CN1163875A - 介电陶瓷组合物 - Google Patents
介电陶瓷组合物 Download PDFInfo
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- CN1163875A CN1163875A CN97102334A CN97102334A CN1163875A CN 1163875 A CN1163875 A CN 1163875A CN 97102334 A CN97102334 A CN 97102334A CN 97102334 A CN97102334 A CN 97102334A CN 1163875 A CN1163875 A CN 1163875A
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- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 239000000919 ceramic Substances 0.000 title claims abstract description 23
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 claims abstract description 3
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002075 main ingredient Substances 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 6
- FKSZLDCMQZJMFN-UHFFFAOYSA-N [Mg].[Pb] Chemical compound [Mg].[Pb] FKSZLDCMQZJMFN-UHFFFAOYSA-N 0.000 claims description 2
- 229910003781 PbTiO3 Inorganic materials 0.000 abstract 1
- 229910002370 SrTiO3 Inorganic materials 0.000 abstract 1
- 238000010586 diagram Methods 0.000 abstract 1
- ZBSCCQXBYNSKPV-UHFFFAOYSA-N oxolead;oxomagnesium;2,4,5-trioxa-1$l^{5},3$l^{5}-diniobabicyclo[1.1.1]pentane 1,3-dioxide Chemical compound [Mg]=O.[Pb]=O.[Pb]=O.[Pb]=O.O1[Nb]2(=O)O[Nb]1(=O)O2 ZBSCCQXBYNSKPV-UHFFFAOYSA-N 0.000 abstract 1
- 239000003990 capacitor Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910002367 SrTiO Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000000498 ball milling 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
- 238000005452 bending Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- C04B35/495—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 vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
- C04B35/497—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 vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates based on solid solutions with lead oxides
- C04B35/499—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 vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates based on solid solutions with lead oxides 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
- H01G4/002—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
- H01G4/1254—Ceramic dielectrics characterised by the ceramic dielectric material based on niobium or tungsteen, tantalum oxides or niobates, tantalates
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Insulating Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Capacitors (AREA)
Abstract
一种主要由镁铌酸铅、钛酸锶和钛酸铅组成的介电陶瓷组合物,其特征在于,此三种主要组分的摩尔比为[Pb(Mg1/3Nb2/3)O3]x·[SrTiO3]y·[PbTiO3]z(其中,x+y+z=100摩尔份数,在三角坐标系中,x、y和z的值位于通过A(72,10,18)、B(76,5,19)、C(57,5,38)和D(48,20,32)四点的各线上或其包围区域内),而且三种主要组分被补充以(Pb1-xBax)(Cu1/2W1/2)O3(其中0≤x≤1),其量少于5摩尔份数(不包括0)/100摩尔份数主要组分。此介电陶瓷组合物能在低温下烧结,并具有高介电常数和高机械强度。
Description
本发明涉及一种介电陶瓷组合物,尤其是一种用作叠片陶瓷电容器原料的介电陶瓷组合物。
以钛酸钡(BaTiO3)为基础的介电陶瓷组合物已被人们广泛应用。但是,其缺点在于需要高温焙烧(通常为1300-1400℃)。在将其用于叠片电容器时,需要能够耐焙烧高温的贵金属内部电极(例如铂和钯)。这提高了生产成本。所以,叠片电容器成本的降低需要一种能够在较低温度下焙烧的介电陶瓷组合物,由此可以不使用贵金属作为内部电极(以银和镍为基础)。
要求介电陶瓷组合物具有的基本电学性能包括高介电常数、低介电损耗以及高绝缘电阻。此外,高机械强度是对绝缘陶瓷组合物的另一项要求。在将这种组合物用于小型叠片电容器时,组合物片装在基材上会因两者的热膨胀差异而发生机械应变,此时,这一点尤为重要。这种应变会导致叠片电容器的碎裂和损坏。所以,叠片电容器的可靠性取决于其制造用介电陶瓷组合物的机械性能。
因此,一直以来,需要一种既能够在较低温度下烧结又具有较优的机械强度的介电陶瓷组合物。
日本专利公开No.21850/1980公开了能够在低温下烧结的介电陶瓷组合物,这是一种由Pb(Fe2/3W1/3)O3和PbZrO3组成的二组分组合物。但是,该组合物的介电损耗高,电阻率低,有待改进。为了克服这些缺点,已经提出了一种含有第三组分Pb(Mn2/3W1/3)O3的三组分组合物(日本专利公开No.23058/1980)。但是,此三组分组合物的抗挠强度较差,所以只能用于某些用途的叠片电容器。日本专利公开No.60670/1983中公开了另一种三元介电陶瓷组合物,由Pb(Mn1/3Nb2/3)O3,Pb(Mg1/2W1/2)O3和PbTiO3组成。与上述介电陶瓷组合物一样,其机械强度也不能令人满意。
本发明目的之一是提供一种既能够在较低温度下烧结又具有高介电常数和足够机械强度的介电陶瓷组合物。
本发明主要为一种主要由镁铌酸铅[Pb(Mg1/3Nb2/3)O3]、钛酸锶[SrTiO3]和钛酸铅[PbTiO3]组成的介电陶瓷组合物,其特征在于所述三种主要组分的摩尔比为[Pb(Mg1/3Nb2/3)O3]x·[SrTiO3]y·[PbTiO3]z(其中,x+y+z=100摩尔份数,而且在三角坐标系中,x、y和z的值位于通过A(72,10,18)、B(76,5,19)、C(57,5,38)和D(48,20,32)四点的线上或这些线包围的区域内,而且所述的三种主要组分被补充以(Pb1-xBax)(Cu1/2W1/2)O3(其中0≤x≤1),相对于每100摩尔份数所述主要组分其量少于5摩尔份数(不包括0摩尔份数)。
本发明的介电陶瓷组合物能够在低温下烧结,而且具有优良的介电性能和前所未有的高机械强度。其抗挠强度高于120MPa。该组合物由于具有高强度而可用作叠片电容器的原料。本发明中有效样品的抗挠强度高于120MPa,相对介电常数高于9000,符合JIS规定的D特性。
参照以下说明和附图,可方便地获知本发明的其它目的和优点。
图1显示的是三角坐标系中,表1各样品中三种主要组分之比。
各样品的准备均以Pb3O4,MgO,TiO2,SrO3,CuO和WO3(工业用)为起始原料。将原料称重,以得到表1中的组成。在去离子水(作为溶剂)中球磨16小时将其混合。形成的粉末在750℃的空气中煅烧2小时。煅烧后的粉末与有机溶剂(如甲苯),粘合剂(如PVB)和增塑剂(如DOP)混合成料浆。利用刮刀法将料浆成形为坯料片(厚50-60μm)。将坯料片制成园片形试样(厚1.0μm,直径10mm)和长方体试样(长45mm,宽5mm,厚1.5mm)。在空气中除去这些试样中的粘合剂,然后在950-1100℃的空气中焙烧。由此获得要求的陶瓷样品。
表 1
样品号 | 组成(摩尔份数) | 抗挠强度 | 相对介电常数 | TCC(%) | ||||
PMN | ST | PT | PBCW | σ(平均值) | -25℃ | 85℃ | ||
1* | 80 | 0 | 20 | 5 | 98(8.3) | 4800 | -25.7 | 111 |
2* | 76 | 5 | 19 | 5 | 131(4.3) | 11300 | -43.8 | -13.3 |
3 | 72 | 10 | 18 | 5 | 135(6.4) | 8400 | -16.6 | -49.7 |
4 | 74.4 | 7 | 18.6 | 5 | 132(6.8) | 9400 | -29.5 | -28.2 |
5 | 60 | 0 | 40 | 5 | 92(12.6) | 2100 | -14.7 | 36 |
6 | 57 | 5 | 38 | 5 | 129(11.8) | 2800 | -21 | 53.7 |
7 | 54 | 10 | 36 | 5 | 128(7.9) | 3500 | -23.4 | 97.8 |
8 | 51 | 15 | 34 | 5 | 152(6.4) | 5600 | -33.6 | 54.3 |
9 | 48 | 20 | 32 | 5 | 138(9.9) | 4700 | 1.3 | -37.4 |
10 | 49.2 | 18 | 32.8 | 5 | 145(8.5) | 5300 | -15.8 | 7.5 |
11 | 63 | 10 | 27 | 5 | 133(6.9) | 10000 | -45 | -20 |
12* | 50 | 10 | 40 | 5 | 90(7.4) | 3000 | -30 | 90 |
13* | 60 | 20 | 20 | 5 | 115(9.5) | 5000 | -5 | -32 |
14* | 80 | 10 | 10 | 5 | 105(8.3) | 11000 | -50 | -10 |
15* | 63 | 10 | 27 | 0 | 即使在1200℃也不能烧结 | |||
16* | 63 | 10 | 27 | 10 | 90(7.9) | 9500 | -41 | -26 |
17 | 63 | 10 | 27 | 5 | 138(7.1) | 9800 | -42 | -23 |
18 | 63 | 10 | 27 | 5 | 131(7.6) | 9900 | -39 | -21 |
*非本发明样品
PMN:Pb(Mg1/3Nb2/3)O3
ST:SrTiO3
PT:PbTiO3
PBCW:(Pb1-xBa1-x)(Cu1/2W1/2)O3
将园片试样两面涂以银涂料并在800℃的空气中烘焙后,试验其介电性能。在25℃测定频率为1kHz电压为1V时(rms)的相对介电常数(εr)。根据-25℃与85℃时的电容量相对于20℃电容量的差异(%),表示出静电容的温度特性。测定频率为1kHz电压为1V时(rms)的电容。
将长方体试样用于按照以下方式利用三点弯曲试验来测定抗挠强度。将试样置于两支点上,相距30mm,以0.5mm/min的速度推进十字头使其弯曲。由以下公式计算抗挠强度(σ)。
σ=3×P×I/2×W×t2
其中,P:断裂载荷
L:支点距离
W:试样宽度
t:试样厚度
抗挠强度的值是由Weibull分布计算而得的15-20次测定的平均值。
表1中概括了试样的抗挠强度和介电特性。
样品1至16含有PBCW,其中的x=0。样品17含有PBCW,x=0.5。样品18含有PBCW,x=1。
抗挠强度以MPa为单位表示,“平均值”得自Weibull分布。
将每一样品的组成都绘制在三角坐标系中(图1)。三角坐标系中的数字对应于样品的号码。
本发明的组成确定如上。理由参见表1和图1。组成在线B-C以下,使得抗挠强度低于100MPa,例如样品1和5。组成在线C-D和A-B之外,使得抗挠强度为90MPa和105MPa,例如样品12和14。这些值与常规铅基陶瓷组合物的相近。
组成高于线A-D,抗挠强度为115MPa,如样品13。该值对本发明而言是不够的。不加辅助组分时,例如样品15,样品即使在1200℃也不能烧结。即,样品不具备铅基介电陶瓷组合物能够在低温下烧结的性能。加入过量的辅助组分(多于5摩尔份数)时,例如样品16,样品的抗挠强度极差(90Mpa)。
如表1所示,样品4的相对介电常数为9400,抗挠强度为132MPa,样品10的相对介电常数为5300,抗挠强度为145MPa。此外,TCC值显示,两种样品均符合JIS规定的D特性。这一点值得注意,因为从未有过如此高性能的常规铅基介电陶瓷组合物。
Claims (1)
1.一种主要由镁铌酸铅[Pb(Mg1/3Nb2/3)O3]、钛酸锶[SrTiO3]和钛酸铅[PbTiO3]组成的介电陶瓷组合物,其特征在于,所述三种主要组分的摩尔比为[Pb(Mg1/3Nb2/3)O3]x·[SrTio3]y·[PbTiO3]z,其中,x+y+z=100摩尔份数,而且在三角坐标系中,x、y和z的值位于通过A(72,10,18)、B(76,5,19)、C(57,5,38)和D(48,20,32)四点的线上或这些线包围的区域内,而且所述的三种主要组分被补充以(Pb1-xBax)(Cu1/2W1/2)O3(其中0≤x≤1),对于每100摩尔份数所述主要组分其量少于5摩尔份(不包括0摩尔份数)。
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Application Number | Priority Date | Filing Date | Title |
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JP8032761A JPH09208312A (ja) | 1996-01-26 | 1996-01-26 | 誘電体磁器組成物 |
JP32761/1996 | 1996-01-26 | ||
JP32761/96 | 1996-01-26 |
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CN1163875A true CN1163875A (zh) | 1997-11-05 |
CN1062540C CN1062540C (zh) | 2001-02-28 |
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EP (1) | EP0788123B1 (zh) |
JP (1) | JPH09208312A (zh) |
KR (1) | KR100231799B1 (zh) |
CN (1) | CN1062540C (zh) |
DE (1) | DE69700414T2 (zh) |
SG (1) | SG50003A1 (zh) |
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CN101531511B (zh) * | 2009-04-11 | 2011-11-09 | 桂林工学院 | 一种低温烧结的高热稳定微波介电陶瓷材料及其制备方法 |
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EP0913843B1 (en) * | 1997-03-31 | 2006-02-08 | TDK Corporation | Non-reducing dielectric ceramic material |
KR20010026107A (ko) * | 1999-09-03 | 2001-04-06 | 이광호 | 저온 소결이 가능한 피엠엔-피아이엔계 고유전율 세라믹 유전체 및 그 제조방법 |
JP4614485B2 (ja) * | 1999-12-20 | 2011-01-19 | 京セラ株式会社 | 誘電体共振器 |
KR20030042483A (ko) * | 2001-11-22 | 2003-06-02 | (주) 디엔에프솔루션 | 납 마그네슘 니오베이트/납 티타네이트 강유전체막 형성용용액 |
US6690567B1 (en) | 2002-09-26 | 2004-02-10 | Ceramphysics, Inc. | Capacitive energy storage device |
WO2005050263A2 (en) * | 2003-11-17 | 2005-06-02 | Red Sky Systems, Inc. | Ternary ceramic dielectric coating for an optical repeater pressure vessel |
CN110845230A (zh) * | 2019-12-25 | 2020-02-28 | 西安工业大学 | 一种三元系铌钪酸铅-铌镁酸铅-钛酸铅陶瓷及其制备方法 |
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JPS5521850A (en) | 1978-08-01 | 1980-02-16 | Tdk Electronics Co Ltd | High dielectric porcelain composition |
JPS5523058A (en) | 1978-08-04 | 1980-02-19 | Tdk Electronics Co Ltd | Highly dielectric ceramic composition |
JPS5860670A (ja) | 1981-10-01 | 1983-04-11 | 日本電気株式会社 | 磁器組成物 |
JPS60670A (ja) * | 1983-06-15 | 1985-01-05 | Fujitsu Kiden Ltd | 磁気カ−ド検証方式 |
JPS62290009A (ja) * | 1986-06-09 | 1987-12-16 | 株式会社村田製作所 | 誘電体磁器組成物 |
US5032558A (en) * | 1987-10-09 | 1991-07-16 | Martin Marietta Corporation | Electrostrictive ceramic material including a process for the preparation thereof and applications thereof |
JP2615977B2 (ja) * | 1989-02-23 | 1997-06-04 | 松下電器産業株式会社 | 誘電体磁器組成物およびこれを用いた積層セラミックコンデンサとその製造方法 |
JPH02303081A (ja) * | 1989-05-17 | 1990-12-17 | Murata Mfg Co Ltd | 圧電性磁器組成物 |
EP0413321B1 (en) * | 1989-08-17 | 1995-06-21 | Matsushita Electric Industrial Co., Ltd. | Dielectric ceramic composition and multi-layer capacitor |
JPH03102705A (ja) * | 1989-09-18 | 1991-04-30 | Murata Mfg Co Ltd | 誘電体磁器組成物 |
SG45241A1 (en) * | 1993-06-30 | 1998-01-16 | Murata Manufacturing Co | Dielectric ceramic composition |
US5658485A (en) * | 1995-10-03 | 1997-08-19 | Lucent Technologies Inc. | Pyrochlore based oxides with high dielectric constant and low temperature coefficient |
-
1996
- 1996-01-26 JP JP8032761A patent/JPH09208312A/ja active Pending
-
1997
- 1997-01-15 EP EP97100547A patent/EP0788123B1/en not_active Expired - Lifetime
- 1997-01-15 DE DE69700414T patent/DE69700414T2/de not_active Expired - Fee Related
- 1997-01-23 CN CN97102334A patent/CN1062540C/zh not_active Expired - Fee Related
- 1997-01-25 KR KR1019970002135A patent/KR100231799B1/ko not_active IP Right Cessation
- 1997-01-25 SG SG1997000173A patent/SG50003A1/en unknown
- 1997-01-27 US US08/790,772 patent/US5733832A/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101531511B (zh) * | 2009-04-11 | 2011-11-09 | 桂林工学院 | 一种低温烧结的高热稳定微波介电陶瓷材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
DE69700414D1 (de) | 1999-09-23 |
KR970060278A (ko) | 1997-08-12 |
CN1062540C (zh) | 2001-02-28 |
EP0788123B1 (en) | 1999-08-18 |
JPH09208312A (ja) | 1997-08-12 |
EP0788123A3 (en) | 1997-09-24 |
US5733832A (en) | 1998-03-31 |
SG50003A1 (en) | 1998-06-15 |
KR100231799B1 (ko) | 1999-12-01 |
EP0788123A2 (en) | 1997-08-06 |
DE69700414T2 (de) | 2000-02-17 |
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