CN101663253B - 超低温烧成的x7r和bx介电陶瓷组合物及制备方法 - Google Patents
超低温烧成的x7r和bx介电陶瓷组合物及制备方法 Download PDFInfo
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- CN101663253B CN101663253B CN200780052848.7A CN200780052848A CN101663253B CN 101663253 B CN101663253 B CN 101663253B CN 200780052848 A CN200780052848 A CN 200780052848A CN 101663253 B CN101663253 B CN 101663253B
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Classifications
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Abstract
根据本发明制备多层陶瓷片式电容器,该电容器满足X7R和BX要求,并且与银-钯内电极兼容。该电容器表现出所想要的介电性能(高电容、低损耗因子、高绝缘电阻)、高加速寿命测试时的优异性能、以及非常优良的抗介电击穿性能。介电层包含无铅无镉的钛酸钡基材料,其掺杂有其它的金属氧化物如锌、硼、铋、铈、钨、铜、锰、钕、铌、银、钡、硅和镍的氧化物,它们可以进行各种组合。在不超过1000℃下,可以将本发明的介电陶瓷材料与包含大于80重量%的银和小于20重量%的钯的内电极烧结到一起(烧成),以形成多层陶瓷电容器。
Description
发明背景
1.技术领域
本发明涉及无铅无镉的钛酸钡基介电组合物,更具体地,涉及具有相对较小比例的分散在钛酸钡晶体母料中的客体离子如锌、硼、铋、铈、钨、铜、锰、钕、铌、银、钡、硅和镍的钛酸钡基介电组合物。这样的介电组合物可以用于形成具有由钯或银、或者两者的混合物或合金所形成的内电极的多层陶瓷片式电容器。
特别地,本发明涉及无铅无镉的超低温烧成的介电陶瓷组合物体系,其中,介电常数在宽的温度范围内变化不超过其基值的15%。另外,当施加直流偏压时,所述介电常数在宽的温度范围内变化不超过其基值的25%。更具体地,本发明涉及介电常数超过2000的介电陶瓷组合物,其通过在不超过1000℃的温度下烧成基本陶瓷氧化物混合物而形成。
2.相关现有技术的描述
多层陶瓷片式电容器(MLCC)已经被广泛用作微型尺寸、高容量和高可靠性的电子元件。根据对高性能电子设备的日益增长的需求,多层陶瓷片式电容器面临对更小的尺寸、更高的容量、更低的成本和更高的可靠性的市场需求。严格的环境规定对电容器产生有利的影响,由此生产无铅无镉的介电组合物。
一般通过形成介电层形成膏和内电极形成膏的交替层来制造多层陶瓷片式电容器。典型地通过形成薄片、印刷或类似技术,接着同时烧成来形成这样的层。通常,所述内电极已经由导体例如钯、金、银或者前述金属的合金来形成。
缺少铅和镉的传统陶瓷介电配方经常需要高于1250℃的烧结温度。添加铅或镉或者含铅和/或镉的化合物可以将烧结温度从高于1250℃降低至约1050℃~约1150℃的范围,从而可以将具有包含小于80%银和超过20%钯的金属成分的金属膏用作内电极。
电子工业协会(EIA)规定了电容器的温度系数(TCC)的标准,被称为X7R特征。X7R特征要求在-55℃~+125℃的温度范围内电容变化不大于±15%。对于设计用于高电压应用的多层陶瓷电容器,该工业还规定在施加直流偏压时电容器的温度系数(TCVC)的标准,被称为BX特征。BX特征要求在施加直流偏压时在-55℃~+125℃的温度范围内电容的变化不大于±25%。X7R和BX特征中的电容偏离百分比都是相对于参考温度25℃来测定的。
发明内容
基于前述,现有技术缺少一种制备可以在小于1000℃的温度下烧成的介电陶瓷组合物体系的方法,所述介电陶瓷组合物体系具有大于2000的介电常数,没有任何形式的铅和镉,且适用于具有超过80%Ag和小于20%Pd的Pd/Ag内电极。此外,现有技术缺少一种介电材料,当烧成该介电材料以形成电子装置时,其具有稳定的TCC(温度特性),且在施加直流偏压时还具有稳定的TCVC(使用DC偏压时的温度特性)。所述材料允许使用较低成本的电极材料而不牺牲电容性能,所述电极材料包括含有较少的Pd(其是相对较贵的)和较多的Ag(其是相对较便宜的)的金属部分,例如至少80%Ag和小于20%Pd,约85%Ag/15%Pd,约90%Ag10%Pd,或者约95%Ag/5%Pd,或者约99%Ag/1%Pd,最高100%Ag以及介于之间的值(重量百分比)。
本发明提供介电组合物体系,该体系可以用来制备与内电极相容的陶瓷多层电容器,所述内电极包含至少80%Ag和小于20%Pd、或者作为所述金属的混合物或合金。本文的介电材料和由其制备的电容器没有任何形式的铅和镉。所述电容器可以由本发明的介电组合物形成,显示出稳定的介电常数和较少的介电损耗,且在施加直流偏压时还具有稳定的介电常数和小的介电损耗。
本发明的介电组合物包含均匀且致密的晶粒微观结构,所述晶粒的平均直径为约0.5-约3微米。均匀且致密的微观结构在获得具有小于约5微米的介电层的高可靠性多层电容器是至关重要的。
在第一种实施方式中,本发明的介电组合物在烧成之前包含氧化物BiTiO3、ZnO、B2O3、Bi2O3、CeO2、WO3、Ag2O、CuO、BaO、SiO2和MnO的混合物,如表1的A栏中所示的。在表1的B和C栏中找到优选的实施方式。在整个说明书和权利要求书中,应当认为每个数值的前面有“约”,除非另有说明。“约”并不适用于金属部分,所述金属部分选自银、钯、它们的混合物以及它们的合金所组成的组,且包含至少80重量%的Ag和小于20重量%的Pd。
表1.实施方式A-C的介电组合物的配方
氧化物,重量% | A | B | C |
BaTiO3 | 85-98 | 90-97 | 90.5-96.5 |
ZnO | 0.3-2.5 | 0.5-2 | 0.7-1.7 |
B2O3 | 0.05-1 | 0.1-0.8 | 0.15-0.4 |
