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EP0351004A2 - Résistance non linéaire dépendent de la tension - Google Patents

Résistance non linéaire dépendent de la tension Download PDF

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Publication number
EP0351004A2
EP0351004A2 EP89201797A EP89201797A EP0351004A2 EP 0351004 A2 EP0351004 A2 EP 0351004A2 EP 89201797 A EP89201797 A EP 89201797A EP 89201797 A EP89201797 A EP 89201797A EP 0351004 A2 EP0351004 A2 EP 0351004A2
Authority
EP
European Patent Office
Prior art keywords
layer
resistance material
zinc oxide
atom
dependent resistor
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
EP89201797A
Other languages
German (de)
English (en)
Other versions
EP0351004A3 (en
EP0351004B1 (fr
Inventor
Detlev Dr. Hennings
Bernd Dr. Hoffmann
Nutto Markus
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.)
Philips Intellectual Property and Standards GmbH
Koninklijke Philips NV
Original Assignee
Philips Patentverwaltung GmbH
Philips Gloeilampenfabrieken NV
Koninklijke Philips Electronics NV
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 Philips Patentverwaltung GmbH, Philips Gloeilampenfabrieken NV, Koninklijke Philips Electronics NV filed Critical Philips Patentverwaltung GmbH
Publication of EP0351004A2 publication Critical patent/EP0351004A2/fr
Publication of EP0351004A3 publication Critical patent/EP0351004A3/de
Application granted granted Critical
Publication of EP0351004B1 publication Critical patent/EP0351004B1/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
    • H01C7/10—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
    • 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
    • H01C7/105—Varistor cores
    • H01C7/108—Metal oxide
    • H01C7/112—ZnO type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/30—Apparatus or processes specially adapted for manufacturing resistors adapted for baking

