US3778389A - Electro-conductive material containing pbo and ruo2 - Google Patents

Electro-conductive material containing pbo and ruo2 Download PDF

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Publication number
US3778389A
US3778389A US00101515A US3778389DA US3778389A US 3778389 A US3778389 A US 3778389A US 00101515 A US00101515 A US 00101515A US 3778389D A US3778389D A US 3778389DA US 3778389 A US3778389 A US 3778389A
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pbo
electro
conductive material
ruo
resistor
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US00101515A
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English (en)
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T Kasanami
O Kano
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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    • 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
    • H01C17/0654—Oxides of the platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides

Definitions

  • An electro-conductive material essentially consisting of a double oxide obtained from PhD and Ru in a molar ratio of 3:1 to 1:3, which is useful as the fundamental composition for production of a resistor paste, a ceramic resistor or the like.
  • the present invention relates to an electro-conductive material essentially consisting of a double oxide obtained from UbO and Ru0 and a resistor composition comprising the same.
  • PbO which is one of the essential components in the electro-conductive material of the invention serves not only as a constituent of the double oxide but also as a binder for the crystal component and the glass component. Because of this reason, a resistor composition produced by the use of the electro-conductive material of the invention is provided with an excellent rigidity even when Nb is incorporated for making minus the temperature coefficient of resistivity.
  • the double oxide of PbO and Ru0 can be dissolved with ease into a glass component at a high temperature and, when cooled, recrystallized to form a crystallized glass material which is thermally and mechanically stable.
  • the thus obtained resistor composition is assured a good contact of the crystal component and of low resistance.
  • the electro-conductive material of the present invention can be utilized for the formation of a ceramic resistor.
  • the ceramic resistor is much more stable to heat and of a higher wattage.
  • the electro-conductive material of the present invention essentially consists of PhD and RuO in a molar ratio of 3:1 to 1:3, favorably of 1.5:1 to 1:15. If necessary, less than 50% by mol of PbO and/or of RuO may be replaced by Bi O /2Bi O and H0 respectively.
  • at least the following four systems may be designed for the electro-conductive material of the invention: (1) PbO-Ru0 (2) Bi O -PbO-RnO (3) PbO-RuO -IrO (4) Bi O -PbO-RuO -IrO
  • a mixture of the component materials and/or their sources may be sintered, for instance, at a temperature from 400 C. to 1100" C.
  • the electro-conductive material may be produced in a conventional deposition procedure from aqueous solution, if necessary, followed by sintering of the deposited material.
  • the electro-conductive material of the invention can be used for a wide variety of use. Among them, the use as a resistor paste is one preferred example.
  • the electroconductive material is admixed with a glass frit, an organic binder and a solvent.
  • the electro-conductive material there may be used the double oxide of any system as above mentioned, if necessary, with replacement of less than 50% by mol' of Ru0 and/or of PhD by TeO W0 V 0 TiO MnO SnO Sb O Sb O CuO, ZnO, Nd O In O Nb O Ta O and/or the like.
  • a resistor paste of high resistance there may be employed, for instance, the electro-conductive material wherein Ta O is incorporated as a replaceable oxide.
  • the electro-conductive material wherein Nb O is incoporated as a replaceable oxide may be employed.
  • the glass frit are the glass systems of borate, silicate and borosilicate containing at least one of Bi O PbO, A1 ZnO, OdO, alkali metal oxides, alkaline earth metal oxides and rare earth metal oxides.
  • the use of a frit of PbO-B O -SiO system glass is recommended.
  • the use of a frit of Bi 0 -Pb0-B O -SiO system glass is preferred.
  • organic binder there may be used ethyl cellulose, nitrocellulose or the like.
  • the solvent include organic solvents such as butyl Carbitol, butyl Carbitol acetate and terepineol.
  • the molar ratio of the electro-conductive material and the glass frit is usually within a range of 0.5 :1 to 0.02:1.
  • the combined amount of the organic binder and the solvent normally does not exceed 50% by weight of the total composition.
  • a ceramic resistor is a preferred example of the use.
  • either one of the said systems for the electroconductive material of the invention is sintered, usually at a temperature from 400 C. to 1300 C. to give a ceramic resistor.
  • any additive such as TeO W03, V205, Tiog, M1102, S1102, Sb O Sbz05, C110, Z110, Nd O In O Nb O Ta O or the like may be incorporated prior to the sintering for regulating the resistivity, the resistance temperature characteristics and the sintering temperature.
  • the use of Ta O or N-b O is particularly preferred.
  • the amount of the additive to be incorporated may be usually 90% by mol or less on the basis of the combined amount with the electro-conductive material.
  • EXAMPLE 1 Production of electro-conductive material of low resistance (A) PbO-RuO system.
  • Pb O and RuO in a polyvinyl chloride made pot mill with agate balls, Pb O and RuO in a molar ratio of 3:1 to 1:3 (in terms of PbOzRuo are admixed with water. After evaporation of water, the resultant mixture is admitted in an alumina crucible, heated to 650 C. with a rate of 3 C./min. and calcinated at the temperature for 1 hour to give an electro-conductive material of low resistance as black powder.
  • EXAMPLE 2 Production of glaze resistor paste (A) PbO-RuO glaze resistor paste.
  • the electroconductive material prepared as in Example 1(A) and a blink of lead borosilicate glass (PbO 30% by mol; B 0 45% by mol; SiO 25% by mol; molecular weight, 113.30) in a molar ratio of 0.4 to 0.025:1 are admixed with ethyl cellulose in 1.5% by weight and ot-terepineol in 30% by weight on the basis of the combined weight of the electro-conductive material and the glass frit to give a resistor paste.
  • the resistor paste is printed in a size of 3 mm. x 3 mm. bridging a pair of silver electrodes provided on an alumina ceramics substrate and fired at a peak firing temperature of 680 C. to 880 C. for 10 minutes with a total cycle of 60 minutes.
  • the sheet resistivity with the peak firing temperature and the molar amount of the electro-conductive material is shown in FIG. 1.
  • the sheet resistivity, the cold temperature coeflicient of resistivity (55 C. to +25 C.), the hot temperature coeflicient of resistivity (+25 C. to +150 C.) and the voltage coefficient of resistivity with the molar amount of the electro-conductive material to 1 mol of the glass component when fired at 760 C. are shown in Table 1.
  • (B) Glaze resistor paste of high resistance An electro-conductive material is produced as in Example 1(A) but replacing less than 50% by mol of RuO by Ta O The resulting product becomes grayish with the increase of the T3305 content.
  • the employed T3205 is served partly to form a solid solution with the PbO-Ru0 system double oxide and partly to produce a PbO-Ta 0 system double oxide (e.g. 3PbO-2Ta O
  • the electro-conductive material (0.2 mol) and the glass frit as in (A) (1 mol) are mixed with ethyl cellulose in 1.5 by weight and a-terepineol in 30% by weight on the basis of the combined weight of the electroconductive material and the glass frit to produce a glaze resistor paste.
  • the load life test (70 C. in air; resistor size, 3 mm. x 3 mm. squares; substrate size, 10 mm. x '10 mm.; power, /2 -W.; 1% hrs. ON-Vz hr. OFF; after 3000 hrs.), the high temperature exposure test (no load: 150 C. in air; after 3000 hrs.), the short time overload test (1% w. for 5 sec.), the humidity exposure test (40 0.; relative humidity, after 1000 hrs.) and the noise test (using a resistor noise tester model 315 manufactured by Quan. Tech. Laboratories) are carried out, and the results are shown in Table 3.
  • Eleetro-eonduetlve material (molar ratio) (Kn/sq.) Cold Hot (percent/V.)
  • Nb O content The employed Nb O is served partly to EXAMPLE 3 form a solid solution with the PbO-RuO system double oxide and partly to produce a Pb0-Nb O system double oxide (e.g. 3PbO-2Nb O
  • the electro-conductive material 0.2 mol, and 0.3 mol or 0.4 mol
  • a frit of bismuth borosilicate glass (PbO, by mol; %Bi O 10% by mol; B 0 45% by mol; SiO by mol) (1 mol) are mixed with ethyl cellulose in 1.5% by weight a-terepineol in by weight on the basis of the combined weight of the electro-conductive material and the glass frit produces a glaze resistor paste.
  • the above obtained glaze resistor pastes are printed and tired as in (A).
  • the sheet resistivity is shown in FIG. 3.
  • the sheet resistivity, the hot temperature coeflicient of resistivity, the cold temperature coefiicient of resistivity, the voltage coefiicient of resistivity and the noise with the molar ratio of the electro-conductive material to the glass component when fired at 760 C. are shown in Table 4.
  • Ceramic resistor (A) Ceramic resistor of low resistance-The electr0 conductive material as prepared in Example 1(A) or 1(B) is admixed with polyvinyl methyl ether in 5% by Weight on the basis of the weight of the electro-conductive material in the presence of water by a wet procedure and, after evaporation of water, the resulting mixture is molded under a pressure of 700 kg./cm. The molded product is heated to 900 C. with a rate of 3 C./ min. and sintered in air at the temperature for 1 hour. The resistivity of the sintered product is shown in Table 6 TABLE 6 Electro-conductive material (molar ratio) Resistivity (Q-cm.)
  • PbO-RuO 3:1 7.8 10 PbO-Ru0 2:1) 4.8 10 rho-R110, (1:1 3.s 10 Pbo-Ruo 1:2) 7.s 10 PbO-RuO (1:3 6.3 10 PbQ- /zBi O -RuO 0.5:0.s:2 6.3 10 PbO /2Bi O -RuO 0.5:0.5:1 4.6 10 Pbo Bi O -Ruo 1:05:15 7.2 10 PbO-V2Bi O -RuO 2:0.5:1.s 8.3 10- Pbo-RuO -Iro (1:1:1 5.1 10 PbO-RuO -IrO 1:05:05 2.3 10 PbO-RuO -IrO (2:1:05 4.3 10
  • PbO-RuO -IrO (311:0.5) 9.8)(10 (B) Ceramic resistor.-For :preparation of ceramic resistors of high resistance, there are used electro-conductive materials of PbO-RuO and PbO-RuO -IrO systems wherein RuO or k; is partly replaced by Ta O Nb O TeO W03, V205, T102, M1103, sbgog, SD02, Z110, Nd O 8 4. The electro-conductive material according to claim 1, wherein less than 50% by mol of PhD and of RuO are respectively replaced by Bi O and IrO 5.
  • a resistor paste which comprises the electro-conductive material according to claim 1, a glass frit, an organic 5 or In O whrch are produced from Pb O Ru0 and b1nder andasolvent. various oxides as shown in Table 7 according to the pro- 6.
  • the electroconductive ma containing at least one of B1 0 PbO, A1 0 ZnO, CdO, terial or a mixture of the electro-conductive material (0.8 10 alkali metal oxides, alkaline earth metal oxides are rare mol) and the glass frit (0.2 mol) is admixed with polyearth metal oxides. vinyl methyl ether in 5% by weight on the basis of the 7.
  • the thus obtained ceramics is shaped in a glass frit is a frit of PbO-B O -SiO system glass. size of 2 mm. x 1 mm x 12 mm., a silver paste is ap- 9.
  • the temperature co- 2 Sb O Sb O CuO, ZnO, Nd o 11: 0., Ta O and efficient of resistivity and the voltage coeflicient of re- Nb O sistivity are shown in Table 7, and the results of the 10.
  • the resistor paste according to claim 5, wherein load life test, the high temperature exposure test and the less than 50% by mol of RuO; in the electro-conductive short time overload test are shown in Table 8. material is replaced by Nb O TABLE 7 '1.o. Glass Resls- (p.p.m./ G.)
  • Electro-conductive material (molar ratio) (mol) (0) Hot Cold Poo-13110235151050:0.5:0.5) 0.2 74.43 +940 +490 rbo-nuorwlezorum 0. 2 165. 4 +390 +270 rbo-Ruorl'rmoi 1:0 0.2 355.4 +95 +27 PbO-RuOa-Vz'TazOa 1:0 0.2 1.7855 -430 -325 PhD-11110746103201 1.5. .0.7) 0.2 168.1 +300 +280 PbO-RuO - ⁇ *Nbz0:(1:0.3:0 7 0. 2 135.
  • PbO-%NdzO RuOrSnO2 (0. 9:0. 1:0. 3:0. 5).-- 0. 2 0.98 1. 21 0. 72 PbO-ZnO-RuO2-%Ta205 (0. 9:0. 1:0. 3:0. 0).... 0. 2 2. 35 2. 7s 1. 05 PbO-%InzO -RuO2-%TazO (0. 9:0. 1:0. 3:0. 5) 0. 2 4 51 3. 23 1. 7s
  • the resistor paste according to claim 5 wherein less than 50% by mol of Ru0 in the electro-conductive material is replaced by Ta O 12.
  • the resistor paste according to claim 13, wherein the noble metal is Ag, Pd, Pt, Au, Rh, Ru or Ir.
  • a ceramic resistor which comprises a ceramic body comprising the electro-conductive material according to claim 1 which has been fired.
  • the ceramic resistor according to claim 18, wherein less than 50% by mol of RuO and of PhD in the 10 electro-conductive material are respectively replaced by Nb 05 and Bi O 23.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Non-Adjustable Resistors (AREA)
  • Conductive Materials (AREA)
  • Glass Compositions (AREA)
US00101515A 1969-12-26 1970-12-28 Electro-conductive material containing pbo and ruo2 Expired - Lifetime US3778389A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3896055A (en) * 1973-01-26 1975-07-22 Du Pont Pyrochlore-related oxides containing copper and/or silver and resistor compositions thereof
US3989877A (en) * 1971-11-22 1976-11-02 Owens-Illinois, Inc. Gas discharge device having improved operating characteristics
US4101708A (en) * 1977-03-25 1978-07-18 E. I. Du Pont De Nemours And Company Resistor compositions
DE2900298A1 (de) * 1978-01-12 1979-07-19 Philips Nv Widerstandsmaterial
US4175061A (en) * 1977-07-09 1979-11-20 Sumitomo Metal Mining Company Limited Method of manufacturing resistor paste
EP0071190A2 (en) * 1981-07-24 1983-02-09 E.I. Du Pont De Nemours And Company Thick film resistor compositions
FR2519182A1 (fr) * 1981-12-29 1983-07-01 Shoei Chemical Ind Co Compositions pour resistances a couche epaisse produites a partir d'elles
JPS58117264A (ja) * 1981-12-29 1983-07-12 Shoei Kagaku Kogyo Kk 抵抗塗料
US4397774A (en) * 1977-10-31 1983-08-09 U.S. Philips Corporation Method of preparing resistance material and resistor bodies produced therewith
EP0086077A1 (en) * 1982-02-04 1983-08-17 Corning Glass Works Glass frits for use in Ru02-based resistors
US4651126A (en) * 1985-05-02 1987-03-17 Shailendra Kumar Electrical resistor material, resistor made therefrom and method of making the same
US5592043A (en) * 1992-03-07 1997-01-07 U.S. Philips Corporation Cathode including a solid body

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63195440A (ja) * 1987-02-06 1988-08-12 Kayaba Ind Co Ltd シヨツクアブソ−バ−

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3989877A (en) * 1971-11-22 1976-11-02 Owens-Illinois, Inc. Gas discharge device having improved operating characteristics
US3896055A (en) * 1973-01-26 1975-07-22 Du Pont Pyrochlore-related oxides containing copper and/or silver and resistor compositions thereof
US4101708A (en) * 1977-03-25 1978-07-18 E. I. Du Pont De Nemours And Company Resistor compositions
US4175061A (en) * 1977-07-09 1979-11-20 Sumitomo Metal Mining Company Limited Method of manufacturing resistor paste
US4397774A (en) * 1977-10-31 1983-08-09 U.S. Philips Corporation Method of preparing resistance material and resistor bodies produced therewith
DE2900298A1 (de) * 1978-01-12 1979-07-19 Philips Nv Widerstandsmaterial
US4292619A (en) * 1978-01-12 1981-09-29 U.S. Philips Corporation Resistance material
EP0071190A2 (en) * 1981-07-24 1983-02-09 E.I. Du Pont De Nemours And Company Thick film resistor compositions
EP0071190A3 (en) * 1981-07-24 1983-08-24 E.I. Du Pont De Nemours And Company Thick film resistor compositions
FR2519182A1 (fr) * 1981-12-29 1983-07-01 Shoei Chemical Ind Co Compositions pour resistances a couche epaisse produites a partir d'elles
JPS58117264A (ja) * 1981-12-29 1983-07-12 Shoei Kagaku Kogyo Kk 抵抗塗料
JPS637585B2 (US07655688-20100202-C00010.png) * 1981-12-29 1988-02-17 Shoei Kagaku Kogyo Kk
EP0086077A1 (en) * 1982-02-04 1983-08-17 Corning Glass Works Glass frits for use in Ru02-based resistors
US4651126A (en) * 1985-05-02 1987-03-17 Shailendra Kumar Electrical resistor material, resistor made therefrom and method of making the same
US5592043A (en) * 1992-03-07 1997-01-07 U.S. Philips Corporation Cathode including a solid body

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