CN1031338C - 非还原性介电陶瓷组合物 - Google Patents
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Abstract
提供了一种多层陶瓷电容器用非还原性介电陶瓷组合物,即使在中性或还原性气氛中煅烧此组合物时,这种电容器的比电阻和使用寿命也不会因介电陶瓷组合物的还原而降低或缩短,而且电容也不随温度变化而剧烈变化。本发明的非还原性介电陶瓷组合物含有86.32~97.64mol BaTiO3,0.01~10.00molY2O3,0.01~10.00mol MgO,和0.001~0.200molV2O5。其中也可以加入含0.01~1.0mol%MnO、Cr2O3和Co2O3中至少一种或多种物质的添加剂以及含0.5~10.0mol%{BaA,Ca(1-A)}SiO3(0≤A≤1)的添加剂。
Description
本发明涉及非还原性介电陶瓷组合物,具体说涉及多层陶瓷电容器中使用的、采用镍等贱金属作为内电极的非还原性介电陶瓷组合物。
随着各种电子装置的快速发展,存在一种日益按小型、轻量化设计生产这些装置的趋势。向小型、轻量化设计发展的这种趋势,在陶瓷集成化磁带录相机、手提电话机、书本型个人电脑和掌上型电脑等中使用的便携式电子装置中尤为明显。
向小型、轻量化电子产品发展的这种趋势中,这些装置中的元器件也越来越按小型和轻量化设计生产。安装这种电子元件的手段,也由在传统的印刷电路板上的过孔中***并焊接要使用的管脚(即电子器件)的方法,改成表面安装技术(SMT),即在印刷电路板的导电图案表面上安装和焊接电子元件的技术。
在这种SMT中使用的电子元件,一般叫作表面安装元件(SMD),其中不仅包括半导体元件,而且还包括电容器、电阻器、电感器、滤波器等等。其中电容器和电阻器等小元件叫作芯片元件,而最具有代表性的是多层陶瓷电容器。
图1是表示某种多层陶瓷电容器的结构的部分剖视图。
此多层陶瓷电容器1为长方体,端电极3和4安装在长方体多层陶瓷电容器体1的二个相对的表面上。
在此多层陶瓷电容器主单元2中,于层压的BaTiO3介电层9、10和11内形成四个内电极5、6、7和8,而且介电材料制的介电层12和13被层叠在内电极的上表面和内电极8的下表面上。
内电极5、6、7和8间隔地被连到端电极上。也就是说,内电极6和8被连到端电极4上,而内电极5和7被连到另一个端电极3上。结果,形成一个在内电极5和6之间,内电极6和7之间,以及内电极7和8之间呈平行状态连接的电容器。
端电极3和4各包括一层导电层,含有玻璃料的导电糊涂或印于其上并经烘烤,以及镀于其上的一层金属覆盖层或压配于其上的一个金属帽。
为了制造多层陶瓷电容器,在介电陶瓷组合物片上印上用作内电极的电极糊,多片这种片经层叠和热压,在空气中烧结如此制成的叠层制品,并在其上安装端电极。
按此制造方法,用作电容器内电极的电极糊和介电陶瓷组合物被同时煅烧。因此,用作内电极的材料必须具有这样一种性质,即在介电陶瓷组合物的烧结温度下形成电极,而且在空气中加热时无氧化作用或者与介电陶瓷组合物不反应。
作为满足上述要求的材料,过去一直使用铂、钯等贵金属。但是,这些贵金属极昂贵而且成为这种多层陶瓷电容器的高成本的主要原因。
为此,人们一直试图使用镍之类的贱金属作为内电极、然而在氧化气氛下煅烧时镍被氧化而且与介电陶瓷组合物反应,因此干扰电极的形成。
在非氧化性气氛中煅烧镍以阻止其氧化的方法披露在美国专利4,241,378号的说明书中,然而此方法中介电陶瓷组合物被还原,比电阻急剧降低,因而不适于作为电容器实际使用。
在特开昭62-2408中,公开了一种含有CaZrO2和MnO2等的BaTiO3介电陶瓷组合物,它作为介电陶瓷组合物具有符合要求的介电性质,如介电常数(相对介电常数)等;但是这种介电陶瓷组合物在非氧化性气氛中煅烧时还原,而且使用寿命较短。
该多层陶瓷电容器按下列步骤制造:
(1)原料称量后混合,使煅烧后的组成与预定的混合比一致;
(2)进行湿法混合和粉碎;
(3)脱水和干燥;
(4)加入适量有机粘合剂,混合后使之变成珐琅态;
(5)用刮刀法将其涂于薄片上,形成介电陶瓷组合物片;
(6)在这样制出的介电陶瓷组合物片上,印制用作内电极材料的镍糊;
(7)层叠并热压此品得到多层品;
(8)将此多层品切成预定形状;
(9)除去粘合剂;
(10)在控制氧气分压下煅烧此品;
(11)在中性气氛下进行再氧化;
