CA1098186A - Capacitor with non-noble metal electrodes and method of making the same - Google Patents
Capacitor with non-noble metal electrodes and method of making the sameInfo
- Publication number
- CA1098186A CA1098186A CA199,023A CA199023A CA1098186A CA 1098186 A CA1098186 A CA 1098186A CA 199023 A CA199023 A CA 199023A CA 1098186 A CA1098186 A CA 1098186A
- Authority
- CA
- Canada
- Prior art keywords
- ceramic
- monolith
- dielectric
- sintering
- 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
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 117
- 239000000919 ceramic Substances 0.000 claims abstract description 101
- 238000005245 sintering Methods 0.000 claims abstract description 52
- 238000010304 firing Methods 0.000 claims abstract description 42
- 239000004020 conductor Substances 0.000 claims abstract description 30
- 239000012298 atmosphere Substances 0.000 claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 22
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 239000007772 electrode material Substances 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 206010037660 Pyrexia Diseases 0.000 claims abstract description 3
- 239000007769 metal material Substances 0.000 claims abstract 4
- 239000000203 mixture Substances 0.000 claims description 52
- 239000003989 dielectric material Substances 0.000 claims description 37
- 229910044991 metal oxide Inorganic materials 0.000 claims description 20
- 150000004706 metal oxides Chemical class 0.000 claims description 19
- 239000010953 base metal Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000003973 paint Substances 0.000 claims description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 3
- 239000011800 void material Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims 34
- 239000000306 component Substances 0.000 claims 6
- 238000010438 heat treatment Methods 0.000 claims 6
- 239000011159 matrix material Substances 0.000 claims 5
- 229910010293 ceramic material Inorganic materials 0.000 claims 3
- 239000013067 intermediate product Substances 0.000 claims 3
- 239000003575 carbonaceous material Substances 0.000 claims 2
- 239000011343 solid material Substances 0.000 claims 2
- 239000012811 non-conductive material Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003985 ceramic capacitor Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- 239000002184 metal Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- 229940000425 combination drug Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
- H01G4/302—Stacked capacitors obtained by injection of metal in cavities formed in a ceramic body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
- H01G4/0085—Fried electrodes
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Ceramic Capacitors (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
CAPACITOR WITH NON-NOBLE METAL
ELECTRODES AND METHOD OF MAKING THE SAME
Abstract of Disclosure A ceramic capacitor having electrodes. The capacitor is formed by cosintering layers of ceramic dielectric and layers of non-noble metal material indifferent to the dielectric layers corresponding in area and position to the electrodes.
The indifferent layers are converted to a conductive state, for example, by chemical conversion and used as such or are removed and replaced by metal or conductive material. One example in which the indifferent layers comprise nickel oxide involves stacking layers of green ceramic coated with nickel oxide in the desired electrode pattern, sintering the stacked layers to produce a monolith, reducing the nickel oxide in the monolith to metallic nickel in a hydrogen atmosphere at a tem-perature low enough to have minimal effect upon the dielectric properties of the ceramic and using the metallic nickel as reduced for the ceramic capacitor electrodes. In another ex-ample, after the reduction step ( which may be at high tempera-ture) the metallic nickel is dissolved, for example by sulfuric acid, the ceramic monolith is reozidized by firing in an oxi-dizing atmosphere such as air, and the voids left by removal of the dissolved metallic nickel are provided with suitable electrodes. In still another example, in which the indifferent layers comprise oxidizable material such as carbon, the stacked layers are sintered in an inert atmosphere to produce a mono-lith of matured ceramic and the indifferent layers are removed by subsequent firing in an oxidizing atmosphere to produce the voids for receiving conductive electrode material.
ELECTRODES AND METHOD OF MAKING THE SAME
Abstract of Disclosure A ceramic capacitor having electrodes. The capacitor is formed by cosintering layers of ceramic dielectric and layers of non-noble metal material indifferent to the dielectric layers corresponding in area and position to the electrodes.
The indifferent layers are converted to a conductive state, for example, by chemical conversion and used as such or are removed and replaced by metal or conductive material. One example in which the indifferent layers comprise nickel oxide involves stacking layers of green ceramic coated with nickel oxide in the desired electrode pattern, sintering the stacked layers to produce a monolith, reducing the nickel oxide in the monolith to metallic nickel in a hydrogen atmosphere at a tem-perature low enough to have minimal effect upon the dielectric properties of the ceramic and using the metallic nickel as reduced for the ceramic capacitor electrodes. In another ex-ample, after the reduction step ( which may be at high tempera-ture) the metallic nickel is dissolved, for example by sulfuric acid, the ceramic monolith is reozidized by firing in an oxi-dizing atmosphere such as air, and the voids left by removal of the dissolved metallic nickel are provided with suitable electrodes. In still another example, in which the indifferent layers comprise oxidizable material such as carbon, the stacked layers are sintered in an inert atmosphere to produce a mono-lith of matured ceramic and the indifferent layers are removed by subsequent firing in an oxidizing atmosphere to produce the voids for receiving conductive electrode material.
Description
-8~6 CAPACITOR WITH NON-NOBLE METAL
ELECTRODES AND METHOD OF MAKING ~HE SAME
Capacltors have been made with titanate dlelectrics and noble metal composition (e.g. platinum, palladium~ gold, etc.) electrodes co~fired in an ox~d~zing atmosphere. These capacitors are expenslve. Other capacitors have been pro-posed with titanate dielectrics and base metal electrodes te.g. Ni etc.) ~ired ln a non-oxidizing or reduclng atmos-phere. These capacitors degrade the dielectric properties because of the reduction of the ceramic or because o~ ad-ditlves to the ceramic which present reduction.
Thi8 in~entlon iB intended to reduce the co~t of ceramic ¢apa¢ltors without degrading the dlelectric properties by ellminating the need for high temperature noble metal elec-trodes such as platinum, palladium and the llke. In lieu of -` such electrodes, the electrode patterns are made with layers of material ~ndifferent to the ceramic which can be ~ired with the ceramdc. During firing the ceramic and indifferent layers are consolidated into a dense ceramic monolith. The indif~er-ent material is then changed to conductive electrodes, for example by chemical converæion of the material to a conductive state or by removlng the indifferent material and substituting conducting electrode material.
In the drawing, Fig. 1 ls a plan view of one of the ceramlc layers used in maklng the capacitor wh~ch has been coated with an electrode pattern of lndifferent material, Fig.
ELECTRODES AND METHOD OF MAKING ~HE SAME
Capacltors have been made with titanate dlelectrics and noble metal composition (e.g. platinum, palladium~ gold, etc.) electrodes co~fired in an ox~d~zing atmosphere. These capacitors are expenslve. Other capacitors have been pro-posed with titanate dielectrics and base metal electrodes te.g. Ni etc.) ~ired ln a non-oxidizing or reduclng atmos-phere. These capacitors degrade the dielectric properties because of the reduction of the ceramic or because o~ ad-ditlves to the ceramic which present reduction.
Thi8 in~entlon iB intended to reduce the co~t of ceramic ¢apa¢ltors without degrading the dlelectric properties by ellminating the need for high temperature noble metal elec-trodes such as platinum, palladium and the llke. In lieu of -` such electrodes, the electrode patterns are made with layers of material ~ndifferent to the ceramic which can be ~ired with the ceramdc. During firing the ceramic and indifferent layers are consolidated into a dense ceramic monolith. The indif~er-ent material is then changed to conductive electrodes, for example by chemical converæion of the material to a conductive state or by removlng the indifferent material and substituting conducting electrode material.
In the drawing, Fig. 1 ls a plan view of one of the ceramlc layers used in maklng the capacitor wh~ch has been coated with an electrode pattern of lndifferent material, Fig.
2 is a cross sectional view of the layers be~ore flring, Fig.
3 i8 a similar ~iew after firlng, Fig. 4 ls an enlarged section ~091~6 on line 4-4 of Fig. 3, Fig. 5 is a view similar to Fig. 4 af'ter reduction of the nickel to the metallic state, Fig. 6 i~ a view of Fig. 5 after removal o~ the metalllc nickel, Fig. 7 is a vlew o~ Fig. 6 after coating of the surfaces of the roids left by dissolving the metallic nickel wlth other electrode material such a~ silver, Fig. 8 i3 a view similar to Fig. 7 in which the voidæ are filled with conductive material such as metal, Fig. 9 is a plan view of one of the ceramic layers which has been coated with another electrode pattern o~ indi~ferent material, and Fig. 10 ls a view like Fig. 9 with still another electrode pattern.
The manufackure of the capacitor start~ with a layer 1 of green ceramic dielectric, for example a high K titanate.
Such ceramlcs cons~st of mlxture~ of barlum titanate with other oxldes, tltanates, zlrconates, stannates, etc. or pre-cursors thereo~. The layer also contains temporary binders and other ingredients which ai~ in processing. These ceramics are well known to the art and many variations are described in the patent literature. The layer 1 has an electrode pattern 2 which extends to one edge 3 and is margined inward from khe other edges to provide an insulating border. The layers 1 are stacked one on top Or the other with alternate layers turned end for end as shown in Fig. 2. The stacked layers are then pressed together and fired or sintered into a monolith as shown in Fig. 3. The firlng temperatures are hlgh, 1000-1400C. The thickness of the layer 1 depends on the voltage rating and may be from 1 to 3 mils or more. In the prior art procedures, the electrode patterns have been formed o~ noble metals such as platinum, palladlum, etc. which with-stand the high ~iring temperatures in oxidizing atmospheres L8~
needed to optimize the propertles o~ titanate dielectrics.
Instead of the high temperature metals~ the electrode patterns 2 are of a material which remains in place and is indifferent to the ceramic at lts sintering temperature and is convertible to a conductive material. For dielectrics which are sintered in air or an oxidizing atmosphere, the indi~ferent material may be a base metal oxides such as nickel oxide either alone or mi~ed wlth compatible metal o~ides such as FeO, CoO, MnO, CrO, V20s, SnO2, CuO, Bi203, etc. ~he lndifferent material is applied as a paint and the vehicle in ~hich the material is ~uspended is vaporized or burned during the early stages of the flring. After ~ir1ng the layer of indifferent material may ha~e a thickness of 2/10 mil or less. If the firing is in an oxidizing atmosphere, the indifferent material may be wholly or partially metal slnce the oxidizing atmosphere converts the metal to the oxlde form. In Fig. 4, which is a diagrammatic section of a ~ired monolith showing a nickel oxide layer 2 sandwiched between two titanate ceramic layers 1, the boundar-ies 5, 6 between the nickel oxide and the titanate ceramic are sharp and well defined. Thi~ monolith is non porous throughout. The ceramic layers are uni~ormlY supported by the nickel oxide layers. Porosity of the nickel oxide layer can he tolerated.
Several procedures are available for converting the monolith at the stage of Fig. 4 to a usable capacitor. Fig. 5 shows the condition o~ the monolith a~ter belng sub~ected to low temperature reduction in a hydrogen atmosphere. At the low temperature, the hydrogen reduces the nickel oxide to metallic nickel but only sllghtly reduces the titanate ceramic.
For example, at a temperature of 280C, in 24 hours the nickel ~C~9~3~86 oxide is reduced to porous metallic nickel as shown at 7, ~hich forms a good capacitor electrode. At this low tempera-ture there i3 some reduction of the tltanate which affects the dielectric and insulating properties. The reduction, how-ever, is only partial and is not sufficient to destroy the utility of the capacitor. For example, with a ti~anate ceramic capacitor dielectric having a normal K of 6000, the low temperature reduction may reduce the K as much as 10 or 15%
and also lower the d.c. insulation resistance one order o~
magnitude wh~ch does not impair the use as a capacitor. The power factor also remains at an acceptable 2%. The reduction of the nickel o~ide is a time-temperature reaction, the lower the temperature, the longer the time. By adding to the nickel oxide other oxides such as tln oxide ln small proportion~, 1% or less, the reduction of the nickel oxide to the metallic state at low temperatures can be speeded up or the reduction temperature can be lowered.
Ano~her procedure for converting the monolith of Figs 3 and 4 to a usable capacitor is shown in Figs. 5, 6 and 7.
Fig. 5 shows the nickel oxide reduced to porous metallic nlckel. Because of the succeeding steps illustrated in Figs.
6 and 7, there is no need for low temperature reduction so that the reduction i8 carried out at hlgh temperatures which not only cause the reduction to metallic nickel but also cause reduction of the titanate ceramic to the semiconductor state. After reaching the Fig. 5 state, the metalllc nickel is removed by dissolving in a solution indif~erent to the ceramlc, for example ln dllute sulfuric acid. The ceramic body is reoxidized by firing ln an oxidizing atmosphere such as air, restoring the ceramic to the dielectric state having ~1~9~8~;
:Lts origlnal dielectric properties. Thi~ leaves a void or slot 8 in each location prevlously occupied by the nickel oxlde powder. The slot 8 will ordlnarily be a few tenths of a mil thick while the dlelectric layers l will ordinarily have thicknesses of from one to three or four mils. The manufacture is completed by filling the slots or by coating the surfaces 9, lO of the slot 8 wlth suitable electrode material. This, for example, could be silver paint intro-duced into the slots 8 by a capillary action or by a com-bination of capillary action and pressure. Many conductive paint~ are known~ some conslstlng of metal plgments ~hich ~orm a conductive coatlng and others having metal compounds which bre~k down into metallic coating. Fusible metal such as solder may be used as shown ln Fig. 8.
The indlfferent materlal 2 1~ not limited to oxldes or chemical compounds. When the monollth i3 sintered in an inert atmosphere, oxidizable materials such as carbon may be used ~or the layers 2. Carbon i8 suspended in a vehicle slmilar to that u~ed for nickel oxide. After firing in an inert atmosphere to mature the ceramic, refiring in an oxi-dizing atmosphere will remove the carbon and supply any oxygen deficiency in the dielectric. The voids left by the removal o~ the carbon may be filled with conductiYe material as shown in Figs. 7~ 8 as descrlbed above.
Figs. 9 and lO show layers 1 o~ green ceramic with electrode patterns 2 of indifferent material which are open at both ends to facilltate fllling by eliminatlng the need for ventlng air during f~lling or for evacuating air before filllng the voids with liquid conductive material. The layers l of Figs. 9 and lO may be stacked and processed in t;he manner shown in Figs. 1-8. -Although the invention has been described in connec-t;ion with titanate ceramlcs, lt is adYantageous ln other c:eramlc dielectrics, particularly those requirin~ high firing temperatures which can be wi~hstood only by the high tempera-ture metals ~uch as platinum, palladium, etc. The materials of the electrode patterns 2 should remaln in place and be indlfferent to the ceramic dielectric at the firing tempera-ture requlred to mature the ceramic, should not melt or sub-lime at the ~iring ~emperature and should be convertible to a conductive state either by chemical conversion in situ or by removal to pro~ide voids for rece$ving conductive materials.
The indifferent material 2 supports the green ceramic 1 during the initial ~lring or sintering to mature the cerami¢. There-after the ceramlc is dimensionally stable and does not re~uire such support during the subsequent firing in reducing or o~i-dizing atmospheres.
The manufackure of the capacitor start~ with a layer 1 of green ceramic dielectric, for example a high K titanate.
Such ceramlcs cons~st of mlxture~ of barlum titanate with other oxldes, tltanates, zlrconates, stannates, etc. or pre-cursors thereo~. The layer also contains temporary binders and other ingredients which ai~ in processing. These ceramics are well known to the art and many variations are described in the patent literature. The layer 1 has an electrode pattern 2 which extends to one edge 3 and is margined inward from khe other edges to provide an insulating border. The layers 1 are stacked one on top Or the other with alternate layers turned end for end as shown in Fig. 2. The stacked layers are then pressed together and fired or sintered into a monolith as shown in Fig. 3. The firlng temperatures are hlgh, 1000-1400C. The thickness of the layer 1 depends on the voltage rating and may be from 1 to 3 mils or more. In the prior art procedures, the electrode patterns have been formed o~ noble metals such as platinum, palladlum, etc. which with-stand the high ~iring temperatures in oxidizing atmospheres L8~
needed to optimize the propertles o~ titanate dielectrics.
Instead of the high temperature metals~ the electrode patterns 2 are of a material which remains in place and is indifferent to the ceramic at lts sintering temperature and is convertible to a conductive material. For dielectrics which are sintered in air or an oxidizing atmosphere, the indi~ferent material may be a base metal oxides such as nickel oxide either alone or mi~ed wlth compatible metal o~ides such as FeO, CoO, MnO, CrO, V20s, SnO2, CuO, Bi203, etc. ~he lndifferent material is applied as a paint and the vehicle in ~hich the material is ~uspended is vaporized or burned during the early stages of the flring. After ~ir1ng the layer of indifferent material may ha~e a thickness of 2/10 mil or less. If the firing is in an oxidizing atmosphere, the indifferent material may be wholly or partially metal slnce the oxidizing atmosphere converts the metal to the oxlde form. In Fig. 4, which is a diagrammatic section of a ~ired monolith showing a nickel oxide layer 2 sandwiched between two titanate ceramic layers 1, the boundar-ies 5, 6 between the nickel oxide and the titanate ceramic are sharp and well defined. Thi~ monolith is non porous throughout. The ceramic layers are uni~ormlY supported by the nickel oxide layers. Porosity of the nickel oxide layer can he tolerated.
Several procedures are available for converting the monolith at the stage of Fig. 4 to a usable capacitor. Fig. 5 shows the condition o~ the monolith a~ter belng sub~ected to low temperature reduction in a hydrogen atmosphere. At the low temperature, the hydrogen reduces the nickel oxide to metallic nickel but only sllghtly reduces the titanate ceramic.
For example, at a temperature of 280C, in 24 hours the nickel ~C~9~3~86 oxide is reduced to porous metallic nickel as shown at 7, ~hich forms a good capacitor electrode. At this low tempera-ture there i3 some reduction of the tltanate which affects the dielectric and insulating properties. The reduction, how-ever, is only partial and is not sufficient to destroy the utility of the capacitor. For example, with a ti~anate ceramic capacitor dielectric having a normal K of 6000, the low temperature reduction may reduce the K as much as 10 or 15%
and also lower the d.c. insulation resistance one order o~
magnitude wh~ch does not impair the use as a capacitor. The power factor also remains at an acceptable 2%. The reduction of the nickel o~ide is a time-temperature reaction, the lower the temperature, the longer the time. By adding to the nickel oxide other oxides such as tln oxide ln small proportion~, 1% or less, the reduction of the nickel oxide to the metallic state at low temperatures can be speeded up or the reduction temperature can be lowered.
Ano~her procedure for converting the monolith of Figs 3 and 4 to a usable capacitor is shown in Figs. 5, 6 and 7.
Fig. 5 shows the nickel oxide reduced to porous metallic nlckel. Because of the succeeding steps illustrated in Figs.
6 and 7, there is no need for low temperature reduction so that the reduction i8 carried out at hlgh temperatures which not only cause the reduction to metallic nickel but also cause reduction of the titanate ceramic to the semiconductor state. After reaching the Fig. 5 state, the metalllc nickel is removed by dissolving in a solution indif~erent to the ceramlc, for example ln dllute sulfuric acid. The ceramic body is reoxidized by firing ln an oxidizing atmosphere such as air, restoring the ceramic to the dielectric state having ~1~9~8~;
:Lts origlnal dielectric properties. Thi~ leaves a void or slot 8 in each location prevlously occupied by the nickel oxlde powder. The slot 8 will ordlnarily be a few tenths of a mil thick while the dlelectric layers l will ordinarily have thicknesses of from one to three or four mils. The manufacture is completed by filling the slots or by coating the surfaces 9, lO of the slot 8 wlth suitable electrode material. This, for example, could be silver paint intro-duced into the slots 8 by a capillary action or by a com-bination of capillary action and pressure. Many conductive paint~ are known~ some conslstlng of metal plgments ~hich ~orm a conductive coatlng and others having metal compounds which bre~k down into metallic coating. Fusible metal such as solder may be used as shown ln Fig. 8.
The indlfferent materlal 2 1~ not limited to oxldes or chemical compounds. When the monollth i3 sintered in an inert atmosphere, oxidizable materials such as carbon may be used ~or the layers 2. Carbon i8 suspended in a vehicle slmilar to that u~ed for nickel oxide. After firing in an inert atmosphere to mature the ceramic, refiring in an oxi-dizing atmosphere will remove the carbon and supply any oxygen deficiency in the dielectric. The voids left by the removal o~ the carbon may be filled with conductiYe material as shown in Figs. 7~ 8 as descrlbed above.
Figs. 9 and lO show layers 1 o~ green ceramic with electrode patterns 2 of indifferent material which are open at both ends to facilltate fllling by eliminatlng the need for ventlng air during f~lling or for evacuating air before filllng the voids with liquid conductive material. The layers l of Figs. 9 and lO may be stacked and processed in t;he manner shown in Figs. 1-8. -Although the invention has been described in connec-t;ion with titanate ceramlcs, lt is adYantageous ln other c:eramlc dielectrics, particularly those requirin~ high firing temperatures which can be wi~hstood only by the high tempera-ture metals ~uch as platinum, palladium, etc. The materials of the electrode patterns 2 should remaln in place and be indlfferent to the ceramic dielectric at the firing tempera-ture requlred to mature the ceramic, should not melt or sub-lime at the ~iring ~emperature and should be convertible to a conductive state either by chemical conversion in situ or by removal to pro~ide voids for rece$ving conductive materials.
The indifferent material 2 supports the green ceramic 1 during the initial ~lring or sintering to mature the cerami¢. There-after the ceramlc is dimensionally stable and does not re~uire such support during the subsequent firing in reducing or o~i-dizing atmospheres.
Claims (44)
1. A monolithic structure comprising: a sintered unitary body in the as sintered state.
a. said body having a matrix of a dielectric ceramic composition, and b. a plurality of vertically spaced solid non-metallic strata in said matrix, each stratum extending to one of a pair of edge regions of said body, alternate strata extending to the same edge region, said nonmetallic strata having been positioned in said matrix prior to the sintering of said body and being further defined as a material which remains solid and nonmetallic and in place and indifferent to said ceramic composition during the sintering of said body and after said sintering is capable of being chemically converted to or replaced by conductive material.
a. said body having a matrix of a dielectric ceramic composition, and b. a plurality of vertically spaced solid non-metallic strata in said matrix, each stratum extending to one of a pair of edge regions of said body, alternate strata extending to the same edge region, said nonmetallic strata having been positioned in said matrix prior to the sintering of said body and being further defined as a material which remains solid and nonmetallic and in place and indifferent to said ceramic composition during the sintering of said body and after said sintering is capable of being chemically converted to or replaced by conductive material.
2. A multilayer structure comprising a sintered unitary body in the as sintered state, said body having a matrix of an electrically insulating composition, and at least one internal area extending to an edge region of said body com-posed of a ceramic composition, and at least one other internal area extending to an edge region of said body composed of a solid nonmetallic material, said internal areas of ceramic composition and of nonmetallic material having been positioned in said matrix prior to the sintering of said body and said nonmetallic material being further defined as a material which remains solid and nonmetallic and in place and indifferent to said ceramic composition during the sintering of said body and after said sintering is capable of being chemically converted to or replaced by conductive material.
3. The structure of claim 1 which has been further processed to provide conducting material in the sites of said strata.
4. The structure of Claim 1 in which said nonmetallic strata comprise nickel oxide.
5. The structure of Claim 1 in which said nonmetallic strata are selected from the group consisting of NiO, FeO, CoO, Sno2, MnO, CrO, Bi2O3, C, combustible material.
6. The structure of Claim 1 in which said nonmetallic strata are combustible.
7. The structure of Claim 1 in which said nonmetallic strata comprise carbon.
8. The structure of Claim 2 which has been further processed to provide electrical conductive material in said other internal area.
9. A process of providing electrodes or conductors in sintered ceramic bodies which comprises providing sheets of a finely divided insulating or dielectric ceramic composition bonded with a temporary binder, which composition forms a dense layer when fired to sintering temperature; forming a stack of said sheets, there being between at least one pair of said sheets a deposit of a second composition of solid nonmetallic material suspended in a vehicle which is elimin-ated during said firing, consolidating a plurality of said sheets and intervening deposits whereby to obtain a bonded, self-sustaining body; heating said body to eliminate said temporary binder and said vehicle; firing said body to sintering temperature in an oxidizing atmosphere to produce a sintered monolithic body having first areas of dense cera-mic material and second areas of said second composition, said second composition being further defined as a material which remains solid and nonmetallic and in place and is indifferent to and supports said ceramic during said sintering, each such second area extending to a region on an outer face of said monolithic body; and providing a conductive material in the site of said second area by chemical conversion or replacement of said second composition.
10. The process of Claim 9 in which the second composi-tion and its vehicle is deposited on said sheets as a paint suspended in a vehicle which is eliminated during said firing.
11. A process for forming a monolithic capacitor which comprises:
a. providing a plurality of this leaves of finely divided ceramic dielectric composition bonded with a temporary binder, said composition forming a dense layer when fired to sintering temperature b. superposing a plurality of said leaves and providing, between at least some of said leaves, layers of a second nonmetallic composition sus-pended in a vehicle which is eliminated during firing, said layers being so arranged and placed that alternate layers extend to one of two different edge portions of said leaves while being spaced from the other edge portions thereof.
c. forming a bonded, self-sustaining body from said stack;
d. heating said self-sustaining body to eliminate said temporary binder and said vehicle;
e. firing said self-sustaining body to sintering temperature in an exidizing atmosphere whereby to produce a monolithic body having strata of dense dielectric, ceramic composition and strata of said second composition, said second composition being further defined as a material which remains solid and nonmetallic and in place and is indifferent to said ceramic dielectric during said sintering;
and f. thereafter providing conductive material in said strata of said second composition by chemical conversion or replacement of said second composition.
a. providing a plurality of this leaves of finely divided ceramic dielectric composition bonded with a temporary binder, said composition forming a dense layer when fired to sintering temperature b. superposing a plurality of said leaves and providing, between at least some of said leaves, layers of a second nonmetallic composition sus-pended in a vehicle which is eliminated during firing, said layers being so arranged and placed that alternate layers extend to one of two different edge portions of said leaves while being spaced from the other edge portions thereof.
c. forming a bonded, self-sustaining body from said stack;
d. heating said self-sustaining body to eliminate said temporary binder and said vehicle;
e. firing said self-sustaining body to sintering temperature in an exidizing atmosphere whereby to produce a monolithic body having strata of dense dielectric, ceramic composition and strata of said second composition, said second composition being further defined as a material which remains solid and nonmetallic and in place and is indifferent to said ceramic dielectric during said sintering;
and f. thereafter providing conductive material in said strata of said second composition by chemical conversion or replacement of said second composition.
12. A sintered unitary body comprising in the as sintered state a plurality of superposed strata, said strata including strata consisting of a dense, impervious, dielectric or insulating ceramic composition; and second strata consist-ing of a solid nonmetallic material, said second strata being interposed between said dense strata and being exposed on at least one surface of said body whereby a conductive material may be introduced into the site thereof, and wherein each of said second strata is smaller in area than the dense strata above and below it, said second strata having been positioned in said body prior to the sintering of said body, said second composition being further defined as a material which remains solid and nonmetallic and in place and is indifferent to and supports said ceramic during said sintering and after said sintering is capable of being replaced by conductive material.
13. A self-sustaining, green ceramic body comprising a plurality of strata of a dielectric or insulating composition having a temporary bond, said composition forming a dense layer when fired to sintering temperature; and strata, inter-posed between said first mentioned strata of a second solid nonmetallic material, said second material suspended in a vehicle which is eliminated during said firing, said second material being further defined as a material which remains solid and nonmetallic and in place and is indifferent to first mentioned strata when fired to said temperature and wherein each stratum of said second material is smaller in area than said first mentioned strata above and below it and after said sintering is capable of being chemically converted to or replaced by conductive material.
14. A structure as set forth in Claim 1 in which said ceramic composition comprises Ba Ti O.
15. A sintered monolith comprising ceramic dielectric material and solid nonmetallic material embedded in and margined inward from edges of the monolith in the positions and of the shapes and sizes required for electrodes in capacity relation to each other through portions of said dielectric material, said nonmetallic material being further defined as a material which remains solid and nonmetallic and in place and is indifferent to the ceramic during said sinter-ing and is convertible to conductive electrodes after said sintering by chemical conversion or replacement of said non-metallic material.
16. The method of making a monolithic capacitor with-out high temperature noble metal electrodes which comprises the steps of superposing layers of green ceramic dielectric material having thereon patterns of nonmetallic material, the patterns being in the positions and of the shapes and sizes required for electrodes in capacity relation to each other through portions of the dielectric and being margined inward from edges of the layers, firing the superposed layers into a sintered monolith, the nonmetallic material being further defined as a material which is solid and in place and is indifferent to said dielectric throughout said firing, and changing the nonmetallic material into conductive elect-rodes after said firing by chemical conversion or replacement of said non metallic material.
17. An intermediate product comprising a sintered monolith of ceramic dielectric material as one component and non noble metallic oxide material as another component, said non noble material being layers in the positions and of the shapes and sizes required for electrodes in capacity relation to each other through portions of said dielectric material, said ceramic dielectric material and non noble material having been first positioned in said monolith and then cofired or sintered into said monolith, said ceramic having been matured by said sintering, said non noble material comprising a material which remains in place and is indifferent to the ceramic during said sinter-ing and is a metal oxide at the end of said sintering and after said sintering is capable of being chemically converted to or replaced by conductive material.
18. An intermediate product comprising a sintered monolith of reduced ceramic dielectric material as one component and a solid non noble material as another compon-ent, said non noble material being layers embedded in said monolith in the positions and of the shapes and sizes re-quired for electrodes in capacity relation to each other through portions of said dielectric material, said reduced ceramic dielectric material and non noble material having been cofired or sintered into said monolith, said ceramic having been matured by said sintering, said non noble material being further defined as a material which remains solid and in place and is indifferent to and supports the ceramic during said sintering and is convertible to capaci-tor electrodes after said sintering.
19. An intermediate product comprising an as sintered monolith of reduced ceramic dielectric material in one compon-ent and a combustible material as another component, said combustible material being embedded in the monolith in the positions and of the shapes and sizes required for electrodes in capacity relation to each other through portions of said dielectric material, said ceramic dielectric material and combustible material having been cofired or sintered into said monolith, said ceramic having been matured by said sintering, said combustible material being further defined as a solid material which remains solid and in place and is indifferent to and supports reduced ceramic during said sintering.
20. A sintered monolith comprising in the as sintered state ceramic dielectric material and solid non noble mater-ial embedded in the monolith in the positions and of the shape and sizes required for electrodes in capacity relation to each other through portions of said dielectric material, said ceramic dielectric material and solid non noble material having been first positioned in said monolith and then cofired or sintered into said monolith, said non noble material being further defined as a material which remains solid and in place and indifferent to said ceramic dielectric during said sintering and which is not an electrode material at the end of said sintering and which is convertible to a conductive electrode material after said sintering by chemical conversion or replacement of said non noble material.
21. The method of making a monolithic capacitor with-out high temperature noble metal electrodes which comprises the steps of superposing layers of green ceramic dielectric material and solid non noble material, the non noble material being in the positions and of the shapes and sizes required for electrodes in capacity relation to each other through portions of the dielectric material and the non noble material being further defined as a material which is indifferent to the dielectric material at the firing conditions required to mature green ceramic, firing the superposed layers into a monolith at said firing conditions, said non noble material being further defined as a material which remains solid and in place in said monolith and indifferent to said ceramic during said firing and which is not electrodes at the end of said firing and changing the non noble material to conductive electrodes after said firing by chemical conversion or re-placement of said non noble material.
22. An as sintered monolith comprising ceramic dielectric material and other material embedded in the monolith in the positions required for electrodes in capa-city relation to each other through portions of said dielectric, said ceramic and other material having been positioned in said monolith as discrete layers in the green state prior to said sintering of said monolith and having been cosintered to mature the ceramic, said other material being further defined as a solid non-conductive material which remains solid and in place and is indifferent to the ceramic during said cosintering and is convertible to a conductive material by chemical conversion after said cosintering.
23. The monolith of Claim 22 in which the ceramic is a titanate ceramic.
24. The monolith of Claim 22 in which the other material comprises nickel oxide.
25. The monolith of Claim 24 in which the nickel oxide is reduced to the metallic state to provide capacitor elect-rodes.
26. An as sintered monolith comprising ceramic dielectric material and non-conductive other material, said other material being embedded in the monolith in the positions required for electrodes in capacity relation to each other through portions of said dielectric, said ceramic and other material having been positioned in said monolith as discrete layers in the green state prior to sintering of said monolith and having been cosintered to mature the ceramic, said other material being further defined as a material which remains solid and in place and is indifferent to the ceramic during said cosintering and is convertible to a conductive material after said cosintering by removing said other material and substituting conducting electrode material.
27. The monolith of Claim 26 in which the other material comprises nickel oxide.
28. The monolith of Claim 27 in which the nickel oxide is reduced to the metallic state after said sintering and is dissolved to remove the same.
29. The method of making a monolithic capacitor with-out high temperature noble metal electrodes which comprises the steps of superposing layers of green ceramic dielectric material and other solid material, the other material being in the positions required for electrodes in capacity relation to each other through portions of the dielectric and remain-ing in place and being indifferent to the dielectric material at the firing conditions to produce a sintered monolith, firing the superposed layers into a sintered monolith in which said other material constitutes discrete solid layers which are non-conductive, and changing the other material to conductive electrodes after said firing by chemical conversion or replacement of said other material.
30. The method of Claim 29 in which the other material in said sintered monolith comprises nickel oxide which is changed to conductive electrodes by subjecting the sintered monolith to a hydrogen atmosphere at temperatures reducing the nickel oxide to metallic nickel and below temperatures substantially affecting the dielectric properties of the ceramic.
31. The method of making a monolith capacitor with-out high temperature noble metal electrodes which comprises the steps of superposing layers of green ceramic dielectric material and combustible material, the combustible material being in the positions required for electrodes in capacity relation to each other through portions of the dielectric and remaining in place and being indifferent to the dielectric material at the firing conditions to produce a sintered monolith, firing the superposed layers into a monolith in a non oxidizing atmosphere, and thereafter changing the material to conductive electrodes by burning out the combustible material and substituting conductive material.
