CN1148332C - 含有硼硅酸钡锂助熔剂和钛酸镁锌粉末的电介质陶瓷粉末混合物 - Google Patents
含有硼硅酸钡锂助熔剂和钛酸镁锌粉末的电介质陶瓷粉末混合物 Download PDFInfo
- Publication number
- CN1148332C CN1148332C CNB011252634A CN01125263A CN1148332C CN 1148332 C CN1148332 C CN 1148332C CN B011252634 A CNB011252634 A CN B011252634A CN 01125263 A CN01125263 A CN 01125263A CN 1148332 C CN1148332 C CN 1148332C
- Authority
- CN
- China
- Prior art keywords
- weight
- powder
- fusing assistant
- sintering
- powder mixture
- 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 - Fee Related
Links
- 239000000843 powder Substances 0.000 title claims abstract description 62
- 239000000919 ceramic Substances 0.000 title claims description 53
- YSZKOFNTXPLTCU-UHFFFAOYSA-N barium lithium Chemical compound [Li].[Ba] YSZKOFNTXPLTCU-UHFFFAOYSA-N 0.000 title claims description 17
- 239000003990 capacitor Substances 0.000 title abstract description 15
- 230000004907 flux Effects 0.000 title abstract 3
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 title abstract 2
- 238000005245 sintering Methods 0.000 claims abstract description 61
- 239000000203 mixture Substances 0.000 claims abstract description 49
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 229910052788 barium Inorganic materials 0.000 claims abstract description 8
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims description 40
- 229910052749 magnesium Inorganic materials 0.000 claims description 30
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 29
- 239000011701 zinc Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 17
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 229910052712 strontium Inorganic materials 0.000 claims 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052709 silver Inorganic materials 0.000 abstract description 9
- 229910052763 palladium Inorganic materials 0.000 abstract description 8
- 239000004332 silver Substances 0.000 abstract description 7
- 239000003985 ceramic capacitor Substances 0.000 abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001252 Pd alloy Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 230000003245 working effect Effects 0.000 description 16
- 238000010304 firing Methods 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 4
- XBJJRSFLZVLCSE-UHFFFAOYSA-N barium(2+);diborate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]B([O-])[O-].[O-]B([O-])[O-] XBJJRSFLZVLCSE-UHFFFAOYSA-N 0.000 description 4
- 239000012700 ceramic precursor Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000010953 base metal Substances 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004110 Zinc silicate Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910021523 barium zirconate Inorganic materials 0.000 description 2
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 2
- 230000009021 linear effect Effects 0.000 description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 2
- 229910052912 lithium silicate Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 2
- 235000019352 zinc silicate Nutrition 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 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
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- -1 plumbous oxide compound Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/6303—Inorganic additives
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
-
- 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
