EP0638910B1 - Céramique frittée pour thermistors stables à hautes températures et leur procédé de fabrication - Google Patents

Céramique frittée pour thermistors stables à hautes températures et leur procédé de fabrication Download PDF

Info

Publication number
EP0638910B1
EP0638910B1 EP94110754A EP94110754A EP0638910B1 EP 0638910 B1 EP0638910 B1 EP 0638910B1 EP 94110754 A EP94110754 A EP 94110754A EP 94110754 A EP94110754 A EP 94110754A EP 0638910 B1 EP0638910 B1 EP 0638910B1
Authority
EP
European Patent Office
Prior art keywords
ceramic
temperature
sintered ceramic
materials system
iii
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
EP94110754A
Other languages
German (de)
English (en)
Other versions
EP0638910A2 (fr
EP0638910A3 (fr
Inventor
Adalbert Prof. Dr. Habil. Feltz
Ralph Dr. Rer. Nat. Kriegel
Franz Dr. Dipl.-Ing. Schrank
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.)
TDK Electronics AG
Original Assignee
Epcos AG
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 Epcos AG filed Critical Epcos AG
Publication of EP0638910A2 publication Critical patent/EP0638910A2/fr
Publication of EP0638910A3 publication Critical patent/EP0638910A3/fr
Application granted granted Critical
Publication of EP0638910B1 publication Critical patent/EP0638910B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • H01C7/04—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 sintered ceramic for stable high temperature thermistors containing basic oxide and a method for producing a such sintered ceramics.
  • a layered ceramic in the form of a manganese (IV) and Manganese (III) containing material system containing Strontium oxide is for example from the article by J.B. MACCHESNEY ET AL, "CHEMICAL AND MAGNETIC STUDY OF LAYERED STRONTIUM LANTHANIUM MANGANATE STRUCTURES "in JOURNAL OF APPLIED PHYSICS, Vol. 40, No. 3, March 1, 1969, Pages 1243 -1244 known. In the article, the investigated the magnetic properties of the material system.
  • the pure-phase spinel MgNi II Mn IV O 4 is characterized by a relatively high B constant of about 4,600 K due to an energetically stable assignment of the transition metal cations to the lattice sites, while the nominal resistance is not too low.
  • the use of a ceramic on the basis of this semiconducting compound as a high-temperature thermistor is described in the older German patent application P 42 13 631.8.
  • the change in the equilibrium composition of phases present next to one another is not necessary in this system when heating up to about 700 ° C., so that a high temporal stability and reproducibility of the electrical parameters is achieved.
  • the invention has for its object a sintered ceramic with a large B constant and high uniformity and phase stability and a method for their Manufacturing specify to be based on such a thermistor with high stability and sensitivity for one To be able to produce a temperature range of up to 1,200 ° C.
  • the essence of the invention consists in stabilizing the oxidation level +4 of the manganese in the compound Sr 7 Mn 4 O 15 due to the increased content of basic oxide by the incorporation of a basic oxide, in particular strontium oxide in strontium manganate, the temperature of the elimination of oxygen thereby Increase 1,200 ° C and at the same time make temperatures up to 1,200 ° C sensitive by measuring resistance.
  • it is a sintered ceramic based on Sr 7-x M x Mn 4 O 15 or Sr 7 M x Mn 4-x O 15 , in which M denotes a dopant which in the first-mentioned system yttrium (Y) , Lanthanum (La) or an element of rare earths and in the second mentioned system can be scandium (Sc), titanium (Ti), zircon (Zr), niobium (Nb) or tantalum (Ta).
  • M denotes a dopant which in the first-mentioned system yttrium (Y) , Lanthanum (La) or an element of rare earths and in the second mentioned system can be scandium (Sc), titanium (Ti), zircon (Zr), niobium (Nb) or tantalum (Ta).
  • the parameter x is basically greater than zero. He can may also be zero, in the latter case the No dopant.
  • the process according to the invention for producing a sintered ceramic it is provided to mix SrCO 3 and Mn 2 O 3 or Mn 3 O 4 in a molar ratio of the compound Sr 7 Mn 4 O 15 in an aqueous slip and, after filtering off and drying, by heating for 12 hours To implement 1,000 ° C.
  • contact is made by brushing on a platinum (Pt) conductive paste.
  • the sinter densification is expediently carried out by heating to 1,350 ° C., holding for several hours at 1,550 ° C. and tempering at 1,200 ° C.
  • the uniform structure of which, according to an X-ray structure analysis, is based on a two-dimensional infinite combination of manganese (IV) oxygen double octahedra [ O 1/2 O 2 Mn IV O 3 Mn IV OO 2/2 ] 7- can be described ⁇ see Z. anorg. general Chem. 617 (1992) 99 ⁇ .
  • the leads are then fixed to the electrodes by bonding thin Pt wires.
  • the semiconducting ceramic is formed in the form of beads between thin platinum wires that are sintered in.
  • the electrical parameters of the Sr 7 Mn 4 O 15 ceramic are specifically provided by targeted doping in the rows Sr II / 7-xLa III / xMn IV / 1-xMn III / xO 15 (0 ⁇ x ⁇ 0.1) Sr II / 7-xY III / xMn IV / 1-xMn III / xO 15 (0 ⁇ x ⁇ 0.1) Sr II / 7Nb V / xMn III / xMn IV / 4-2xO 15 (0 ⁇ x ⁇ 0.1) Sr II / 7Mn IV / 4-xSc III / xO 15-x / 2 (0 ⁇ x ⁇ 0.1) Sr II / 7Ti IV / xMn IV / 4-xO 15 (0 ⁇ x ⁇ 0.1) to be modified in order to be able to adjust the electrical conductivity and the B constant to certain value ranges.
  • the starting mixture consisting of SrCO 3 and Mn 2 O 3 or Mn 3 O 4 is first prepared by mixing in an aqueous slip according to the composition given for a specific x value, without the addition of the doping component, and after filtering by heating to 1,000 ° C calcined.
  • the reaction product is suspended in water and the composition is completed by adding the doping component in the form of a suspension of freshly precipitated lanthanum, yttrium, scandium, niobium or titanium oxide hydroxide. Further processing is carried out as described for the undoped Sr 7 Mn 4 O 15 ceramic.