(12)安装端电极。
在特开平3-18261中公开了一种含有{BaA,Ca(1-A)}SiO3(其中0≤A≤1)(以下叫作“BCG”)作为BaTiO3、MinO2和Y2O3的添加剂的介电陶瓷组合物,这种非还原性介电陶瓷组合物具有较长的使用寿命。但是,用这种介电陶瓷组合物生产的多层陶瓷电容器,电容随温度变化而变化。
除上述之外,非还原性介电陶瓷组合物还记载在特开昭61-248304、特开昭57-71866、美国专利4,115,493和由Y.SAKABE,T.TAKAGI和K.WAKINO于“Proceedings of the ElectronicsDivision Fall Meeting”(美国陶瓷会,1985年10月13-16)中刊载的“贱金属多层陶瓷电容器用介电材料”一文之中。
本发明的目的在于提供一种适于生产多层陶瓷电容器用的非还原性介电陶瓷组合物,其中即使使用镍作内电极,在中性或还原性气氛中煅烧以阻止氧化时,均不存在因所说介电陶瓷组合物的还原而产生比电阻降低和使用寿命缩短的现象,而且电容也不随温度变化而大幅度变化。
为了达到上述目的,所说的非还原性介电陶瓷组合物含有86.32~97.64摩尔BaTiO3,0.01~10.00摩尔Y2O3,0.01~10.00摩尔MgO以及0.001~0.200摩尔V2O5。
图1表明一种多层陶瓷电容器的结构,图2是说明所说非还原性介电陶瓷组合物的加工过程的流程图。
以下,结合具体实施方案对本发明的特点进行说明。
图2中示出一种说明本发明的非还原性介电陶瓷组合物的加工过程的流程图。
(1)将BaTiO3、Y2O3、MgO、V2O5、MnO、Cr2O3、Co2O3等称量后混合成煅烧后组成如表1和表2中所示的组合物。
表1
No. | 组成 (mol%) | 煅烧温度T2(℃) | |||||||||
BaTiO3 | Y2O3 | MgO | V2O5 | BCGr | XMnO | YCr2O3 | ZCo2O3 | X·Y·Z总量 | |||
A | 量 | ||||||||||
1 | 97.69 | 0 | 0.02 | 0.001 | 0.58 | 1.95 | 0.05 | 0.29 | -- | 0.34 | 1400 |
2 | 97.54 | 0.20 | 0.02 | 0 | 0.58 | 1.95 | -- | 0.29 | -- | 0.29 | 1380 |
3 | 96.88 | 0.58 | 0.02 | 0 | 0.58 | 1.94 | 0.29 | 0.29 | -- | 0.58 | 1380 |
4 | 97.04 | 0.58 | 0 | 0.005 | 0.58 | 1.94 | 0.15 | 0.29 | -- | 0.44 | 1380 |
5 | 96.25 | 0.58 | 0.96 | 0.005 | 0.58 | 1.92 | 0.29 | -- | -- | 0.29 | 1340 |
6 | 96.89 | 0.58 | 0.01 | 0.30 | 0.58 | 1.94 | 0.29 | 0.29 | -- | 0.58 | 1340 |
7 | 96.61 | 0.58 | 0.01 | 1.00 | 0.58 | 1.93 | 0.29 | 0.58 | -- | 0.87 | 1340 |
8 | 96.39 | 0.58 | 0.96 | 0.005 | 0.58 | 1.93 | 0.14 | -- | -- | 0.14 | 1300 |
9 | 92.68 | 0.58 | 4.63 | 0.002 | 0.58 | 1.85 | 0.28 | -- | -- | 0.28 | 1300 |
10 | 95.86 | 0.01 | 1.92 | 0.005 | 0.58 | 1.92 | 0.29 | -- | -- | 0.29 | 1380 |
11 | 87.43 | 0.53 | 10.00 | 0.001 | 0.58 | 1.77 | 0.27 | -- | -- | 0.27 | 1300 |
12 | 85.95 | 0.53 | 11.50 | 0 | 0.58 | 1.76 | 0.26 | -- | -- | 0.26 | 1300 |
13 | 96.48 | 0.58 | 0.96 | 0.005 | 0.58 | 1.93 | 0.05 | -- | -- | 0.05 | 1340 |