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
-
- 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
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
-
- 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
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
-
- 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
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1236—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates
- H01G4/1245—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates containing also titanates
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/02—Noble metals
- B32B2311/08—Silver
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
- C04B2235/3234—Titanates, not containing zirconia
- C04B2235/3236—Alkaline earth titanates
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
- C04B2235/365—Borosilicate glass
-
- 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
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/32—Ceramic
- C04B2237/34—Oxidic
- C04B2237/345—Refractory metal oxides
- C04B2237/346—Titania or titanates
-
- 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
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/40—Metallic
- C04B2237/408—Noble metals, e.g. palladium, platina or silver
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Capacitors (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Inorganic Insulating Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
在钛酸镁锌和硼硅酸钡助熔剂的原料粉末混合物中,发现在助熔剂中加入锂能使用该粉末混合物来制造符合包括加速使用寿命试验在内的符合COG标准的多层陶瓷电容器。加入锂还能够在低至950℃的温度下烧结使COG多层电容器熟化,这转而能使用高银和低钯含量的银-钯合金的掩埋电极,就能够获得较高Q值的电容器,而制造成本也较低。
Description
有关申请的相互参考
本申请是于1998年12月31日提交的未审定专利申请09/224,536的部分延续。
发明的领域
本发明涉及符合COG标准并含有陶瓷电介质的多层陶瓷电容器,所述陶瓷电介质基于与含烧结助熔剂的玻璃进行混合的钛酸镁锌,所述混合材料在远低于1100℃的温度下能够烧结熟化。
发明的背景
符合EIA标准、COG(a.k.a.NPO)的温度稳定的陶瓷电容器在从-55℃至125℃的温度范围内的电容变化必须保持在+/-30ppm内。这种电容器还必须具有在1兆赫下大于1,000的品质因子Q,品质因子大于1000相当于耗散因子(DF)不大于0.01。已经在一定条件下烧制了陶瓷前体粉末,获得95%理论密度的熟化陶瓷,这种陶瓷是很适合作为这种高质量电介质陶瓷的。高烧结温度的陶瓷前体材料如钛酸镁锌的烧结一般在1100℃的温度下完成。众所周知的是,在高温烧制(high-firing)的陶瓷粉末中加入少量含助熔剂的玻璃作为烧结助剂来降低制造熟化电介质陶瓷所需的烧结温度。在约1100℃可烧结的COG陶瓷组合物的例子披露于1989年11月11日公布的美国专利4,882,650和1985年8月6日公布的美国专利4,533,974中。
在制造多层电容器(MLC)时,将一些金属层状电极分别夹置在包含助熔剂(若有的话)的生料前体陶瓷粉末的各连续层之间。这样,掩埋在生料(未烧结)陶瓷中的金属电极必然会经受高得足以将陶瓷烧结成熟化的温度。金属电极最常用的材料配方是70重量%的Ag和30重量%的Pd。这种组成的合金的熔化温度为1150℃,它一般用于加热到不高于1140℃温度的MLC电容器的电极,以免金属熔化和流出的危险。当使用不能将温度保持在10℃偏差内的烧结炉时,就得使用设置在更低温度的炉子,在制造MLC时一般进一步采用10℃的安全因子。
加入较多量的烧结助熔剂能降低MLC的烧结温度,但它是以降低介电常数(K)和降低其它性能指标如Q为代价的。能在低于约1100℃的温度下烧结成高密度的陶瓷前体加上助熔剂的已知原料配方是比较少的,而工业上实际使用这种原料粉末混合物甚至更少,因为该配方和烧结条件较为苛刻,导致较低的产率。
钯的费用比银的费用高一个数量级,钯一般是制造MLC电容器成本中最大的因素。一种在掩埋的电极中代替钯的办法是使用一种贱金属如镍和/或铜。然而,用贱金属电极,必须在低于贱金属熔点(对镍来说是1453℃,对铜来说是1083℃)的温度下进行烧结。并且烧结必须在很少有氧的气氛中进行,这就大大地使工艺复杂化。对氧压力低的气氛进行控制本身会提高成本,并且对由于在烧结时不会由于失去氧而变成半导体性的陶瓷组合物的选择要获得特定的电介质陶瓷性能来说,就受到很大限制。
在许多空气烧制的MLC电容器中所用的助熔剂包含铋、镉和铅的氧化物,这些氧化物特别能有效地降低助熔剂的熔点。对于给定量的助熔剂,这就能有利地进一步降低烧结温度。然而,这些氧化物往往会降低MLC电容器的Q值,并且铋会与银钯电极发生反应,甚至使品质因子更差。这些挥发性的重金属氧化物还会污染烧结炉,产生缺乏规律性的烧结结果。也许最重要的是它们会对环境构成危险,尤其是对身处制造陶瓷粉末和MLC电容器的人员构成健康上的危险。
因此本发明的一个目的是提供一种用于制造符合COG标准的多层陶瓷电容器的陶瓷粉末,这种原料粉末能够在1000°+/-50℃温度在空气气氛中烧结成熟化,使得MLC可以用银含量较多而昂贵组分含量较少如85%Ag/15%Pd的电极。
本发明的再一个目的是提供这样一种陶瓷粉末,它包含由钛酸镁锌组成的高温烧制部分和基本不含铅、铋和镉这些有害重金属氧化物的低温烧结助熔剂部分。
发明的概述
一种电介质陶瓷粉末混合物主要由聚集颗粒组成,每个聚集颗粒是由两种粉末颗粒经温和煅烧并发生表面共反应而均匀结合起来,形成聚集颗粒的。这两种粉末,一种是高温烧制的陶瓷前体粉末,它是钛酸镁锌,占电介质陶瓷粉末混合物的87-98重量%。另一种是粉末状的硼硅酸钡锂烧结助熔剂,占电介质陶瓷粉末混合物的2-13重量%。
钛酸镁锌粉末较好是充分反应的化合物Mg2/3Zn1/3TiO3,其中可以有高达20摩尔%的Mg被等摩尔量的碱土金属所取代,仅被钡所取代时,也可以取代高达60摩尔%。
对硼硅酸钡锂助熔剂来说,一种特别有效的组成范围是10-55重量%的Li4SiO4,3-40重量%的BaO·B2O3和10-76重量%的3BaO·B2O3。另一种较好的助熔剂组成范围是22-26重量%的Li4SiO4,20.5-23.5重量%的BaO·B2O3和50-56重量%的3BaO·B2O3。
上述电介质陶瓷粉末混合物经下述过程制得,将87-98重量%的钛酸镁锌与2-13重量%的粉末状硼硅酸钡锂烧结助熔剂加在一起,混合成均匀的粉末混合物;在600-750℃的温度下进行温和煅烧,获得由均匀粉末混合物的聚集颗粒组成的粉末,其中各聚集颗粒基本上具有与总体粉末中相同的钛酸镁锌和硼硅酸钡锂的组成。然后可以对温和煅烧的聚集颗粒进行粉碎,使电介质陶瓷粉末混合物成为平均聚集颗粒大小约为1.2微米的自由流动的粉末。
一种制造多层陶瓷电容器的方法需要先制备浆料,其方法是在有机载体中研磨上述电介质陶瓷粉末混合物,再形成浆料层,然后干燥。将第一层有图案的钯银合金膜沉积到一层干燥层上。然后将至少第二层生陶瓷层置于上述第一层有图案的合金膜上,获得一个堆叠(stack)。再将第二层有图案的合金膜沉积在第二层生陶瓷层上,又将至少第三层生陶瓷层堆积在第二层有图案的合金膜的上面。然后在950-1120℃的温度范围内烧结此堆叠,冷却后,将银糊料施涂到第一和第二合金层的边缘延伸到的(陶瓷)体的两个端面上。使银糊料热固化,就形成与第一和第二合金层都接触的终端。然后在固化的银终端上电镀-层镍膜。
这就获得了一种多层陶瓷电容器,它包含致密熟化的陶瓷体和至少一层掩埋在陶瓷体内的层状电极,陶瓷体包含87-98重量%的钛酸镁锌和2-13重量%的粉末状硼硅酸钡锂烧结助熔剂。埋入的电极可以由银和钯的合金组成,其中银的含量至少为80重量%。本发明认为,在制造COG型MLC电容器中,陶瓷所需烧结温度的降低可允许埋入银含量提高的电极,并且具有此较高导电率的掩埋电极的MLC电容器会显示出较高的Q值。对Q值较为取决于电极电阻率而不太取决于电介质陶瓷本身固有Q值的COG MLC电容器,尤其如此,这样,COG多层电容器较低烧结温度的这个好处就可以导致较低的制造成本和较好的COG性能。
本发明还认为在陶瓷粉末的助熔剂部分中包含锂可以降低助熔剂的熔化温度,并可以意想不到地减少多层COG电容器使用寿命试验中不合格的现象。
本发明的上述目的可以使用上述硼硅酸镁锂烧结助熔剂而达到。事实上,使用本发明的原料粉末并在约940-1100℃的温度范围内进行烧结就可以制得MLC电容器,在这个意义上本发明的上述目的已被超越。
附图的简要说明
图1表示盘形陶瓷电容器的侧面剖视图。
图2表示具有掩埋电极的多层陶瓷(MLC)电容器的侧面剖视图。
较好实施方案的描述
制造了试验盘形陶瓷电容器,其中原料粉末的高温烧制组分是钛酸镁锌。这些试验盘形电容器制成如图1所示。薄的电介质陶瓷盘10具有粘合在盘形电容器两个相反主表面上的电极11和12。盘形电容器的制造比多层电容器容易得多,除了DF和Q性能指标外,对于盘形电容器特定组成和烧结条件的所有其它指标都是可由使用相同原料粉末组合物的相应多层电容器所要获得性能的有用指标。
-制造原料陶瓷粉末一
制造陶瓷粉末原料混合物的一种方法,先是制备平均颗粒大小约为1.0微米的高温烧制粉末混合物,其办法是将96-98摩尔%的化学计量钛酸镁锌(MZT)的一些前体物质混合起来,其中高达4摩尔%的镁可被钙取代。这可以通过用等摩尔量的钛酸钙替代钛酸镁部分(如2.9摩尔%)实现。同样地,也可以采用用来调节烧结粉末电容器体的TCC的其它这样的镁的部分取代物例如等摩尔量的氧化钡或锆酸钡。在锆酸钡的情况下,它可以用来取代等摩尔量的钛酸镁。如上面提到的美国专利4,882,650所述,钡在钛酸镁锌中的取代量可以高达60摩尔%。
将第二种含低熔玻璃成形物质的粉末加到上述高烧结温度的陶瓷粉末中。该低熔粉末用作烧结助熔剂,它由钡、硼和硅的氧化物或其等同物质组成。
然后研磨上述粉末混合物成为均匀的粉末混合物,而后在约600℃的温度下温和煅烧之,获得由粉末混合物的聚集颗粒组成的粉末,其中各聚集颗粒基本上具有与均匀前体粉末混合物相同的组成,聚集颗粒的平均大小约为1.2微米。
-制造盘形电容器-
制造诸如图1所示盘形电容器所用的方法如下所述。在直径为半英寸(12.7毫米)的模具中以15,000磅/平方英寸的压力将原料粉末混合物压至厚度约为35密耳(0.89毫米)。然后在1100℃时(除非下面另有说明外)将所得的圆形生盘烧结3小时。冷却后,将银糊料施涂到各烧结盘10的两个相反的表面上,随后将所述盘加热到800℃,使电极11和12固化。
在某些实施例中主要的高温烧制原料粉末的组成是Mg2/3Zn1/3TiO3,其中用少量的钙取代等摩尔量(如2.9摩尔%)的镁。在其它的实施例中则只加入一些BaZrO3。这种碱土金属在钛酸镁锌中的取代或加入能够有利地用来调节烧结盘形电容器的电容温度系数(TCC)。还加入了约0.01重量%的碳酸锰,它一般用于改进许多不同种类的电介质陶瓷配方的使用寿命试验性能。在原料混合物中同样加入了粉末状的硼硅酸钡烧结助熔剂。
参见表I和II,当在1100-1150℃的温度范围内烧结电介质陶瓷粉末时,硼酸钡和硅酸锌的双组分助熔剂是有效的,但表II中的实施例6a除外。仅使用0.5重量%的3BaO·B2O3和1.0重量%的Zn2SiO4时,烧制的电容器产生了非常高的密度并且K值为23或24。
而且,TCC的值均在COG标准内。另外,DF的值很低,尤其是实施例3、4和7。这些电容器实施例的Q因子至少为10,000。尽管实施例2(由1.2重量%的3BaO2·B2O3和1.0重量%的Zn2SiO4制得)和实施例6a未达到熟化,而在1150℃烧制同样的配方能达到熟化,并且其初始性能在一定程度上很好。
在测试含有硼酸钡和硅酸锌双组分烧结助熔剂的实施例1至6b的MZCT时,发现烧制的电容器未能通过使用寿命试验。如表II所示,使用了一些不同的添加剂,目的是延长使用寿命,但无效果,尽管某些添加剂是众所周知的,并且曾用来延长使用寿命(BaCO3、BaZrO3、MnCO3和Y2O3)。如表II中的实施例1至6b所示,这些电容器没有通过使用寿命试验。
当试验了少量的碳酸锂(0.3重量%)来看碳酸锂是否会影响使用寿命时,碳酸锂的效果竟是很大,意想不到的。如表I和II中实施例7所示,那些含有Li2CO3的电容器通过了使用寿命试验,并且仍具有优良的电性能和线性性能。随后,试验了Li2SiO4对使用寿命的影响。如表I和II中实施例8所示,与Li2CO3相比,那些含有Li2SiO4的电容器通过了使用寿命试验,并且达到了良好的电性能和线性性能。实施例8的Q因子比实施例7的低,这很可能是由于其1,110℃较低烧结温度的缘故。实施例7和8都在COG标准范围内。
-含有硼硅酸钡锂助熔剂的钛酸镁锌钙-
制造了一系列的试验盘形电容器,其中原料粉末的组成是90重量%的上述钛酸镁锌钙和10重量%的硅酸锂硼酸钡助熔剂。
参见表III,第一组A组的试验盘形电容器(即实施例9-12)包含由1摩尔硅酸锂(Li4SiO4)、3摩尔硼酸高钡(3BaO·B2O3)和1摩尔硼酸钡(BaO·B2O3)组成的原料粉末助熔剂。如表III另外三个栏内所示,也可以将各实施例中助熔剂的组成表示成占助熔剂总量的重量%。各实施例有4个盘形电容器。在1000℃烧结实施例9的4个盘形电容器,实施例10的电容器在975℃烧结。实施例11的电容器在950℃烧结,实施例12的电容器在925℃烧结,均如表III所示。
第二至第九组试验盘形电容器,即实施例13-16、17-20、21-24、25-28、29-32、33-36、37-40和41-44的助熔剂组成(B、C、D、E、F、G、H和I)分别类似地表示在表III的中间六个栏内。
在烧结和冷却后,测量各实施例中4个盘形电容器的耗散因子(DF)、23℃室温的介电常数(K)和在-55℃和+125℃测得的电容温度系数(TCC),以K的百分数变化表示,并对所得的4个值取平均。这些数据列于表III的最后五个栏内。
在925℃烧制九种组合物,所得样品没有一种是致密和熟化的,都是多孔的。进一步可以看出,具有A组原料粉末组成且在1000℃和975℃烧结的实施例9和10的电容器未达到COG标准的TCC要求;所述要求是在-55℃或+125℃的介电常数(K)的变化不大于室温K值的30%。在1000℃较高温度下烧结C、D、E和F组组成的电容器(对应于实施例17、21、25和29)也未达到COG标准的这个TCC要求。对于所有在烧结后致密的实施例,包括A组至I组组成中的至少两个实施例,介电常数的范围为21-23,这是已有技术中通常在1100℃和更高温度下烧制而得的典型COG电容器,并且在烧制后达到熟化的这里所有的九种试验组合物都具有令人满意的K值。但是从表III所列的电容器性能可以看出,诸如G、H和I组的某些原料粉末配方在包括1000℃、975℃和950℃的范围内进行烧结,能提供异乎寻常好的符合COG标准的性能。而且,在表III中所列的所有原料粉末组成配方在包括975℃和950℃的范围内的某个温度进行烧结后能提供符合COG标准性能。
-在MLC电容器体两端提供导电性终端的方法对COG标准规定的性能的影响-
按下述已有技术的方法制造多层陶瓷(MLC)电容器,评价电容器的电终端施加方法对COG标准规定的性能有怎样的影响。
在一种液体有机载体中研磨上述原料粉末混合物,制得浆料。将一层浆料涂在一块平的基材上,然后干燥。将一层钯银油墨按某一图案丝网印刷在陶瓷浆料的干燥层上。
采用帘流涂布法或上述带式法(tape process)施加另外几层陶瓷浆料和电极糊料,使最终的钯银油墨图案膜分别沉积在连续相邻的两层陶瓷层之间,获得有图案的电极层夹置于其中的干“生”陶瓷层的堆叠。
如图2所示,多层电容器体20具有一些陶瓷层21和一些掩埋的电极22。从堆叠上切割下来的一部分暂时还是一种生的陶瓷体,对该生的陶瓷体进行加热,除去有机组分并使其硬化,可供烧结之用。
参见表IV,采用上述方法制造实施例45、46、47、48、49、50、51、52和53的一系列MLC电容器体,其中高温烧制原料粉末是与实施例1-8中相同的钛酸镁锌钙(MZCT),但是加上一个引入终端的步骤。采用原料粉末中的不同MZCT含量、不同烧结温度以及不同的引入终端的方法。
一种将可焊的导电终端沉积到多层陶瓷电容器电极层的相对两端上的常用方法是要求将银糊料施涂到该电容器体20(图2)的两端上(在此两端露出一组交替排列的掩埋电极),在750℃加热几分钟,形成银终端25和26。然而,尤其是对于COG MLC电容器,人们知道还要采取一些步骤,即在银终端上电镀形成一层镍阻挡层,而后在镍层上施加一层锡铅焊料层。这就提供了低的电阻,并且在掩埋的电极端部和银终端层之间获得更为可靠的连接。这样提供的终端可以使电容器更容易地表面安装到电路板上。
引入终端的方法可以有所改变,即在这些试验中的某些试验中不采用所需的镍电镀和施加焊料的步骤,这些试验的数据也列于表IV中。电容器冷却到室温后,对这些烧结电容器的样品组将银糊料直接施涂到其两端上而后加热固化,这样来引入终端。测量此样品组电容器的电容(以便计算介电常数K)、耗散因子(DF)和TCC。对其余的烧结体则进行镍电镀和焊料涂覆,而后进行使用寿命试验,即在两个终端之间施加300伏直流电压,使得达到12-15伏/微米电介质厚度,此时电容器的温度保持在125℃。若在使用寿命试验的最初一百个小时内,电容器绝缘电阻由初始值降低两个数量级,则认为电容器没有通过使用寿命试验。
在表IV的实施例45、47、49和52中MLC电容器的银终端都经镍电镀并经焊料涂覆,而实施例46、48、50、51和53的电容器终端没有经历这些过程。可以看出实施例45、46和47的电容器具有相同的陶瓷组成,即包含10重量%的助熔剂(与表III的C组中相同的助熔剂),但不管其烧结温度如何,实施例45和47经电镀镍的电容器都没有通过使用寿命试验。然而,其余实施例48-53的电容器都通过了使用寿命试验,而不管它们是否预先进行过镍电镀;这些电容器都包含5重量%或7.5重量%的助熔剂。较大量的助熔剂会危及COG电容器的使用寿命试验,而该电容器在其它方面的性能都是良好的。所以当涂银的MLC电容器两端要进行镍电镀时,较好的是在本发明的MLC电容器中使用少于8重量%的硼硅酸钡锂助熔剂。
从表III和IV所列的数据可以看出,可以使用较多量的硼硅酸钡锂助熔剂来制造COG电容器,这就可以使掩埋的电极所含的钯比常用的70%Ag/30%Pd合金少得多。
-不同量的硼硅酸钡锂助熔剂对COG标准规定的性能的影响-
制造了一系列MLC电容器,其所用原料粉末混合物中的助熔剂的量在0-12重量%的范围内变化,并且烧结温度从950℃变化到1130℃。这些变量连同相应的试验数据列于表V中。对于这一系列的试验电容器,原料粉末使用Mg2/3Zn1/3TiO3加上2.9重量%的CaO,助熔剂由22.61重量%的BaO·B2O3、53.23重量%的3BaO·B2O3和24.16重量%的Li4SiO4组成。在这里证实了可以使用适当量的助熔剂在950℃至1130℃范围内的任何温度下烧结这些原料至熟化。使用大量助熔剂(10-12重量%)的实施例62、63、64和64能提供优良的COG标准规定的性能。使用中等量助熔剂(5-8重量%)的实施例59-61也是非常好的。实施例58表明在助熔剂的量为5重量%时,1000℃的烧结温度对原料粉末来说要完全反应和达到熟化是太低了。全都在1130℃烧制的实施例54-57能烧结并制得了良好的电介质体,但不符合COG标准的TCC极限。可以认为,在钛酸镁锌钙中用少量的钛酸钡取代钛酸钙会很可能使TCC性能更接近COG标准的极限。然而,可以认为本发明所含助熔剂的量限制于不小于2重量%,不包括实施例56的配方。
表I
组成(重量%)
实施例 | MZCT | Nb2O5 | CcaTiO3 | 3BaO·B2O3 | Zn2SiO4 | BaCO3 | BaZrO3 | Mg2TiO4 | MnCO3 | BaTiO3 | Y2O3 | Li2CO3 | Li4SO4 |
1 | 97.85 | 0.25 | 0.2 | 0.5 | 1 | 0.2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
2 | 91.55 | 0.25 | 0 | 1.2 | 1 | 0 | 0 | 3 | 0 | 3 | 0 | 0 | 0 |
3 | 97.65 | 0.25 | 0.2 | 0.5 | 1 | 0.4 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
4 | 97.75 | 0.25 | 0.2 | 0.5 | 1 | 0.2 | 0 | 0 | 0.1 | 0 | 0 | 0 | 0 |
5 | 92.05 | 0.25 | 0.2 | 0.5 | 1 | 0 | 6 | 0 | 0 | 0 | 0 | 0 | 0 |
6 | 91.55 | 0.25 | 0.2 | 0.5 | 1 | 0 | 6 | 0 | 0 | 0 | 0.5 | 0 | 0 |
7 | 96.25 | 0.25 | 0.2 | 0.5 | 1 | 0 | 1.5 | 0 | 0 | 0 | 0 | 0.3 | 0 |
8 | 96.25 | 0.25 | 0.2 | 0.5 | 1 | 0 | 1.5 | 0 | 0 | 0 | 0 | 0 | 0.3 |
表Ia
钛酸镁锌钙(MZCT)
氧化物 | 重量% | 摩尔% |
MgO | 18.66 | 31 |
ZnO | 18.84 | 15.5 |
CaO | 2.89 | 3.5 |
Ti02 | 59.6 | 50 |
表II
实施例 | 烧结温度℃ | 密度g/cm3 | 电容(1MHz)pf | K | %DF1MHz | UDBD伏 | 经过300V、125℃、0.5小时的IR(ohm) | 使用寿命试验300V、125℃、100小时 |
