EP0810611A1 - Thermistance pour des températures élevées contenant des métaux du groupe de terres rares - Google Patents

Thermistance pour des températures élevées contenant des métaux du groupe de terres rares Download PDF

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Publication number
EP0810611A1
EP0810611A1 EP97201494A EP97201494A EP0810611A1 EP 0810611 A1 EP0810611 A1 EP 0810611A1 EP 97201494 A EP97201494 A EP 97201494A EP 97201494 A EP97201494 A EP 97201494A EP 0810611 A1 EP0810611 A1 EP 0810611A1
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EP
European Patent Office
Prior art keywords
mixed crystal
temperature
rare earth
thermistor
semiconductor ceramic
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.)
Granted
Application number
EP97201494A
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German (de)
English (en)
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EP0810611B1 (fr
Inventor
Wilhelm-Albert Dr. Groen
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Philips Intellectual Property and Standards GmbH
Koninklijke Philips NV
Original Assignee
Philips Patentverwaltung GmbH
Koninklijke Philips Electronics NV
Philips Electronics NV
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Publication of EP0810611A1 publication Critical patent/EP0810611A1/fr
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Publication of EP0810611B1 publication Critical patent/EP0810611B1/fr
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    • 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
    • H01C7/04—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 negative temperature coefficient
    • H01C7/042—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 negative temperature coefficient mainly consisting of inorganic non-metallic substances
    • H01C7/043—Oxides or oxidic compounds