Definitions

  • the invention relates to a nonlinear voltage-dependent resistor with a ceramic sintered body made of resistance material based on at least one alkaline earth metal, rare earth metal and iron group metal present as an oxide, and with at least one of the metals from the group aluminum, gallium and / or indium doped zinc oxide and with electrodes attached to the opposing main surfaces of the sintered body.
  • the invention further relates to a method for producing such a resistor.
  • ⁇ current index, non-linearity factor or control factor; it depends on the material and is a measure of the steepness of the current-voltage characteristic; typical values are in the range from 30 to 80.
  • Varistors are used in many ways to protect electrical systems, devices and expensive components against overvoltages and voltage peaks.
  • the operating voltages of varistors are in the order of 3 V to 3000 V.
  • low-voltage varistors are increasingly required, whose response voltage U A is below approximately 30 V and the highest possible Have values for the non-linearity coefficient ⁇ .
  • Varistors based on zinc oxide have relatively good non-linearity coefficients ⁇ in the range from 20 to 60.
  • varistors based on zinc oxide with about 3 to 10 mol% of metal oxide additives such as Mg0, Ca0, La203, Pr203, Cr203, Co304 as doping.
  • metal oxide additives such as Mg0, Ca0, La203, Pr203, Cr203, Co304 as doping.
  • the interior of the polycrystalline Zn0 grains becomes low-resistance and high-resistance barriers form at the grain boundaries.
  • the contact resistance between two grains is relatively high at voltages ⁇ 3.2 V, but decreases at voltages> 3.2 V with increasing voltage by several orders of magnitude.
  • DE-OS 33 23 579 discloses varistors with sintered bodies based on zinc oxide doped with rare earth metal, cobalt, boron, alkaline earth metal and with at least one of the metals aluminum, gallium and / or indium.
  • DE-PS 33 24 732 discloses varistors with sintered bodies based on rare earth metal, cobalt, alkaline earth metal, alkali metal, chromium, boron and zinc oxide doped with at least one of the metals aluminum, gallium and / or indium. Both the varistors known from DE-OS 33 23 579 and from DE-PS 33 24 732 only show useful values for the non-linearity coefficient ⁇ at response voltages U A above 100 V with ⁇ > 30.
  • the usual way of producing low-voltage varistors based on doped zinc oxide is to use coarse-grained resistance material.
  • Sintered bodies made of doped zinc oxide with a relatively coarse grain structure with grain sizes> 100 ⁇ m are obtained, for example, if material of the system Zn0-Bi203 is doped with about 0.3 to about 1 mol% Ti02.
  • Ti02 forms a low-melting eutectic with Bi203 during sintering, which promotes the grain growth of polycrystalline Zn0.
  • a disadvantage, however, is that relatively long, rod-shaped ZnO crystallites often form, which make it very difficult to control the microstructure of the ceramic structure.
  • the invention has for its object to provide varistors and in particular low-voltage varistors that reproducibly low values for the response voltage U A in the range 30 V in addition to values for the non-linearity coefficient ⁇ > 30 and show methods for their production.
  • the sintered body has a multilayer structure with at least one layer sequence consisting of a layer of resistance material on a carrier layer based on zinc oxide, which has a higher electrical conductivity than the resistance material.
  • a cover layer based on zinc oxide, which has a higher electrical conductivity than the resistor material, is applied to the layer of resistor material.
  • the invention is based on the knowledge that the response voltage U A in the case of varistors based on zinc oxide with dopants forming high-resistance grain boundaries is essentially determined by the number of grain boundaries that the current I must pass between the electrodes. If relatively thin layers of resistance material are present, the number of grain boundaries can be kept within relatively narrow limits.
  • the invention is also the based on further knowledge that, in addition, a particularly uniform grain growth can be achieved in a relatively thin layer of resistance material if the layer of resistance material is covered in as large a surface area as possible by layers of a material which has a grain growth similar to that of the resistance material during the sintering process which, however, does not affect the resistance properties of the finished varistor.
  • Nonlinear voltage-dependent resistors with average response voltages U A ⁇ 20 V are already obtained if the varistor has only one layer sequence made of a layer of resistance material on a carrier layer. If a cover layer is also provided, the layer of resistance material is covered in an even larger surface area by material with a similar sintering behavior, but with higher electrical conductivity, varistors with reproducible values for the response voltage U A ⁇ 10 V with improved values for the non-linearity coefficient ⁇ receive.
  • the resistor material consists of 0.01 to 3.0 atom% praseodymium, 1.0 to 3.0 atom% cobalt, calcium to 1.0 atom% and 10 to 100 ppm aluminum doped zinc oxide, preferably from zinc atom doped with 0.5 atom% praseodymium, 2 atom% cobalt, 0.5 atom% calcium and 60 ppm aluminum.
  • the material for the carrier layer (s) and for the cover layer is doped with aluminum; the material for the backing layer (s) and the covering layer is preferred doped with 30 to 100 ppm aluminum, in particular with 60 ppm aluminum.
  • the electrodes are applied as layer electrodes without wire connections, preferably made predominantly of silver. This enables the varistors according to the invention to be used as SMD components.
  • the layer (s) made of resistance material have a thickness in the range from 65 to 250 ⁇ m and the carrier layer (s) and the cover layer each have a thickness in the range from 250 to 600 ⁇ m .