Bi2O3 | 1-8 | 1.5-6 | 2-5 |
CeO2 | 0.05-1.5 | 0.1-1 | 0.2-0.7 |
WO3 | 0.01-2 | 0.2-1.7 | 0.4-1.4 |
Ag2O | 0-2 | ||
CuO | 0.01-0.5 | 0.05-0.35 | 0.05-0.25 |
BaO | 0-1 | ||
SiO2 | 0-0.5 | ||
MnO | 0.01-0.5 | 0.03-0.3 | 0.04-0.2 |
在表1的实施方式中,使用Ag2O、BaO和SiO2都是任选的,正如A栏中的零下限、以及B和C栏中的空白所示的。当使用Ag2O时,最广泛地,它可以以不超过总氧化物含量的约2重量%的量存在,优选约0.05~约0.5重量%,更优选约0.1~约0.25重量%。当使用BaO时(提供超过存在于大部分BiTiO3中的钡的另外钡),最广泛地,它以不超过1重量%,优选0.05~约0.5重量%,更优选地0.1~约0.25重量%的量存在。当使用SiO2时,它以不超过约0.5重量%,优选0.01~约0.25重量%,更优选约0.02~约0.2重量%的量存在。可以理解的是,本文所有的介电配方即表1、2、3、4、9和12中的介电配方,以在烧成之前各成分的混合物形式给出。
在包含Nd2O3和TiO2的第二种实施方式中,本发明的介电组合物在烧成之前包含氧化物BaTiO3、ZnO、B2O3、Bi2O3、CeO2、WO3、Nd2O3、TiO2、Ag2O、CuO和MnO的混合物。每个氧化物成分的重量百分比如表2中所示的。宽范围的配方如D栏中所示的,而优选的实施方式出现在E和F栏中
表2.包含Nd2O3和TiO2的介电组合物的配方
氧化物,重量% | D | E | F |
BaTiO3 | 85-98 | 92-97 | 93.5-96.5 |
ZnO | 0.2-2 | 0.5-1.5 | 0.6-1.2 |
B2O3 | 0.1-1 | 0.15-0.7 | 0.2-0.5 |
Bi2O3 | 1-4 | 1.7-3.3 | 2-3 |
CeO2 | 0.1-1 | 0.2-0.7 | 0.25-0.6 |
WO3 | 0.1-1.5 | 0.4-1.2 | 0.5-1 |
Nd2O3 | 0.05-0.5 | 0.05-0.3 | 0.1-0.25 |
TiO2 | 0.01-0.5 | 0.05-0.3 | 0.08-0.2 |
Ag2O | 0-2.5 | ||
CuO | 0.01-1.5 | 0.015-0.7 | 0.02-0.06 |
MnO | 0.01-0.5 | 0.02-0.07 | 0.03-0.06 |
在表2的实施方式中,使用Ag2O是任选的,正如D栏中的零下限、以及E和F栏的空白所显示的。当使用Ag2O时,最广泛地,它可以以不超过总氧化物含量的约2.5重量%,优选约0.01~约2.5重量%,更优选约0.05~约0.5重量%,甚至更优选约0.1~约0.25重量%的量存在。
在包含NiO、Nb2O5和BaSO4的第三种实施方式中,本发明的介电组合物在烧成之前包含BaTiO3、ZnO、B2O3、NiO、Nb2O5、Bi2O3、CeO2、WO3、Ag2O、CuO、BaSO4和MnO的混合物。这些实施方式的配方如表3中所示,其中G栏中是宽范围配方,H和J栏是优选的实施方式。
表3.包含NiO、Nb2O5和BaSO4的介电组合物的配方
氧化物,重量% | G | H | J |
BaTiO3 | 85-98 | 92-96 | 93-95 |
ZnO | 0.5-2 | 1-2 | 1-1.5 |
B2O3 | 0.1-1.5 | 0.2-0.6 | 0.3-0.5 |
NiO | 0.05-0.5 | 0.1-0.4 | 0.15-0.35 |
Nb2O5 | 0.1-1 | 0.2-0.7 | 0.3-0.5 |
Bi2O3 | 0.5-3 | 1.5-2.5 | 1.7-2.3 |
CeO2 | 0.1-0.5 | 0.2-0.45 | 0.25-0.35 |
WO3 | 0.2-2 | 0.3-1 | 0.5-0.8 |
Ag2O | 0-0.5 | ||
CuO | 0.01-1.5 | 0.02-0.4 | 0.02-0.2 |
BaSO4 | 0.05-0.5 | 0.1-0.3 | 0.12-0.25 |
MnO | 0.01-0.5 | 0.03-0.35 | 0.04-0.2 |
在表3的实施方式中,使用Ag2O是任选的,正如G栏中的零下限、以及E和F栏的空白所显示的。当使用Ag2O时,最广泛地,它可以以不超过总氧化物含量的约0.5重量%,优选约0.01~约0.5重量%,更优选约0.01~约0.25重量%,甚至更优选约0.05~约0.2重量%的量存在。
下文将更充分地描述上述及其它的本发明特征,并且在权利要求中特别指出。以下详细的描述解释了本发明的某些实施方式,然而,这些仅表示其中使用了本发明原则的几种不同方式。
附图说明
图1是根据本发明的优选实施方式的多层陶瓷片式电容器的截面图。
本发明的详细描述
本发明提供了一种介电组合物体系,其可以用来制造与内电极相容的陶瓷多层电容器,所述内电极含有至少80重量%Ag和小于20重量%Pd、或者作为所述金属的混合物或合金。本文的介电材料以及由其制造的电容器没有任何形式的铅和镉。所述电容器可以由本发明的介电组合物来形成,显示出稳定的介电常数以及小的介电损耗,且在施加直流偏压时,还具有稳定的介电常数以及小的介电损耗。
本发明的介电组合物包含均匀且致密的晶粒微观结构,晶粒的平均直径为约0.5-约3微米。均匀且致密的微观结构对于获得具有小于约5微米的介电层的高可靠性多层电容器是至关重要的。
在第一种实施方式中,本发明的介电组合物在烧成之前包含氧化物BiTiO3、ZnO、B2O3、Bi2O3、CeO2、WO3、Ag2O、CuO、BaO、SiO2和MnO,如在表1的A栏中所示的。在表1的B和C栏中找到优选的实施方式。在整个说明书和权利要求书中,一般认为每个数值之前有“约”,除非另有说明。“约”并不适应于金属部分,所述金属部分选自由银、钯、它们的混合物以及它们的合金所组成的组,且包含至少80重量%的Ag和小于20重量%的Pd。
表1(重复).实施方式A-C的介电组合物的氧化物配方