Landscapes

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

Claims (4)

  1. Céramique frittée pour des thermistances à hautes températures qui sont stables, sous la forme d'un système de substance contenant du manganèse(IV), ayant une teneur en oxyde de strontium, caractérisée par le système de substance Sr7-xMxMn4O15 dans laquelle x est supérieur à 0 et
    M signifie une substance de dopage choisie parmi l'yttrium, le lanthane ou un élément des terres rares.
  2. Céramique frittée pour des thermistances à hautes températures qui sont stables, sous la forme d'un système de substance contenant du manganèse (IV), ayant une teneur en oxyde de strontium, caractérisée par le système de substance Sr7-xMxMn4O15 dans laquelle x est supérieur à 0 et
    M est une substance de dopage choisie parmi le scandium, le titane, le zirconium, le niobium ou le tantale.
  3. Procédé de fabrication d'une céramique frittée suivant l'une des revendications 1 ou 2, dans lequel on calcine un mélange de SrCO3 et Mn2O3 ou Mn3O4, on ajoute à une suspension aqueuse du mélange d'oxyde calciné, un oxyhydroxyde d'une substance de dopage en la quantité x en mole, et on effectue ensuite une compression à la presse du système de substance.
  4. Procédé suivant la revendication 3, dans lequel on prépare à partir du système de substance par formage à la presse des comprimés de thermistances et on fritte les comprimés à une température de l'ordre de 1 550°C.
EP94110754A 1993-08-13 1994-07-11 Céramique frittée pour thermistors stables à hautes températures et leur procédé de fabrication Expired - Lifetime EP0638910B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4327285 1993-08-13
DE4327285 1993-08-13

Publications (3)

Publication Number Publication Date
EP0638910A2 EP0638910A2 (fr) 1995-02-15
EP0638910A3 EP0638910A3 (fr) 1997-01-08
EP0638910B1 true EP0638910B1 (fr) 2002-11-20

Family

ID=6495162

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94110754A Expired - Lifetime EP0638910B1 (fr) 1993-08-13 1994-07-11 Céramique frittée pour thermistors stables à hautes températures et leur procédé de fabrication

Country Status (4)