14 | 96.67 | 0.29 | 0.97 | 0.005 | 0.58 | 1.93 | 0.14 | -- | -- | 0.14 | 1340 |
15 | 97.28 | 0.58 | 0 | 0.001 | 0.58 | 1.95 | -- | 0.19 | -- | 0.19 | 1320 |
16 | 97.45 | 0.58 | 0.02 | 0 | 0.58 | 1.95 | -- | -- | -- | 0 | 1320 |
17 | 96.51 | 0.58 | 0.97 | 0.005 | 0.58 | 1.93 | 0.01 | -- | -- | 0.01 | 1320 |
18 | 95.47 | 0.57 | 1.91 | 0.002 | 0.58 | 1.91 | 0.14 | -- | -- | 0.14 | 1340 |
19 | 92.80 | 0.56 | 4.64 | 0.002 | 0.58 | 1.86 | 0.14 | -- | -- | 0.14 | 1340 |
20 | 95.47 | 0.57 | 1.91 | 0.050 | 0.58 | 1.91 | 0.14 | -- | -- | 0.14 | 1340 |
21 | 95.42 | 0.57 | 1.91 | 0.001 | 0.58 | 1.91 | -- | 0.19 | -- | 0.19 | 1380 |
22 | 97.24 | 0.58 | 0.05 | 0.050 | 0.58 | 1.94 | -- | 0.19 | -- | 0.19 | 1380 |
23 | 95.42 | 0.57 | 1.91 | 0.030 | 0.58 | 1.91 | -- | 0.19 | -- | 0.19 | 1360 |
表2
No. | 组成 (mol%) | 煅烧温度T2(℃) | |||||||||
BaTiO3 | Y2O3 | MgO | V2O5 | BCGr | XMnO | YCr2O3 | ZCo2O3 | X·Y·Z总量 | |||
A | 量 | ||||||||||
24 | 95.42 | 0.57 | 1.91 | 0.003 | 0.58 | 1.91 | -- | 0.19 | -- | 0.19 | 1360 |
25 | 95.42 | 0.57 | 1.91 | 0.010 | 0.58 | 1.91 | -- | 0.19 | -- | 0.19 | 1360 |
26 | 95.48 | 0.57 | 1.91 | 0.240 | 0.58 | 1.90 | 0.14 | -- | -- | 0.14 | 1360 |
27 | 96.53 | 0.39 | 0.96 | 0.190 | 0.58 | 1.93 | -- | 0.19 | -- | 0.19 | 1360 |
28 | 97.26 | 0.58 | 0.01 | 0.002 | 0.58 | 1.95 | -- | 0.20 | -- | 0.20 | 1320 |
29 | 95.05 | 0.95 | 0.90 | 0.002 | 0.58 | 1.91 | -- | 0.19 | -- | 0.19 | 1360 |
30 | 91.58 | 4.58 | 1.83 | 0.002 | 0.58 | 1.83 | -- | 0.18 | -- | 0.18 | 1340 |
31 | 86.32 | 10.00 | 1.75 | 0.005 | 0.58 | 1.75 | -- | 0.18 | -- | 0.18 | 1340 |
32 | 85.39 | 11.00 | 1.72 | 0.001 | 0.58 | 1.72 | -- | 0.17 | -- | 0.17 | 1340 |
33 | 98.14 | 0.59 | 0.98 | 0.001 | 0.58 | 0 | 0.29 | -- | -- | 0.29 | 1380 |
34 | 97.64 | 0.59 | 0.98 | 0.001 | 0.58 | 0.50 | 0.29 | -- | -- | 0.29 | 1320 |
35 | 93.54 | 0.56 | 0.94 | 0.001 | 0.58 | 4.68 | 0.28 | -- | -- | 0.28 | 1340 |