1 | 1100 | 4.17 | 355 | 24 | 0.03 | 655 | >109 | 在1小时后未通过 |
2 | 1130 | 4.07 | 265 | 24 | N/A | N/A | N/A | 在20小时后未通过 |
3 | 1130 | 4.19 | 428 | 24 | 0.01 | 2100 | >109 | 在10小时后未通过 |
4 | 1130 | 4.26 | 420 | 23 | 0.01 | 2340 | >109 | 在10小时后未通过 |
5 | 1140 | 4.02 | 432 | 23 | N/A | N/A | >105 | 在1小时后未通过 |
6a | 1130 | 多孔 | N/A | N/A | N/A | N/A | N/A | N/A |
6b | 1150 | 4.18 | 417 | 23 | 0.09 | 1860 | >105 | 在2小时后未通过 |
7 | 1130 | 4.27 | 411 | 23 | 0 | 2110 | >1011 | 通过 |
8 | 1110 | 4.2 | 407 | 23 | 0.04 | 1800 | >1011 | 通过 |
表III
组 | 实施例 | 烧结温度℃ | 摩尔 | 重量% | 密度g/cm3 | K | %DF | TCC | |||||
Li4SiO4 | 3BaO·B2O3 | BaO·B2O3 | Li4SiO4 | 3BaO·B2O3 | BaO·B2O3 | -55到25 | -25到125 | ||||||
A | 9 | 1000 | 50 | 12.5 | 37.5 | 28.6 | 31.4 | 40 | 4.16 | 23 | 0.05 | -40 | 30 |
10 | 975 | 50 | 12.5 | 37.5 | 28.6 | 31.4 | 40 | 4.18 | 23 | 0.1 | -49 | 52 | |
11 | 950 | 50 | 12.5 | 37.5 | 28.6 | 31.4 | 40 | 4.13 | 22 | 0.04 | 1 | 24 | |
12 | 925 | 50 | 12.5 | 37.5 | 28.6 | 31.4 | 40 | 多孔 | - | - | - | - | |
B | 13 | 1000 | 50 | 37.5 | 12.5 | 21 | 69.2 | 9.8 | 4.15 | 22 | 0 | 17 | 3 |
14 | 975 | 50 | 37.5 | 12.5 | 21 | 69.2 | 9.8 | 4.12 | 22 | 0.01 | 8 | 16 | |
15 | 950 | 50 | 37.5 | 12.5 | 21 | 69.2 | 9.8 | 4.04 | 21 | 0 | 2 | 21 | |
16 | 925 | 50 | 37.5 | 12.5 | 21 | 69.2 | 9.8 | 多孔 | - | - | - | - | |
C | 17 | 1000 | 50 | 25 | 25 | 24.2 | 53.2 | 22.6 | 4.11 | 22 | 0 | 24 | -66 |
18 | 975 | 50 | 25 | 25 | 24.2 | 53.2 | 22.6 | 4.1 | 22 | 0.02 | 25 | 2 | |
19 | 950 | 50 | 25 | 25 | 24.2 | 53.2 | 22.6 | 3.97 | 21 | 0 | 21 | 5 | |
20 | 925 | 50 | 25 | 25 | 24.2 | 53.2 | 22.6 | 多孔 | - | - | - | - | |
D | 21 | 1000 | 30 | 25 | 45 | 13.4 | 49.1 | 37.5 | 4.12 | 21 | 0 | 0 | -53 |
22 | 975 | 30 | 25 | 45 | 13.4 | 49.1 | 37.5 | 4.12 | 21 | 0.02 | -8 | 25 | |
23 | 950 | 30 | 25 | 45 | 13.4 | 49.1 | 37.5 | 4.11 | 21 | 0 | -5 | 28 | |
24 | 925 | 30 | 25 | 45 | 13.4 | 49.1 | 37.5 | 多孔 | - | - | - |
表III(续)
组 | 实施例 | 烧结温度℃ | 摩尔 | 重量% | 密度g/cm3 | K | %DF | TCC | |||||
Li4SiO4 | 3BaO·B2O3 | BaO·B2O3 | Li4SiO4 | 3BaO·B2O3 | BaO·B2O3 | -55到25 | -25到125 | ||||||
E | 25 | 1000 | 60 | 25 | 15 | 30.3 | 55.5 | 14.2 | 4.17 | 22 | 0 | 22 | -67 |
26 | 975 | 60 | 25 | 15 | 30.3 | 55.5 | 14.2 | 4.15 | 22 | 0.01 | 15 | 7 | |
27 | 950 | 60 | 25 | 15 | 30.3 | 55.5 | 14.2 | 4.05 | 21 | 0 | 12 | 14 | |
28 | 925 | 60 | 25 | 15 | 30.3 | 55.5 | 14.2 | 多孔 | - | - | - | - | |
F | 29 | 1000 | 70 | 25 | 5 | 37 | 58 | 5 | 4.16 | 22 | 0 | 16 | -58 |
30 | 975 | 70 | 25 | 5 | 37 | 58 | 5 | 4.15 | 21 | 0.02 | 6 | 13 | |
31 | 950 | 70 | 25 | 5 | 37 | 58 | 5 | 4.08 | 21 | 0 | 8 | 19 | |
32 | 925 | 70 | 25 | 5 | 37 | 58 | 5 | 多孔 | - | - | - | - | |
G | 33 | 1000 | 30 | 45 | 25 | 11 | 72 | 17 | 4.17 | 22 | 0.01 | 22 | 5 |
34 | 975 | 30 | 45 | 25 | 11 | 72 | 17 | 4.18 | 22 | 0.04 | -1 | 18 | |
35 | 950 | 30 | 45 | 25 | 11 | 72 | 17 | 4.04 | 21 | 0.03 | 15 | 11 | |
36 | 925 | 30 | 45 | 25 | 11 | 72 | 17 | 多孔 | - | - | - | - | |
H | 37 | 1000 | 60 | 15 | 25 | 34.8 | 38.2 | 27 | 4.1 | 21 | 0 | 13 | 18 |
38 | 975 | 60 | 15 | 25 | 34.8 | 38.2 | 27 | 4.1 | 21 | 0.01 | -3 | 27 | |
39 | 950 | 60 | 15 | 25 | 34.8 | 38.2 | 27 | 4.07 | 21 | 0 | 1 | 26 | |
40 | 925 | 60 | 15 | 25 | 34.8 | 38.2 | 27 | 多孔 | - | - | - | - | |
I | 41 | 1000 | 70 | 5 | 25 | 50.6 | 15.8 | 33.6 | 4.03 | 21 | 0.01 | 6 | 24 |
42 | 975 | 70 | 5 | 25 | 50.6 | 15.8 | 33.6 | 4.04 | 21 | 0.02 | -4 | 25 | |
43 | 950 | 70 | 5 | 25 | 50.6 | 15.8 | 33.6 | 4.02 | 21 | 0 | 7 | 21 | |
44 | 925 | 70 | 5 | 25 | 50.6 | 15.8 | 33.6 | 多孔 | - | - | - | - |
表IV
实施例 | MZT重量% | 助熔剂重量% | MnCO3重量% | 油墨Ag/Pd | 烧结温度℃ | 密度g/cm3 | 电容(1KHz)pf | %DF(1KHz) | 电容(1MHz)pf | %DF(1MHz) | UVDB(v) | K | TCC(PPM/℃) | 使用寿命试验 | 注释 | |
-55℃ | +125℃ | |||||||||||||||
45 | 90 | 10 | 0.1 | 85/15 | 1000 | 4.07 | 305 | 0.25 | 195 | 0.01 | 1930 | 22 | 0 | 26.5 | 未通过 | 电镀样品 |
46 | 90 | 10 | 0.1 | 85/15 | 975 | 3.97 | 371 | 0.01 | 371 | 0 | 1930 | 22 | 0 | 26.5 | 通过 | 未电镀 |
47 | 90 | 10 | 0.1 | 85/15 | 975 | 3.97 | 386 | 0.4 | 386 | 0.01 | 1930 | 22 | 0 | 26.5 | 未通过 | 电镀样品 |
48 | 95 | 5 | 0.1 | 85/15 | 925 | 4.12 | 310 | 0 | 358 | 0 | 1980 | 22.6 | 28 | 8 | 通过 | 未电镀 |
49 | 95 | 5 | 0.1 | 85/15 | 925 | 4.12 | 346 | 0.019 | 346 | 0 | 1980 | 22.6 | 28 | 8 | 通过 | 电镀样品 |
50 | 95 | 5 | 0.1 | 85/15 | 1000 | 3.92 | 342 | 0 | 342 | 0 | 1980 | 22.6 | 6 | 26 | 通过 | 未电镀 |
51 | 92.5 | 7.5 | 0.1 | 85/15 | 1025 | 4.18 | 337 | 0 | 352 | 0 | 2030 | 23.2 | 25 | 11 | 通过 | 未电镀 |
52 | 92.5 | 7.5 | 0.1 | 85/15 | 1025 | 4.18 | 349 | 0.02 | 349 | 0 | 2030 | 23.2 | 25 | 11 | 通过 | 电镀样品 |
53 | 92.5 | 7.5 | 0.1 | 85/15 | 1000 | 4.14 | 354 | 0 | 354 | 0 | 2030 | 23.2 | 18 | 15 | 通过 | 未电镀 |
表V
实施例 | MZT+Ca(重量%) | 助熔剂(重量%) | MnCO3(重量%) | 烧结温度℃ | 密度gm/cc | K | %DF | TCC(PPM) | |
-55℃ | +125℃ | ||||||||
54 | 99.9 | 0 | 0.1 | 1130 | 4.07 | 22 | 0.09 | 19 | -66 |
55 | 97.9 | 2 | 0.1 | 1130 | 4.23 | 23 | 0 | 30 | -70 |
56 | 96.9 | 3 | 0.1 | 1130 | 4.21 | 23 | 0 | 35 | -78 |
57 | 95.9 | 4 | 0.1 | 1130 | 4.18 | 23 | 0 | 35 | -81 |
58 | 95 | 5 | 0 | 950 | 多孔 | 18 | 0 | -9 | 18 |
59 | 95 | 5 | 0 | 1000 | 4.12 | 22 | 0 | 11 | 8 |
60 | 92 | 8 | 0 | 950 | 3.91 | 20 | 0 | -14 | 27 |
61 | 92 | 8 | 0 | 1000 | 4.14 | 22 | 0 | 12 | 6 |
62 | 90 | 10 | 0 | 950 | 4.11 | 21 | 0.01 | 9 | 19 |
63 | 88 | 12 | 0 | 950 | 4.12 | 21 | 0.01 | 11 | 23 |
64 | 88 | 12 | 0 | 950 | 4.02 | 20 | 0 | -11 | 19 |
65 | 88 | 12 | 0 | 1000 | 4.11 | 22 | 0 | 7 | 11 |
Claims (6)
1.一种电介质陶瓷粉末混合物,它主要由聚集颗粒组成,每个所述聚集颗粒都是由两种粉末颗粒经温和煅烧并发生表面共反应而均匀结合起来,形成聚集颗粒的,在所述每个聚集颗粒中的所述两种粉末颗粒分别由87-98重量%的钛酸镁锌粉末和2-13重量%的粉末状硼硅酸钡锂烧结助熔剂组成,所述硼硅酸钡锂助熔剂由10-55重量%的Li4SiO4、3-40重量%的BaO·B2O3和10-76重量%的3BaO·B2O3组成,所述钛酸镁锌粉末是完全反应的化合物Mg2/3Zn1/3TiO3,有高达20%的所述Mg被等摩尔量的碱土金属所取代。
2.如权利要求1所述的电介质陶瓷粉末混合物,其中所述硼硅酸钡锂助熔剂由22-26重量%的Li4SiO4、20.5-23.5重量%的BaO·B2O3和50-56重量%的3BaO·B2O3组成。
3.如权利要求1所述的电介质陶瓷粉末混合物,其中所述碱土金属选自钙、锶、钡和它们的组合。
4.如权利要求1所述的电介质陶瓷粉末混合物,其中所述钛酸镁锌粉末是完全反应的化合物Mg2/3Zn1/3TiO3,有高达60%的所述Mg被等摩尔量的钡所取代。
5.一种制造电介质陶瓷粉末混合物的方法,它包括:
a)将87-98重量%的钛酸镁锌与2-13重量%的粉末状硼硅酸钡锂烧结助熔剂加在一起;
b)将所述加在一起的两种粉末混合成均匀的粉末混合物;
c)在600-750℃的温度下温和煅烧所述均匀的混合物,获得由所述均匀粉末混合物的聚集颗粒组成的粉末,其中各所述聚集颗粒基本上具有与所述整体粉末混合物中相同的钛酸镁锌和硼硅酸钡锂的组成,
其中所述硼硅酸钡锂助熔剂由10-55重量%的Li4SiO4、3-40重量%的BaO·B2O3和10-76重量%的3BaO·B2O3组成,所述钛酸镁锌粉末是完全反应的化合物Mg2/3Zn1/3TiO3,有高达20%的所述Mg被等摩尔量的碱土金属所取代。
6.如权利要求5所述的方法,它还包括对所述经温和煅烧的粉末进行粉碎,获得平均聚集颗粒大小约为1.2微米的能自由流动的电介质陶瓷粉末混合物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/652,562 US6309995B1 (en) | 1998-12-31 | 2000-08-31 | Magnesium zinc titanate powder with a barium boron lithium silicate flux and a multilayer ceramic COG capacitor made therefrom |
US09/652,562 | 2000-08-31 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2003101046413A Division CN100385583C (zh) | 1998-12-31 | 2001-08-27 | 制造多层陶瓷电容器的方法和由其制成的多层陶瓷电容器 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1341575A CN1341575A (zh) | 2002-03-27 |
CN1148332C true CN1148332C (zh) | 2004-05-05 |
Family
ID=24617274
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB011252634A Expired - Fee Related CN1148332C (zh) | 2000-08-31 | 2001-08-27 | 含有硼硅酸钡锂助熔剂和钛酸镁锌粉末的电介质陶瓷粉末混合物 |
Country Status (9)
Country | Link |
---|---|
US (1) | US6309995B1 (zh) |
EP (1) | EP1199290B1 (zh) |
JP (1) | JP2002137963A (zh) |
KR (1) | KR100437883B1 (zh) |
CN (1) | CN1148332C (zh) |
AT (1) | ATE315013T1 (zh) |
DE (1) | DE60116449T2 (zh) |
HK (1) | HK1062955A1 (zh) |
TW (1) | TWI236462B (zh) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20020037038A (ko) * | 1999-08-23 | 2002-05-17 | 마싸 앤 피네간 | 규산염 기재의 소결 보조제 및 소결 방법 |
US6723673B2 (en) * | 2000-08-31 | 2004-04-20 | Mra Laboratories, Inc. | High dielectric constant very low fired X7R ceramic capacitor, and powder for making |
US6727200B2 (en) | 2000-08-31 | 2004-04-27 | Mra Laboratories, Inc. | High dielectric constant very low fired X7R ceramic capacitor, and powder for making |
US7720443B2 (en) * | 2003-06-02 | 2010-05-18 | Kyocera Wireless Corp. | System and method for filtering time division multiple access telephone communications |
US7582147B1 (en) * | 2004-08-19 | 2009-09-01 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Composite powder particles |
US7378363B2 (en) * | 2005-05-20 | 2008-05-27 | Skyworks Solutions, Inc. | Dielectric ceramic composition having wide sintering temperature range and reduced exaggerated grain growth |
US7161795B1 (en) | 2005-09-26 | 2007-01-09 | Ferro Corporation | COG dielectric composition for use with copper electrodes |
CN101272991B (zh) * | 2005-09-28 | 2012-01-18 | 费罗公司 | 用于与镍电极一起使用的cog电介质组合物 |
US7547408B1 (en) * | 2006-07-28 | 2009-06-16 | General Electric Company | Process for reducing non-uniformities in the density of sintered materials |
CN101494116B (zh) * | 2008-11-27 | 2011-08-10 | 成都宏明电子科大新材料有限公司 | 一种耐热冲击陶瓷电容器的制备方法 |
CN103578764B (zh) * | 2013-11-01 | 2016-08-17 | 广州创天电子科技有限公司 | 一种提高陶瓷电容器q值的方法 |
KR102059804B1 (ko) | 2015-08-05 | 2019-12-27 | 페로 코포레이션 | 고유전 상수-k ltcc 유전성 조성물 및 장치 |
CN107417273A (zh) * | 2017-04-28 | 2017-12-01 | 武汉理工大学 | 一种低损耗高温度稳定性npo电容器介质材料及其制备方法 |
CN112408975B (zh) * | 2019-08-23 | 2022-11-04 | 兴勤电子工业股份有限公司 | 陶瓷组成物、陶瓷烧结体、叠层型陶瓷电子元件及其制法 |
CN114773056B (zh) * | 2022-05-11 | 2023-03-24 | 丽智电子(南通)有限公司 | 一种npo mlcc用陶瓷材料的助烧剂、陶瓷材料及制备方法 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2520729B1 (fr) | 1982-02-02 | 1986-01-31 | Europ Composants Electron | Composition ceramique dielectrique a base de titanate de baryum, d'oxyde de lithium et de fluorure de zinc, condensateur utilisant une telle composition et procede de fabrication de ladite composition |
US4533974A (en) | 1984-04-09 | 1985-08-06 | Sprague Electric Company | Low-firing high Q monolithic ceramic capacitor |
US4612600A (en) | 1984-10-29 | 1986-09-16 | Tam Ceramics Inc. | Low fire ceramic compositions |
US4898844A (en) * | 1986-07-14 | 1990-02-06 | Sprague Electric Company | Process for manufacturing a ceramic body having multiple barium-titanate phases |
US4882650A (en) * | 1988-12-05 | 1989-11-21 | Sprague Electric Company | Magnesium titanate ceramic and dual dielectric substrate using same |
US5051863A (en) * | 1989-10-31 | 1991-09-24 | Taiyo Yuden Co., Ltd. | Solid dielectric capacitor and method of manufacture |
US5089933A (en) * | 1989-12-04 | 1992-02-18 | Taiyo Yuden Co., Ltd. | Solid dielectric capacitor and method of manufacture |
JPH06349335A (ja) * | 1993-06-11 | 1994-12-22 | Ube Ind Ltd | 誘電体磁器組成物 |
SE505243C2 (sv) * | 1994-11-29 | 1997-07-21 | Kyocera Corp | Dielektrisk keramisk komposition, flerlagrig resonator framställd av kompositionen och flerlagrigt filter användande resonatorn |
DE19546237A1 (de) | 1995-12-12 | 1997-06-19 | Philips Patentverwaltung | Vielschichtkondensator mit Dielektrikum aus modifiziertem Bariumstrontiumtitanat |
US6251816B1 (en) * | 1998-12-31 | 2001-06-26 | Mra Laboratories, Inc. | Capacitor and dielectric ceramic powder based upon a barium borate and zinc silicate dual-component sintering flux |
-
2000
- 2000-08-31 US US09/652,562 patent/US6309995B1/en not_active Expired - Lifetime
-
2001
- 2001-08-22 JP JP2001251512A patent/JP2002137963A/ja active Pending
- 2001-08-27 CN CNB011252634A patent/CN1148332C/zh not_active Expired - Fee Related
- 2001-08-28 TW TW090121140A patent/TWI236462B/zh not_active IP Right Cessation
- 2001-08-29 EP EP01307323A patent/EP1199290B1/en not_active Expired - Lifetime
- 2001-08-29 KR KR10-2001-0052402A patent/KR100437883B1/ko not_active IP Right Cessation
- 2001-08-29 DE DE60116449T patent/DE60116449T2/de not_active Expired - Fee Related
- 2001-08-29 AT AT01307323T patent/ATE315013T1/de not_active IP Right Cessation
-
2004
- 2004-08-03 HK HK04105702A patent/HK1062955A1/xx not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
KR100437883B1 (ko) | 2004-06-30 |
EP1199290A1 (en) | 2002-04-24 |
EP1199290B1 (en) | 2006-01-04 |
KR20020018094A (ko) | 2002-03-07 |
DE60116449T2 (de) | 2006-07-06 |
TWI236462B (en) | 2005-07-21 |
HK1062955A1 (en) | 2004-12-03 |
CN1341575A (zh) | 2002-03-27 |
DE60116449D1 (de) | 2006-03-30 |
US6309995B1 (en) | 2001-10-30 |
JP2002137963A (ja) | 2002-05-14 |
ATE315013T1 (de) | 2006-02-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1167082C (zh) | 介电陶瓷组合物和单块陶瓷电容器 | |
CN1100330C (zh) | 独石陶瓷电容器 | |
CN1076510C (zh) | 叠层陶瓷电容器 | |
CN1179379C (zh) | 介电陶瓷组成物及叠层陶瓷电容器 | |
KR100841506B1 (ko) | 유전체 자기조성물 및 그 제조방법 | |
CN1085636C (zh) | 介电陶瓷组合物及使用该组合物的叠层陶瓷电容器 | |
CN1085635C (zh) | 介电陶瓷组合物及使用该组合物的叠层陶瓷电容器 | |
CN1148332C (zh) | 含有硼硅酸钡锂助熔剂和钛酸镁锌粉末的电介质陶瓷粉末混合物 | |
CN1183561C (zh) | 叠层陶瓷电容器及其制法 | |
EP0794542A2 (en) | Dielectric ceramic and monolithic ceramic electronic part using the same | |
CN1100332C (zh) | 叠层陶瓷电容器 | |
CN1093101C (zh) | 介电陶瓷组合物和层叠陶瓷元件 | |
KR100983046B1 (ko) | 소결조제용 붕규산염계 유리 조성물, 유전체 조성물 및 이를 이용한 적층 세라믹 커패시터 | |
CN1072831C (zh) | 叠层陶瓷电容器 | |
KR100586961B1 (ko) | 내환원성 유전체 자기조성물과 초박층 적층세라믹 콘덴서 | |
CN1216388C (zh) | 叠层陶瓷电容器及其制造方法 | |
EP1837316B1 (en) | Electronic device, dielectric ceramic composition and the production method | |
US9522847B2 (en) | Dielectric ceramic, laminated ceramic electronic component, laminated ceramic capacitor, and method for producing laminated ceramic capacitor | |
CN105693236A (zh) | 低温烧结介电组合物以及由其形成的多层陶瓷电容器 | |
US9064638B2 (en) | Dielectric ceramic, stack ceramic electronic component, and method of manufacturing these | |
KR20120091655A (ko) | 적층 세라믹 전자부품 및 이의 제조방법 | |
JP2001230148A (ja) | 積層セラミックコンデンサとその製造方法 | |
CN1495816A (zh) | 制造多层陶瓷电容器的方法和由其制成的多层陶瓷电容器 | |
KR101771715B1 (ko) | 적층 세라믹 전자부품 및 이의 제조방법 | |
JP2004289087A (ja) | 積層セラミック電子部品の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C06 | Publication | ||
PB01 | Publication | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040505 Termination date: 20090928 |