Country Link
US (1) US5536449A (fr)
EP (1) EP0638910B1 (fr)
JP (1) JPH0766008A (fr)
DE (1) DE59410207D1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5854587A (en) * 1997-06-26 1998-12-29 The United States Of America As Represented By The Secretary Of The Navy REx M1-x Mny O.sub.δ films for microbolometer-based IR focal plane arrays
DE19942176C2 (de) * 1999-09-03 2003-07-24 Epcos Ag Verfahren zur Verhinderung einer Thermistordrift bei einem NTC-Thermistor
US7138901B2 (en) 2004-03-30 2006-11-21 General Electric Company Temperature measuring device and system and method incorporating the same
JP5773567B2 (ja) * 2009-11-02 2015-09-02 石原産業株式会社 赤外線反射材料及びその製造方法並びにそれを含有した塗料、樹脂組成物
CN110542488A (zh) * 2019-09-23 2019-12-06 安徽晶格尔电子有限公司 一种利用热敏电阻基片进行高温测定的方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE63804C (de) * ELASTIC NUT COMPANY in Milwaukee, Wisconsin, V. St. A Maschine zur Herstellung von Schraubenmuttern
US2703354A (en) * 1950-02-23 1955-03-01 Rca Corp Alkaline earth manganate ceramics
US4110260A (en) * 1975-09-25 1978-08-29 Tokyo Denki Kagaku Kogyo Kabushiki Kaisha (Tdk Electronics Co., Ltd.) Electroconductive composite ceramics
US4076611A (en) * 1976-04-19 1978-02-28 Olin Corporation Electrode with lanthanum-containing perovskite surface
US4324702A (en) * 1979-11-02 1982-04-13 Matsushita Electric Industrial Co., Ltd. Oxide thermistor compositions
JPS6022302A (ja) * 1983-07-18 1985-02-04 松下電器産業株式会社 サ−ミスタ用酸化物半導体
US4891158A (en) * 1984-11-08 1990-01-02 Matsushita Electric Industrial Co., Ltd. Oxide semiconductor for thermistor and manufacturing method thereof
DD295941A5 (de) * 1990-06-26 1991-11-14 Friedrich-Schiller-Universitaet,De Verfahren zur herstellung einer sinterkeramik fuer thermistoren erhoehter empfindlichkeit und stabilitaet
JPH07505857A (ja) * 1992-04-24 1995-06-29 シーメンス　マツシタ　コンポーネンツ　ゲゼルシヤフト　ミツト　ベシユレンクテル　ハフツング　ウント　コンパニ　コマンデイート　ゲゼルシヤフト 高安定サーミスタ用焼結セラミツクス並びにその製造方法
US5432024A (en) * 1992-10-14 1995-07-11 Ngk Insulators, Ltd. Porous lanthanum manganite sintered bodies and solid oxide fuel cells

Also Published As

Publication number Publication date
EP0638910A2 (fr) 1995-02-15
JPH0766008A (ja) 1995-03-10
DE59410207D1 (de) 2003-01-02
EP0638910A3 (fr) 1997-01-08
US5536449A (en) 1996-07-16

Similar Documents

Publication Publication Date Title
DE3150558C2 (fr)
DE2702071C2 (de) Verfahren zur Herstellung einer Kondensatorkeramik auf Strontiumtitanatbasis
DE2605804A1 (de) Hochtemperaturthermistormasse
EP3504169B1 (fr) Matériau ceramique, composant et procédé de fabrication dudit composant
DE69833203T2 (de) Verfahren zur herstellung von ptc-halbleiterkeramiken
Feltz Perovskite forming ceramics of the system SrxLa1− x TiIVx+ yCoIIyCoIII1− x− 2yO3 for NTC thermistor applications
DE3732054C2 (fr)
DE3913596C2 (fr)
DE112013005662T5 (de) Verfahren zum Herstellen einer Piezokeramik, Pietokeramik und piezoelektrisches Element
DE2736688C2 (de) Verfahren zur Herstellung eines Dielektrikums mit Perowskitstruktur
DE4406276A1 (de) Elektrisch leitendes Keramikmaterial und unter dessen Verwendung hergestellte Brennstoffzelle
EP2326604B1 (fr) Matériau céramique, procédé de fabrication d'un matériau céramique, et composant électrocéramique comprenant le matériau céramique
EP0810611B1 (fr) Thermistance pour des températures élevées contenant des métaux du groupe de terres rares
DE69923635T2 (de) Piezoelektrische Keramiken
EP2118037B1 (fr) Matériau céramique et composant électrocéramique contenant le matériau céramique
EP0638910B1 (fr) Céramique frittée pour thermistors stables à hautes températures et leur procédé de fabrication
DE2824870C2 (fr)
DE19909087B4 (de) Halbleitende Keramik und daraus hergestelltes elektronisches Bauelement
EP0066333B1 (fr) Résistance non-linéaire et procédé pour sa fabrication
EP0065806B1 (fr) Résistance dépendant de la tension et procédé pour sa fabrication
DE19740262C1 (de) Sinterkeramik für hochstabile Thermistoren und Verfahren zur Herstellung
DE19983730B4 (de) Yttriumchromit-Chromoxid-Thermistoren
DE3520839C2 (fr)
DE3206502C2 (fr)
EP0357113B1 (fr) Procédé de production d'une résistance non linéaire dépendant de la tension

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE FR GB NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB NL

17P Request for examination filed

Effective date: 19970130

R17P Request for examination filed (corrected)

Effective date: 19970121

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EPCOS AG

17Q First examination report despatched

Effective date: 20010418

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20021120

REF Corresponds to:

Ref document number: 59410207

Country of ref document: DE

Date of ref document: 20030102

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030711

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: EPCOS AG

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: EPCOS AG

26N No opposition filed

Effective date: 20030821

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040203

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20030711

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040331

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20040201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST