US3052573A - Resistor and resistor composition - Google Patents
Resistor and resistor composition Download PDFInfo
- Publication number
- US3052573A US3052573A US12256A US1225660A US3052573A US 3052573 A US3052573 A US 3052573A US 12256 A US12256 A US 12256A US 1225660 A US1225660 A US 1225660A US 3052573 A US3052573 A US 3052573A
- Authority
- US
- United States
- Prior art keywords
- resistor
- pdo
- finely divided
- oxide
- composition
- 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
Links
- 239000000203 mixture Substances 0.000 title claims description 62
- 229910044991 metal oxide Inorganic materials 0.000 claims description 41
- 150000004706 metal oxides Chemical class 0.000 claims description 41
- 239000000919 ceramic Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000000037 vitreous enamel Substances 0.000 description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 21
- 239000002245 particle Substances 0.000 description 17
- 229910052709 silver Inorganic materials 0.000 description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 239000011521 glass Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 238000010304 firing Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 13
- 229910052737 gold Inorganic materials 0.000 description 13
- 239000010931 gold Substances 0.000 description 13
- 229910003445 palladium oxide Inorganic materials 0.000 description 12
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 11
- 229910052697 platinum Inorganic materials 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 229910052749 magnesium Inorganic materials 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- 229910052761 rare earth metal Inorganic materials 0.000 description 9
- 150000002910 rare earth metals Chemical group 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- 229910052712 strontium Inorganic materials 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 229910052726 zirconium Inorganic materials 0.000 description 9
- 229910052763 palladium Inorganic materials 0.000 description 8
- 239000010944 silver (metal) Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 5
- 229910002113 barium titanate Inorganic materials 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- -1 refractory Inorganic materials 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- RUJPNZNXGCHGID-UHFFFAOYSA-N (Z)-beta-Terpineol Natural products CC(=C)C1CCC(C)(O)CC1 RUJPNZNXGCHGID-UHFFFAOYSA-N 0.000 description 2
- 229910011255 B2O3 Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- ZPPSOOVFTBGHBI-UHFFFAOYSA-N lead(2+);oxido(oxo)borane Chemical compound [Pb+2].[O-]B=O.[O-]B=O ZPPSOOVFTBGHBI-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- QJVXKWHHAMZTBY-GCPOEHJPSA-N syringin Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QJVXKWHHAMZTBY-GCPOEHJPSA-N 0.000 description 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- VSYMNDBTCKIDLT-UHFFFAOYSA-N [2-(carbamoyloxymethyl)-2-ethylbutyl] carbamate Chemical compound NC(=O)OCC(CC)(CC)COC(N)=O VSYMNDBTCKIDLT-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000006105 batch ingredient Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000005385 borate glass Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000012671 ceramic insulating material Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5122—Pd or Pt
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/88—Metals
-
- 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
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
-
- 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
- H01C17/06526—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of metals
-
- 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
- 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
- H01C17/06553—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of a combination of metals and oxides
-
- 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
- Y10T29/49099—Coating resistive material on a base
Definitions
- This invention relates to ceramic electrical resistor compositions and to electrical resistor films produced therewith. More particularly, the invention relates to vitreous enamel-palladium oxide compositions which may be applied to and fired on a ceramic dielectric material to produce an electrical resistor, and electrical resistors so produced.
- the recently issued patent to J. B. DAndrea, No. 2,924,540 discloses a new type of ceramic resistor composition and electrical resistors produced therefrom, comprising finely divided palladium metal, with or without addition of silver, in combination with a vitreous enamel flux.
- the DAndrea type resistor material constituted a great improvement over previously known types of printed ceramic resistor material, it was not altogether satisfactory since the use of different vitreous enamel frits of different maturing temperatures gave resistors of rather widely divergent resistances.
- vitreous enamel containing resistor compositions that will have substantially uniform resistances even when mixed with vitreous enamels of varying maturing temperatures and fired at such varying temperatures.
- the resistor compositions of this invention may be prepared by mixing finely divided palladium oxide Wi-th finely divided vitreous enamel frit.
- the dry finely divided palladium oxide-enamel frit composition may, if desired, be
- the palladium oxide may, if desired, be replaced by rhodium oxide with substantially like results. Since RhO has substantially the same characteristics as PDO for the purposes and objects of this invention, where reference is made to Pd or PdO throughout the specification and claims it is to be understood that the Pd or PdO may be respectively replaced by Rh or RhO.
- the finished resistor may be produced by applying the resistor composition to a ceramic dielectric and firing the same at a temperature that will fuse (mature) the vitreous enamel to the dielectric surface.
- a still further improvement in reproducibility of resistors of a given resistance value maybe obtained by the use of finely divided palladium oxide with an oxide of a metal from the group consisting of Zr, Al, Sr, Ca, Sn, Mg, Zn, and the rare earth metals bonded to it.
- Finely divided palladium oxide for use in accordance with this invention may be prepared by heating finely divided palladium metal in air.
- the palladium metal may be produced by chemical precipitation or by mechanical comminution or disintegration in known manner. It is highly desirable, however, that the fineness of division be less than 325 mesh and preferably of an average particle size of between 0.1 and 50 microns.
- the finely divided palladium oxide with or without silver, gold or platinum powder is mixed with the finely divided (less than 325 mesh) vitreous enamel flux in the following proportions:
- the resistor compositions with PdO modified by the presence of certain other metal oxides are greatly to be preferred.
- finely divided PdO containing 10% by weight of Zr0 will produce a resistor the resistance of which will vary by only 20% when fired during a given period at a temperature varying between 1300 F. and 1500 F., and will vary by about 2 fold when fired at periods varying between 30 and 90 minutes at a constant temperature between 1300" F. and 1400 F. and less than 3 fold at similar varying periods at 1500 F.
- the similar addition of the other listed metal oxides to PdO will produce improvements of the same order.
- a palladium oxide that is associated with a metal oxide of the kind referred to above, it may be obtained in any manner whereby at least a portion of the surface of the PdO particles is coated with an ad herent coating of the metal oxide additive.
- the following proportions of the metal oxides to PdO may be used:
- Resistor formulations prepared with PdO modified with one of said metal oxides, silver and Vitreous enamel frit may contain the following proportions:
- the additive metal oxide may be the oxide of Zr, Al, Sr, Ca, Sn, Mg, Zn or a rare earth or combinations thereof.
- the rare earths consist of the metals scandium, yttrium, lanthanum, cerium prascodymium, neodymium, Samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, neoytterbium, and lutecium. Of these the most common are probably lanthanum and cerium, both of which have given good results as PdO additives in accordance with this invention.
- the characteristics of the rare earths are very much alike and although they would undoubtedly all be operative for the purposes of this invention, many of them are probably too rare and expensive to be practical.
- FIGURE 1 is a cross-sectional view, on a highly exaggerated scale, of a resistor produced in accordance with this invention.
- FIGURE 2 is a smaller cross-sectional view of a second embodiment of the resistor of this invention.
- 1 designates a ceramic dielectric base such as a glass, porcelain, refractory, barium titanate or a similar dielectric base.
- a resistor unit 2 is formed on the base 1 by firing a resistor composition of the invention and comprising PdO or RhO particles mixed with a glass frit. The resulting resistor unit 2 is comprised of the PdO or RhO particles 3 bonded in a glass matrix 4.
- FIGURE 2 shows a similar resistor comprised of a ceramic base 1 and containing metal oxide particles 5 both coated on at least parts of the surfaces of the PdO particles 3 and also interspersed bet-ween the PdO particles, all in a glass matrix 4.
- the metal oxide particles 5 as stated in the specification may consist of Zr, Al, Sr, Ca, Sn, Mg, Zn or a rare earth or combinations thereof.
- the additive metal oxide is produced from a Water-soluble salt of the metal by decomposition to the oxide on the surface of the PdO particles. This may be accomplished, for example, by dissolving the nitrate salt of the desired metal oxide in water and mixing therewith finely divided palladium metal (less than 325 mesh). The water is then evaporated from the mixture and when dry the residue is placed in a furnace and fired at 750 C. for 1 /2 to 20 hours. The resulting homogeneous mixture of PdO and the additive metal oxide is crushed and ballmilled in the presence of an inert liquid for a period of 2 to 20 hours.
- Another method consists in adding the nitrate solution of the additive salt to palladium oxide powder and heat treating as above described.
- a third method that is particularly applicable with aluminum nitrate solution comprises the addition of an1- monium hydroxide to palladium chloride solution to form a fine suspension of ammonium chloropalladate to which is then added a measured amount of colloidal hydrous aluminum oxide (formed by adding ammonium hydroxide to aluminum nitrate solution). The mixture is thoroughly stirred and filtered. The residue from the filter is heated at about 750 C. for minutes to produce a finely divided Al O -PdO powder.
- the vitreous enamel frit used in the production of the vitreous enamel resistor compositions of the invention may be composed of any glass frit, such as a borosilicate frit, lead borosilicate frit, cadmium, barium, calcium, or other borosilicate frit.
- a glass frit such as a borosilicate frit, lead borosilicate frit, cadmium, barium, calcium, or other borosilicate frit.
- the preparation of such frits is well known and consists, for example, in melting together boric oxide, silicon dioxide and lead oxide, cadmium oxide, or barium oxide and pouring such molten composition into Water to form the frit.
- the batch ingredients may, of course, be any compound that will yield the desired oxides under the fusing conditions of frit production, i.e., boric oxide will be obtained from boric acid or borax, silicon dioxide will be produced from flint, lead oxide will be produced from red lead or white lead, barium oxide will be produced from barium carbonate, etc.
- the coarse frit is preferably milled for 2 to 20 hours, for example, in a ball-mill with water.
- the frit may contain varying amounts of other oxides, such as zinc oxide, magnesium oxide, or the like.
- the vitreous enamel frit and palladium oxide powder may be mixed in any manner, for example, in a ball-mill, and the resulting dry composition sold as such.
- the dry composition is, however, preferably first mixed with a liquid vehicle and sold in the form of a liquid or paste.
- the vehicle may vary widely in composition.
- any inert liquid may be employed for this purpose, for example, Water, organic solvents, with or without thickening agents, stabilizling agents, or the like, for example, methyl, ethyl, butyl, propyl or higher alcohols, the corresponding esters such as the acetates, propionates, etc., the terpenes and liquid resins, for example, pine oil, alpha-terpineol, betaterpineol, and the like, and other liquids without limitation, the function of the liquid vehicle being mainly to form a liquid or paste of the desired consistency for application purposes.
- inert liquid for example, Water, organic solvents, with or without thickening agents, stabilizling agents, or the like, for example, methyl, ethyl, butyl, propyl or higher alcohols, the corresponding esters such as the acetates, propionates, etc., the terpenes and liquid resins, for example, pine oil, alpha-terpineol,
- the vehicles may contain or be composed of volatile liquids to promote fast setting after application, or they may contain waxes, thermoplastic resins, or wax-like materials Which are thermofluid by nature whereby the composition may be applied to a ceramic insulator while at an elevated temperature to set immediately upon contact with the ceramic base.
- any desired amount of vehicle or organic binder may be added whereby to stencil, spray or brush the finely divided metal oxide onto a ceramic dielectric base material.
- concentration of solids and the viscosity of the paste must be controlled since these will affect the thickness of the prints and the resistance value of the resistors.
- the viscosity of the compositions (preferably about to thousand centipoises) may be adjusted so that the fired fihn is of the desired thickness.
- a very suitable thickness would be of the order of 15 to 25 microns.
- the ceramic dielectric base material may be comprised of any ceramic material that can withstand the firing temperature of the vitreous enamel-palladium oxide composition.
- any ceramic material that can withstand the firing temperature of the vitreous enamel-palladium oxide composition.
- glass, porcelain, refractory, barium titanate, or the like may be used.
- the ceramic insulating materials should have a smooth, sub- .5 stantially uniform surface structure but this is not absolutely necessary.
- the resistor composition is then applied in a uniform thickness on the ceramic dielectric. This may be done by any of the application methods above disclosed.
- the dielectric and applied resistor composition is then dried, if necessary, to remove solvent from the vehicle and then fired in a conventional lehr or furnace at a temperature at which the enamel frit is molten, whereby the conductive material is bonded to the ceramic dielectric.
- Example I 10.44 grams of zirconyl nitrate are dissolved in water in a large evaporating dish. To this is added 23.47 grams of finely divided palladium metal. The resulting mixture is heated with continuous stirring until all the water is evaporated therefrom, after which the dry mixture is placed in a furnace and fired for 90 minutes at a temperature of 750 C. The fired product, after cooling, is then ball-milled in acetone for a period of 16 hours. The resulting finely divided metal oxide contained about 90% PdO and ZrO Example 11 44 grams of aluminum nitrate is dissolved in water and 30 grams of finely divided palladium powder is added thereto. The mixture is dried, fired and ball-milled in the manner described in Example I.
- the ball-milled product may be further milled with glass beads for 16 to 70 hours.
- the dried ball-milled product contained about 85% PdO and A1203- Example III
- a resistor composition was prepared by blending: 60 grams of the ball-milled product of Example I, 40 grams of commercial precipitated silver having a particle size of about 2 microns, 180 grams of lead borosilicate frit consisting of 65% PbO, 10% B 0 and 25% SiO and 130 grams of a vehicle composed of beta-terpineol viscosified with 6% by weight of ethyl cellulose.
- the ethyl cellulose used was that sold under the designation T-200 lay Hercules Powder Company of Wilmington, Delaware.
- the resulting composition was roll-milled thoroughly and then printed with a thickness of about 1 mil. with a 200 mesh stainless steel squeegee stencil screen onto a barium titanate dielectric disc and fired to produce electric resistors.
- the following table gives the resistance per square in K 1000 ohms) of the resulting resistors obtained using given firing times and temperatures.
- Example IV A paste resistor composition was prepared by the procedure of Example III with the sole exception that the 16-hour ball-milled product of Example H replaced the product of Example I.
- Example V A resistor composition was prepared by the procedure of Example IV but containing the metal oxide product of Example II ball-milled 16 hours in acetone and beadmilled further for 16 more hours. A resistance per square ranging from 10K to 15K was obtained using the firing conditions of Example IV.
- Example VI Following the procedure of Example III using the metal oxide product of Example II, the glass frit of Example III, finely divided silver powder having a particle size of about 2 microns, in the proportions by weight given in the following table and firing the printed resistors at 1400 F. for 60 minutes, the resistance Values set forth in the table were obtained:
- Example VII Following the procedure of Example III but replacing the metal oxide product of Example I with the following metal oxide combinations, produced substantially in accordance with the procedure of Example I, the following resistance values were obtained at the various given times and temperatures of firing:
- Example VIII Two resistor compositions were prepared by the procedure of Example III using as the glass frit a lead borate glass having a softening point of 430 C., a finely divided precipitated silver powder having a particle size of about 2 microns, and as the metal oxide, one of the compositions is formulated with the aluminum oxide modified PdO of Example II and the other composition with PdO prepared by heat treating finely divided Pd in normal atmosphere at 750 C. for 16 hours and ball-milled for 16 hours.
- the two compositions contained the following compositions of total metal oxide, silver powder and lead borate frit.
- compositions were placed on barium titanate alumina and steatite dielectric discs by the procedure of Example III.