Definitions

  • the present invention relates to a high-temperature thermistor with a semiconductor ceramic made of a mixed crystal oxide of rare earth oxides, in particular a thermistor that can be used over the entire temperature range from room temperature to 1100 ° C.
  • Thermistors for high temperatures have become increasingly important in recent years due to new areas of application in immissions protection. They are used, for example, as a temperature sensor for industrial exhaust gas temperature measurements or for temperature control and overtemperature protection for catalytic exhaust gas combustion in cars.
  • the typical application temperatures in cars are between 600 ° C and 1100 ° C, only at these elevated temperatures does the catalytic exhaust gas combustion work optimally.
  • Thermistors made of oxidic semiconductor ceramics offer the advantage over thermocouples in this temperature range that they have a much larger output signal, so that a simpler circuit technology is sufficient for signal processing.
  • Thermistors are also called NTC resistors because their resistance has a negative temperature coefficient (NTC).
  • thermistors are based on oxidic semiconductor ceramics, which are based on oxidic compounds of the transition metals of the spinel or perovskite type.
  • Multi-phase systems are often used, in which the base material is modified by additional components.
  • Today's NTC components consist almost exclusively of mixed crystals with a spinel structure, which are composed of 2 to 4 cations from the group Mn, Ni, Co, Fe, Cu and Ti.
  • the nominal resistance R 25 and the B constant relevant for temperature sensitivity are set to variable values by appropriate reaction control during manufacture, so that the production of a certain range of thermistors is possible with a given offset.
  • NTC thermistors The production spread of NTC thermistors is quite critical because the contamination content in the sintered material is difficult to control.
  • the ceramic compounds and their crystal structures that form during manufacture can change over time, especially at high temperatures. At high temperatures, there can also be a slow reaction with the oxygen in the atmosphere, which causes a permanent change in the resistance value and the temperature characteristic.
  • mixed crystal oxides of the spinel or perovskite type can only be used up to about 500 ° C. At higher temperatures, their long-term stability is too low and their specific resistance is too low for many areas of application.
  • a thermistor is suitable as a temperature sensor for temperatures up to 1100 ° C. It is characterized by its particular stability at very high operating temperatures above 1000 ° C. It is therefore particularly suitable as a sensor in the hot area of catalytic exhaust gas cleaning or for temperature control for engine control.
  • the mixed crystal oxide has a cubic crystal structure of the CM 2 O 3 type.
  • Thermistors with a semiconductor ceramic made of such mixed crystal oxides are characterized by a special high temperature stability.
  • the mixed crystal oxide contains, as further dopants, an element from the group of neodymium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
  • a semiconductor ceramic which is characterized in that the mixed crystal oxide has a cubic crystal structure of the CM 2 O 3 type is particularly preferred.
  • the semiconductor ceramic with a mixed crystal oxide of the rare earth metals according to the invention contains binary, ternary, quaternary, etc. generally multiple mixed crystal oxides, the essential component of which is terbium and at least one further rare earth metal oxide from the group yttrium, samarium, gadolinium.
  • the mixed crystal oxide can also contain neodymium, europium, dyspprosium, holmium, erbium, thulium, ytterbium or lutetium as further dopants.
  • the semiconductor ceramic Due to the terbium content in the structure, the semiconductor ceramic contains movable electrons, which make a significant contribution to the conductivity of the semiconductor ceramic.
  • the composition of the mixed crystal oxide is preferably chosen so that a cubic CM 2 O 3 type crystal structure is obtained.
  • the prerequisite for this is that the average ionic radius of the cations is based on that of RD Shannon, Acta Cryst. A32 (1976) 751 values are less than 1.06 angstroms.
  • These semiconductor ceramics are monomorphic, ie they do not change their crystal structure at higher temperatures.
  • the mixed crystal oxides according to the invention which crystallize in the CM 2 O 3 type have an outstandingly improved stability at very high temperatures, because in the mixed crystal oxides according to the invention with cations according to the definition given, the crystal structure does not change at higher temperatures.
  • the semiconductor ceramics are manufactured according to the usual ceramic manufacturing methods.