  • a method for producing a nonlinear voltage-dependent resistor with a ceramic sintered body based on zinc oxide as the resistance material which contains at least one alkaline earth metal, rare earth metal and iron group metal as well as at least one of the metals from the group aluminum, gallium and / or indium is endowed and with electrodes attached to the opposite main surfaces of the sintered body is characterized in that a multilayer sintered body is produced with at least one layer sequence consisting of a layer of resistance material on a carrier layer based on zinc oxide, which has a higher electrical conductivity than the resistance material.
  • dry powder mixtures of the resistance material and the material for the carrier layer (s) and the cover layer are produced, and these powder mixtures are compressed and deformed in accordance with the desired layer sequence and the desired layer thickness in a die under pressure, such that that the powder mixtures are individually compacted one after the other in accordance with the layers to be produced and deformed in the process.
  • the layers of the powder mixtures are preferably compressed at a pressure in the range from 8.107 to 1.8.108 Pa. It is advantageous to vary the pressure for pressing the individual layers of powder mixtures from layer to layer in such a way that the carrier layer is compressed at the highest pressure, the layer of resistance material is then compressed at a lower pressure, and the cover layer is compressed again when the pressure is reduced again. In this way it is ensured that there are relatively sharply delimited transitions between the individual layer layers, that is to say that material of the subsequent layer (s) is not pressed into the layer below, forming an undesirably deep boundary layer.
  • the layer structure of the varistors according to the invention can of course also be produced by means of other manufacturing processes. E.g. it is also possible to use liquid slurries of the layer materials which are cast or layer structures can be produced from higher-viscosity masses by rolling or extrusion.
  • the method according to the invention are selected from the powder mixtures pressed green shaped body at a temperature in the range 1260 to 1300 o C in air at a heating rate of ⁇ 10 o C / sintered min, wherein the sintering of the molded body is preferably performed so is that the maximum sintering temperature is maintained for a period of 0 to 240 min before the cooling process is initiated.
  • the level of the sintering temperature and also the duration of the maximum sintering temperature (holding time at maximum temperature) influence the grain growth in the layers in the sintered body and thus the values for the response voltage U A.
  • FIGS. 1a and 1b each show a multi-layer varistor 1 with a layer 3 made of resistance material and a carrier layer 5 (FIG. 1a) and a cover layer 7 (FIG. 1b) and metal layer electrodes 9, 11 made of a silver-based contact material.
  • the varistors according to FIGS. 1a and 1b represent only examples of several possible embodiments.
  • Low-voltage varistors with good electrical properties can also be made from one Layer sequence made up of a multiplicity of layers 3 of resistance material, each on a carrier layer 5 and with a cover layer 7; the electrodes 9, 11 are then attached to the lower surface of the lowermost carrier layer 5 and to the upper surface of the cover layer 7 (compare the principle of FIG. 1b).
  • Zinc oxide was doped with 0.5 atom% praseodymium, 2 atom% cobalt, 0.5 atom% calcium and 60 ppm aluminum as the resistance material (designated IV in the tables below).
  • aqueous solution 0.023 g Al (N03) 3.9H20 in a ball mill. The slip is then dried at a temperature of 100 o C.
  • Zinc oxide was doped with 60 ppm aluminum as the material for the carrier layer (s) 5 and the cover layer 7 (referred to as material A in the tables below).
  • material A the material for the carrier layer (s) 5 and the cover layer 7
  • 81.38 g of Zn0 are mixed with an aqueous solution of 0.023 g of Al (N03) 3.9H20 in a ball mill.
  • the slip is then dried at a temperature of 100 o C.
  • Multi-layer varistors were manufactured as follows: The material A and the resistance material IV are combined with one another and sintered together, as shown in the schematic representations of FIGS. 1a and 1b. A summary of the combinations carried out is shown in Table 1 below.
  • the combination of carrier layer / cover layer and layer of resistance material was carried out in the following way: 0.15 g of powder of material A (prepared according to the examples given above) were placed in a cylindrical steel die with a diameter of 9 mm under pressure mechanically compressed from 1.8.108 Pa.
  • the resistance material (material IV) (produced according to the example given above) was then coated in amounts of 0.025 g to 0.1 g onto the pre-compressed substrate and pressed together with this under a pressure of 1.3.108 Pa.
  • the pressed green bodies were then sintered at temperatures in the range 1260 to 1300 o C and hold times of the maximum temperature in the range of 0 to 120 min at a heating rate of ⁇ 10 o C / min in air.
  • Layer sequence material A / material IV 1 2nd 65 3-9 30-40 U A depends on the thickness of the resistance layer 2nd 2nd 130 9-12 50-60 3rd 2nd 195 ⁇ 40 50-60 4th 2nd 260 ⁇ 80 50-60
  • Layer sequence material A / material IV / material A (sandwich) 5 3rd 125 3-6 40-50 U A depends on the thickness of the resistance layer 6 3rd 190 9-12 50-60 7 3rd 250 27-30 70-100 Different sintering temperatures without holding time at maximum temperature 6/1 (1260 °) 3rd 190 18-20 50-60 U A depends on the sintering temperature 6/2 (1285 °) 3rd 190 9-12 50-60 6/3 (1300 °) 3rd 190 8-9 40-60 Different holding times at a sintering temperature of 1285 ° C 6/4 (30 min) 3rd 190 8-9 50-70