氧化物,重量% | A | B | C |
BaTiO3 | 85-98 | 90-97 | 90.5-96.5 |
ZnO | 0.3-2.5 | 0.5-2 | 0.7-1.7 |
B2O3 | 0.05-1 | 0.1-0.8 | 0.15-0.4 |
Bi2O3 | 1-8 | 1.5-6 | 2-5 |
CeO2 | 0.05-1.5 | 0.1-1 | 0.2-0.7 |
WO3 | 0.01-2 | 0.2-1.7 | 0.4-1.4 |
Ag2O | 0-2 | ||
CuO | 0.01-0.5 | 0.05-0.35 | 0.05-0.25 |
BaO | 0-1 | ||
SiO2 | 0-0.5 | ||
MnO | 0.01-0.5 | 0.03-0.3 | 0.04-0.2 |
在表1的实施方式中,使用Ag2O、BaO和SiO2都是任选的,正如A栏中的零下限、B和C栏中的空白所示的。当使用Ag2O时,最广泛地,它可以以不超过总氧化物含量的约2重量%,优选约0.05~约0.5重量%,更优选约0.1~约0.25重量%的量存在。当使用BaO时(提供超过存在于大部分BiTiO3中的钡的另外钡),最广泛地,它以不超过1重量%,优选0.05~约0.5重量%,更优选地0.1~约0.25重量%的量存在。当使用SiO2时,它以不超过约0.5重量%,优选0.01~约0.25重量%,更优选约0.02~约0.2重量%的量存在。可以理解的是,本文所有的介电配方即表1、2、3、4、9和12中的配方,以在烧成之前各成分的混合物形式给出。
在包含Nd2O3和TiO2的第二种实施方式中,本发明的介电组合物在烧成之前包含氧化物BaTiO3、ZnO、B2O3、Bi2O3、CeO2、WO3、Nd2O3、TiO2、Ag2O、CuO和MnO的混合物。每个氧化物成分的重量百分比如表2中所示。宽范围配方如D栏中所示的,而优选的实施方式出现在E和F栏中
表2(重复).包含Nd2O3和TiO2的介电组合物的配方
氧化物,重量% | D | E | F |
BaTiO3 | 85-98 | 92-97 | 93.5-96.5 |
ZnO | 0.2-2 | 0.5-1.5 | 0.6-1.2 |
B2O3 | 0.1-1 | 0.15-0.7 | 0.2-0.5 |
Bi2O3 | 1-4 | 1.7-3.3 | 2-3 |
CeO2 | 0.1-1 | 0.2-0.7 | 0.25-0.6 |
WO3 | 0.1-1.5 | 0.4-1.2 | 0.5-1 |
Nd2O3 | 0.05-0.5 | 0.05-0.3 | 0.1-0.25 |
TiO2 | 0.01-0.5 | 0.05-0.3 | 0.08-0.2 |
Ag2O | 0-2.5 | ||
CuO | 0.01-1.5 | 0.015-0.7 | 0.02-0.06 |
MnO | 0.01-0.5 | 0.02-0.07 | 0.03-0.06 |
在表2的实施方式中,使用Ag2O是任选的,正如D栏中的零下限、以及E和F栏的空白所显示的。当使用Ag2O时,最广泛地,它可以以不超过总氧化物含量的约2.5重量%,优选约0.01~约2.5重量%,更优选约0.05~约0.5重量%,甚至更优选约0.1~约0.25重量%的量存在。
在包含NiO、Nb2O5和BaSO4的第三种实施方式中,本发明的介电组合物在烧成之前包含BaTiO3、ZnO、B2O3、NiO、Nb2O5、Bi2O3、CeO2、WO3、Ag2O、CuO、BaSO4和MnO的混合物。这些实施方式的配方如表3中所示的,其中G栏中的是宽范围配方,H和J栏中的是优选实施方式。
表3(重复).包含NiO、Nb2O5和BaSO4的介电组合物的配方
氧化物,重量% | G | H | J |
BaTiO3 | 85-98 | 92-96 | 93-95 |
ZnO | 0.5-2 | 1-2 | 1-1.5 |
B2O3 | 0.1-1.5 | 0.2-0.6 | 0.3-0.5 |
NiO | 0.05-0.5 | 0.1-0.4 | 0.15-0.35 |
Nb2O5 | 0.1-1 | 0.2-0.7 | 0.3-0.5 |
Bi2O3 | 0.5-3 | 1.5-2.5 | 1.7-2.3 |
CeO2 | 0.1-0.5 | 0.2-0.45 | 0.25-0.35 |
WO3 | 0.2-2 | 0.3-1 | 0.5-0.8 |
Ag2O | 0-0.5 | ||
CuO | 0.01-1.5 | 0.02-0.4 | 0.02-0.2 |
BaSO4 | 0.05-0.5 | 0.1-0.3 | 0.12-0.25 |
MnO | 0.01-0.5 | 0.03-0.35 | 0.04-0.2 |
在表3的实施方式中,使用Ag2O是任选的,正如G栏中的零下限、以及H和J栏的空白所显示的。当使用Ag2O时,最广泛地,它可以以不超过总氧化物含量的约0.5重量%,优选约0.01~约0.5重量%,更优选约0.01~约0.25重量%,甚至更优选约0.05~约0.2重量%的量存在。
多层片式电容器是通过交替层叠介电层和内电极以形成粗基片来制造的。本文所关注的内电极由包含诸如银和钯的混合物或合金;铂、铂和钯的混合物或合金;以及铂、钯和金的混合物或合金构成。形成介电层的介电组合物是通过湿磨介电组分与有机载体体系来生产的。将介电组合物沉积在负载膜如聚酯或聚丙烯、带状物如不锈钢、纸张或基板如氧化铝或玻璃上,涂覆所述膜且形成薄片,将该薄片与电极交替层叠以形成粗基片。
优选实施方式包括含有金属组分的内电极,所述金属部分包含至少80重量%Ag和小于20重量%Pd,约85%Ag/15%Pd,约90%Ag10%Pd,或者约95%Ag/5%Pd,或者约99%Ag/1%Pd,最高100%Ag和介于之间的值(以重量百分比计),而没有牺牲电容性能。
在形成粗基片之后,通过在空气中加热到小于约350℃的温度来去除所述有机载体。一旦去除所述有机载体,然后在约900℃~约1000℃的温度下在空气中在批处理窑或隧道窑中烧成所述粗基片。可以使用各种加热曲线来去除粘结剂和烧成所述基片。多层陶瓷电容器的结构在本领域中是众所周知的。参照附图1,显示了多层陶瓷片式电容器1的示例性结构。电容器1的外电极4被设置在电容器基片1的侧面,并且与内电极层3电连接。电容器基片1具有多个交替层叠的介电层2。电容器基片1的形状并不是关键的,尽管它经常是矩形的。此外,大小也不是关键的,根据具体的应用,所述基片可以具有合适的尺寸,通常在1.0-5.6毫米×0.5-5.0毫米×0.5-1.9毫米范围内。将内电极层3层叠为使得在相对的两端,它们交替露出于所述基片1的相对侧面上。即,一组内电极层3露出于所述基片1的一侧面上,另一组内电极层3露出于所述基片1的相对侧面上。将一个外电极4施加于电容器基片1的一侧面上,与所述一组内电极层3电连接,并且将另一个的外电极4施加于所述基片1的相对侧面上,与所述另一组的内电极层3电连接。
对于本领域的技术人员来说熟知的是,任何或所有上述氧化物(除了BaTiO3外)可以预混合以形成预混合物,或者预反应以形成中间体化合物。其效果将会是相同的,只要以氧化物形式表示的最终组成是相同的。对本领域的技术人员来说显而易见的是,金属盐如碳酸盐、硝酸盐、氢氧化物、草酸盐、乙酸盐以及有机化合物具有相同的效果,只要以所想要的量提供所想要的金属离子。
在介电材料中可以存在其它的化合物,条件是其它化合物不会对介电性能产生不利影响。通常作为杂质在原料中发现这样的化合物。
此处的介电组合物具有精细的晶体颗粒,通常具有约0.5-约3微米的平均尺寸,小于约0.7微米的粒度是优选的。每个介电层具有最高约50微米的厚度。优选地,每个介电层的厚度为约0.5-约50微米。更优选地,每个介电层的厚度为约2微米-约10微米。可以使用此处的组合物来制备具有薄的介电层的多层陶瓷片式电容器,以确保在使用期限内最小程度的电容降低。
在片式电容器中层叠的介电层的数量通常最高为约2~约800,优选为约3-约400。本发明的多层陶瓷片式电容器一般通过使用膏由传统的印刷法和形成薄片法而形成粗基片、以及烧成所述基片来制备。在烧成之后,将该基片在诸如氧化铝或二氧化硅的介质中转笼干燥以磨掉边角。然后将含有银、或银和钯的混合物或合金的导电膏施加在两端,以将露出的内电极连接在一起来制备端电极。然后在约800℃下在空气中进行端电极烧成,以在两端将导体(例如银)烧结为坚固的导电垫片,从而形成多层电容器。端电极是如图1所示的外电极4。
介电膏。用于形成介电层的膏可以通过将有机载体与此处所公开的介电原料混合来获得。还有用的是在烧成时转化为如上所述的氧化物和复合氧化物的前体化合物。通过选择含这样的氧化物的化合物或所述氧化物的前体;以及以合适的比例将它们混合来获得所述介电材料。这样的化合物在介电材料原料中的比例被确定为使得在烧成之后可以获得所想要的介电层组合物。通常以具有约0.1-约3微米,优选约1微米或更少的平均粒度的粉末形式使用所述介电原料。
有机载体。有机载体是有机溶剂中的粘合剂或水中的粘合剂。此处所使用的粘合剂不是关键的;传统的粘合剂如乙基纤维素、聚乙烯丁醇(polyvinylbutanol)、乙基纤维素和羟丙基纤维素以及它们的组合适合与溶剂一起使用。有机溶剂也不是关键的,可以根据特定的应用方法(例如印刷或形成薄片)从以下传统的有机溶剂中选择:例如丁基卡必醇、丙酮、甲苯、乙醇、二甘醇丁醚;2,2,4-三甲基戊二醇单异丁酯(TexanolTM);α-松油醇;β-松油醇;γ-松油醇;三癸基醇;二甘醇乙醚(CarbitolTM)、二甘醇丁醚(Butyl CarbitolTM)以及丙二醇;以及它们的混合物。以商标销售的产品可以从田纳西州金斯波特的伊士曼化工公司(Eastman Chemical Company,Kingsport,TN)获得;以和商标销售的那些产品可以从密歇根州米德兰的陶氏化学公司(Dow Chmeical Co.,Midland,MI)获得。或者,所述粘合剂可以从混合水的聚乙烯醇(PVA)或聚醋酸乙烯酯(PVAC)中选择。
对各个膏(介电膏或电极膏)的有机载体的含量没有强加特别的限制。通常所述膏含有约1-5重量%的粘合剂和约10-50重量%的有机溶剂,其余量是金属组分(用于电极)或介电组分(用于介电层)。如果需要,各个膏可以包含最多约10重量%的其它添加剂,例如分散剂、增塑剂和绝缘化合物。
内电极。用于形成内电极层的膏是通过将导电材料与有机载体混合来获得的。本文所使用的导电材料包括导体如本文提到的银和钯金属以及它们的合金,以及在烧成时转化为所述导体的各种化合物,例如氧化物、有机金属化合物和树脂酸盐。合适的Ag/Pd膏是由费罗公司(Ferro Corporation)获得的EL44-010Ag/Pd膏,其含有90重量%的Ag和10重量%的Pd。
参考附图1,形成内电极层3的导体通常是银/钯混合物或合金。内电极层的厚度可以被确定为适于特定的应用,但是所述层通常最高为约5微米厚。优选地,内电极层具有约0.5-约3微米的厚度,更优选约1-约2微米。。
外电极。形成外电极4的导体通常是Ag或Ag/Pd混合物或Ag和Pd的合金。可以确定外电极层的厚度以适于特定的应用,但是该层通常最高为约10-约50微米厚,优选为约20-约40微米厚。用于形成外电极的膏是通过用于形成内电极的相同方法来制备。
粗基片的形成。然后可以由介电层形成膏和内电极层形成膏来制备粗基片。在印刷方法的情况中,通过将所述膏以叠层的形式交替印刷在聚酯膜(例如聚对苯二甲酸乙二醇酯(PET))衬底上;将叠层的层叠体切割成预定形状;以及将其从衬底上分离来制备粗基片。还可用的是形成薄片法,其中通过由介电层形成膏来形成粗薄片;将内电极层形成膏印刷在各个粗薄片上;以及层叠所印刷的粗薄片来制备粗基片。
干燥。在传统的条件下可以去除(干燥)有机载体,即通过以0.01℃-20℃/小时,更优选约0.03-0.1℃/小时的速率加热;保持温度为约150℃-约350℃,优选约250℃;保温时间为约30-700分钟,优选为约200-300分钟;在空气气氛中。在从粗基片中去除有机载体之后,将它烧成。在烧成之前可以将所述基片冷却至室温,或者在去除有机载体之后可以直接烧成,而没有冷却。
烧成。然后在空气中在约900℃~约1000℃的温度下烧成干燥的粗基片。本文所述的介电组合物要求不超过1000℃,以实现充分熔合所述介电材料和烧结所述电极。将烧成温度保持约两小时以增加其致密度。较低的保持温度提供不足的致密度,而较高的保持温度可能导致较大的晶粒。烧成温度升温速率通常为5℃/分钟,尽管可以使用其它的升温速率(每分钟)如1℃、2℃、10℃、15℃或20℃。
可以连续或分开地进行有机载体的去除和烧成。如果是连续的,则该过程包括有机载体的去除;将温度升高至烧成温度而没有冷却;在该烧成温度下保温规定的时间;以及随后冷却。如果是分开的,则在有机载体去除和冷却之后,将所述基片的温度升高至烧结温度。所得到的基片可以通过转鼓抛光和/或喷砂处理来抛光两端面,例如在印刷或转印外电极形成膏且烧成以形成外电极(端电极)之前。外电极形成膏的烧成可以在空气中在约600℃-800℃下进行约10分钟至约1小时。如果需要,通过电镀或者本领域中熟知的其它方法在外电极上形成垫片。本发明的多层陶瓷片式电容器可以安装在印刷电路板上,例如通过焊接。
一般说来,本文的介电组合物可以用于制备具有大于约2000的介电常数、小于约2%的损耗因子且满足X7R和BX标准的多层陶瓷电容器,其中,所述介电体包含本文所描述的任何介电材料和内电极材料的交替层叠的层的烧成集合体,所述内电极材料选自由银、钯、以及它们的混合物和合金所组成的组。
此外,本发明还包含形成电子元件的方法,该方法包括:将此处所述的任何介电材料的层和内电极材料的层交替施加在衬底上以形成叠层体,所述内电极材料包含选自由银、钯、它们的合金和它们的混合物的金属部分;以及在不超过1000℃的温度下烧成所述叠层体,使得熔合所述介电体且烧结所述金属。
实施例
制备具有Ag/Pd电极、20个活性层的多层陶瓷电容器且在900~1000℃下烧成,所述Ag/Pd电极含有至少80重量%Ag,每个活性层的厚度为5~15微米。进行物理和电性能测试。烧成后的基片显示出超过2000的介电常数、在1KHz下小于4.00%的DF、在-55℃~+125℃范围内小于±15%的TCC、在施加约1.5伏/微米的直流偏压时小于±25%的TCVC、在25℃下大于1000秒的RC、以及在125℃下大于20秒的RC。介电击穿电压超过40伏/微米。提供如下示例性组合物以说明本发明的优选方面并且不打算限制本发明的范围。
实施例1-4
通过在水中混合、掺和和/或研磨合适量(以重量百分比计)的氧化物(如表4所示)来形成介电组合物。
表4.实施例1-4的组合物
实施例 | BaTiO3 | ZnO | B2O3 | Bi2O3 | CeO2 | WO3 | Ag2O | CuO | BaO | SiO2 | MnO | 总量 |
1 | 96.237 | 0.730 | 0.170 | 2.080 | 0.200 | 0.403 | -0- | 0.060 | 0.057 | 0.023 | 0.040 | 100 |
2 | 95.952 | 0.730 | 0.171 | 2.080 | 0.294 | 0.594 | -0- | 0.094 | -0- | -0- | 0.084 | 100 |
3 | 95.878 | 0.657 | 0.295 | 2.077 | 0.294 | 0.593 | 0.146 | 0.020 | -0- | -0- | 0.040 | 100 |
4 | 90.895 | 1.662 | 0.388 | 4.737 | 0.670 | 1.354 | -0- | 0.215 | -0- | -0- | 0.078 | 100 |
在研磨之后,干燥和粉碎所述粉末。最终的粉末具有0.4~0.9微米的平均粒径。然后添加一百克的每种上述粉末和28.8克的有机载体,所述有机载体包含聚乙烯丁醇、甲苯和甲醇,湿磨24小时以制备用于流延成型的浆料。将湿浆料施加在聚酯膜上以形成介电体粗带。介电体粗带的厚度为约20~30微米,这取决于对它们所进行的特定测试。使用传统的Ag/Pd膏通过传统的丝网印刷法,将90%Ag/10%Pd或者95%Ag/5%Pd的电极印刷在干燥的粗介电材料带上。在5100psi的压力[~347大气压下]和130°F的温度下层叠和粘接总数20片另加没有印刷电极的顶部和底部覆盖层,以形成粗基片。在切割成合适尺寸以后,即在烧结和收缩(通常在长度和宽度方向收缩15~20%)以后所述基片尺寸为约0.120”(L)×0.060”(W)(EIA 1206尺寸),根据表5的烧尽循环,对所述粗基片加热以去除有机载体。
表5.粘合剂去除条件
阶段 | 温度(℃) | 持续时间(小时) | 气氛 |
从室温开始升温 | 255 | 20 | 空气 |
保温 | 255 | 6 | 空气 |
冷却 | 25 | 4 | 空气 |
在冷却至室温时,将使用表4的粉末的基片(实施例1-4)在表6所记载的条件下在纳博热批处理窑(Nabertherm batch kiln)中在空气中烧成,以获得多层电容器基片。
表6.实施例1-4的烧成条件
阶段 | 温度(℃) | 持续时间(小时) | 气氛 |
升温 | 900~1000 | 4~6 | 空气 |
保温 | 900~1000 | 4~6 | 空气 |
冷却 | 25 | 4~6 | 空气 |
对于所有的实施例,将基片放置在ZrO2底座上或者在封闭的Al2O3坩埚中,且在900~950℃的温度下在空气中烧结。因此所获得的基片通过转笼圆化边角。形成外部电极的Ag膏是由俄亥俄州克利夫兰的费罗公司(FerroCorporation)获得的TK33008,将其应用于端面,且在空气中在720℃下烧成约15分钟,以形成外部电极。因此加工的多层电容器具有约0.120”(L)×0.06”(W)(EIA 1206尺寸),其中高度可以变化。介电层为10~15微米厚,内部银/钯电极层为约1.5微米厚,诸如“920/6”的值意指在920℃的保温温度下进行烧成六小时。
然后,在1KHz的测试频率下和1.0伏RMS的测试电压下测量多层片式电容器的电性能:电容(Cap.)、损耗因子(DF)、温度特性(TCC)。还测试绝缘电阻(IR)和击穿电压。由所述基片的物理尺寸以及活性介电层的活性介电厚度和数量,可以计算出介电常数(K)、绝缘电阻×电容常数(RC)以及所述组合物的击穿强度。测试结果如表7中所示。
表7.实施例1-4的电性能总结
实施例 | 烧成(℃/小时) | 厚度(μm) | 电容(nF) | DF(%) | K | TCC-55℃ | TCC85℃ | TCC125℃ | RC 25℃(秒) | RC 125℃(秒) | 击穿(伏/微米) |
1 | 920/6 | 9.9 | 101.6 | 2.09 | 2558 | -13.3 | -7.2 | -5.0 | 3952 | 78 | 101 |
1 | 940/4 | 9.4 | 102.8 | 2.11 | 2650 | -12.5 | -7.8 | -63 | 3967 | 61 | 132 |
2 | 920/6 | 9.5 | 104.8 | 1.90 | 2880 | -11.5 | -7.7 | -7.5 | 5903 | 153 | 110 |
2 | 940/2 | 9.4 | 108.7 | 1.87 | 2719 | -10.3 | -11.7 | -14.2 | 4728 | 92 | 112 |
3 | 920/6 | 11.7 | 77.0 | 2.01 | 2317 | -15.0 | -09 | 3.8 | 4447 | 384 | 93 |
3 | 940/4 | 11.0 | 78.8 | 2.02 | 2369 | -14.7 | -2.1 | 2.8 | 4611 | 179 | 118 |
4 | 930/6 | 9.7 | 112.8 | 1.96 | 2873 | -8.2 | -9.6 | -9.1 | 3069 | 40 | 94 |
4 | 940/4 | 9.2 | 111.5 | 1.93 | 2530 | -7.2 | -9.7 | -7.3 | 2530 | 22 | 104 |
K=电容×(1/8.854E-14)×(厚度/(L×W))×(1/N)
L=活性电极的长度(cm)W=活性电极的宽度(cm)
RC=电容(nF)×绝缘电阻(G-欧姆)
N=活性介电层的数量
由实施例1-4的组合物形成的示例性基片具有非常高的介电常数、低的DF、致密微结构和高的击穿强度。TCC满足X7R标准,且在25℃下和在125℃下的RC都超过EIA规定。
还测试实施例2的基片在施加DC偏压时的TCC。表8的结果显示出非常稳定的性能。所述基片满足BX特性:在施加约1.6伏/微米或更小的直流偏压时,TCVC在±25%内。
表8.在施加DC偏压时实施例2的TCC
实施例5-11
以与实施例1-4所公开的完全相同的方式形成介电组合物。在表9中描述了所述组合物。
表9.实施例5-11的组合物
实施例 | BaTiO3 | ZnO | B2O3 | Bi2O3 | CcO2 | WO3 | Nd2O3 | TiO2 | Ag2O | CuO | MnO | 总量 |
5 | 96.019 | 0.656 | 0.221 | 1.971 | 0.279 | 0.563 | 0.102 | 0.060 | 0.069 | 0.019 | 0.040 | 100 |
6 | 95.956 | 0.668 | 0.224 | 2.005 | 0.284 | 0.572 | 0.103 | 0.061 | 0.070 | 0.019 | 0.036 | 100 |
7 | 95.892 | 0.692 | 0.162 | 1.973 | 0.279 | 0.564 | 0.203 | 0.121 | -0- | 0.057 | 0.057 | 100 |
8 | 95.757 | 0.786 | 0.233 | 2.077 | 0.294 | 0.593 | 0.107 | 0.063 | -0- | 0.040 | 0.050 | 100 |
9 | 94.043 | 0.987 | 0.332 | 2.959 | 0.419 | 0.845 | 0.153 | 0.091 | 0.103 | 0.029 | 0.040 | 100 |
10 | 94.020 | 1.001 | 0.233 | 2853 | 0.403 | 0.815 | 0.294 | 0.174 | 0.146 | 0.020 | 0.040 | 100 |
11 | 93.985 | 0.995 | 0.334 | 2.986 | 0.423 | 0.853 | 0.154 | 0.091 | 0.105 | 0.029 | 0.044 | 100 |
以与实施例1-4相同的方式加工和测试粉末。烧成条件和电性能如表10中所示。由实施例5-11的组合物制成的示例性基片具有非常高的介电常数、低的DF、致密的微结构以及高的击穿电压。TCC满足X7R标准,且在25℃下和125℃下的IR都超过EIA规定。
表10.实施例5-11的电性能总结
实施例 | 烧成(℃/小时) | 厚度(微米) | 电容(nF) | DF(%) | 计算的K | TCC-55℃ | TCC85℃ | TCC125℃ | RC25℃(秒) | RC125℃(秒) | 击穿(伏/微米) |
5 | 920/6 | 10.7 | 87.3 | 2.01 | 2431 | -12.5 | -3.9 | -0.6 | 3992 | 306 | 44 |
5 | 940/4 | 11.1 | 91.6 | 1.83 | 2642 | -10.4 | -4.5 | -1.7 | 3372 | 152 | 66 |
6 | 930/4 | 10.6 | 85.4 | 2.07 | 2409 | -15.4 | -6.0 | -5.5 | 1457 | 31 | 83 |
6 | 940/4 | 10.5 | 79.4 | 1.92 | 2197 | -13.8 | -5.2 | -4.3 | 1693 | 29 | 104 |
7 | 920/6 | 9.9 | 88.9 | 1.71 | 2401 | -8.2 | -7.9 | -7.9 | 2908 | 61 | 86 |
7 | 940/4 | 9.1 | 92.7 | 1.76 | 2316 | -7.7 | -10.0 | -10.5 | 2054 | 24 | 99 |
8 | 920/6 | 10.6 | 88.3 | 1.93 | 2604 | -11.9 | -5.3 | -1.8 | 3092 | 70 | 93 |
8 | 940/4 | 11.0 | 88.6 | 1.89 | 2603 | -9.9 | -5.9 | -3.4 | 2348 | 44 | 94 |
9 | 930/6 | 10.3 | 81.3 | 1.89 | 2423 | -14.4 | 1.6 | 6.5 | 9025 | 528 | 105 |
9 | 940/4 | 10.5 | 82.7 | 1.86 | 2615 | -13.1 | 0.5 | 5.4 | 7354 | 402 | 92 |
10 | 930/6 | 10.0 | 81.6 | 3.93 | 2158 | -16.2 | 1.0 | 6.4 | 472 | 728 | 77 |
10 | 940/4 | 9.9 | 78.7 | 3.70 | 2074 | -15.9 | 0.3 | 5.2 | 755 | 684 | 70 |
11 | 920/6 | 9.3 | 85.1 | 2.09 | 2046 | -16.9 | 3.3 | 10.9 | 3857 | 1335 | 72 |
11 | 940/4 | 9.5 | 91.6 | 2.08 | 2330 | -15.5 | 2.0 | 9.6 | 7643 | 760 | 110 |
还测试了实施例7的基片在施加DC偏压时的TCC。表11中的结果显示出非常稳定的性能。所述基片满足BX特性:当施加约1.6伏/微米或更小的DC偏压时,TCVC在±25%内。
表11.在施加DC偏压时实施例7的TCC
实施例12
以实施例1-4所公开的完全相同的方式形成介电组合物。表12中描述了所述组合物。
表12.实施例12的组合物
实施例 | BaTiO3 | ZnO | B2O3 | NiO | Nb2O5 | Bi2O3 | CeO2 | WO3 | Ag2O | CuO | BaSO4 | MnO | 总量 |
12 | 94.318 | 1.380 | 0.408 | 0.210 | 0.318 | 2.106 | 0.297 | 0.602 | 0.148 | 0.020 | 0.153 | 0.040 | 100 |
以与实施例1-4中相同的方式加工和测试粉末。烧成条件和电性能如表13所示。
表13.实施例12的电性能总结
实施例 | 烧成(℃/小时) | 厚度(微米) | 电容(nF) | DF(%) | 计算的K | TCC-55℃ | TCC85℃ | TCC125℃ | RC25℃(秒) | RC 125℃(秒) | 击穿(伏/微米) |
12 | 930/6 | 12.1 | 65.4 | 1.91 | 2075 | -7.0 | -2.9 | 1.2 | 1758 | 77 | 76 |
940/4 | 10.9 | 66.3 | 1.86 | 2019 | -6.6 | -3.0 | 1.1 | 1293 | 35 | 108 |
由实施例12的组合物制成的示例性基片具有非常高的介电常数、低的DF、致密的微结构以及高的击穿电压。TCC满足X7R标准,且在25℃下和125℃下的IR都超过EIA规定。
还测试了实施例12的基片在施加DC偏压时的TCC。表14中的结果显示出非常稳定的性能,表示在施加约2.3伏/微米或更小的DC偏压时它们满足EIA BX特性。
表14.在施加DC偏压时实施例12的TCC
对于本领域的技术人员将容易想到另外的优点和改进。因此,本发明在更广泛的方面并不限于此处显示和描述的具体细节和说明性实施例。因此,可以进行各种改进,而不偏离由所附的权利要求及其对等物所限定的一般本发明概念的精神或范围。
Claims (25)
1.一种用于制造多层陶瓷电容器的无铅无镉陶瓷介电组合物,包含:
a.85-98重量%的BaTiO3,
b.0.3-2.5重量%的ZnO,
c.0.05-1重量%的B2O3,
d.1-8重量%的Bi2O3,
e.0.05-1.5重量%的CeO2,
f.0.01-2重量%的WO3,
g.0.01-0.5重量%的CuO,以及
h.0.01-0.5重量%的MnO。
2.根据权利要求1所述的组合物,包含:
a.90-97重量%的BaTiO3,
b.0.5-2重量%的ZnO,
c.0.1-0.8重量%的B2O3,
d.1.5-6重量%的Bi2O3,
e.0.1-1重量%的CeO2,
f.0.2-1.7重量%的WO3,
g.0.05-0.35重量%的CuO,以及
h.0.03-0.3重量%的MnO。
3.根据权利要求1所述的组合物,包含:
a.90.5-96.5重量%的BaTiO3,
b.0.7-1.7重量%的ZnO,
c.0.15-0.4重量%的B2O3,
d.2-5重量%的Bi2O3,
e.0.2-0.7重量%的CeO2,
f.0.4-1.4重量%的WO3,
g.0.05-0.25重量%的CuO,以及
h.0.04-0.2重量%的MnO。
4.根据权利要求1所述的组合物,进一步包含Ag2O,其中Ag2O的含量不超过2重量%。
5.根据权利要求2所述的组合物,进一步包含BaO和SiO2中的至少一种,其中BaO的含量不超过1重量%,且SiO2的含量不超过0.5重量%。
6.一种用于制造多层陶瓷电容器的无铅无镉陶瓷介电组合物,包含:
a.85-98重量%的BaTiO3,
b.0.2-2重量%的ZnO,
c.0.1-1重量%的B2O3,
d.1-4重量%的Bi2O3,
e.0.1-1重量%的CeO2,
f.0.1-1.5重量%的WO3,
g.0.05-0.5重量%的Nd2O3,
h.0.01-0.5重量%的TiO2,
i.0.01-0.5重量%的CuO,以及
j.0.01-0.5重量%的MnO。
7.根据权利要求6所述的组合物,包含:
a.92-97重量%的BaTiO3,
b.0.5-1.5重量%的ZnO,
c.0.15-0.7重量%的B2O3,
d.1.7-3.3重量%的Bi2O3,
e.0.2-0.7重量%的CeO2,
f.0.4-1.2重量%的WO3,
g.0.05-0.3重量%的Nd2O3,
h.0.05-0.3重量%的TiO2,
i.0.015-0.07重量%的CuO,以及
j.0.02-0.07重量%的MnO。
8.根据权利要求6所述的组合物,包含:
a.93.5-96.5重量%的BaTiO3,
b.0.6-1.2重量%的ZnO,
c.0.2-0.5重量%的B2O3,
d.2-3重量%的Bi2O3,
e.0.25-0.6重量%的CeO2,
f.0.5-1重量%的WO3,
g.0.1-0.25重量%的Nd2O3,
h.0.08-0.2重量%的TiO2,
i.0.02-0.06重量%的CuO,以及
j.0.03-0.06重量%的MnO。
9.根据权利要求6所述的组合物,进一步包含Ag2O,其中Ag2O的含量不超过2.5重量%。
10.根据权利要求7所述的组合物,进一步包含0.05~0.5重量%的Ag2O。
11.一种用于制造多层陶瓷电容器的无铅无镉陶瓷介电组合物,包含:
a.85-98重量%的BaTiO3,
b.0.5-2重量%的ZnO,
c.0.1-1.5重量%的B2O3,
d.0.05-0.5重量%的NiO,
e.0.1-1重量%的Nb2O5,
f.0.5-3重量%的Bi2O3,
g.0.1-5重量%的CeO2,
h.0.2-2重量%的WO3,
i.0.01-0.5重量%的CuO,
j.0.05-0.5重量%的BaSO4,以及
k.0.01-0.5重量%的MnO。
12.根据权利要求11所述的组合物,包含:
a.92-96重量%的BaTiO3,
b.1-2重量%的ZnO,
c.0.2-0.6重量%的B2O3,
d.0.1-0.4重量%的NiO,
e.0.2-0.7重量%的Nb2O5,
f.1.5-2.5重量%的Bi2O3,
g.0.2-0.45重量%的CeO2,
h.0.3-1重量%的WO3,
i.0.02-0.4重量%的CuO,
j.0.1-0.3重量%的BaSO4,以及
k.0.03-0.35重量%的MnO。
13.根据权利要求11所述的组合物,包含:
a.93-95重量%的BaTiO3,
b.1-1.5重量%的ZnO,
c.0.3-0.5重量%的B2O3,
d.0.15-0.35重量%的NiO,
e.0.3-0.5重量%的Nb2O5,
f.1.7-2.3重量%的Bi2O3,
g.0.25-0.35重量%的CeO2,
h.0.5-0.8重量%的WO3,
i.0.02-0.2重量%的CuO,
j.0.12-0.25重量%的BaSO4,以及
k.0.04-0.2重量%的MnO。
14.根据权利要求11所述的组合物,进一步包含Ag2O,其中Ag2O的含量不超过0.5重量%。
15.根据权利要求12所述的组合物,进一步包含0.1~0.2重量%的Ag2O。
16.一种多层陶瓷片式电容器,其介电常数大于2000,损耗因子小于2%,且满足X7R和BX标准,所述电容器包括交替层叠以下a和b的烧成集合体:
a.权利要求1所述的陶瓷介电组合物的层,
b.包含金属部分的内电极材料的层,所述金属部分选自由银、钯、它们的混合物和它们的合金所组成的组。
17.根据权利要求16所述的电容器,其中,所述金属部分包含至少80重量%的银和小于20重量%的钯。
18.一种多层陶瓷片式电容器,其介电常数大于2000,损耗因子小于2%,且满足X7R和BX标准,所述电容器包括交替层叠的以下a和b的烧成集合体:
a.权利要求6所述的陶瓷介电组合物的层,
b.包含金属部分的内电极材料的层,所述金属部分选自由银、钯、它们的混合物和它们的合金所组成的组。
19.根据权利要求18所述的电容器,其中,所述金属部分包含至少80重量%的银和小于20重量%的钯。
20.一种多层陶瓷片式电容器,其介电常数大于2000,损耗因子小于2%,且满足X7R和BX标准,所述电容器包括交替层叠的下列a和b的烧成集合体:
a.权利要求11所述的陶瓷介电组合物的层,
b.包含金属部分的内电极材料的层,所述金属部分选自由银、钯、它们的混合物和它们的合金所组成的组。
21.根据权利要求20所述的电容器,其中,所述金属部分包含至少80重量%的银和小于20重量%的钯。
22.一种形成电子元件的方法,包括:
a.将以下i和ii交替施加在衬底上以形成层叠体:
i.权利要求1的陶瓷介电组合物的层,
ii.包含金属部分的内电极材料的层,所述金属部分选自由银、钯、它们的混合物和它们的合金所组成的组;以及
b.在不超过1000℃的温度下烧成所述层叠体,使得所述介电材料熔合且所述金属烧结。
23.根据权利要求22所述的方法,其中,所述金属部分包含至少80重量%的银和小于20重量%的钯。
24.一种形成电子元件的方法,包括:
a.将以下i和ii交替施加在衬底上以形成层叠体:
i.权利要求6的陶瓷介电组合物的层,
ii.包含金属部分的内电极材料的层,所述金属部分选自由银、钯、它们的混合物和它们的合金所组成的组;以及
b.在不超过1000℃的温度下烧成所述层叠体,使得所述介电材料熔合且所述金属烧结。
25.根据权利要求24所述的方法,其中,所述金属部分包含至少80重量%的银和小于20重量%的钯。
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PCT/US2007/085590 WO2008108897A1 (en) | 2007-03-05 | 2007-11-27 | Ultra low temperature fired x7r and bx dielectric ceramic composition and method of making |
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CN102020465A (zh) * | 2010-11-04 | 2011-04-20 | 仙桃市中星电子材料有限公司 | 抗还原性的多层陶瓷电容介质陶瓷材料 |
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WO2016007255A1 (en) | 2014-07-09 | 2016-01-14 | Ferro Corporation | Mid-k ltcc compositions and devices |
WO2016137790A1 (en) | 2015-02-27 | 2016-09-01 | Ferro Corporation | Low-k and mid-k ltcc dielectric compositions and devices |
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