  • the binary oxides of the rare earth metals mentioned or, for example, their oxalates, carbonates, hydroxides or the like are used as starting compounds. used.
  • the starting mixtures are weighed, then mixed dry or wet and ground. This is preferably followed by a calcination process at 1000 ° C. for better chemical homogenization and for better compaction.
  • the shaping process for the green body follows by pressing, film drawing, screen printing or the like.
  • the shaped green bodies go through a binder burnout and are then sintered at 1250 ° C to 1400 ° C.
  • the sintering process is not very susceptible to faults and is not dependent on the gas atmosphere or the cooling curve.
  • connection electrodes preferably made of platinum
  • platinum paste can also be applied and baked using the screen printing process.
  • Other methods are also possible, such as application using vacuum evaporation technology.
  • the resistance and its temperature dependency were determined in the temperature range from 200 ° C to 1100 ° C.
  • the thermal resistance of the thermistors was also measured at high temperatures.
  • Mixed crystal oxides are produced which contain Y 2 O 3 and 3, 10 and 30 at% terbium.
  • the starting compounds Y 2 O 3 and Tb 4 O 7 are mixed in the appropriate mixing ratio and ground with zircon grinding balls for 16 hours.
  • This 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 1350 ° C.
  • X-ray diffraction pictures show that the semiconductor ceramic thus obtained from mixed crystal oxides is a single-phase material with a CM 2 O 3 structure.
  • the average ionic radius of the mixed crystal oxides is 1.016 ⁇ , 1.018 ⁇ and 1.023 ⁇ , respectively.
  • the relative density of the mixed crystal oxides is greater than 94% of the theoretical density.
  • Quaternary mixed crystal oxides of yttrium oxide, samarium oxide and terbium oxide with the composition Y 0.5 Sm 0.9 Tb 0.6 O 3 and Y 0.5 Sm 0.5 Tb 1.0 O 3 are produced by the same method as in Example 1.
  • X-ray diffraction images show that the material is single-phase and crystallizes in the CM 2 O 3 type.
  • the average ionic radius of the mixed crystal oxides is 1.056 ⁇ and 1.046 ⁇ , respectively.
  • the relative density is greater than 95% of the theoretical density.
  • a ternary mixed crystal oxide with the composition Gd 1.4 Tb 0.6 O 3 is produced by the same method as in Example 1.
  • X-ray diffraction images show that the material is single-phase and crystallizes in the CM 2 O 3 type.
  • the average ion radius of the mixed crystal oxide is 1.054 ⁇ .
  • the density is greater than 95% of the theoretical density.
  • tablets made from the semiconductor ceramic according to the invention are coated with platinum paste on both sides for contacting.
  • the specific resistance is measured while the temperature is varied.
  • the reciprocal temperature is plotted against the logarithm of the specific conductivity ⁇ .
  • You get according to the Arrhenius curve, the slope of which gives the coefficient of thermal resistance B according to the formula B (lnR 1 -lnR 2nd ) / (1 / T 1 - 1 / T 2nd ) calculated.
  • Thermistors are required to have a linear relationship between temperature and electrical output.
  • the semiconductor ceramic can be used as a thermistor.
  • Yttrium-terbium mixed crystal oxides with a terbium content of more than 10 at% have particularly favorable properties. They can be used up to temperatures of 1100 ° C.
  • Fig. 2 shows the Arrhenius curve for Y 0.5 Sm 0.9 Tb 0.6 O 3 (lower curve) and Y 0.5 Sm 0.5 Tb 1.0 O 3 (upper curve). Due to the lower resistance and the non-linearity of the Arrhenius curves above 600 ° C, mixed crystal oxides can be used as a sensor at temperatures from 20 ° C to 600 ° C.
  • the temperature-resistance characteristic must be reliably reproducible even at high temperatures. Especially for applications in motor vehicle construction, the deviations in the temperature ⁇ T at 600 ° C to 1000 ° C should not exceed +/- 2%, i.e. 20 ° C at 1000 ° C.
  • Two identical thermistors are selected for each of these measurements.
  • One thermistor is heated to 1000 ° C for 100 h. Then the resistance-temperature characteristics of both thermistors are measured. If the resistance as a function of temperature is plotted for both thermistors, two parallel curves are obtained which are shifted by ⁇ t against each other. The result of the measurements is shown in Table 4.5. The results show that mixed crystal oxides based on yttrium oxide showed the best results. No aging effect was observed in 70% at% Y 2 O 3 with 30 at% terbium oxide. Tab.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Ceramic Engineering (AREA)
  • Thermistors And Varistors (AREA)
  • Compositions Of Oxide Ceramics (AREA)
EP97201494A 1996-05-31 1997-05-16 Thermistance pour des températures élevées contenant des métaux du groupe de terres rares Expired - Lifetime EP0810611B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19621934A DE19621934A1 (de) 1996-05-31 1996-05-31 Seltenerdmetallhaltiger Hochtemperatur-Thermistor
DE19621934 1996-05-31

Publications (2)

Publication Number Publication Date
EP0810611A1 true EP0810611A1 (fr) 1997-12-03
EP0810611B1 EP0810611B1 (fr) 1999-10-06

Family

ID=7795826

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97201494A Expired - Lifetime EP0810611B1 (fr) 1996-05-31 1997-05-16 Thermistance pour des températures élevées contenant des métaux du groupe de terres rares

Country Status (7)

Country Link
US (1) US5955937A (fr)
EP (1) EP0810611B1 (fr)
JP (1) JPH1087367A (fr)
KR (1) KR100427900B1 (fr)
CN (1) CN1118834C (fr)
DE (2) DE19621934A1 (fr)
TW (1) TW353233B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008055108A1 (de) 2008-12-22 2010-07-01 Robert Bosch Gmbh Sensoranordnung mit Temperaturfühler

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19736855A1 (de) 1997-08-23 1999-02-25 Philips Patentverwaltung Schaltungsanordnung mit einem SMD-Bauelement, insbesondere Temperatursensor und Verfahren zur Herstellung eines Temperatursensors
US7574369B1 (en) * 2001-10-11 2009-08-11 Eanesthesia Software Llc Data recording, billing, charges, and quality assurance software for mobile devices
US7138901B2 (en) 2004-03-30 2006-11-21 General Electric Company Temperature measuring device and system and method incorporating the same
JP2005294452A (ja) * 2004-03-31 2005-10-20 Fujitsu Ltd 薄膜積層体、その薄膜積層体を用いたアクチュエータ素子、フィルター素子、強誘電体メモリ、および光偏向素子
DE602007004871D1 (de) * 2007-12-21 2010-04-01 Vishay Resistors Belgium Bvba Stabiler Thermistor
DE102008009817A1 (de) * 2008-02-19 2009-08-27 Epcos Ag Verbundwerkstoff zur Temperaturmessung, Temperatursensor aufweisend den Verbundwerkstoff und Verfahren zur Herstellung des Verbundwerkstoffs und des Temperatursensors
JP5445689B2 (ja) * 2010-10-27 2014-03-19 株式会社村田製作所 半導体セラミックおよび抵抗素子
DE102014110553A1 (de) * 2014-07-25 2016-01-28 Epcos Ag Sensorelement, Sensoranordnung und Verfahren zur Herstellung eines Sensorelements
DE102014110560A1 (de) 2014-07-25 2016-01-28 Epcos Ag Sensorelement, Sensoranordnung und Verfahren zur Herstellung eines Sensorelements und einer Sensoranordnung
CN114544023B (zh) * 2022-01-25 2022-11-11 北京科技大学 一种阵列式稀土镍基氧化物精密测温系统及使用方法
CN116023140B (zh) * 2023-01-03 2023-08-22 中国科学院新疆理化技术研究所 基于高熵稀土锡酸盐的氧不敏感型负温度系数热敏材料

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2234639A1 (fr) * 1973-06-21 1975-01-17 Ngk Spark Plug Co
FR2309961A1 (fr) * 1975-04-28 1976-11-26 Siemens Ag Thermistance pour les temperat
FR2309963A1 (fr) * 1975-04-28 1976-11-26 Siemens Ag Thermistance pour des temperatures elevees
FR2309962A1 (fr) * 1975-04-28 1976-11-26 Siemens Ag Thermistance pour des temperatures elevees
US4126583A (en) * 1976-08-18 1978-11-21 Siemens Aktiengesellschaft High temperature thermistors (NTC)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4097345A (en) * 1976-10-15 1978-06-27 E. I. Du Pont De Nemours And Company Na5 GdSi4 O 12 and related rare earth sodium ion conductors and electrolytic cells therefrom
JPH07115872B2 (ja) * 1990-06-14 1995-12-13 財団法人国際超電導産業技術研究センター 酸化物超電導体およびその製造方法
JP2871258B2 (ja) * 1991-01-18 1999-03-17 日本碍子株式会社 酸化物超電導体及びその製造方法
DE69500411T2 (de) * 1994-04-27 1997-10-23 Matsushita Electric Ind Co Ltd Temperatursensor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2234639A1 (fr) * 1973-06-21 1975-01-17 Ngk Spark Plug Co
FR2309961A1 (fr) * 1975-04-28 1976-11-26 Siemens Ag Thermistance pour les temperat
FR2309963A1 (fr) * 1975-04-28 1976-11-26 Siemens Ag Thermistance pour des temperatures elevees
FR2309962A1 (fr) * 1975-04-28 1976-11-26 Siemens Ag Thermistance pour des temperatures elevees
US4126583A (en) * 1976-08-18 1978-11-21 Siemens Aktiengesellschaft High temperature thermistors (NTC)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008055108A1 (de) 2008-12-22 2010-07-01 Robert Bosch Gmbh Sensoranordnung mit Temperaturfühler

Also Published As

Publication number Publication date
DE59700516D1 (de) 1999-11-11
EP0810611B1 (fr) 1999-10-06
CN1175778A (zh) 1998-03-11
KR100427900B1 (ko) 2004-08-04
TW353233B (en) 1999-02-21
JPH1087367A (ja) 1998-04-07
KR970076910A (ko) 1997-12-12
US5955937A (en) 1999-09-21
DE19621934A1 (de) 1997-12-04
CN1118834C (zh) 2003-08-20

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