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Manufacturing & Machinery (AREA)
  • Thermistors And Varistors (AREA)
  • Compositions Of Oxide Ceramics (AREA)
EP89201797A 1988-07-13 1989-07-07 Résistance non linéaire dépendent de la tension Expired - Lifetime EP0351004B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3823698 1988-07-13
DE3823698A DE3823698A1 (de) 1988-07-13 1988-07-13 Nichtlinearer spannungsabhaengiger widerstand

Publications (3)

Publication Number Publication Date
EP0351004A2 true EP0351004A2 (fr) 1990-01-17
EP0351004A3 EP0351004A3 (en) 1990-03-21
EP0351004B1 EP0351004B1 (fr) 1993-10-06

Family

ID=6358567

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89201797A Expired - Lifetime EP0351004B1 (fr) 1988-07-13 1989-07-07 Résistance non linéaire dépendent de la tension

Country Status (5)

Country Link
US (1) US5008646A (fr)
EP (1) EP0351004B1 (fr)
JP (1) JPH0266901A (fr)
KR (1) KR0142574B1 (fr)
DE (2) DE3823698A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0578046A1 (fr) * 1992-07-10 1994-01-12 Asahi Glass Company Ltd. Couche conductrice transparente, et cible de pulvérisation et matériau pour la déposition de vapeur utilisés pour sa production
EP0617436A1 (fr) * 1992-10-09 1994-09-28 TDK Corporation Element de resistance a sensibilite a la tension non lineaire et procede pour sa fabrication

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0509582B1 (fr) * 1991-04-16 1996-09-04 Koninklijke Philips Electronics N.V. Résistance SMD
US5167537A (en) * 1991-05-10 1992-12-01 Amphenol Corporation High density mlv contact assembly
US5699035A (en) * 1991-12-13 1997-12-16 Symetrix Corporation ZnO thin-film varistors and method of making the same
DE4142523A1 (de) * 1991-12-21 1993-06-24 Asea Brown Boveri Widerstand mit ptc - verhalten
JPH05275958A (ja) * 1992-03-25 1993-10-22 Murata Mfg Co Ltd ノイズフィルタ
US5391432A (en) * 1993-04-28 1995-02-21 Mitchnick; Mark Antistatic fibers
AU6627394A (en) * 1993-04-28 1994-11-21 Mark Mitchnick Conductive polymers
US5441726A (en) * 1993-04-28 1995-08-15 Sunsmart, Inc. Topical ultra-violet radiation protectants
DE59406312D1 (de) * 1993-10-15 1998-07-30 Abb Research Ltd Verbundwerkstoff
EP1233427B1 (fr) * 1994-07-14 2012-10-10 Surgx Corporation Dispositifs de protection monocouches et multicouches à tension variable
JP3293403B2 (ja) 1995-05-08 2002-06-17 松下電器産業株式会社 酸化亜鉛バリスタ用側面高抵抗剤とそれを用いた酸化亜鉛バリスタとその製造方法
JP3223830B2 (ja) * 1997-02-17 2001-10-29 株式会社村田製作所 バリスタ素子の製造方法
US6519129B1 (en) * 1999-11-02 2003-02-11 Cooper Industries, Inc. Surge arrester module with bonded component stack
DE10056283A1 (de) * 2000-11-14 2002-06-13 Infineon Technologies Ag Künstliches Neuron, elektronische Schaltungsanordnung und künstliches neuronales Netz
US7015786B2 (en) * 2001-08-29 2006-03-21 Mcgraw-Edison Company Mechanical reinforcement to improve high current, short duration withstand of a monolithic disk or bonded disk stack
KR100441863B1 (ko) * 2002-03-28 2004-07-27 주식회사 에이피케이 프라세오디뮴계 산화아연 바리스터 및 그 제조방법
JP4123957B2 (ja) * 2003-02-10 2008-07-23 株式会社村田製作所 電圧依存性抵抗器
US7436283B2 (en) * 2003-11-20 2008-10-14 Cooper Technologies Company Mechanical reinforcement structure for fuses
US8117739B2 (en) * 2004-01-23 2012-02-21 Cooper Technologies Company Manufacturing process for surge arrester module using pre-impregnated composite
US7075406B2 (en) * 2004-03-16 2006-07-11 Cooper Technologies Company Station class surge arrester
US7633737B2 (en) * 2004-04-29 2009-12-15 Cooper Technologies Company Liquid immersed surge arrester
JP4893371B2 (ja) * 2007-03-02 2012-03-07 Ｔｄｋ株式会社 バリスタ素子
JP5304772B2 (ja) * 2010-12-06 2013-10-02 Ｔｄｋ株式会社 チップバリスタ及びチップバリスタの製造方法
JP5375810B2 (ja) * 2010-12-06 2013-12-25 Ｔｄｋ株式会社 チップバリスタ
EP3178098A4 (fr) * 2014-08-08 2018-06-06 Dongguan Littelfuse Electronics, Co., Ltd. Varistance présentant un revêtement multicouche et son procédé de fabrication
US11894166B2 (en) 2022-01-05 2024-02-06 Richards Mfg. Co., A New Jersey Limited Partnership Manufacturing process for surge arrestor module using compaction bladder system

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928242A (en) * 1973-11-19 1975-12-23 Gen Electric Metal oxide varistor with discrete bodies of metallic material therein and method for the manufacture thereof
EP0062314A2 (fr) * 1981-04-03 1982-10-13 Hitachi, Ltd. Résistance non linéaire et procédé pour sa fabrication
DE3323579A1 (de) * 1982-06-30 1984-01-05 Fuji Electric Co., Ltd., Kawasaki, Kanagawa Spannungsabhaengiger nicht-linearer zinkoxid-widerstand

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5385400A (en) * 1977-01-06 1978-07-27 Tdk Corp Porcelain composite for voltage non-linear resistor
US4400683A (en) * 1981-09-18 1983-08-23 Matsushita Electric Industrial Co., Ltd. Voltage-dependent resistor
US4908597A (en) * 1987-04-28 1990-03-13 Christopher Sutton Circuit module for multi-pin connector

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928242A (en) * 1973-11-19 1975-12-23 Gen Electric Metal oxide varistor with discrete bodies of metallic material therein and method for the manufacture thereof
EP0062314A2 (fr) * 1981-04-03 1982-10-13 Hitachi, Ltd. Résistance non linéaire et procédé pour sa fabrication
DE3323579A1 (de) * 1982-06-30 1984-01-05 Fuji Electric Co., Ltd., Kawasaki, Kanagawa Spannungsabhaengiger nicht-linearer zinkoxid-widerstand

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0578046A1 (fr) * 1992-07-10 1994-01-12 Asahi Glass Company Ltd. Couche conductrice transparente, et cible de pulvérisation et matériau pour la déposition de vapeur utilisés pour sa production
US5458753A (en) * 1992-07-10 1995-10-17 Asahi Glass Company, Ltd. Transparent conductive film consisting of zinc oxide and gallium
EP0617436A1 (fr) * 1992-10-09 1994-09-28 TDK Corporation Element de resistance a sensibilite a la tension non lineaire et procede pour sa fabrication
EP0617436A4 (fr) * 1992-10-09 1995-08-02 Tdk Corp Element de resistance a sensibilite a la tension non lineaire et procede pour sa fabrication.
US5640136A (en) * 1992-10-09 1997-06-17 Tdk Corporation Voltage-dependent nonlinear resistor

Also Published As

Publication number Publication date
JPH0266901A (ja) 1990-03-07
KR0142574B1 (ko) 1998-08-17
KR900002353A (ko) 1990-02-28
EP0351004A3 (en) 1990-03-21
US5008646A (en) 1991-04-16
DE3823698A1 (de) 1990-01-18
EP0351004B1 (fr) 1993-10-06
DE58905814D1 (de) 1993-11-11

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