36 | 88.30 | 0.54 | 0.89 | 0.001 | 0.58 | 10.00 | 0.27 | -- | -- | 0.27 | 1300 |
37 | 85.79 | 0.53 | 0.88 | 0.001 | 0.58 | 12.54 | 0.26 | -- | -- | 0.26 | 1300 |
38 | 96.40 | 0.58 | 0.10 | 0.001 | 0.58 | 1.93 | 0.31 | 0.68 | -- | 1.00 | 1360 |
39 | 92.51 | 0.74 | 0.09 | 0.001 | 0.58 | 5.55 | 0.65 | 0.46 | -- | 1.11 | 1360 |
40 | 96.11 | 0.58 | 0.96 | 0.001 | 0.58 | 1.92 | -- | 0.29 | 0.14 | 0.43 | 1360 |
41 | 96.11 | 0.58 | 0.96 | 0.001 | 0.58 | 1.92 | 0.14 | -- | 0.29 | 0.43 | 1320 |
42 | 97.19 | 0.58 | 0.05 | 0.001 | 0.58 | 1.94 | 0.05 | -- | 0.19 | 0.24 | 1360 |
43 | 91.85 | 4.58 | 1.83 | 0.002 | 1.0 | 1.83 | -- | 0.18 | -- | -- | 1390 |
44 | 91.58 | 4.58 | 1.83 | 0.002 | 0.7 | 1.83 | -- | 0.18 | -- | -- | 1360 |
45 | 91.58 | 4.58 | 1.83 | 0.002 | 0.3 | 1.83 | -- | 0.18 | -- | -- | 1340 |
46 | 91.58 | 4.58 | 1.83 | 0.002 | 0 | 1.83 | -- | 0.18 | -- | -- | 1340 |
作为起始原料,使用这样一种BaTiO3,它是按摩尔比1∶1混合BaO和TiO2后于900~1200℃下进行化学反应得到的。作为这种BaTiO3,可以使用用溶液法制备的粉末(50%颗粒的粒度为0.8~1.2μ),或者是由经超雾粉碎机粉碎成粒度约为1μm的BaCO3和TiO2得到的BaTiO3。
(2)湿法混合及粉碎;
(3)脱水和干燥;
(4)加入适量有机粘合剂,混合,使之变成珐琅态;
(5)用刮刀法将这样制出的材料涂在薄片上形成20μm厚度的膜,制成介电陶瓷组合物片;
(6)将作为内电极材料使用的镍糊,印在该介电陶瓷组合物片上;
(7)将此品叠成五层热压,制造多层品;
(8)将这样制成的多层品切成3216形状,即尺寸为3.2mm(长)×1.6mm;
(9)在250~300℃稳定化,进行除粘合剂处理10小时;
(10)控制氧分压为7×10-9~9×10-13大气压,并在T2=1200~1300℃煅烧温度下稳定化,煅烧2小时;
(11)在中性气氛中在700~1200℃下稳定化,进行9小时再氧化处理;
(12)在其中安装铟-镓(In-Ga)合金端电极。
这样制出的电容器,每层的电容为20pF,总电容100pF。
对于按上述制成的电容器样品测定了诸电学性质,如介电常数(εs)、介电损耗tgδ、绝缘电阻IR(Ω)、电容的温度特性T·C(%)以及使用寿命μ(小时)。结果列于表3和表4之中。
表3
No. | εs | tanδ | IR(Ω) | T·C(%) | μ(小时) | |||
-55℃ | -25℃ | 85℃ | 125℃ | |||||
1 | 难烧结 | |||||||
2 | 3390 | 2.6 | 5×1010 | -13.2 | -8.0 | -8.5 | -1.0 | 3 |
3 | 3800 | 2.2 | 8×1010 | -5.0 | -4.0 | 0 | 6.0 | 4 |
4 | 3920 | 2.8 | 2×1010 | -16.8 | -12.7 | -7.0 | -1.3 | 9 |
5 | 3600 | 1.9 | 5×1011 | -13.2 | -7.8 | -5.4 | 2.0 | 100 |
6 | 2100 | 2.3 | 5×109 | -12.0 | -7.5 | -5.4 | -3.1 | 7 |
7 | 1400 | 5.4 | 8×107 | -10.9 | -6.0 | -1.0 | 2.8 | 3 |
8 | 3100 | 2.0 | 2×1011 | -14.2 | -9.0 | -4.0 | -1.0 | 90 |
9 | 2900 | 1.8 | 3×1011 | -8.0 | -5.3 | -8.5 | -4.0 | 34 |
10 | 3250 | 1.8 | 3×1011 | -8.4 | -5.8 | -6.4 | -1.7 | 31 |
11 | 2560 | 1.6 | 1×1011 | -7.6 | -5.3 | -9.6 | -8.7 | 37 |
12 | 1810 | 1.4 | 1×1011 | -8.9 | -5.3 | -11.4 | -13.4 | 0 |
13 | 2820 | 2.2 | 2×1011 | -15.0 | -9.8 | -1.1 | 2.0 | 36 |
14 | 3180 | 2.6 | 2×1011 | -14.8 | -8.7 | 3.7 | 0 | 29 |
15 | 3790 | 5.9 | 2×1011 | -17.8 | -11.9 | -1.0 | 2.0 | 45 |
16 | 变成半导体状态 | |||||||
17 | 3000 | 1.8 | 2×1010 | -14.8 | -9.8 | 0 | 12.5 | 39 |
18 | 3180 | 1.8 | 3×1011 | -8.6 | -6.2 | -5.1 | 1.0 | 60 |
19 | 3050 | 2.2 | 1×1011 | -10.2 | -6.1 | -7.8 | -3.7 | 48 |
20 | 2480 | 1.5 | 2×1011 | -11.7 | -8.4 | -4.4 | 4.6 | 200 |
21 | 3210 | 2.0 | 2×1011 | -7.4 | -5.1 | -6.3 | 0 | 25 |
22 | 2800 | 2.2 | 3×1010 | -8.3 | -6.1 | -6.4 | 1.0 | 150 |
23 | 3000 | 2.2 | 1×1011 | -5.7 | -3.3 | -7.8 | -3.8 | 110 |
表4
No. | εs | tan δ | IR(Ω) | T·C(%) | μ(小时) | |||
-55℃ | -25℃ | 85℃ | 125℃ | |||||
24 | 3180 | 2.1 | 2×1011 | -8.5 | -5.0 | -5.0 | 4.0 | 52 |
25 | 3260 | 2.1 | 1×1011 | -7.9 | -5.5 | -6.2 | 2.0 | 100 |
26 | 2480 | 1.8 | 8×109 | -10.6 | -7.9 | -6.1 | 0 | 6 |
27 | 3100 | 1.9 | 3×1010 | -8.5 | -6.2 | -7.5 | -3.2 | 200 |
28 | 3010 | 3.0 | 2×1011 | -15.0 | -9.8 | -2.4 | -3.4 | 33 |
29 | 3150 | 2.0 | 3×1011 | -8.5 | -5.9 | -6.3 | -2.0 | 28 |
30 | 2950 | 1.9 | 2×1011 | -10.5 | -8.7 | -4.4 | -5.0 | 25 |
31 | 2650 | 1.6 | 3×1011 | -7.5 | -5.4 | -3.8 | -9.0 | 46 |
32 | 变成半导体状态 | |||||||
33 | 4330 | 5.2 | 1×1011 | -35.2 | -20.0 | -11.3 | -18.5 | 8 |
34 | 3210 | 1.7 | 3×1011 | -15.0 | -10.0 | 0 | 7.5 | 28 |
35 | 2880 | 1.9 | 1×1011 | -13.0 | -6.1 | -6.5 | -4.0 | 40 |
36 | 2610 | 1.6 | 2×1011 | -8.9 | -7.0 | -6.0 | -5.5 | 38 |
37 | 1910 | 1.4 | 3×1011 | -5.0 | -4.0 | -3.0 | -5.0 | 9 |
