CN1244720A - 抗还原的介电陶瓷组合物和含该组合物的单块陶瓷电容器 - Google Patents
抗还原的介电陶瓷组合物和含该组合物的单块陶瓷电容器 Download PDFInfo
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Abstract
一种介电常数为100或更高并在高温负载下的寿命试验中有优良可靠性的改进的抗还原介电陶瓷组合物,和一种用该组合物形成的单块陶瓷电容器。该组合物包括含金属元素M(M:Ca,或Ca和Sr)、Zr和Ti的复合氧化物,以式(Ca1-xSrx)m(Zr1-yTiy)O3表示时,x、y和m满足0≤x< 0.5,0.60< Y≤0.85,0.85< m< 1.30,该氧化物构成主要组分,每100摩尔主要组分与辅助组分锰化合物和镁化合物中的至少一种混合在一起,以MnO和MgO计该辅助组分含量为0.1—6摩尔。所述组合物还含有烧结助剂,如SiO2。
Description
本发明涉及抗还原的介电陶瓷组合物和使用该介电陶瓷组合物的单块陶瓷电容器。
当使用主要含钛酸盐的介电材料形成单块陶瓷电容器时,遇到的问题是这种介电材料是在低氧分压(中性或还原性气氛)条件下烧结的,介电材料会不合需求地还原,并因此不合需求地变成半导体。由于这些问题,为了形成内电极,需要使用即使在烧结介电陶瓷材料的烧结温度下也不会熔融,并且不会使介电陶瓷材料转化成半导体以及其本身在高氧分压下不会氧化的贵金属(如钯和铂)。结果,难以低成本地制得单块陶瓷电容器。
因此,为了解决上述问题,通常需要使用价格低廉的贱金属(如镍和铜)作为内电极材料。但是,当将这种贱金属用作内电极材料并在常规条件下烧结时,所述电极材料被氧化。结果,不能获得所需的电极功能。出于这个原因,为了将这种贱金属用作内电极材料,需要使用具有优良介电性能的介电材料,即使在具有低氧分压的中性或还原性条件下这种介电材料的陶瓷层也具有抗拒成为半导体的能力。为了满足这个要求,日本公开专利申请No 63-289707和63-224106提出一种改进的介电材料,它是(Ca1-xSrx)(Zr1-yTiy)O3的组合物。通过使用这种改进的介电材料,可获得即使在还原性气氛中烧结也不会转变成半导体的介电陶瓷,从而可以使用贱金属材料(如镍或铜)形成内电极来制造单块陶瓷电容器。
然而,对于上述日本公开专利No 63-289707所述的抗还原介电陶瓷组合物,尽管其具有优良的电容量和温度特性,但是其介电常数低至46。另一方面,对于所述日本公开专利No 63-224106所述的抗还原介电陶瓷组合物,如果将叠层陶瓷体的厚度制得非常薄以便获得小体积大容量的单块陶瓷电容器,则在高温负载时在寿命测量试验中难以确保所需的可靠性。
本发明提供一种改进的抗还原介电陶瓷组合物,它的介电常数为100或更高,并在高温负载下在寿命试验中具有优良的可靠性;本发明还提供一种用所述改进的抗还原介电陶瓷组合物形成的单块陶瓷电容器。
本发明一个方面是提供一种抗还原介电陶瓷组合物,它包括含金属元素M(M:Ca,或Ca和Sr)、Zr和Ti的复合氧化物,当以组成式(C a 1-xSrx)m(Zr1-yTiy)O3表示时,x、y和m满足关系0≤x<0.5,0.60<y≤0.85,0.85<m<1.30,以构成主要组分,每100摩尔主要组分与作为辅助组分的锰化合物和镁化合物中的至少一种混合在一起,以MnO和MgO计所述辅助组分的量分别为0.1-6摩尔。
所述组合物还可含有烧结助剂。
所述烧结助剂较好含有Si和B中的至少一种。
另外,烧结助剂可以是SiO2。
此外,烧结助剂可以是Li2O-(Si,Ti)O2-MO系列物料(其中MO是Al2O3和ZrO2中的至少一种)。
另外,烧结助剂可以是SiO2-TiO2-XO系列物料(其中XO选自BaO、SrO、CaO、MgO、ZnO和MnO中的至少一种)。较好的是,烧结助剂选自Al2O3和ZrO2中的至少一种。
另外,烧结助剂可以是Li2O-B2O3-(Si,Ti)O2系列物料。较好的是,烧结助剂含有至少一种选自Al2O3和ZrO2的物料。
烧结助剂还可以是B2O3-Al2O3-XO系列物料(其中XO是至少一种选自BaO、SrO、CaO、MgO、ZnO和MnO的物料)。
每100重量份主要组分和辅助组分总量中,烧结助剂的含量可为20重量份或更少。
本发明单块陶瓷电容器包括多层介电陶瓷层、在介电陶瓷层之间的内电极和与所述内电极电气相连的外电极,其特征在于所述介电陶瓷层是由上述介电陶瓷组合物制得的,各个内电极含贱金属作为其主要组分。
上述贱金属较好是镍和铜。
图1是本发明单块陶瓷电容器的剖面图;
图2是本发明陶瓷坯料片的平面图;
下面通过实施例描述本发明较好的实施方式。
实施例1
先制得纯度为99%或更高的SrCO3、CaCO3、ZrO2、TiO2、MnCO3和MgCO3粉作为原料。
将SrCO3、CaCO3、ZrO2、TiO2粉末称重并混合,得到以通式(Ca1-xSrx)m(Zr1-yTiy)O3表示的主要组分的原料,通式中x、y和m列于表1。另外,将MnCO3和MgCO3称重并与上述SrCO3、CaCO3、ZrO2、TiO2混合物混合在一起制得原料,MnCO3和MgCO3作为辅助组分的原料,相对于100摩尔主要组分,该辅助组分含w摩尔MnO和z摩尔MgO(见表1)。接着将原料置于球磨机中进行湿磨,随后在空气中以1000-1200℃的温度煅烧2小时,从而获得煅烧的粉末。在下表1中用记号“*”表示超出本发明范围的试样,无标记“*”的试样是本发明范围内的试样。
表1
试样 | x | y | m | w | z |
*1 | 0.50 | 0.70 | 1.00 | 3.0 | 1.0 |
*2 | 0.20 | 0.60 | 0.90 | 1.0 | 0 |
*3 | 0.30 | 0.90 | 1.20 | 2.0 | 2.0 |
*4 | 0.15 | 0.65 | 0.85 | 0 | 1.0 |
*5 | 0.40 | 0.85 | 1.30 | 0.5 | 1.5 |
*6 | 0.20 | 0.70 | 1.10 | 0 | 0 |
*7 | 0 | 0.65 | 1.00 | 7.0 | 0 |
*8 | 0.10 | 0.80 | 0.95 | 0 | 7.0 |
*9 | 0.30 | 0.75 | 1.25 | 3.0 | 4.0 |
10 | 0 | 0.85 | 0.90 | 0.0 | 0.1 |
11 | 0.45 | 0.65 | 1.20 | 4.0 | 1.0 |
12 | 0.20 | 0.70 | 0.90 | 0 | 6.0 |
13 | 0.15 | 0.80 | 1.25 | 3.0 | 3.0 |
14 | 0 | 0.75 | 1.10 | 0.1 | 0 |
15 | 0.35 | 0.80 | 1.00 | 6.0 | 0 |
*表示超出了本发明的范围
随后向该煅烧粉末中加入有机溶剂(如聚乙烯醇缩丁醛(polyvinylbutyl)基粘合剂)和乙醇,并在球磨机中充分湿磨,从而获得陶瓷糊浆。接着,使用刮刀涂覆法将该陶瓷糊浆制成多片片材,从而获得多片坯料片材2b,各个片材为矩形并且厚度为10微米。随后,将主要含镍的导电膏4印涂在陶瓷坯料片上,从而制得用作内电极的导电膏层。
另外,将上面形成有导电膏层的陶瓷坯料层叠合在一起,叠合时在所述坯料层的边缘部分导电膏层被引出的侧面交错地排列,从而获得所需的叠合物。接着在氮气氛中将获得的叠合物加热至350℃的温度以分解粘合剂,随后在由H2-N2-H2O气体组成的还原性气氛中进行烧制,获得烧结的陶瓷物。
烧制后,将银膏5施涂在制得的陶瓷烧结物相反的两个端面上,接着在600℃在N2中进行焙烧处理,从而形成与内电极电气相连的外电极。随后在外电极上形成镀镍薄膜6,最后在所述镀镍薄膜上形成镀焊剂薄膜7。
单块陶瓷电容器1的宽度为1.6mm,长度为3.2mm,厚度为1.2mm,介电陶瓷层2a的厚度为6微米。另外,单块陶瓷电容器1总共具有150片有效介电陶瓷层。
随后,测量单块陶瓷电容器1的电学性能,从而获得在1kHz、1Vrms和25℃条件下的静电电容量和介电损失(tanδ),从而由静电电容率计算出介电常数(ε)。接着,在25℃的温度下向该电容器持续施加25V直流电压2分钟,从而测定绝缘电阻,并计算出电阻率。
另外,在1kHz和1Vrms的条件下,测得静电电容随温度变化而改变的情况,并根据下列公式得到其变化率:
TC(ppm/℃)={(ε85℃-ε20℃)/ε20℃}×{1/(85℃-20℃)}×106
另外,在高温负载下的寿命试验中,使用各含36片的试样,并在150℃向这些试样施加150V直流电压,测定绝缘电阻随时间的变化情况。另一方面,在这种试验中,将各试样绝缘电阻达到106Ω或更低所需的时间视为电容器的寿命,从而得到平均寿命。
评价结果列于表2。
表2
试样 | 烧结温度(℃) | 介电常数 | 介电损失(%) | TC(ppm/℃) | 电阻率(Ω·cm) | 平均寿命(小时) |
*1 | 1300 | 180 | 0.05 | -1200 | >1013 | 20 |
*2 | 1350 | 70 | 0.06 | -800 | >1013 | 120 |
*3 | 1270 | 140 | 0.07 | -1000 | >1013 | 10 |
*4 | 1250 | 110 | 1.00 | -750 | >1013 | 5 |
*5 | 1350 | 未烧结 | ||||
*6 | 1350 | 未烧结 | ||||
*7 | 1300 | 150 | 0.03 | -2000 | >1013 | 50 |
*8 | 1350 | 120 | 0.09 | -1500 | >1013 | 80 |
*9 | 1270 | 105 | 0.07 | -1800 | >1013 | 70 |
10 | 1300 | 110 | 0.05 | -800 | >1013 | 150 |
11 | 1270 | 140 | 0.10 | -1000 | >1013 | 60 |
12 | 1270 | 100 | 0.08 | -850 | >1013 | 70 |
13 | 1320 | 110 | 0.06 | -950 | >1013 | 90 |
14 | 1300 | 120 | 0.05 | -750 | >1013 | 120 |
15 | 1270 | 100 | 0.07 | -800 | >1013 | 110 |
使用*表示超出本发明范围的试样
由表2可见,使用本发明抗还原介电陶瓷组合物获得的单块陶瓷电容器的介电常数为100或更高,介电损失为0.1%或更低,静电电容量随温度变化的变化率(TC)低至1000ppm/℃。此外,在高温负载下的寿命试验中,在150℃的温度下施加150V静电电压,发现平均寿命长达50小时或更长。
下面将说明将本发明组成限于上述数值的原因。
对于组合物通式(Ca1-xSrx)m(Zr1-yTiy)O3(0≤x<0.5,0.60<y≤0.85,0.85<m<1.30),如果如试样1那样x值为0.5或更高,静电电容量随温度的变化率(TC)将变大,因此平均寿命将缩短。出于该原因,较好将Sr的量控制在0≤x<0.5的范围内。
如果如试样2那样,y值为0.6或更低,其介电常数将下降。另一方面,如果如试样3那样y值大于0.85,则平均寿命将缩短,因此较好将Ti的量控制在0.60<y≤0.85的范围内。
另外,如果如试样4那样,m值为0.85或更低,则介电损失将变大,平均寿命将缩短。另一方面,如果如试样5那样m值为1.30或更高,则烧结性将变得很差。因此较好将m值控制在0.85<m<1.30的范围内。
如果如试样6那样,MnO和MgO中至少一种的含量低于0.1摩尔,则烧结性将变得很差。另一方面,如果如试样7-9那样,MnO和MgO中至少一种的含量高于6摩尔,则静电电容量随温度变化的变化率(TC)将变大。因此,相对于100摩尔上述主要组分,较好将作为辅助组分的锰化合物(换算成MnO)和镁化合物(换算成MgO)控制在0.1-6摩尔范围内。
实施例2
先制得纯度为99%或更高的SrCO3、CaCO3、ZrO2、TiO2、MnCO3和MgCO3粉作为原料。
定量称取上述原料粉末,形成可用式(Ca0.8Sr0.2)1.05(Zr0.3Ti0.7)O3表示的组合物。接着将原料粉置于球磨机中进行湿磨,随后在空气中以1000-1200℃的温度煅烧2小时,从而获得煅烧的粉末材料。另外,定量称取MnCO3和MgCO3原料并将其与上述主要组分混合,得到原料粉末,使得用作辅助组分的原料MnCO3和MgCO3,按100摩尔主要组分中MnO和MgO计,其含量为0.5摩尔MnO和1.0摩尔MgO。另外,将预定量的表3所示的烧结助剂与所述原料粉末混合。但是,烧结助剂的加入量(重量份)是按100重量份上述主要组分和辅助组分的总量计算的。
表3
试样 | 烧结助剂(摩尔比) | 加入量(重量份) |
21 | 0.35Li2O-0.50B2O3-0.15(0.90Si-0.10Ti)O2 | 25 |
22 | SiO2 | 5 |
23 | 0.25Li2O-0.65(O.30Si-0.70Ti)O2-0.10Al2O3 | 1 |
24 | 0.66SiO2-0.17TiO2-0.15BaO-0.02MnO | 0.1 |
25 | 0.45SiO2-0.22TiO2-0.28BaO-0.05Al2O3 | 10 |
26 | 0.35Li2O-0.50B2O3-0.15(0.90Si-0.10Ti)O2 | 3 |
27 | 0.35Li2O-0.15B2O3-0.45(0.30Si-0.70Ti)O2-0.05ZrO2 | 6 |
28 | 0.70B2O3-O.15Al2O3-0.10BaO-0.03ZnO-0.02MnO | 20 |
使用上述原料粉末制得单块陶瓷电容器,使用与实施例1相同的方法测得其电学性能,测量结果列于下表4。
表4
试样 | 烧结温度(℃) | 介电常数 | 介电损失(%) | TC(ppm/℃) | 电阻率(Ω·cm) | 平均寿命(小时) |
21 | 950 | 100 | 1.50 | -900 | >1013 | 20 |
22 | 1100 | 110 | 0.05 | -830 | >1013 | 80 |
23 | 1150 | 110 | 0.06 | -850 | >1013 | 90 |
24 | 1150 | 120 | 0.05 | -900 | >1013 | 60 |
25 | 1050 | 100 | 0.08 | -810 | >1013 | 55 |
26 | 1070 | 120 | 0.08 | -880 | >1013 | 100 |
27 | 980 | 110 | 0.07 | -780 | >1013 | 75 |
28 | 950 | 100 | 0.10 | -950 | >1013 | 50 |
由表4中试样22-28可见,使用本发明抗还原介电陶瓷组合物获得的单块陶瓷电容器的介电常数为100或更高,介电损失为0.1%或更低,静电电容量随温度变化的变化率(TC)低至1000ppm/℃或更低(绝对值)。此外,在高温负载下的寿命试验中,在150℃的温度下施加150V直流电压,发现平均寿命长达50小时或更长。另外,通过加入烧结助剂,可在1150℃或更低的温度下进行烧结处理。另一方面,如果烧结助剂的含量大于20重量份,如试样21那样介电损失将变大,其平均寿命将变短。因此,按100重量份主要组分和辅助组分计,较好将烧结助剂的含量控制在20重量份或更低。
由上面描述可清楚地看到,使用本发明介电陶瓷组合物形成的单块陶瓷电容器具有100或更高的介电常数,并在高温负载下的寿命测量试验中具有优良的可靠性。因此,本发明介电陶瓷组合物能作为电容器(condenser)材料用于温度补偿,能作为介电谐振器材料用于微波,使之具有高的工业使用价值。
Claims (13)
1.一种抗还原介电陶瓷组合物,它包括金属元素M、Zr和Ti,所述M为Ca,或Ca和Sr,当以通式(Ca1-xSrx)m(Zr1-yTiy)O3表示时,x、y和m满足关系
0≤x<0.5,
0.60<y≤0.85,
0.85<m<1.30,
以构成主要组分,每100摩尔主要组分与作为辅助组分的锰化合物和镁化合物中的至少一种混合在一起,分别以MnO和MgO计所述辅助组分的量为0.1-6摩尔。
2.如权利要求1所述的抗还原介电陶瓷组合物,其特征在于所述组合物还含有烧结助剂。
3.如权利要求2所述的抗还原介电陶瓷组合物,其特征在于所述烧结助剂含有Si和B中的至少一种。
4.如权利要求2所述的抗还原介电陶瓷组合物,其特征在于所述烧结助剂是SiO2。
5.如权利要求2所述的抗还原介电陶瓷组合物,其特征在于所述烧结助剂是Li2O-(Si,Ti)O2-MO系列的物料,其中MO是Al2O3和ZrO2中的至少一种。
6.如权利要求2所述的抗还原介电陶瓷组合物,其特征在于所述烧结助剂是SiO2-TiO2-XO系列的物料,其中XO是选自BaO、SrO、CaO、MgO、ZnO和MnO中的至少一种。
7.如权利要求6所述的抗还原介电陶瓷组合物,其特征在于所述烧结助剂是选自Al2O3和ZrO2中的至少一种。
8.如权利要求2所述的抗还原介电陶瓷组合物,其特征在于所述烧结助剂是Li2O-B2O3-(Si,Ti)O2系列的物料。
9.如权利要求8所述的抗还原介电陶瓷组合物,其特征在于所述烧结助剂含有至少一种选自Al2O3和ZrO2的物料。
10.如权利要求2所述的抗还原介电陶瓷组合物,其特征在于所述烧结助剂是B2O3-Al2O3-XO系列的物料,其中XO是至少一种选自BaO、SrO、CaO、MgO、ZnO和MnO的物料。
11.如权利要求2-10中任何一项所述的抗还原介电陶瓷组合物,其特征在于每100重量份主要组分和辅助组分总量中,所述烧结助剂的含量为20重量份或更少。
12.一种单块陶瓷电容器,它包括多层介电陶瓷层、在介电陶瓷层之间形成的内电极和与所述内电极电气相连的外电极,其特征在于所述介电陶瓷层是由权利要求1-11中任何一项所述的介电陶瓷组合物制得的,所述各个内电极含贱金属作为其主要组分。
13.如权利要求12所述的单块陶瓷电容器,其特征在于所述贱金属是镍或铜。
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JP22422398A JP3346293B2 (ja) | 1998-08-07 | 1998-08-07 | 非還元性誘電体磁器組成物およびそれを用いた積層セラミックコンデンサ |
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EP (1) | EP0978853B1 (zh) |
JP (1) | JP3346293B2 (zh) |
KR (1) | KR100324721B1 (zh) |
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KR100324721B1 (ko) | 2002-02-28 |
KR20000017138A (ko) | 2000-03-25 |
JP3346293B2 (ja) | 2002-11-18 |
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EP0978853B1 (en) | 2006-01-11 |
CN1144243C (zh) | 2004-03-31 |
JP2000053466A (ja) | 2000-02-22 |
EP0978853A1 (en) | 2000-02-09 |
DE69929378D1 (de) | 2006-04-06 |
DE69929378T2 (de) | 2006-07-27 |
US6233134B1 (en) | 2001-05-15 |
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