn 2.33-x In x Ni 0.67 O 4 with 0.5 ≤ x ≤ 0.66.
Thermistor nach Anspruch 1,
dadurch gekennzeichnet,
daß der Oxid- Spinell die Zusammensetzung Mn2,33-xInxNi0,67O4 mit x =0.58 ± 0,02 hat.
Thermistor according to claim 1,
characterized by
that the oxide spinel has the composition Mn 2.33-x In x Ni 0.67 O 4 with x = 0.58 ± 0.02.
EP97201533A 1996-06-01 1997-05-22 Oxide ceramic thermistor containing indium Expired - Lifetime EP0810612B1 (en)

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DE19622112 1996-06-01
DE19622112A DE19622112A1 (en) 1996-06-01 1996-06-01 Oxide ceramic thermistor containing indium

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DE102008009817A1 (en) * 2008-02-19 2009-08-27 Epcos Ag Composite material for temperature measurement, temperature sensor comprising the composite material and method for producing the composite material and the temperature sensor
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YAMAMOTO H ET AL: "THE DEVELOPMENT OF HIGH SENSITIVITIY NTC THERMISTORS", 7 August 1994, PROCEEDINGS OF THE NINTH IEEE INTERNATIONAL SYMPOSIUM ON APPLICATIONS OF FERROELECTRICS (ISAF), UNIVERSITY PARK, PENNSYLVANIA, AUG. 7 - 10. 1994, NR. SYMP. 9, PAGE(S) 735 - 738, PANDEY R K;LIU M; AHMAD SAFARI, XP000553200 *

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DE59700382D1 (en) 1999-10-07
EP0810612B1 (en) 1999-09-01
DE19622112A1 (en) 1997-12-04
JPH1092609A (en) 1998-04-10
US5976421A (en) 1999-11-02
TW406061B (en) 2000-09-21

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