32. The method of Claim 31 in which the firing atmo-sphere is inert to said combustible material.
33. The method of Claim 31 in which said combustible material is carbon.
34. An as sintered monolith comprising ceramic dielectric material and non conductive other material embedded in the monolith in the position required for conductors, said ceramic and other material having been positioned in said monolith in the green state and in discrete layers and said ceramic and other material having been cosintered into said monolith, said other material being further defined as a material which remains solid and in place and indifferent to the ceramic during said cosintering and which is nonmetallic at the end of said cosintering and is capable of being changed to conductive material after said cosintering by chemical conversion or replacement of said other material.
35. The method of making a sintered monolithic capaci-tor without high temperature noble material electrodes which comprises the steps of superposing layers Or green ceramic dielectric material and solid other material, the other material being in the positions required for electrodes in capacity related to each other through portions of the dielectric and being further defined as a material which remains solid and in place and indifferent to the dielectric material at the firing conditions, firing the superposed layers into a cosintered monolith, the other material being further defined as a material which is non conductive and solid at the end of said cosintering and is capable of being changed to conductive material after said cosintering, and changing the other material to conductive electrodes after said sintering by chemical conversion or replacement of said other material.
36. An as sintered, unitary, ceramic body having a plurality of cosintered regions and comprising a plurality of regions of dielectric ceramic composition and at least one region of base metal oxide material which remains solid and in place and indifferent to the ceramic during its sintering and by processing subsequent to said sintering and in reducible to the metallic state, the base metal oxide material extending to a region on the outer face of the body.
37. A process of providing electrodes or conductors in sintered ceramic bodies which comprises providing sheets of a finely divided insulating or dielectric ceramic composi-tion bonded with a temporary binder, which composition forms a dense layer when fired to sintering temperature, introduc-ing between the sheets a deposit of a base metal oxide composition, the base metal oxide composition being sus-pended in a vehicle which is eliminated during firing, the base metal oxide composition developing a base metal oxide layer when fired, consolidating a plurality of these sheets and intervening deposits whereby to obtain a self-sustaining body, heating this body to eliminate the vehicle and tempor-ary binder, firing the body to sintering temperature in an oxidizing atmosphere to produce a sintered monolithic body having regions of dense ceramic material and regions of metal oxide material, each such region extending to a region on an outer face of the monolithic body; and providing a conductive material in the metal oxide regions.
38. A process for forming a monolithic capacitor which comprises:
a. providing a plurality of thin leaves of finely divided ceramic dielectric composition bonded with a temporary binder, this composition forming a dense layer when fired to sintering temperature;
b. providing, between the leaves, layers of a base metal oxide composition suspended in a vehicle, the base metal oxide composition developing a base metal oxide layer when fired, the layers being so arranged and placed that alternate layers extend to one of two different portions of the leaves while being spaced from the other edge portions thereof;
c. forming a stack of the alternated leaves and layers;
d. heating the stack to eliminate the temporary binder and vehicle;
e. firing the self-sustaining stack to sintering temperature in an oxidizing atmosphere so as to produce a monolithic body having alternate strata of dense, dielectric, ceramic composition and of a base metal oxide; and f. providing a conductive material in the base metal oxide strata.
a. providing a plurality of thin leaves of finely divided ceramic dielectric composition bonded with a temporary binder, this composition forming a dense layer when fired to sintering temperature;
b. providing, between the leaves, layers of a base metal oxide composition suspended in a vehicle, the base metal oxide composition developing a base metal oxide layer when fired, the layers being so arranged and placed that alternate layers extend to one of two different portions of the leaves while being spaced from the other edge portions thereof;
c. forming a stack of the alternated leaves and layers;
d. heating the stack to eliminate the temporary binder and vehicle;
e. firing the self-sustaining stack to sintering temperature in an oxidizing atmosphere so as to produce a monolithic body having alternate strata of dense, dielectric, ceramic composition and of a base metal oxide; and f. providing a conductive material in the base metal oxide strata.
39. A method of making a capacitor without high tempera-ture noble metal electrodes which comprises the steps of superposing layers of green ceramic dielectric material and base metal oxide material, the base metal oxide material being in the position required for electrodes in capacity relation to each other through portions of the dielectric material and being further defined as a material which re-mains solid and in place and is indifferent to the dielectric material at the firing conditions required for maturing the dielectric material, firing the superposed layers into a monolith, and changing the base metal oxide material to conductive electrodes by a process which includes reduction of the base metal oxide to the metallic state.
40. An as sintered, unitary, ceramic body comprising a plurality of regions of dense insulating or dielectric ceramic composition and at least one region of solid combust-ible material which remains in place and is indifferent to the ceramic during its sintering and by processing subsequent to said sintering is removable to provide at least one void for receiving conductive material, the combustible material extending to a region on the outer face of the body.
41. An as sintered, unitary, ceramic body comprising a plurality of regions of dense insulating or dielectric ceramic composition and at least one region of carbon material which remains solid and in place and is indifferent to the ceramic during its sintering and by processing subsequent to said sintering is removable to provide at least one void for receiving conductive material, the carbon material extending to a region on the outer face of the body.
42. A process of providing electrodes or conductors in sintered ceramic bodies which comprises providing sheets of a finely divided insulating or dielectric ceramic composi-tion bonded with a temporary binder, which composition forms a dense layer when fired to sintering temperature, introduc-ing between the sheets a deposit of a combustible composition, the combustible composition being suspended in a vehicle which is eliminated during firing, the combustible composition developing a combustible layer when fired, consolidating a plurality of these sheets and intervening deposits whereby to obtain a self-sustaining body; heating this body to eliminate the vehicle and temporary binder, firing the body to sintering temperature in a non oxidizing atmosphere to produce a sintered monolithic body having regions of dense ceramic material and regions of combustible material, each such region extending to a region on an outer face of the monolithic body; and provided a conductive material in the combustible regions.
43. A process for forming a monolithic capacitor which comprises:
a. providing a plurality of thin leaves of finely divided ceramic dielectric composition bonded with a temporary binder, this composition forming a dense layer when fired to sintering temperature;
b. providing, between the leaves, layers of a combustible composition suspended in a vehicle, the combustible composition developing a combust-ible layer when fired in a non oxidizing atmosphere, the layers being so arranged and placed that alter-nate layers extend to one of two different portions of the leaves while being spaced from the other edge portions thereof;
c. forming a stack of the alternated leaves and layers;
d. heating the stack to eliminate the temporary binder vehicle e. firing the self-sustaining stack to sintering temperature in a non oxidizing atmosphere so as to produce a monolithic body having alternate strata of a dense, dielectric, ceramic composition and of a combustible composition; and f. providing a conductive material in the combust-ible composition strata.
a. providing a plurality of thin leaves of finely divided ceramic dielectric composition bonded with a temporary binder, this composition forming a dense layer when fired to sintering temperature;
b. providing, between the leaves, layers of a combustible composition suspended in a vehicle, the combustible composition developing a combust-ible layer when fired in a non oxidizing atmosphere, the layers being so arranged and placed that alter-nate layers extend to one of two different portions of the leaves while being spaced from the other edge portions thereof;
c. forming a stack of the alternated leaves and layers;
d. heating the stack to eliminate the temporary binder vehicle e. firing the self-sustaining stack to sintering temperature in a non oxidizing atmosphere so as to produce a monolithic body having alternate strata of a dense, dielectric, ceramic composition and of a combustible composition; and f. providing a conductive material in the combust-ible composition strata.
44. The method of making a monolithic capacitor with-out high temperature noble metal electrodes which comprises the step of superposing layers of green ceramic dielectric material and other material, the other material being in the position required for electrodes in capacity relation to each other through portions of the dielectric and remaining in place and being indifferent to the dielectric material at the firing conditions to produce a sintered monolith, firing the superposed layers into a sintered monolith in which said other material constitutes discrete layers which are non conductive and comprises nickel oxide which is changed to conductive electrodes by subjecting the sintered monolith to a reducing atmosphere at temperatures reducing the nickel oxide to metallic nickel and below temperatures substantially affecting the dielectric properties of the ceramic.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US35963573A | 1973-05-13 | 1973-05-13 | |
| US359,635 | 1982-03-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1098186A true CA1098186A (en) | 1981-03-24 |
Family
ID=23414680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA199,023A Expired CA1098186A (en) | 1973-05-13 | 1974-05-06 | Capacitor with non-noble metal electrodes and method of making the same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5041049A (en) |
| CA (1) | CA1098186A (en) |
| DE (1) | DE2422801A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4055850A (en) * | 1975-12-23 | 1977-10-25 | Union Carbide Corporation | Capacitor with electrode containing nickel |
| JPS61144813A (en) * | 1984-12-19 | 1986-07-02 | 松下電器産業株式会社 | Laminated ceramic capacitor and manufacture thereof |
| JPH03241723A (en) * | 1984-12-19 | 1991-10-28 | Matsushita Electric Ind Co Ltd | Manufacture of laminated ceramic capacitor |
-
1974
- 1974-05-06 CA CA199,023A patent/CA1098186A/en not_active Expired
- 1974-05-10 DE DE2422801A patent/DE2422801A1/en not_active Ceased
- 1974-05-14 JP JP49053799A patent/JPS5041049A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5041049A (en) | 1975-04-15 |
| DE2422801A1 (en) | 1974-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4189760A (en) | Monolithic capacitor with non-noble metal electrodes and method of making the same | |
| US4241378A (en) | Base metal electrode capacitor and method of making the same | |
| US4097911A (en) | Base metal electrode capacitor and method of making the same | |
| JP2018182128A (en) | Multilayer ceramic capacitor and method of manufacturing the same | |
| KR100826388B1 (en) | Electronic parts and method for manufacture thereof | |
| JPH113834A (en) | Multilayer ceramic capacitor and its manufacture | |
| JPH0650701B2 (en) | Multilayer capacitor element and manufacturing method thereof | |
| JP2022154959A (en) | Ceramic electronic component and manufacturing method thereof | |
| EP0492518B1 (en) | A ceramic substrate for electronic circuit and a method for producing the same | |
| CA1098186A (en) | Capacitor with non-noble metal electrodes and method of making the same | |
| JPH0620014B2 (en) | Multilayer chip inductor and manufacturing method thereof | |
| JP3323801B2 (en) | Porcelain capacitors | |
| JP2020035878A (en) | Multilayer ceramic capacitor and method of manufacturing the same | |
| JP3685656B2 (en) | Manufacturing method of multilayer ceramic electronic component | |
| JPH0559522B2 (en) | ||
| JPH0432213A (en) | Ceramic capacitor | |
| JPH11102835A (en) | Laminated ceramic electronic component and manufacture thereof | |
| JPH07122456A (en) | Manufacture of multilayered ceramic capacitor | |
| JPH0722065B2 (en) | Thick film capacitor and manufacturing method thereof | |
| JP3142013B2 (en) | Multilayer electronic components | |
| JP3196524B2 (en) | Electronic component manufacturing method | |
| JP3239666B2 (en) | Manufacturing method of grain boundary insulated multilayer ceramic component | |
| JPH07111899B2 (en) | Heater element manufacturing method | |
| JP2847822B2 (en) | Method for manufacturing dielectric porcelain and method for manufacturing multilayer ceramic capacitor | |
| JP2803227B2 (en) | Multilayer electronic components |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |