EP0000864B1 - Procédé de fabrication de varistances à film épais - Google Patents

Procédé de fabrication de varistances à film épais Download PDF

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Publication number
EP0000864B1
EP0000864B1 EP78100192A EP78100192A EP0000864B1 EP 0000864 B1 EP0000864 B1 EP 0000864B1 EP 78100192 A EP78100192 A EP 78100192A EP 78100192 A EP78100192 A EP 78100192A EP 0000864 B1 EP0000864 B1 EP 0000864B1
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EP
European Patent Office
Prior art keywords
varistor
thick
paste
film
varistors
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
Application number
EP78100192A
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German (de)
English (en)
Other versions
EP0000864A1 (fr
Inventor
Naresh Chakrabarty
Richard Einzinger
Artur Weitze
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Siemens AG
Original Assignee
Siemens AG
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Application filed by Siemens AG filed Critical Siemens AG
Publication of EP0000864A1 publication Critical patent/EP0000864A1/fr
Application granted granted Critical
Publication of EP0000864B1 publication Critical patent/EP0000864B1/fr
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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
    • H01C7/1006—Thick film varistors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides
    • H01C17/06546—Oxides of zinc or cadmium
    • 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
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49082—Resistor making

Definitions

  • the invention relates to a method for producing thick film varistors with zinc oxide as the main component, in which the varistor materials and an organic binder are applied as varistor paste to an insulating substrate and are converted into a thick film varistor by sintering the varistor paste.
  • the current flowing through the varistor, V the applied voltage, C a constant and the exponent n denote the so-called steepness of the varistor.
  • the numerical value of the slope n should be as high as possible, since this exponent indicates the degree of deviation of the varistor from an ohmic characteristic.
  • the known varistors are generally designed as discrete components, which are produced by pressing and sintering the pulverized varistor materials. From US Pat. No. 3,725,836 it is also already known to produce varistors in thick-film technology and to integrate them directly into thick-film circuits. To produce these known thick-film varistors belonging to the group of ZnO varistors, the varistor materials are mixed with glass frit and an organic binder, applied as a screen-printable varistor paste to an insulating substrate and sintered to form the varistor. The electrodes required for contacting the varistor can then also be applied to the surface of the varistor using thick-film technology. The steep he i tn thick film of the varistors produced in this manner is in the order 4-8 and is therefore for the most applications too low.
  • DE-A-2 446 708 describes the production of varistor material without glass components, which has the greatest possible steepness.
  • the material dealt with in this published publication relates to the classic manufacture of varistor components, which amounts to a powder pressing technique.
  • This manufacturing method involves a discrete varistor, which e.g. is soldered into a plastic circuit board.
  • the invention has for its object to provide a method for producing thick film varistors with improved values of the slope n.
  • the invention is a thick film varistor that can be integrated with resistors and conductor tracks, the structures of which are e.g. applied by screen printing.
  • glass frit is always used as an inorganic binder in conductor pastes, resistance pastes and the known varistor pastes.
  • the pastes mentioned are sintered, the glass frit forms a solid glass matrix, which ensures the cohesion of the other solids and the bond to the substrate.
  • varistor paste which contains 87.5 to 98.0% by weight of zinc oxide, based on the solids content.
  • a varistor paste which contains bismuth oxide, tricobalt tetroxide and manganese dioxide is advantageously used.
  • the addition of these oxides to the zinc oxide favors the crystal formation in the manufacture of the thick film varistor and thus leads to a further improvement in the electrical properties.
  • a varistor paste which relates to the solids content contains.
  • Thick film varistors produced with such a varistor paste are particularly suitable for higher operating voltages. These operating voltages are, for example, in the range of 200 volts per millimeter of active varistor material.
  • a varistor paste which relates to the solids content contains.
  • Thick film varistors produced with such a varistor paste are particularly suitable for lower operating voltages. These operating voltages are, for example, in the range of 30 V / mm active varistor material.
  • the response voltage of the thick-film varistor can also be influenced by the choice of temperature.
  • the peak temperature during sintering of the varistor paste is preferably maintained for a period of between 5 and 20 minutes.
  • a further advantage of the crystal formation and thus a further improvement of the electrical properties can be achieved in that the thick film varistor is cooled after the sintering at a temperature gradient between 2 and 8 ° C / min.
  • the varistor paste is preferably applied to the insulating substrate in such a way that the thick-film varistor has a thickness between 100 and 200 ⁇ m after sintering. With such thick film varistor thicknesses, particularly favorable electrical properties are achieved.
  • a varistor paste that could be screen-printed was first produced from the varistor materials.
  • the powdery solids were weighed in as follows:
  • the solids were wet-mixed and ground in ball mills for 18 hours, then freed of water by filter suction and then dried in a drying oven at a temperature of 150 ° C. for 24 hours.
  • the maximum particle size distribution of the powder mixture after this treatment was 1 ⁇ m.
  • an organic binder 75 g of an organic binder were mixed into a batch of 100 g of the powder mixture thus prepared and homogenized on a roller mill.
  • Other known organic binders such as e.g. a solution of nitrocellulose in butyl carbitol acetate are equally suitable.
  • the viscosity and flow behavior of the varistor paste produced in this way was adjusted so that it could be processed using the screen printing process.
  • the finished varistor paste was then screen printed onto an insulating substrate made of A1 2 0 3 ceramic at the locations provided for the varistors.
  • the approx. 150 ⁇ m thick layer of varistor paste was then dried in a drying oven at a temperature of approx. 60 ° C.
  • the varistor properties were formed. Sintering was carried out in an oxidizing atmosphere at a temperature between 1 100 and 1 200 ° C, the peak temperature being held for 10 minutes. The temperature increase during heating was about 10 ° C per minute, while a temperature drop of 7 ° C per minute was observed during cooling.
  • the thick-film varistors produced according to the procedure described above are particularly suitable for operating voltages in the Suitable range of 200 volts per millimeter of active varistor material.
  • the powdered varistor materials were first weighed out as follows:
  • the powdery varistor materials were then processed in the manner described in Example 1 to form a screen-printable varistor paste and screen-printed onto an insulating substrate made of A1 2 0 3 - Ceramic printed.
  • the approx. 150 ⁇ m thick layer of varistor paste was then dried at a temperature of approx. 60 ° C.
  • the subsequent sintering was carried out at a temperature between 1 100 and 1 200 ° C, the peak temperature being held for 10 minutes.
  • the temperature increase during heating was about 10 ° C per minute, while when cooling down to a temperature of approx. 1000 ° C a temperature drop of 3 ° C per minute and below 1000 ° C a temperature drop of 6 to 7 ° C per minute Minute was observed.
  • the varistor electrodes and the other elements of the thick-film circuit can be produced in a known manner.
  • the fully contacted thick film varistors again had excellent electrical properties compared to the known glass thick film varistors.
  • the thick-film varistors produced according to the procedure described above are particularly suitable for operating voltages in the range of 30 volts per millimeter of active varistor material.
  • thick-film circuits with integrated thick-film varistors can be produced.
  • thick film varistors as discrete components.
  • a large number of varistor elements are applied and sintered on an insulating substrate using the screen printing process.
  • conductor tracks for contacting the varistor elements are applied using screen printing technology, dried and sintered.
  • the substrate is then perforated in a known manner, for example with the aid of a laser, and separated into individual elements. These individual elements can then be soldered into printed circuits or layer circuits as so-called varistor chips.

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Thermistors And Varistors (AREA)

Claims (8)

1. Procédé pour fabriquer des varistances à couche épaisse comportant de l'oxyde de zinc comme composant principal, selon lequel les matériaux prévus pour la varistance et un liant organique sont déposés sous la forme d'une pâte pour varistance sur un substrat isolant et sont transformés, par frittage de cette pâte, en une varistance à couche épaisse, caractérisé par le fait qu'on utilise une pâte pour varistances exempte de verre.
2. Procédé suivant la revendication 1, caractérisé par le fait qu'on utilise une pâte pour varistances qui contient en pourcentages, rapportés à la partie de substances solides, 87,5 à 98 % en poids d'oxyde de zinc.
3. Procédé suivant la revendication 1 ou 2, caractérisé par le fait qu'on utilise une pâte pour varistances qui contient de l'oxyde de bismuth, de l'oxyde salin de cobalt et du bioxyde de manganèse.
4. Procédé suivant la revendication 3, caractérisé par le fait qu'on utilise une pâte pour varistances qui contient, en pourcentages rapportés à la partie de substances solides :
Figure imgb0010
5. Procédé suivant la revendication 3, caractérisé par le fait qu'on utilise une pâte pour varistances qui contient, en pourcentages rapportés à la partie de substances solides :
Figure imgb0011
6. Procédé suivant l'une des revendications précédentes, caractérisé par le fait que la pâte pour varistances est frittée à une température comprise entre 1 100 et 1 360 °C.
7. Procédé suivant la revendication 6, caractérisé par le fait que la température maximum lors du frittage de la pâte pour varistances est maintenue pendant une durée comprise entre 5 et 20 minutes.
8. Procédé suivant l'une des revendications précédentes, caractérisé par le fait que la pâte pour varistances est déposée sur le substrat isolant de telle manière que la varistance à couche épaisse possède, après le frittage, une épaisseur comprise entre 100 et 200 microns.
EP78100192A 1977-08-05 1978-06-19 Procédé de fabrication de varistances à film épais Expired EP0000864B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2735484A DE2735484C2 (de) 1977-08-05 1977-08-05 Verfahren zur Herstellung von Dickfilm-Varistoren mit Zinkoxid als Hauptkomponente
DE2735484 1977-08-05

Publications (2)

Publication Number Publication Date
EP0000864A1 EP0000864A1 (fr) 1979-03-07
EP0000864B1 true EP0000864B1 (fr) 1981-04-15