- the resistance values of the resulting resistors fired at the given times and temperatures were as follows:
- the resistor compositions of this invention are outstandingly useful for the production of electrical resistors having good stability, low temperature coeflicient of resistance (the percentage change in resistance at two given temperatures divided by the ditference in temperature between said two temperatures in degrees centigrade) low voltage coefficient of resistance (the percentage chang in resistance at two given voltages divided by the difference between said two voltages) being readily reproducible and being relatively non-sensitive to times and temperatures of firing.
- a resistor composition formulated with PdO and a vitreous enamel (glass) frit will produce resistors having a positive temperature coefficient of resistance (TCR) varying between 0.05% and 0.08% per degree C.
- TCR temperature coefficient of resistance
- a resistor composition formulated with PdO modified with another of the aforesaid metal oxides will produce resistors with either a positive or negative TCR.
- This TCR is dependent on the type of the added oxide and its relative proportion to the PdO, on the heat treatment and fineness of division of the metal oxide combination, the resistor formulation (i.e., ratio of metal oxide, silver and glass frit) and the type of dielectric on which the resistor composition is printed. It has been found that by suitable control of these variables the TCR does not vary widely with the firing conditions of the resistor. In this way a uniform and reproducible TCR of less than 0.01% per degree C. may be maintained, if desired.
- a resistor composition adapted to be applied to and fired on a ceramic dielectric to form readily reproducible electric resistors consisting essentially of 4% to 90% finely divided metal oxide taken from the group consisting of PdO and RhO, as a conductive component, to 50% finely divided metal taken from the group consisting of Ag, Au and Pt as a conductive component, a total of 8% to 90% of said conductive component and 10% to 92% finely divided vitreous enamel frit.
- a resistor composition adapted to be applied to and fired on a ceramic dielectric to form readily reproducible electric resistors consisting essentially of 10% to 70% finely divided metal oxide taken from the group consisting of PdO and RhO containing bonded thereto 0.1% to 35 by weight of a metal oxide taken from the group consisting of Zr, Al, Sr, Ca, Sn, Mg, Zn and the rare earth metals, as a conductive component, 0% to 30% finely divided metal taken from the group consisting of Ag, Au and Pt, as a conductive component, a total of 10% to 70% of said conductive component, and 30% to finely divided vitreous enamel frit.
- a resistor composition adapted to be applied to and fired on a ceramic dielectric to form readily reproducible electric resistors consisting essentially of 10% to 70% finely divided metal oxide taken from the group consisting of PdO and R containing bonded thereto 8% to 15 by weight of a metal oxide taken from the group consisting of Zr, Al, Sr, Ca, Sn, Mg, Zn and the rare earth metals, as a conductive component, 0% to 30% finely divided metal taken from the group consisting of Ag, Au and Pt, as a conductive component, a total of 10% to 70% of said conductive component and 30% to 90% finely divided vitreous enamel frit.
- a resistor composition adapted to be applied to and fired on a ceramic dielectric to form readily reproducible electric resistors consisting essentially of 15% to 35% of finely divided metal oxide taken from the group consisting of PdO and RhO containing bonded thereto 0.1% to 35% by weight of a metal oxide taken from the group consisting of Zr, Al, Sr, Ca, Sn, Mg, Zn, and the rare earth metals, as a conductive component, 5% to 25% finely divided metal taken from the group consisting of Ag, Au and Pt, as a conductive component, a total of 20% to 60% of said conductive component, and 40% to 80% finely divided vitreous enamel frit.
- An electrical resistor comprising a ceramic dielectric containing on the surface thereof a vitreous enamel resistor element comprising between 10% and 70% of a metal oxide taken from the group consisting of PdO and RhO containing bonded thereto 0.1% to 35 by weight of a metal oxide taken from the group consisting of Zr, Al, Sr, Ca, Sn, Mg, Zn and the rare earth metals, as a conductive component, 0% to 30% metal taken from the group consisting of Ag, Au and Pt, as a conductive component, a total of 10% to 70% of said conductive component, said conductive component embedded in a glass matrix.
- An electrical resistor comprising a ceramic dielectric containing on the surface thereof, a vitreous enamel resistor element comprising between 15 and 35 of a metal oxide taken from the group consisting of PdO and F110 containing bonded thereto 0.1% to 35 by weight of a metal oxide taken from the group consisting of Zr, Al, Sr, Ca, Sn, Mg, Zn, and the rare earth metals, as a conductive component, 5% to 25% metal taken from the group consisting of Ag, Au and Pt, as a conductive component, a total of 20% to 60% of said conductive component, said conductive component embedded in a glass matrix.
- An electrical resistor comprising a ceramic dielectric containing on the surface thereof a vitreous enamel resistor element consisting essentially of 4% to 90% of a 5 finely divided metal oxide taken from the group consisting of PdO and RhO, as a conductive component, 0% to 50% finely divided metal taken from the group consisting of Ag, Au and Pt, as a conductive component, a total of 8% to 90% of said conductive component, said 0011- 10 ductive components embedded in a glass matrix.
Description
Sept. 1962 M. E. DUMESNIL 3,052,573
RESISTOR AND RESISTOR COMPOSITION Filed March 2, 1960 2- Resistor unit 1- Ceramic bose .FIG. 2
5- Metol oxide coating and particles 4-Gloss matrix 0 pflrficles l-Ceromic base INVENTOR MAURICE E. DUMESNIL ATTORNEY United States Patent 3,052,573 RESISTOR AND RESISTOR COMPOSITION Maurice Edward Dumesnil, Metuchen, N.J., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware Filed Mar. 2, 1960, Ser. No. 12,256 13 Claims. (Cl. 117-221) This invention relates to ceramic electrical resistor compositions and to electrical resistor films produced therewith. More particularly, the invention relates to vitreous enamel-palladium oxide compositions which may be applied to and fired on a ceramic dielectric material to produce an electrical resistor, and electrical resistors so produced.
The recently issued patent to J. B. DAndrea, No. 2,924,540, discloses a new type of ceramic resistor composition and electrical resistors produced therefrom, comprising finely divided palladium metal, with or without addition of silver, in combination with a vitreous enamel flux. Although the DAndrea type resistor material constituted a great improvement over previously known types of printed ceramic resistor material, it was not altogether satisfactory since the use of different vitreous enamel frits of different maturing temperatures gave resistors of rather widely divergent resistances.
It is an object of this invention to produce vitreous enamel containing resistor compositions that will have substantially uniform resistances even when mixed with vitreous enamels of varying maturing temperatures and fired at such varying temperatures.
It is another object of this invention to produce vitreous enamel containing resistor compositions of high stability to firing temperatures.
It is yet another object to produce a more easily reproducible electrical resistor.
Other objects of the invention will appear hereinafter.
The resistor compositions of this invention may be prepared by mixing finely divided palladium oxide Wi-th finely divided vitreous enamel frit. The dry finely divided palladium oxide-enamel frit composition may, if desired, be
-miXed with a liquid or pasty vehicle for application to a ceramic dielectric.
The palladium oxide may, if desired, be replaced by rhodium oxide with substantially like results. Since RhO has substantially the same characteristics as PDO for the purposes and objects of this invention, where reference is made to Pd or PdO throughout the specification and claims it is to be understood that the Pd or PdO may be respectively replaced by Rh or RhO.
As in the DAndrea patent, so that the voltage and temperature coefficients of the resulting resistors may be more readily controlled, it is usually preferred that a quantity of finely divided (less than 325 mesh) silver, gold or platinum be added to the palladium oxide in the resistor composition.
The finished resistor may be produced by applying the resistor composition to a ceramic dielectric and firing the same at a temperature that will fuse (mature) the vitreous enamel to the dielectric surface.
A still further improvement in reproducibility of resistors of a given resistance value maybe obtained by the use of finely divided palladium oxide with an oxide of a metal from the group consisting of Zr, Al, Sr, Ca, Sn, Mg, Zn, and the rare earth metals bonded to it.
Finely divided palladium oxide for use in accordance with this invention may be prepared by heating finely divided palladium metal in air. The palladium metal may be produced by chemical precipitation or by mechanical comminution or disintegration in known manner. It is highly desirable, however, that the fineness of division be less than 325 mesh and preferably of an average particle size of between 0.1 and 50 microns. When palladium metal powder is heated in air it begins to oxidize readily at 300 C. and reaches a maximum Weight gain at 700 C. to 750 C. to form the non-stoichiometric structure PdO (1), being essentially palladium monoxide. Beyond this temperature the oxide becomes unstable and reverts to the metal in the same way that silver oxide decomposes to metal at about 300 C. The use of PdO in place of metallic Pd in vitreous resistor compositions oifers the advantage of using very soft vitreous enamel (450600 C.) as well as vitreous enamel having a fairly high melting point (700800 C.) without completely varying the resistance values of the finished resistors produced therefrom.
The finely divided palladium oxide with or without silver, gold or platinum powder, is mixed with the finely divided (less than 325 mesh) vitreous enamel flux in the following proportions:
[Percentages by weight] Operable Preferred proportions proportions 4 to 4 to 15 0 to 50 0 to 12 8 to 90 8 to 27 92 to 10 92 to 73 firing period and a 10 fold variance with a varying firing period of 30 to 90 minutes under a constant firing temperature.
It is therefore greatly to be preferred to prepare the resistor compositions with PdO modified by the presence of certain other metal oxides. For examples, finely divided PdO containing 10% by weight of Zr0 will produce a resistor the resistance of which will vary by only 20% when fired during a given period at a temperature varying between 1300 F. and 1500 F., and will vary by about 2 fold when fired at periods varying between 30 and 90 minutes at a constant temperature between 1300" F. and 1400 F. and less than 3 fold at similar varying periods at 1500 F. The similar addition of the other listed metal oxides to PdO will produce improvements of the same order.
Where a palladium oxide is desired that is associated with a metal oxide of the kind referred to above, it may be obtained in any manner whereby at least a portion of the surface of the PdO particles is coated with an ad herent coating of the metal oxide additive. The following proportions of the metal oxides to PdO may be used:
[Percentages by weight] Operable Preferred proportions proportions PdO (replaceable with RhO) 65 to 99. 9 85 to 92 Metal oxide 01' the group Zr, Al, Sr, Ca, Sn,
Mg, Zn, and rare earth metals 35 to 0.1 15 t 8 Resistor formulations prepared with PdO modified with one of said metal oxides, silver and Vitreous enamel frit may contain the following proportions:
[Percentages by weight] As above stated, the additive metal oxide may be the oxide of Zr, Al, Sr, Ca, Sn, Mg, Zn or a rare earth or combinations thereof. The rare earths consist of the metals scandium, yttrium, lanthanum, cerium prascodymium, neodymium, Samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, neoytterbium, and lutecium. Of these the most common are probably lanthanum and cerium, both of which have given good results as PdO additives in accordance with this invention. The characteristics of the rare earths are very much alike and although they would undoubtedly all be operative for the purposes of this invention, many of them are probably too rare and expensive to be practical.
Resistors prepared in accordance with this invention are illustrated in the accompanying drawings, in which,
FIGURE 1 is a cross-sectional view, on a highly exaggerated scale, of a resistor produced in accordance with this invention.
FIGURE 2 is a smaller cross-sectional view of a second embodiment of the resistor of this invention.
Referring to the drawings, 1 designates a ceramic dielectric base such as a glass, porcelain, refractory, barium titanate or a similar dielectric base. A resistor unit 2 is formed on the base 1 by firing a resistor composition of the invention and comprising PdO or RhO particles mixed with a glass frit. The resulting resistor unit 2 is comprised of the PdO or RhO particles 3 bonded in a glass matrix 4.
FIGURE 2 shows a similar resistor comprised of a ceramic base 1 and containing metal oxide particles 5 both coated on at least parts of the surfaces of the PdO particles 3 and also interspersed bet-ween the PdO particles, all in a glass matrix 4. The metal oxide particles 5 as stated in the specification may consist of Zr, Al, Sr, Ca, Sn, Mg, Zn or a rare earth or combinations thereof.
The following methods are given as suitable methods for preparing the finely divided PdO (replaceable wholly or partially with RhO) containing the additive metal oxide. These methods are not, however, to be taken as limitative of the invention, other methods being equally applicable to the production of the metal oxide modified PdO. r
Preferably, the additive metal oxide is produced from a Water-soluble salt of the metal by decomposition to the oxide on the surface of the PdO particles. This may be accomplished, for example, by dissolving the nitrate salt of the desired metal oxide in water and mixing therewith finely divided palladium metal (less than 325 mesh). The water is then evaporated from the mixture and when dry the residue is placed in a furnace and fired at 750 C. for 1 /2 to 20 hours. The resulting homogeneous mixture of PdO and the additive metal oxide is crushed and ballmilled in the presence of an inert liquid for a period of 2 to 20 hours.
Another method consists in adding the nitrate solution of the additive salt to palladium oxide powder and heat treating as above described.
A third method that is particularly applicable with aluminum nitrate solution comprises the addition of an1- monium hydroxide to palladium chloride solution to form a fine suspension of ammonium chloropalladate to which is then added a measured amount of colloidal hydrous aluminum oxide (formed by adding ammonium hydroxide to aluminum nitrate solution). The mixture is thoroughly stirred and filtered. The residue from the filter is heated at about 750 C. for minutes to produce a finely divided Al O -PdO powder.
The vitreous enamel frit used in the production of the vitreous enamel resistor compositions of the invention may be composed of any glass frit, such as a borosilicate frit, lead borosilicate frit, cadmium, barium, calcium, or other borosilicate frit. The preparation of such frits is well known and consists, for example, in melting together boric oxide, silicon dioxide and lead oxide, cadmium oxide, or barium oxide and pouring such molten composition into Water to form the frit. The batch ingredients may, of course, be any compound that will yield the desired oxides under the fusing conditions of frit production, i.e., boric oxide will be obtained from boric acid or borax, silicon dioxide will be produced from flint, lead oxide will be produced from red lead or white lead, barium oxide will be produced from barium carbonate, etc.
The coarse frit is preferably milled for 2 to 20 hours, for example, in a ball-mill with water. The frit may contain varying amounts of other oxides, such as zinc oxide, magnesium oxide, or the like.
The vitreous enamel frit and palladium oxide powder, with or Without silver, gold or platinum powder, may be mixed in any manner, for example, in a ball-mill, and the resulting dry composition sold as such. The dry composition is, however, preferably first mixed with a liquid vehicle and sold in the form of a liquid or paste. The vehicle may vary widely in composition. Any inert liquid may be employed for this purpose, for example, Water, organic solvents, with or without thickening agents, stabilizling agents, or the like, for example, methyl, ethyl, butyl, propyl or higher alcohols, the corresponding esters such as the acetates, propionates, etc., the terpenes and liquid resins, for example, pine oil, alpha-terpineol, betaterpineol, and the like, and other liquids without limitation, the function of the liquid vehicle being mainly to form a liquid or paste of the desired consistency for application purposes. The vehicles may contain or be composed of volatile liquids to promote fast setting after application, or they may contain waxes, thermoplastic resins, or wax-like materials Which are thermofluid by nature whereby the composition may be applied to a ceramic insulator while at an elevated temperature to set immediately upon contact with the ceramic base.
Any desired amount of vehicle or organic binder may be added whereby to stencil, spray or brush the finely divided metal oxide onto a ceramic dielectric base material. For stencil screen application the concentration of solids and the viscosity of the paste must be controlled since these will affect the thickness of the prints and the resistance value of the resistors. The viscosity of the compositions (preferably about to thousand centipoises) may be adjusted so that the fired fihn is of the desired thickness. A very suitable thickness would be of the order of 15 to 25 microns.
The ceramic dielectric base material may be comprised of any ceramic material that can withstand the firing temperature of the vitreous enamel-palladium oxide composition. For example, glass, porcelain, refractory, barium titanate, or the like may be used. Preferably, the ceramic insulating materials should have a smooth, sub- .5 stantially uniform surface structure but this is not absolutely necessary.
The resistor composition is then applied in a uniform thickness on the ceramic dielectric. This may be done by any of the application methods above disclosed. The dielectric and applied resistor composition is then dried, if necessary, to remove solvent from the vehicle and then fired in a conventional lehr or furnace at a temperature at which the enamel frit is molten, whereby the conductive material is bonded to the ceramic dielectric.
The following examples are given to illustrate certain preferred details of the invention, it being understood that the details of the examples are not to be taken as in any way limiting the invention thereto. In all of the examples the particle size of the palladium, palladium oxide, metal oxides, silver, gold, platinum, and frit averaged between about 1 and 5 microns. Although it is desirable to maintain the particle sizes fairly consistent to obtain good reproducible results, the actual particle sizes used are not critical.
Example I 10.44 grams of zirconyl nitrate are dissolved in water in a large evaporating dish. To this is added 23.47 grams of finely divided palladium metal. The resulting mixture is heated with continuous stirring until all the water is evaporated therefrom, after which the dry mixture is placed in a furnace and fired for 90 minutes at a temperature of 750 C. The fired product, after cooling, is then ball-milled in acetone for a period of 16 hours. The resulting finely divided metal oxide contained about 90% PdO and ZrO Example 11 44 grams of aluminum nitrate is dissolved in water and 30 grams of finely divided palladium powder is added thereto. The mixture is dried, fired and ball-milled in the manner described in Example I. If a still finer particle size is desired, the ball-milled product may be further milled with glass beads for 16 to 70 hours. The dried ball-milled product contained about 85% PdO and A1203- Example III A resistor composition was prepared by blending: 60 grams of the ball-milled product of Example I, 40 grams of commercial precipitated silver having a particle size of about 2 microns, 180 grams of lead borosilicate frit consisting of 65% PbO, 10% B 0 and 25% SiO and 130 grams of a vehicle composed of beta-terpineol viscosified with 6% by weight of ethyl cellulose. The ethyl cellulose used was that sold under the designation T-200 lay Hercules Powder Company of Wilmington, Delaware.
The resulting composition was roll-milled thoroughly and then printed with a thickness of about 1 mil. with a 200 mesh stainless steel squeegee stencil screen onto a barium titanate dielectric disc and fired to produce electric resistors. The following table gives the resistance per square in K 1000 ohms) of the resulting resistors obtained using given firing times and temperatures.
Similar results were obtained by using alumina or steatite dielectric discs in place of the barium titanate dielectric.
Example IV A paste resistor composition was prepared by the procedure of Example III with the sole exception that the 16-hour ball-milled product of Example H replaced the product of Example I.
v minutes Firing time 1,300 F. 1,400" F. l,500 F.
30 minutes 2. 1 3. 7
Example V A resistor composition was prepared by the procedure of Example IV but containing the metal oxide product of Example II ball-milled 16 hours in acetone and beadmilled further for 16 more hours. A resistance per square ranging from 10K to 15K was obtained using the firing conditions of Example IV.
Example VI Following the procedure of Example III using the metal oxide product of Example II, the glass frit of Example III, finely divided silver powder having a particle size of about 2 microns, in the proportions by weight given in the following table and firing the printed resistors at 1400 F. for 60 minutes, the resistance Values set forth in the table were obtained:
Pd0(85), A1zO (l5)OfEXaD1- 20 20 30 25 20 25 25 10 ple II, percent Silver powder, percent 1O 15 7.5 15 17.5 20 25 30 Glass frit of Example III,
percent 70 62.5 60 62.5 55 50 60 Resistance per square (taken to nearest whole numbers),
Example VII Following the procedure of Example III but replacing the metal oxide product of Example I with the following metal oxide combinations, produced substantially in accordance with the procedure of Example I, the following resistance values were obtained at the various given times and temperatures of firing:
Example VIII Two resistor compositions were prepared by the procedure of Example III using as the glass frit a lead borate glass having a softening point of 430 C., a finely divided precipitated silver powder having a particle size of about 2 microns, and as the metal oxide, one of the compositions is formulated with the aluminum oxide modified PdO of Example II and the other composition with PdO prepared by heat treating finely divided Pd in normal atmosphere at 750 C. for 16 hours and ball-milled for 16 hours. The two compositions contained the following compositions of total metal oxide, silver powder and lead borate frit.
The compositions were placed on barium titanate alumina and steatite dielectric discs by the procedure of Example III. The resistance values of the resulting resistors fired at the given times and temperatures were as follows:
Throughout the examples where silver is used, it can be replaced wholly or partially with either gold or platinum or both with substantially similar results, and where PdO is used it can be replaced wholly or in part by RhO.
The resistor compositions of this invention are outstandingly useful for the production of electrical resistors having good stability, low temperature coeflicient of resistance (the percentage change in resistance at two given temperatures divided by the ditference in temperature between said two temperatures in degrees centigrade) low voltage coefficient of resistance (the percentage chang in resistance at two given voltages divided by the difference between said two voltages) being readily reproducible and being relatively non-sensitive to times and temperatures of firing.
A resistor composition formulated with PdO and a vitreous enamel (glass) frit will produce resistors having a positive temperature coefficient of resistance (TCR) varying between 0.05% and 0.08% per degree C. On the other hand, a resistor composition formulated with PdO modified with another of the aforesaid metal oxides will produce resistors with either a positive or negative TCR. This TCR is dependent on the type of the added oxide and its relative proportion to the PdO, on the heat treatment and fineness of division of the metal oxide combination, the resistor formulation (i.e., ratio of metal oxide, silver and glass frit) and the type of dielectric on which the resistor composition is printed. It has been found that by suitable control of these variables the TCR does not vary widely with the firing conditions of the resistor. In this way a uniform and reproducible TCR of less than 0.01% per degree C. may be maintained, if desired.
Throughout the specification and claims, any reference to parts, proportions and percentages refers to parts, proportions and percentages by weight unless otherwise specified.
Since it is obvious that many changes and modifications can be made in the above-described details without departing from the nature and spirit of the invention, it is to be understood that the invention is not to be limited to said details except as set forth in the appended claims.
I claim:
1. A resistor composition adapted to be applied to and fired on a ceramic dielectric to form readily reproducible electric resistors consisting essentially of 4% to 90% finely divided metal oxide taken from the group consisting of PdO and RhO, as a conductive component, to 50% finely divided metal taken from the group consisting of Ag, Au and Pt as a conductive component, a total of 8% to 90% of said conductive component and 10% to 92% finely divided vitreous enamel frit.
2. A vitreous enamel resistor composition as defined in claim 1 in combination with sufficient inert liquid vehicle to form a paste with said composition components.
3. A resistor composition adapted to be applied to and fired on a ceramic dielectric to form readily reproducible electric resistors consisting essentially of 4% tofinely divided metal oxide taken from the group consisting of PdO and RM), as a conductive component, 0% to 12% finely divided metal taken from the group consisting of Ag, Au and Pt, as a conductive component, a total of 8% to 27% of said conductive component and 73% to 92% finely divided vitreous enamel frit.
4. A vitreous enamel resistor composition as defined in claim 3 in combination with suflicient inert liquid vehicle to form a paste with said composition components.
5. A resistor composition adapted to be applied to and fired on a ceramic dielectric to form readily reproducible electric resistors consisting essentially of 10% to 70% finely divided metal oxide taken from the group consisting of PdO and RhO containing bonded thereto 0.1% to 35 by weight of a metal oxide taken from the group consisting of Zr, Al, Sr, Ca, Sn, Mg, Zn and the rare earth metals, as a conductive component, 0% to 30% finely divided metal taken from the group consisting of Ag, Au and Pt, as a conductive component, a total of 10% to 70% of said conductive component, and 30% to finely divided vitreous enamel frit.
6. A vitreous enamel resistor composition as defined in claim 5 in combination with sufiicient inert liquid vehicle to form a paste with said composition components.
7. A resistor composition adapted to be applied to and fired on a ceramic dielectric to form readily reproducible electric resistors consisting essentially of 10% to 70% finely divided metal oxide taken from the group consisting of PdO and R containing bonded thereto 8% to 15 by weight of a metal oxide taken from the group consisting of Zr, Al, Sr, Ca, Sn, Mg, Zn and the rare earth metals, as a conductive component, 0% to 30% finely divided metal taken from the group consisting of Ag, Au and Pt, as a conductive component, a total of 10% to 70% of said conductive component and 30% to 90% finely divided vitreous enamel frit.
8. A vitreous enamel resistor composition as defined in claim 7 in combination with sufficient inert liquid ehicle to form a paste with said composition components.
9. A resistor composition adapted to be applied to and fired on a ceramic dielectric to form readily reproducible electric resistors consisting essentially of 15% to 35% of finely divided metal oxide taken from the group consisting of PdO and RhO containing bonded thereto 0.1% to 35% by weight of a metal oxide taken from the group consisting of Zr, Al, Sr, Ca, Sn, Mg, Zn, and the rare earth metals, as a conductive component, 5% to 25% finely divided metal taken from the group consisting of Ag, Au and Pt, as a conductive component, a total of 20% to 60% of said conductive component, and 40% to 80% finely divided vitreous enamel frit.
10. A vitreous enamel resistor composition as defined in claim 9 in combination with sufficient inert liquid ve hicle to form a paste with said composition components.
11. An electrical resistor comprising a ceramic dielectric containing on the surface thereof a vitreous enamel resistor element comprising between 10% and 70% of a metal oxide taken from the group consisting of PdO and RhO containing bonded thereto 0.1% to 35 by weight of a metal oxide taken from the group consisting of Zr, Al, Sr, Ca, Sn, Mg, Zn and the rare earth metals, as a conductive component, 0% to 30% metal taken from the group consisting of Ag, Au and Pt, as a conductive component, a total of 10% to 70% of said conductive component, said conductive component embedded in a glass matrix.
12. An electrical resistor comprising a ceramic dielectric containing on the surface thereof, a vitreous enamel resistor element comprising between 15 and 35 of a metal oxide taken from the group consisting of PdO and F110 containing bonded thereto 0.1% to 35 by weight of a metal oxide taken from the group consisting of Zr, Al, Sr, Ca, Sn, Mg, Zn, and the rare earth metals, as a conductive component, 5% to 25% metal taken from the group consisting of Ag, Au and Pt, as a conductive component, a total of 20% to 60% of said conductive component, said conductive component embedded in a glass matrix.
13. An electrical resistor comprising a ceramic dielectric containing on the surface thereof a vitreous enamel resistor element consisting essentially of 4% to 90% of a 5 finely divided metal oxide taken from the group consisting of PdO and RhO, as a conductive component, 0% to 50% finely divided metal taken from the group consisting of Ag, Au and Pt, as a conductive component, a total of 8% to 90% of said conductive component, said 0011- 10 ductive components embedded in a glass matrix.
References Cited in the file of this patent UNITED STATES PATENTS Iira May 4,
Christensen et a1. Feb. 15,
Huttar June 3,
DAndrea Feb. 9,
Place et al. Aug. 30,
FOREIGN PATENTS Great Britain June 8,
Claims (1)
1. A RESISTOR COMPOSITION ADAPTED TO BE APPLIED TO AND FIRED ON A CERAMIC DIELECTRIC TO FORM READILY REPRODUCIBLE ELECTRIC RESISTORS CONSISTING ESSENTIALLY OF 4% TO 90% FINELY DIVIDED METAL OXIDE TAKEN FROM THE GROUP CONSISTING OF PDO AND RHO, AS A CONDUCTIVE COMPONENT, 0% TO 50% FINELY DIVIDED METAL TAKEN FROM THE GROUP CONSISTING
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB36901/58A GB874257A (en) | 1960-03-02 | 1958-11-17 | Improvements in or relating to circuit-breaker actuating mechanisms |
GB36583/59A GB874157A (en) | 1960-03-02 | 1959-10-28 | Improvements in or relating to vitreous enamel compositions |
DEP23780A DE1132220B (en) | 1959-10-28 | 1959-10-28 | Glaze composition containing metal particles for the production of electrical resistances and electrical resistance |
FR810741A FR1240979A (en) | 1959-11-20 | 1959-11-20 | Composition of vitreous enamel and ceramic object |
US12256A US3052573A (en) | 1960-03-02 | 1960-03-02 | Resistor and resistor composition |
FR853008A FR79239E (en) | 1960-03-02 | 1961-02-17 | Composition of vitreous enamel and ceramic object |
DEP26619A DE1194539B (en) | 1960-03-02 | 1961-02-20 | Resistance glaze compound |
GB7130/61A GB904936A (en) | 1960-03-02 | 1961-02-27 | Improvements in or relating to vitreous enamel compositions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12256A US3052573A (en) | 1960-03-02 | 1960-03-02 | Resistor and resistor composition |
Publications (1)
Publication Number | Publication Date |
---|---|
US3052573A true US3052573A (en) | 1962-09-04 |
Family
ID=21754082
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12256A Expired - Lifetime US3052573A (en) | 1959-10-28 | 1960-03-02 | Resistor and resistor composition |
Country Status (3)
Country | Link |
---|---|
US (1) | US3052573A (en) |
DE (1) | DE1194539B (en) |
GB (3) | GB874257A (en) |
Cited By (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3180841A (en) * | 1962-08-28 | 1965-04-27 | Int Resistance Co | Resistance material and resistor made therefrom |
US3207706A (en) * | 1962-09-20 | 1965-09-21 | Du Pont | Resistor compositions |
US3232886A (en) * | 1962-09-20 | 1966-02-01 | Du Pont | Resistor compositions |
US3238151A (en) * | 1963-06-07 | 1966-03-01 | Air Reduction | Resistor composition |
US3248345A (en) * | 1963-10-01 | 1966-04-26 | Ibm | Electrical resistance compositions, elements and methods of making same |
US3271193A (en) * | 1962-09-20 | 1966-09-06 | Cts Corp | Electrical resistance element and method of making the same |
US3274669A (en) * | 1961-12-11 | 1966-09-27 | Beckman Instruments Inc | Method of making electrical resistance element |
US3277419A (en) * | 1963-11-20 | 1966-10-04 | Du Pont | Laminated heating unit |
US3304199A (en) * | 1963-11-12 | 1967-02-14 | Cts Corp | Electrical resistance element |
US3329526A (en) * | 1965-06-14 | 1967-07-04 | Cts Corp | Electrical resistance element and method of making the same |
US3337365A (en) * | 1963-03-25 | 1967-08-22 | Ibm | Electrical resistance composition and method of using the same to form a resistor |
US3343985A (en) * | 1963-02-12 | 1967-09-26 | Beckman Instruments Inc | Cermet electrical resistance material and method of using the same |
US3345158A (en) * | 1964-08-10 | 1967-10-03 | Ibm | Electrical conductor material and method of making same |
US3359632A (en) * | 1965-02-10 | 1967-12-26 | Victory Engineering Corp | Method of making a thermistor |
US3364565A (en) * | 1965-02-10 | 1968-01-23 | Victory Engineering Corp | Method of making a thermistor |
US3372058A (en) * | 1963-12-18 | 1968-03-05 | Ibm | Electrical device, method and material |
US3380835A (en) * | 1965-06-29 | 1968-04-30 | Du Pont | Metalizing compositions |
US3394087A (en) * | 1966-02-01 | 1968-07-23 | Irc Inc | Glass bonded resistor compositions containing refractory metal nitrides and refractory metal |
US3413240A (en) * | 1965-03-25 | 1968-11-26 | Du Pont | Compositions |
US3414641A (en) * | 1965-07-30 | 1968-12-03 | Ibm | Method of fabricating resistor compositions |
US3435496A (en) * | 1963-10-11 | 1969-04-01 | Quality Components Inc | Method of manufacturing cylindrical ceramic capacitors |
US3442822A (en) * | 1965-12-22 | 1969-05-06 | Air Reduction | Method of making electrical resistor by recrystallization |
DE1301020B (en) * | 1964-11-04 | 1969-08-14 | Beckman Instruments Inc | Cermet resistor |
US3475213A (en) * | 1965-09-13 | 1969-10-28 | Minnesota Mining & Mfg | Electrically conductive adhesive tape |
US3519891A (en) * | 1968-04-16 | 1970-07-07 | Westinghouse Electric Corp | Thin film resistor and method for making same |
US3611047A (en) * | 1970-03-06 | 1971-10-05 | Sylvania Electric Prod | Printed circuit with components |
US3663276A (en) * | 1970-05-25 | 1972-05-16 | Rca Corp | Method of adjusting the resistivity of thick-film screen-printed resistors |
US3700857A (en) * | 1971-04-14 | 1972-10-24 | Bell Telephone Labor Inc | Electrical resistance heater |
US3725836A (en) * | 1971-05-21 | 1973-04-03 | Matsushita Electric Ind Co Ltd | Thick film varistor and method for making the same |
US3919441A (en) * | 1972-12-20 | 1975-11-11 | Seinosuke Horiki | Panel-styled calorific devices and a process for manufacturing the same |
US3928245A (en) * | 1973-07-09 | 1975-12-23 | Gen Electric | Metal oxide voltage-variable resistor composition |
US4243710A (en) * | 1978-12-06 | 1981-01-06 | Ferro Corporation | Thermoplastic electrode ink for the manufacture of ceramic multi-layer capacitor |
US4397774A (en) * | 1977-10-31 | 1983-08-09 | U.S. Philips Corporation | Method of preparing resistance material and resistor bodies produced therewith |
US4599950A (en) * | 1985-01-28 | 1986-07-15 | Design Institute America, Inc. | Article of furniture and method of making same |
EP1739688A1 (en) * | 2005-06-29 | 2007-01-03 | E.I. Dupont De Nemours And Company | Method for manufacturing a conductive composition and a rear substrate of a plasma display |
EP1950766A3 (en) * | 2005-06-29 | 2008-10-08 | E.I. Du Pont De Nemours And Company | A conductive composition and a rear substrate of a plasma display |
WO2010097767A1 (en) * | 2009-02-24 | 2010-09-02 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Compliant material |
US8992852B2 (en) | 2009-02-24 | 2015-03-31 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Coated ceramic part |
US9023288B2 (en) | 2009-02-24 | 2015-05-05 | Saint-Gobain Centre de Recheches et d'Etudes European | Flush joint |
US9133966B2 (en) | 2009-02-24 | 2015-09-15 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Joining device |
US9370048B2 (en) | 2009-12-22 | 2016-06-14 | Saint-Gobain Glass France | Pane having electrical connecting element |
US9573846B2 (en) | 2008-04-10 | 2017-02-21 | Saint-Gobain Glass France | Transparent window with a heatable coating and low-impedance conducting structures |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3374110A (en) * | 1964-05-27 | 1968-03-19 | Ibm | Conductive element, composition and method |
US3470019A (en) * | 1965-02-04 | 1969-09-30 | Matthey Bishop Inc | Platinum coating composition,process and platinum-coated materials |
JPS521113B1 (en) * | 1966-05-16 | 1977-01-12 | ||
NL7602663A (en) * | 1976-03-15 | 1977-09-19 | Philips Nv | RESISTANCE MATERIAL. |
US4205298A (en) * | 1978-11-20 | 1980-05-27 | Trw Inc. | Resistor material, resistor made therefrom and method of making the same |
DE3721000C1 (en) * | 1987-06-25 | 1988-07-21 | Heraeus Gmbh W C | Use of a precious metal preparation for microwave-resistant precious metal decorations |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB486639A (en) * | 1937-09-10 | 1938-06-08 | Rosenthal Isolatoren Gmbh | An improved method of making high ohmic resistances with low temperature coefficient |
US2440691A (en) * | 1945-03-07 | 1948-05-04 | Continental Carbon Inc | Alloy metal film resistor |
US2461878A (en) * | 1944-11-01 | 1949-02-15 | Bell Telephone Labor Inc | Metallizing composition |
US2837487A (en) * | 1956-01-25 | 1958-06-03 | Du Pont | Resistor enamel and resistor made therefrom |
US2924540A (en) * | 1958-05-23 | 1960-02-09 | Du Pont | Ceramic composition and article |
US2950995A (en) * | 1957-03-18 | 1960-08-30 | Beckman Instruments Inc | Electrical resistance element |
-
1958
- 1958-11-17 GB GB36901/58A patent/GB874257A/en not_active Expired
-
1959
- 1959-10-28 GB GB36583/59A patent/GB874157A/en not_active Expired
-
1960
- 1960-03-02 US US12256A patent/US3052573A/en not_active Expired - Lifetime
-
1961
- 1961-02-20 DE DEP26619A patent/DE1194539B/en active Pending
- 1961-02-27 GB GB7130/61A patent/GB904936A/en not_active Expired
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB486639A (en) * | 1937-09-10 | 1938-06-08 | Rosenthal Isolatoren Gmbh | An improved method of making high ohmic resistances with low temperature coefficient |
US2461878A (en) * | 1944-11-01 | 1949-02-15 | Bell Telephone Labor Inc | Metallizing composition |
US2440691A (en) * | 1945-03-07 | 1948-05-04 | Continental Carbon Inc | Alloy metal film resistor |
US2837487A (en) * | 1956-01-25 | 1958-06-03 | Du Pont | Resistor enamel and resistor made therefrom |
US2950995A (en) * | 1957-03-18 | 1960-08-30 | Beckman Instruments Inc | Electrical resistance element |
US2924540A (en) * | 1958-05-23 | 1960-02-09 | Du Pont | Ceramic composition and article |
Cited By (48)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3274669A (en) * | 1961-12-11 | 1966-09-27 | Beckman Instruments Inc | Method of making electrical resistance element |
US3180841A (en) * | 1962-08-28 | 1965-04-27 | Int Resistance Co | Resistance material and resistor made therefrom |
DE1496620B1 (en) * | 1962-09-20 | 1970-03-12 | E I Du Pont Nemours & Company | Glaze composition containing metal particles, in particular for use for electrical resistors |
US3271193A (en) * | 1962-09-20 | 1966-09-06 | Cts Corp | Electrical resistance element and method of making the same |
US3232886A (en) * | 1962-09-20 | 1966-02-01 | Du Pont | Resistor compositions |
US3207706A (en) * | 1962-09-20 | 1965-09-21 | Du Pont | Resistor compositions |
US3343985A (en) * | 1963-02-12 | 1967-09-26 | Beckman Instruments Inc | Cermet electrical resistance material and method of using the same |
US3337365A (en) * | 1963-03-25 | 1967-08-22 | Ibm | Electrical resistance composition and method of using the same to form a resistor |
US3238151A (en) * | 1963-06-07 | 1966-03-01 | Air Reduction | Resistor composition |
US3248345A (en) * | 1963-10-01 | 1966-04-26 | Ibm | Electrical resistance compositions, elements and methods of making same |
US3435496A (en) * | 1963-10-11 | 1969-04-01 | Quality Components Inc | Method of manufacturing cylindrical ceramic capacitors |
US3304199A (en) * | 1963-11-12 | 1967-02-14 | Cts Corp | Electrical resistance element |
US3277419A (en) * | 1963-11-20 | 1966-10-04 | Du Pont | Laminated heating unit |
US3372058A (en) * | 1963-12-18 | 1968-03-05 | Ibm | Electrical device, method and material |
US3345158A (en) * | 1964-08-10 | 1967-10-03 | Ibm | Electrical conductor material and method of making same |
US3479216A (en) * | 1964-11-04 | 1969-11-18 | Beckman Instruments Inc | Cermet resistance element |
DE1301020B (en) * | 1964-11-04 | 1969-08-14 | Beckman Instruments Inc | Cermet resistor |
US3359632A (en) * | 1965-02-10 | 1967-12-26 | Victory Engineering Corp | Method of making a thermistor |
US3364565A (en) * | 1965-02-10 | 1968-01-23 | Victory Engineering Corp | Method of making a thermistor |
US3413240A (en) * | 1965-03-25 | 1968-11-26 | Du Pont | Compositions |
US3329526A (en) * | 1965-06-14 | 1967-07-04 | Cts Corp | Electrical resistance element and method of making the same |
US3380835A (en) * | 1965-06-29 | 1968-04-30 | Du Pont | Metalizing compositions |
US3414641A (en) * | 1965-07-30 | 1968-12-03 | Ibm | Method of fabricating resistor compositions |
US3475213A (en) * | 1965-09-13 | 1969-10-28 | Minnesota Mining & Mfg | Electrically conductive adhesive tape |
US3442822A (en) * | 1965-12-22 | 1969-05-06 | Air Reduction | Method of making electrical resistor by recrystallization |
US3394087A (en) * | 1966-02-01 | 1968-07-23 | Irc Inc | Glass bonded resistor compositions containing refractory metal nitrides and refractory metal |
US3519891A (en) * | 1968-04-16 | 1970-07-07 | Westinghouse Electric Corp | Thin film resistor and method for making same |
US3611047A (en) * | 1970-03-06 | 1971-10-05 | Sylvania Electric Prod | Printed circuit with components |
US3663276A (en) * | 1970-05-25 | 1972-05-16 | Rca Corp | Method of adjusting the resistivity of thick-film screen-printed resistors |
US3700857A (en) * | 1971-04-14 | 1972-10-24 | Bell Telephone Labor Inc | Electrical resistance heater |
US3725836A (en) * | 1971-05-21 | 1973-04-03 | Matsushita Electric Ind Co Ltd | Thick film varistor and method for making the same |
US3919441A (en) * | 1972-12-20 | 1975-11-11 | Seinosuke Horiki | Panel-styled calorific devices and a process for manufacturing the same |
US3928245A (en) * | 1973-07-09 | 1975-12-23 | Gen Electric | Metal oxide voltage-variable resistor composition |
USRE29731E (en) * | 1973-07-09 | 1978-08-15 | General Electric Company | Metal oxide voltage-variable resistor composition |
US4397774A (en) * | 1977-10-31 | 1983-08-09 | U.S. Philips Corporation | Method of preparing resistance material and resistor bodies produced therewith |
US4243710A (en) * | 1978-12-06 | 1981-01-06 | Ferro Corporation | Thermoplastic electrode ink for the manufacture of ceramic multi-layer capacitor |
US4599950A (en) * | 1985-01-28 | 1986-07-15 | Design Institute America, Inc. | Article of furniture and method of making same |
KR100799062B1 (en) | 2005-06-29 | 2008-01-29 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Method for manufacturing a conductive composition and a rear substrate of a plasma display |
KR100798240B1 (en) | 2005-06-29 | 2008-01-24 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Method for manufacturing a conductive composition and a rear substrate of a plasma display |
EP1739688A1 (en) * | 2005-06-29 | 2007-01-03 | E.I. Dupont De Nemours And Company | Method for manufacturing a conductive composition and a rear substrate of a plasma display |
EP1950766A3 (en) * | 2005-06-29 | 2008-10-08 | E.I. Du Pont De Nemours And Company | A conductive composition and a rear substrate of a plasma display |
US9573846B2 (en) | 2008-04-10 | 2017-02-21 | Saint-Gobain Glass France | Transparent window with a heatable coating and low-impedance conducting structures |
WO2010097767A1 (en) * | 2009-02-24 | 2010-09-02 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Compliant material |
US8622439B2 (en) | 2009-02-24 | 2014-01-07 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Compliant material |
US8992852B2 (en) | 2009-02-24 | 2015-03-31 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Coated ceramic part |
US9023288B2 (en) | 2009-02-24 | 2015-05-05 | Saint-Gobain Centre de Recheches et d'Etudes European | Flush joint |
US9133966B2 (en) | 2009-02-24 | 2015-09-15 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Joining device |
US9370048B2 (en) | 2009-12-22 | 2016-06-14 | Saint-Gobain Glass France | Pane having electrical connecting element |
Also Published As
Publication number | Publication date |
---|---|
GB874157A (en) | 1961-08-02 |
GB904936A (en) | 1962-09-05 |
DE1194539B (en) | 1965-06-10 |
GB874257A (en) | 1961-08-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3052573A (en) | Resistor and resistor composition | |
US2924540A (en) | Ceramic composition and article | |
DE2746320C2 (en) | Copper-glass composition of matter and its uses | |
US3304199A (en) | Electrical resistance element | |
US4065743A (en) | Resistor material, resistor made therefrom and method of making the same | |
US3207706A (en) | Resistor compositions | |
KR910005524B1 (en) | Copper conductor compositions | |
EP0115798B1 (en) | Stain-resistant ruthenium oxide-based resistors | |
US4362656A (en) | Thick film resistor compositions | |
US4060663A (en) | Electrical resistor glaze composition and resistor | |
JPH03170347A (en) | Thermister compound | |
JPS62184704A (en) | Overprinting copper composition | |
CN101990522A (en) | Lead-free resistive compositions having ruthenium oxide | |
US4209764A (en) | Resistor material, resistor made therefrom and method of making the same | |
US4168344A (en) | Vitreous enamel material for electrical resistors and method of making such resistors | |
US2837487A (en) | Resistor enamel and resistor made therefrom | |
JPS5951721B2 (en) | thick film composition | |
US3630969A (en) | Resistor compositions containing pyrochlore-related oxides and platinum | |
KR890004940B1 (en) | Resistor compositions | |
US3560410A (en) | Resistor compositions containing pyrochlore-related oxides and cadmium oxide | |
KR0130831B1 (en) | Thick film resistor composition | |
JPS6359999B2 (en) | ||
US3775347A (en) | Compositions for making resistors comprising lead-containing polynary oxide | |
EP0206282B1 (en) | Hexaboride resistor composition | |
US4278725A (en) | Cermet resistor and method of making same |