Resistors and compositions therefor

Abstract

Powder compositions for producing high resistivity resistors capable of withstanding high voltage surges without large changes in resistivity, said compositions comprising finely divided pyrochlore-related oxides, lead glasses and metal titanates. Alternately to comprising titanates, the compositions may comprise metal titanate precursors such as crystallizable glasses capable of forming metal titanates upon being heated or titanium oxide plus a glass which react to form metal titanates.

I claim: 
     
       1. A film resistor adherent to a dielectric substrate wherein the resistor comprises a conductive phase of crystalline particles of (1) pyrochlore-related oxides and (2) metal titanates, each dispersed in a matrix of a lead containing glass, said .[.pyrochlore-related oxides being selected from among those of formula   (M.sub.x Bi.sub.2-x)(M'.sub.y Ru.sub.z-y)O.sub.7-z,     wherein   M is at least one metal selected from the group consisting of yttrium, indium, cadmium, lead, and the rare earth metals of atomic number 57-71, inclusive;   M' is at least one metal selected from the group consisting of platinum, titanium, tin, chromium, rhodium, iridium, zirconium, antimony, and germanium;   x is a number in the range 0-2;   y is a number in the range 0-2; and   z is a number in the range 0-1, being at least equal to about x/2 when M is a divalent metal; those of the formula   M.sub.x M'.sub.2-x M".sub.2 O.sub.7-z,     wherein     M is at leat one of Ag or Cu;   M' is Bi or a mixture of at least one half Bi plus up to one half of one or more cations from among a. bivalent Cd or Pb and   b. trivalent Y, Tl, In, and rare earth metals of atomic number 57-71, inclusive;     M" is at least one of a. Ru,   b. Ir, and   c. a mixture of at least three-fourths of at least one of Ru and Ir and up to one-fourth of at least one of Pt, Ti, and Rh;     x is in the range 0.10 to 0.60, and   z is in the range 0.10 to 1.0, and is equivalent to the sum of monovalent cations M and half of divalent cations in said formula; and mixtures thereof.]. .Iadd.resistor being a sintered composition of claim 19.Iaddend.. .[.   
     
     
       2.  A resistor according to claim 1 comprising 5-15 weight percent of said metal titanate..]. .[.3. A resistor according to claim 1 wherein said glass contains at least 5 weight percent PbO dissolved therein..]. .[.4. A resistor according to claim 2 wherein said glass contains at least 5 weight percent PbO dissolved therein..]. .[.5. A film resistor according to claim 1 wherein said metal titanate comprises a multivalent cation..]. .[.6. A film resistor according to claim 2 wherein said metal titanate comprises a multivalent cation..]. .[.7. A film resistor according to claim 1 where the anion in said titanate is (TiO 3 ) 2- ..]. .[.8. A film resistor according to claim 2 where the anion in said titanate is (TiO 3 ) 2- ..]. .[.9. A film resistor according to claim 5 where the anion in said titanate is (TiO 3 ) 2- ..]. .[.10. A film resistor according to claim 6 where the anion in said titanate is (TiO 3 ) 2- ..]. .[.11. A film resistor according to claim 1 comprising 10-50 weight percent pyrochlore-related oxide..]. .[.12. A film resistor according to claim 2 comprising 10-50 weight percent pyrochlore-related oxide..]. .[.13. A resistor according to claim 1 wherein the pyrochlore-related oxide is Pb 2  Ru 2  O 6 ..]. .[.14. A film resistor according to claim 1 wherein said pyrochlore-related oxide is Bi 2  Ru 2  O 7 ..]. .[.15. A film resistor according to claim 1 wherein said pyrochlore-related oxide is Pb 2  Ir 2  O 6 ..]. .[.16. A resistor according to claim 1 
     
     
        wherein said titanate comprises barium titanate..]. .[.17.  A resistor according to claim 1 wherein said titanate comprises lead titanate..]. .[.18. A resistor according to claim 1 wherein said titanate comprises 
     
     
        lead zirconate titanate..]. 19. A powder composition useful for forming film resistors on a dielectric substrate, the powder comprising pyrochlore-related oxides and a titanium material selected from the class consisting of 1. a metal titanate and a glass comprising at least 10 weight percent PbO dissolved therein, .Iadd.and .Iaddend.   2. .[.one or more glasses at least one of which comprises at least 5 weight percent titanium dioxide dissolved therein and a metal oxide and is capable of crystallization to form a metal titanate upon being heated and.]..[.3..].titanium oxide and a glass comprising at least 10 weight percent PbO dissolved therein, said pyrochlore-related oxides being selected from among those of the formula     (M.sub.x Bi.sub.2-x)(M'.sub.y Ru.sub.2-y)O.sub.7-z,     wherein     M is at least one metal selected from the group consisting of yttrium, indium, cadmium, lead, and the rare earth metals of atomic number 57-71, inclusive;   M' is at least one metal selected from the group consisting of platinum, titanium, tin, chromium, rhodium, iridium, zirconium, antimony, and germanium,   x is a number in the range 0-2;   y is a number in the range 0-2; and   z is a number in the range 0-1, being at least equal to about x/2 when M is a divalent metal; those of the formula   M x  M' 2-x  M" 2  O 7-7 , wherein   M is at least one of Ag or Cu;   M' is Bi or a mixture of at least one half Bi plus up to one half of one or more cations from among a. bivalent Cd or Pb and   b. trivalent Y, Tl, In, and rare earth metals of atomic number 57-71, inclusive;     M" is at least one of a. Ru,   b. Ir, and   c. a mixture of at least three-fourths of at least one of Ru and Ir and up to one-fourth of at least one of Pt, Ti, and Rh;     x is in the range 0.10 to 0.60, and   z is in the range 0.10 to 1.0, and is equivalent to the sum of monovalent cations M and half of divalent cations in said formula; and mixtures   
     
     
        thereof. 20. A composition according to claim 19 comprising titanium 
     
     
        material (1). 21. A composition according to claim 20 wherein said glass 
     
     
        comprises at least 50% PbO dissolved therein. 22. A composition according to claim 19 comprising titanium material (2). .[.23. A composition according to claim 22 wherein said glass comprises 50-70% PbO, 5-15% TiO 2 , 15-35% SiO 2  and 0-15% Al 2  O 3 ..]. .[.24. A composition according to claim 19 comprising titanium material (3)..]. 
     
     
            A composition according to claim .[.24.]. .Iadd.22 .Iaddend.wherein 
     
     
        said glass comprises at least 50% PbO dissolved therein. 26. A composition according to claim .[.24.]. .Iadd.22 .Iaddend.wherein said titanium oxide 
     
     
        is TiO 2 . 27. A composition according to claim 25 wherein said 
     
     
        titanium oxide is TiO 2 . 28. A powder composition according to claim 20 comprising sufficient titanium material to produce an amount of metal titanate equal to 5-15 weight percent of the total composition weight. 
     
     
            A powder composition according to claim 22 comprising sufficient titanium material to produce an amount of metal titanate equal to 5-15 
     
     
        weight percent of the total composition weight. 30. A powder composition according to claim .[.24.]. .Iadd.27 .Iaddend.comprising sufficient titanium material to produce an amount of metal titanate equal to 5-15 
     
     
        weight percent of the total composition weight. 31. A powder composition according to claim 19 wherein said pyrochlore-related oxide is Pb 2   
     
     
        Ru 2  O 6 . 32. A powder composition according to claim 19 wherein 
     
     
        said pyrochlore-related oxide is Bi 2  Ru 2  O 7 . 33. A powder composition according to claim 19 wherein said pyrochlore-related oxide is 
     
     
        Pb 2  Ir 2  O 6 . 34. A powder composition according to claim 20 
     
     
        wherein said pyrochlore-related oxide is Pb 2  Ru 2  O 6 . 35. A powder composition according to claim 20 wherein said pyrochlore-related 
     
     
        oxide is Bi 2  Ru 2  O 7 . 36. A powder composition according to claim 20 wherein said pyrochlore-related oxide is Pb 2  Ir 2   
     
     
        O 6 . 37. A powder composition according to claim 22 wherein said 
     
     
        pyrochlore-related oxide is Pb 2  Ru 2  O 6 . 38. A powder composition according to claim 22 wherein said pyrochlore-related oxide is 
     
     
        Bi 2  Ru 2  O 7 . 39. A powder composition according to claim 22 
     
     
        wherein said pyrochlore-related oxide is Pb 2  Ir 2  O 6 . 40. A powder composition according to claim .[.24.]. .Iadd.27 .Iaddend.wherein 
     
     
        said pyrochlore-related oxide is Pb 2  Ru 2  O 6 . 41. A powder composition according to claim .[.24.]. .Iadd.27 .Iaddend.wherein said 
     
     
        pyrochlore-related oxide is Bi 2  Ru 2  O 7 . 42. A powder composition according to claim .[.24.]. .Iadd.27 .Iaddend.wherein said 
     
     
        pyrochlore-related oxide is Pb 2  Ir 2  O 6 . 43. A composition according to claim 20 wherein the metal in said metal titanate is 
     
     
        multivalent. 44. A composition according to claim 22 wherein the metal in 
     
     
        said metal oxide is multivalent. 45. A composition according to claim 19 
     
     
        comprising 10-50 weight percent pyrochlore-related oxide. 46. A composition according to claim 20 comprising 10-50 weight percent 
     
     
        pyrochlore-related oxide. 47. A composition according to claim 22 
     
     
        comprising 10-50 weight percent pyrochlore-related oxide. 48. A composition according to claim .[.24.]. .Iadd.27 .Iaddend.comprising 10-50 
     
     
        weight percent pyrochlore-related oxide. 49. The composition of claim 19 
     
     
        dispersed in an inert liquid vehicle. 50. The composition of claim 20 
     
     
        dispersed in an inert liquid vehicle. 51. The composition of claim 22 
     
     
        dispersed in an inert liquid vehicle. 52. The composition of claim 
     
     
        .[.24.]. .Iadd.27 .Iaddend.dispersed in an inert liquid vehicle. 53. The 
     
     
        composition of claim 45 dispersed in an inert liquid vehicle. .Iadd.54.  A film resistor adherent to a dielectric substrate wherein the resistor comprises a conductive phase of crystalline particles of (1) pyrochlore-related oxides and (2) metal titanates, each dispersed in a matrix of a lead containing glass, said resistor being a sintered composition of claim 20. .Iaddend. .Iadd.55. A film resistor adherent to a dielectric substrate wherein the resistor comprises a conductive phase of crystalline particles of (1) pyrochlore-related oxides and (2) metal titanates, each dispersed in a matrix of a lead containing glass, said resistor being a sintered composition of claim 21. .Iaddend. .Iadd.56. A film resistor adherent to a dielectric substrate wherein the resistor comprises a conductive phase of crystalline particles of (1) pyrochlore-related oxides and (2) metal titanates, each dispersed in a matrix of a lead containing glass, said resistor being a sintered composition of claim 22. .Iaddend. .Iadd.57. A film resistor adherent to a dielectric substrate wherein the resistor comprises a conductive phase of crystalline particles of (1) pyrochlore-related oxides and (2) metal titanates, each dispersed in a matrix of a lead containing glass, said resistor being a sintered composition of claim 25. .Iaddend. .Iadd.58. A film resistor adherent to a dielectric substrate wherein the resistor comprises a conductive phase of crystalline particles of (1) pyrochlore-related oxides and (2) metal titanates, each dispersed in a matrix of a lead containing glass, said resistor being a sintered composition of claim 26. .Iaddend. .Iadd.59. A film resistor adherent to a dielectric substrate wherein the resistor comprises a conductive phase of crystalline particles of (1) pyrochlore-related oxides and (2) metal titanates, each dispersed in a matrix of a lead containing glass, said 
     
     
        resistor being a sintered composition of claim 27. .Iaddend. .Iadd.60.  A film resistor adherent to a dielectric substrate wherein the resistor comprises a conductive phase of crystalline particles of (1) pyrochlore-related oxides and (2) metal titanates, each dispersed in a matrix of a lead containing glass, said resistor being a sintered composition of claim 28. .Iaddend. .Iadd.61. A film resistor adherent to a dielectric substrate wherein the resistor comprises a conductive phase of crystalline particles of (1) pyrochlore-related oxides and (2) metal titanates, each dispersed in a matrix of a lead containing glass, said resistor being a sintered composition of claim 29. .Iaddend. .Iadd.62. A film resistor adherent to a dielectric substrate wherein the resistor comprises a conductive phase of crystalline particles of (1) pyrochlore-related oxides and (2) metal titanates, each dispersed in a matrix of a lead containing glass, said resistor being a sintered composition of claim 30. .Iaddend. .Iadd.63. A film resistor adherent to a dielectric substrate wherein the resistor comprises a conductive phase of crystalline particles of (1) pyrochlore-related oxides and (2) metal titanates, each dispersed in a matrix of a lead containing glass, said resistor being a sintered composition of claim 31. .Iaddend. .Iadd.64. A film resistor adherent to a dielectric substrate wherein the resistor comprises a conductive phase of crystalline particles of (1) pyrochlore-related oxides and (2) metal titanates, each dispersed in a matrix of a lead containing glass, said resistor being a sintered composition of claim 32. .Iaddend. .Iadd.65. A film resistor adherent to a dielectric substrate wherein the resistor comprises a conductive phase of crystalline particles of (1) pyrochlore-related oxides and (2) metal titanates, each dispersed in a matrix of a lead containing glass, said 
     
     
        resistor being a sintered composition of claim 33. .Iaddend. .Iadd.66.  A film resistor adherent to a dielectric substrate wherein the resistor comprises a conductive phase of crystalline particles of (1) pyrochlore-related oxides and (2) metal titanates, each dispersed in a matrix of a lead containing glass, said resistor being a sintered composition of claim 45. .Iaddend. .Iadd.67. A film resistor adherent to a dielectric substrate wherein the resistor comprises a conductive phase of crystalline particles of (1) pyrochlore-related oxides and (2) metal titanates, each dispersed in a matrix of a lead containing glass, said resistor being a sintered composition of claim 46. .Iaddend. .Iadd.68. A film resistor adherent to a dielectric substrate wherein the resistor comprises a conductive phase of crystalline particles of (1) pyrochlore-related oxides and (2) metal titanates, each dispersed in a matrix of a lead containing glass, said resistor being a sintered composition of claim 47. .Iaddend. .Iadd.69. A film resistor adherent to a dielectric substrate wherein the resistor comprises a conductive phase of crystalline particles of (1) pyrochlore-related oxides and (2) metal titanates, each dispersed in a matrix of a lead containing glass, said resistor being a sintered composition of claim 48. .Iaddend.