38 | 2680 | 1.2 | 2×1010 | -6.9 | -3.5 | -2.5 | -4.8 | 85 |
39 | 1380 | 1.0 | 4×109 | -4.6 | -2.6 | -8.0 | -9.0 | 7 |
40 | 3080 | 1.9 | 1×1011 | -13.8 | -10.0 | -9.0 | -8.5 | 35 |
41 | 2980 | 2.0 | 7×1010 | -11.8 | -7.4 | -4.6 | -1.9 | 36 |
42 | 3850 | 3.0 | 4×1010 | -14.9 | -8.9 | -7.8 | -4.0 | 40 |
43 | 3160 | 2.2 | 2×1011 | -11.5 | -9.0 | -2.0 | -7.0 | 35 |
44 | 3120 | 2.0 | 1×1011 | -10.6 | -8.4 | -4.9 | -5.0 | 30 |
45 | 3000 | 2.0 | 3×1011 | -14.5 | -10.0 | -7.0 | -8.5 | 25 |
46 | 2850 | 1.4 | 3×1011 | -14.9 | -9.8 | -5.0 | -9.8 | 26 |
表中介电常数εs和介电损耗tgδ诸数值是在20℃和1KHz频率下的数值,绝缘电阻IR是在加了50伏电压30秒后在20℃下测定的,电容的温度特性T·C是指电容在各温度下相对于电容在20℃的温度特性,而使用寿命μ是在200℃下加200伏电压时的加速使用寿命。
评价上述测量结果时,符合要求的数值是指介电常数εs为2500或更高,介电损耗tgδ为3.0或更低,绝缘电阻IR为1010Ω或更高,电容的温度特性T·C处于±15%范围内,使用寿命μ为10小时或更高。若所说数值不符合这些标准,则产品视为有缺陷。
难于烧结或变成半导体状态的产品,视为有缺陷产品,因为这种产品不适于作电容器使用。
按上述标准评价的结果,第5、8、9、10、11、13、14、17、18、19、21、22、23、24、25、27、28、29、30、31、34、35、36、38、40、41、42、43、44、45和46号样品被判定为符合要求,而第1、2、3、4、6、7、12、15、16、20、26、32、33、37和39号样品被判定为有缺陷。
根据上面的判定结果,组成范围定义如下:
如果Y2O3低于0.01mol%(样品1),则即使煅烧温度(T2)为1400℃也难于烧结,不适于实际使用。如果它高于10.0mol%(样品32),则组合物还原变成半导体状态,因而不适于作为介电物质使用。
因此,为了获得满意的结果,Y2O3必须处于0.01~10.0mol%的范围内。
如果MgO含量低于0.01mol%(样品4和15),则电容的温度特性T·C增大到超过±15%,而且介电损耗tgδ可以高达5.9。如果它超过10.0mol%(样品12),则加速使用寿命急剧降低。
因此,为了获得满意的结果,MgO必须处于0.01~10.0mol%的范围内。
V2O3加入量高于0.001mol%(除2、3、12和16号之外的全部样品),加速使用寿命得到显著改善。如果其加入量高于0.20mol%(样品6、7和26),则介电常数εs为2500或更低而且绝缘电阻为1×1010Ω或更低,因而此产品不适于实际使用。
因此,为了获得满意结果,V2O3必须处于0.001~0.20mlo%的范围内。
如果{BaA,Ca(1-A)}SiO3(其中0≤A≤1)作为添加剂BCG的加入量低于0.5mol%(样品33),则电容的温度特性超过±15%:若其超过10mol%(样品37),则εs为2500或更低。
因此,为了获得满意结果,添加剂BCG必须处于0.5~10mol%的范围内。
若MnO·Cr2O3·Co2O3的总量低于0.01mol%(样品16),则组合物变成半导体状态。若它超过1.0mol%(样品39),则绝缘电阻为1×1010Ω或更低。
因此,为了获得满意的结果,MnO·Cr2O3·Co2O3的总量必须处于0.01~1.0mol%的范围内。
利用处于上述组成范围内的本发明的非还原性介电陶瓷组合物,可以得到多层陶瓷电容器,在这种电容器中即使用镍作内电极在中性或还原性气氛中煅烧以阻止氧化时,其比电阻和使用寿命也不会因介电陶瓷组合物的还原而降低或缩短,而且电容也不随温度变化而急剧变化。
Claims (3)
1、一种非还原性介电陶瓷组合物,其中含有:
86.32~97.64molBaTiO3,
0.01~10.00molY2O3,
0.01~10.00molMgO,和
0.001~0.200molV2O5。
2、权利要求1的非还原性介电陶瓷组合物,其中含有0.01~1.0mol%MnO、Cr2O3和Co2O3中的至少一种或多种物质作为添加剂。
3、权利要求1或2的非还原性介电陶瓷组合物,其中含有0.5~10.0mol%{BaA,Ca(1-A)}SiO3(其中0≤A≤1)作为添加剂。
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JP5008304A JP2764513B2 (ja) | 1993-01-21 | 1993-01-21 | 耐還元性誘電体磁器組成物 |
JP008304/93 | 1993-01-21 |
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CN1092198A CN1092198A (zh) | 1994-09-14 |
CN1031338C true CN1031338C (zh) | 1996-03-20 |
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US (1) | US5403797A (zh) |
EP (1) | EP0615262B1 (zh) |
JP (1) | JP2764513B2 (zh) |
KR (1) | KR100190244B1 (zh) |
CN (1) | CN1031338C (zh) |
CA (1) | CA2113060C (zh) |
DE (1) | DE69400932T2 (zh) |
MY (1) | MY110393A (zh) |
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-
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- 1993-01-21 JP JP5008304A patent/JP2764513B2/ja not_active Expired - Lifetime
- 1993-12-30 KR KR1019930031440A patent/KR100190244B1/ko not_active IP Right Cessation
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100440392C (zh) * | 2000-02-09 | 2008-12-03 | Tdk株式会社 | 具有介电层的电子器件及其生产方法 |
CN100400463C (zh) * | 2000-12-25 | 2008-07-09 | Tdk株式会社 | 介电陶瓷组合物和电子装置 |
Also Published As
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EP0615262A3 (en) | 1994-09-21 |
CA2113060C (en) | 2000-10-24 |
KR100190244B1 (ko) | 1999-06-01 |
TW258724B (zh) | 1995-10-01 |
US5403797A (en) | 1995-04-04 |
CN1092198A (zh) | 1994-09-14 |
CA2113060A1 (en) | 1994-07-22 |
DE69400932T2 (de) | 1997-03-13 |
KR940018337A (ko) | 1994-08-16 |
MY110393A (en) | 1998-04-30 |
JPH06215979A (ja) | 1994-08-05 |
EP0615262B1 (en) | 1996-11-20 |
JP2764513B2 (ja) | 1998-06-11 |
EP0615262A2 (en) | 1994-09-14 |
DE69400932D1 (de) | 1997-01-02 |
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