Family

ID=6015775

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100192A Expired EP0000864B1 (fr) 1977-08-05 1978-06-19 Procédé de fabrication de varistances à film épais

Country Status (6)

Country Link
US (1) US4186367A (fr)
EP (1) EP0000864B1 (fr)
JP (1) JPS5928962B2 (fr)
CA (1) CA1117223A (fr)
DE (1) DE2735484C2 (fr)
IT (1) IT1097664B (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3754458A (en) * 1971-06-09 1973-08-28 Polaroid Corp Light seal for a reflex camera viewfinder
US4349496A (en) * 1981-03-26 1982-09-14 General Electric Company Method for fabricating free-standing thick-film varistors
FR2512240A1 (fr) * 1981-08-25 1983-03-04 Thomson Csf Dispositif de visualisation a commande electrique utilisant un element non lineaire en couche epaisse et son procede de fabrication
FR2545259B1 (fr) * 1983-04-29 1985-12-27 Ceraver Isolateur electrique presentant une insensibilite amelioree a la pollution
DE3335195A1 (de) * 1983-09-28 1985-04-04 Siemens AG, 1000 Berlin und 8000 München Kombinierte schaltung mit varistor
FR2726941A1 (fr) * 1986-01-28 1996-05-15 Cimsa Cintra Dispositif integre de protection par varistance d'un composant electronique contre les effets d'un champ electro-magnetique ou de charges statiques
JPS62190801A (ja) * 1986-02-18 1987-08-21 松下電器産業株式会社 電圧非直線性素子の製造方法
JPS62190807A (ja) * 1986-02-18 1987-08-21 松下電器産業株式会社 電圧非直線性素子の製造方法
JPS62193211A (ja) * 1986-02-20 1987-08-25 松下電器産業株式会社 電圧非直線性素子の製造方法
DE3619620A1 (de) * 1986-06-11 1987-12-17 Siemens Ag Verfahren zur herstellung keramischen zinkoxid-varistormaterials und verwendung des nach diesem verfahren hergestellten materials
DE3627682A1 (de) * 1986-08-14 1988-02-25 Bbc Brown Boveri & Cie Praezisionswiderstandsnetzwerk, insbesondere fuer dickschicht-hybrid-schaltungen
US4803100A (en) * 1987-10-21 1989-02-07 International Business Machines Corporation Suspension and use thereof
GB2242068C (en) * 1990-03-16 1996-01-24 Ecco Ltd Varistor manufacturing method and apparatus
US5973588A (en) 1990-06-26 1999-10-26 Ecco Limited Multilayer varistor with pin receiving apertures
GB2242065C (en) * 1990-03-16 1996-02-08 Ecco Ltd Varistor ink formulations
US6183685B1 (en) 1990-06-26 2001-02-06 Littlefuse Inc. Varistor manufacturing method
JP3251134B2 (ja) * 1994-08-29 2002-01-28 松下電器産業株式会社 酸化亜鉛焼結体の製造方法
US6965510B1 (en) 2003-12-11 2005-11-15 Wilson Greatbatch Technologies, Inc. Sintered valve metal powders for implantable capacitors
JP4432489B2 (ja) * 2003-12-25 2010-03-17 パナソニック株式会社 静電気対策部品の製造方法
JP4432586B2 (ja) * 2004-04-02 2010-03-17 パナソニック株式会社 静電気対策部品
WO2007046076A1 (fr) * 2005-10-19 2007-04-26 Littelfuse Ireland Development Company Limited Varistor et procédé de fabrication
JP4835153B2 (ja) * 2005-12-22 2011-12-14 富士電機リテイルシステムズ株式会社 自動販売機の商品送出装置
WO2008035319A1 (fr) * 2006-09-19 2008-03-27 Littelfuse Ireland Development Company Limited Fabrication de varistances comprenant une couche de passivation
DE102007013986A1 (de) * 2007-03-23 2008-09-25 Osram Opto Semiconductors Gmbh Optoelektronisches Bauteil mit einer Schutzstruktur gegen Überspannungen und Herstellungsverfahren

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US3857174A (en) * 1973-09-27 1974-12-31 Gen Electric Method of making varistor with passivating coating
US3900432A (en) * 1973-10-15 1975-08-19 Du Pont Varistor compositions
JPS5083790A (fr) * 1973-11-28 1975-07-07
JPS5083789A (fr) * 1973-11-28 1975-07-07
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Also Published As

Publication number Publication date
DE2735484A1 (de) 1979-02-15
EP0000864A1 (fr) 1979-03-07
CA1117223A (fr) 1982-01-26
US4186367A (en) 1980-01-29
DE2735484C2 (de) 1984-06-07
IT7826492A0 (it) 1978-08-04
IT1097664B (it) 1985-08-31
JPS5429096A (en) 1979-03-03
JPS5928962B2 (ja) 1984-07-17

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