CN104341144A - 低温烧结c0g特性微波介质材料及其制备方法 - Google Patents

低温烧结c0g特性微波介质材料及其制备方法 Download PDF

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CN104341144A
CN104341144A CN201310331698.0A CN201310331698A CN104341144A CN 104341144 A CN104341144 A CN 104341144A CN 201310331698 A CN201310331698 A CN 201310331698A CN 104341144 A CN104341144 A CN 104341144A
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陈仁政
宋蓓蓓
程华容
杨喻钦
杨魁勇
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Beijing yuan six Hongyuan electronic Polytron Technologies Inc
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Abstract

本发明提供的低温烧结C0G特性微波介质材料及其制备方法,涉及电子信息材料与元器件技术领域,包括主料、副料、改性添加剂和烧结助剂,所述主料是CaMgSi2O6;所述的副料是BaZrO3;所述改性添加剂是MnO、Al2O3、Co3O4、ZnO中的一种或几种;所述的烧结助剂是Li2O、CaO、MgO、SiO2、B2O3中的一种或几种,其中,主料50~58wt%、副料21~26wt%、改性添加剂3~8wt%、烧结助剂12~22wt%。本发明提供一种低温烧结C0G特性微波介质材料及其制备方法,有效提高品质因素,使得陶瓷能够在较低温度烧结下,保持良好介电性能的同时,拥有稳定的温度系数。

Description

低温烧结C0G特性微波介质材料及其制备方法
技术领域
本发明涉及电子信息材料与元器件技术领域,尤其涉及一种低温烧结C0G特性微波介质材料及其制备方法。 
背景技术
微波陶瓷电容器是目前世界上用量最大、发展最快的电子元件之一。微波陶瓷电容器主要应用于各类军用民用整机的震荡、耦合、滤波、旁路电路中,应用领域已经拓展到自动控制仪表、计算机、手机、数字家电、汽车、电力等行业。目前,微波陶瓷电容器已经成为了电容器市场的重要组成,全球市场的需求量增长速度近15%。市场需求巨大,产业化市场前景非常广阔。 
对于射频、微波多层陶瓷电容器来说,还要求具备以下性能:高耐压、大电流、大功率、超高Q值、稳定温度系数,超低等效串联电阻ESR等。电容器的损耗是由金属损耗和介质损耗两部分构成。在30MHz以下,陶瓷的介质损耗占主导地位;在30MHz以上,金属损耗占主导地位。为了获得高频下更低的ESR,必须降低金属损耗,因此现在开始采用方阻更低的Ag来做内部电极,由于Ag的熔点低,必须要求陶瓷的烧结温度降低到920℃以下。BaZrO3具有优异的介电性能和容量温度系数(TCC),但是存在烧结温度高的问题。因此在实际生产使用中,需要通过一些方法在不影响介电性能的前提下,降低烧结温度,以生产出满足纯银内电极使用的低温烧结C0G特性微波介质材料。 
发明内容
本发明提供一种低温烧结C0G特性微波介质材料及其制备方法,有 效提高品质因素,使得陶瓷能够在较低温度烧结下,保持良好介电性能的同时,拥有稳定的温度系数。 
为了解决上述问题,本发明提供一种低温烧结C0G特性微波介质材料,包括主料、副料、改性添加剂和烧结助剂,所述主料是CaMgSi2O6;所述的副料是BaZrO3;所述改性添加剂是MnO、Al2O3、Co3O4、ZnO中的一种或几种;所述的烧结助剂是Li2O、CaO、MgO、SiO2、B2O3中的一种或几种,其中,主料50~58wt%、副料21~26wt%、改性添加剂3~8wt%、烧结助剂12~22wt%。 
进一步的,所述主料CaMgSi2O6是CaCO3、Mg(OH)2、SiO2按摩尔比1:1:2球磨混合均匀后,在1100~1200℃煅烧2~4小时后获得。 
进一步的,所述副料BaZrO3是BaCO3、ZrO2按摩尔比1:1~1:1.02的比例球磨混合均匀后,在1100~1200℃煅烧3~5小时后获得。 
进一步的,所述改性添加剂在整个介质材料组成是MnO0.1~0.3wt%,Al2O30.5~3wt%,Co3O40.1~1wt%以及ZnO0.5~5wt%。 
进一步的,所述烧结助剂的组成是Li2O10~40wt%、CaO10~30wt%、MgO5~20wt%、SiO210~20wt%以及B20310~45wt%。 
进一步的,所述改性添加剂和烧结助剂元素的组成形式为氧化物,碳酸盐和/或氧化物与碳酸盐的混合物。 
本发明还公布了一种低温烧结C0G特性微波介质材料的制备方法,包括: 
按照化学计量配比主料CaMgSi2O6,CaCO3:Mg(OH)2:SiO2=1:1:2,在1100~1200℃煅烧2~4小时; 
按照化学计量配比副料BaZrO3,BaCO3:ZrO2=1:1~1:1.02,在1100~1200℃煅烧3~5小时; 
按照化学计量配比烧结助剂,重量百分比是Li2O10~40wt%、CaO10~30wt%、MgO5~20wt%、SiO210~20wt%、B20310~45wt%,将配比后氧化物混合后以去离子水为介质球磨4~8小时后,出料烘干过筛后,再在700~850℃煅烧1~2个小时,然后冷却粉碎; 
球磨后已合成的主粉体,按化学计量比例加入主料50~58wt%,副料21~26wt%,改性添加剂3%~8wt%,包括MnO0.1~0.3wt%,Al2O30.5~3wt%,Co3O40.1~1wt%,ZnO0.5~5wt%,烧结助剂12~22wt%。按照粉料、介质重量与去离子水比1:4:4混合后球磨6~8个小时;干燥后获得所制备的微波介质陶瓷粉末。 
进一步的,所述助熔剂元素的组成形式为氧化物,碳酸盐和/或氧化物与碳酸盐的混合物。 
综上,本发明所提供的低温烧结C0G特性微波介质材料及其制备方法,以CaMgSi2O6微波介电陶瓷为基础,通过调节改性添加剂的量调整TCC和介电性能,使其符合C0G标准;并使用烧结助剂降低烧结温度至920℃以下,这种低温烧结微波介电陶瓷的组成以及制备比较简单,原材料成本低,且绿色环保,可用于MLCC、微波天线等微波器件的制造。 
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,下面结合实例对本发明作进一步详细说明。但所举实例不作为对本发明的限定。 
本发明提供的一种低温烧结C0G特性微波介质材料,包括主料、副料、改性添加剂和烧结助剂,所述主料是CaMgSi2O6;所述的副料是BaZrO3;所述改性添加剂是MnO、Al2O3、Co3O4、ZnO中的一种或几种;所述的烧结助剂是Li2O、CaO、MgO、SiO2、B2O3中的一种或几种,其中,主料50~58wt%、副料21~26wt%、改性添加剂3~8wt%、烧结助剂12~22wt%。 
优选的,所述主料CaMgSi2O6是CaCO3、Mg(OH)2、SiO2按照摩尔比例1:1:2球磨混合均匀后,在1100~1200℃煅烧2~4小时后获得。 
优选的,所述副料BaZrO3是BaCO3、ZrO2按摩尔比1:1~1:1.02的比例球磨混合均匀后,在1100~1200℃煅烧3~5小时后获得。 
优选的,所述改性添加剂在整个介质材料组成是MnO0.1~0.3wt%,Al2O30.5~3wt%,Co3O40.1~1wt%以及ZnO0.5~5wt%。 
优选的,所述烧结助剂的组成是Li2O10~40wt%、CaO10~30wt%、MgO5~20wt%、SiO210~20wt%以及B20310~45wt%。 
优选的,所述改性添加剂和烧结助剂元素的组成形式为氧化物,碳酸盐和/或氧化物与碳酸盐的混合物。 
本发明还提供一种低温烧结C0G特性微波介质材料的制备方法,包括: 
按照化学计量配比主料CaMgSi2O6,CaCO3:Mg(OH)2:SiO2=1:1:2,在1100~1200℃煅烧2~4小时; 
按照化学计量配比副料BaZrO3,按摩尔比BaCO3:ZrO2=1:1~1:1.02进行配料,在1100~1200℃煅烧3~5小时; 
按照化学计量配比烧结助剂,重量百分比是Li2O10~40wt%、CaO10~30wt%、MgO5~20wt%、SiO210~20wt%、B20310~45wt%,将配比后氧化物混合后以去离子水为介质球磨4~8小时后,出料烘干过筛后,再在700~850℃煅烧1~2个小时,然后冷却粉碎; 
球磨后已合成的主料,按化学计量比例加入主料50~58wt%,副料21~26wt%,改性添加剂3~8wt%,包括MnO0.1~0.3wt%,Al2O30.5~3wt%,Co3O40.1~1wt%,ZnO0.5~5wt%,烧结助剂12~22wt%。按照粉料、介质重量与去离子水比1:4:4混合后球磨6~8个小时;干燥后获得所制备的微波介质陶瓷粉末。 
优选的,所述助熔剂元素的组成形式为氧化物,碳酸盐和/或氧化物与碳酸盐的混合物。 
本发明的主旨是采用CaMgSi2O6体系作为主料,加入BaZrO3调节瓷料的介电性能和温度系数,加入较高比例的烧结助剂降低烧结温度,得到一种低温烧结C0G特性微波介质材料。该瓷料具有介电性能优异、工艺性能好、原料环保、烧结温度低等特点,下面对本发明的内容进一步详述,本发明公布的一种低温烧结C0G特性微波介质材料,原材料均采用化学纯及以上。按照化学计量配比主料CaMgSi2O6如下,CaCO3:Mg(OH)2:SiO2=1:1:2,在1100~1200℃煅烧2~4小时。 
按照化学计量配比副料BaZrO3,BaCO3:ZrO2=1:1~1:1.02,在1100~1200℃煅烧3~5小时。 
按照化学计量配比烧结助剂,具体重量百分比是Li2O10~40wt%、CaO10~30wt%、MgO5~20wt%、SiO210~20wt%、B2O310~45wt%,将配比后氧化物混合后以去离子水为介质球磨4~8小时后,出料烘干过筛后,再在700~850℃煅烧1~2个小时,然后冷却粉碎。 
球磨后已合成的主粉体,按表一中的配方1~12加入主料50~58wt%,副料21~26wt%,改性添加剂3~8wt%,包括MnO0.1~0.3wt%,Al2O30.5~3wt%,Co3O40.1~1wt%,ZnO0.5~5wt%,烧结助剂12~22wt%,烧结助剂方案1~5如表二所示。按照粉料、介质重量与去离子水比1:4:4混合后球磨6~8个小时;干燥后获得所制备的微波介质陶瓷粉末。 
按瓷料生产工艺流程制作MLCC瓷料,然后按MLCC的制作流程加入有机粘合剂和乙醇等溶剂球磨,从而形成浆料,把浆料流延制作成薄膜片,在膜片上印刷全银内电极,交替层叠所需层数,形成生坯电容器芯片,然后在280~400℃温度热处理生坯电容器芯片,以排除有机粘合剂和溶剂,在880~920℃温度烧结2.5~5小时电容器芯片,然后,经表面抛光处理,再在芯片的两端封上一对外部铜Cu电极,使外部电极与内部电极连接,在700~800℃温度范围内热处理外电极,再经电镀处理等工艺,即可得到多层片式陶瓷电容器。 
经过测试得到产品性能如表三所示。 
表一:主料、副料、改性添加剂、烧结助剂配方组成(wt%) 
表二:烧结助剂配方(wt%) 
助熔剂方案 Li2O MgO ZnO B2O3 SiO2
1 20 20 20 20 20
2 10 20 20 35 15
3 15 15 20 15 35
4 40 5 5 10 40
5 30 10 10 35 15
表三:上述瓷料配方所制得的产品性能参数 
编号 介电常数 Qf 温度系数TCC(ppm/℃) 绝缘电阻(Ω)
1 10.1 38400 2~15 >1011
2 10.3 33500 0~12 >1011
3 11.2 21200 -20~-6 >1011
4 10.6 27900 -10~5 >1011
5 10.2 39900 1~13 >1011
6 10.1 34700 2~15 >1011
7 10 37600 4~16 >1011
8 10.2 38900 -2~12 >1011
9 10.4 36100 -3~10 >1011
10 10.5 32200 -6~8 >1011
11 9.8 26500 5~20 >1011
12 10.8 18000 -11~3 >1011
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。 

Claims (8)

1.一种低温烧结C0G特性微波介质材料,包括主料、副料、改性添加剂和烧结助剂,其特征在于,所述主料是CaMgSi2O6;所述的副料是BaZrO3;所述改性添加剂是MnO、Al2O3、Co3O4、ZnO中的一种或几种;所述的烧结助剂是Li2O、CaO、MgO、SiO2、B2O3中的一种或几种,其中,主料50~58wt%、副料21~26wt%、改性添加剂3~8wt%、烧结助剂12~22wt%。
2.如权利要求1所述的低温烧结C0G特性微波介质材料,其特征在于,所述主料CaMgSi2O6是CaCO3、Mg(OH)2、SiO2按摩尔比1:1:2球磨混合均匀后,在1100~1200℃煅烧2~4小时后获得。
3.如权利要求1所述的低温烧结C0G特性微波介质材料,其特征在于,所述副料BaZrO3是BaCO3、ZrO2按摩尔比1:1~1:1.02球磨混合均匀后,在1100~1200℃煅烧3~5小时后获得。
4.如权利要求1所述的低温烧结C0G特性微波介质材料,其特征在于,所述改性添加剂在整个介质材料组成是MnO0.1~0.3wt%,Al2O30.5~3wt%,Co3O40.1~1wt%以及ZnO0.5~5wt%。
5.如权利要求1所述的低温烧结C0G特性微波介质材料,其特征在于,所述烧结助剂的组成是Li2O10~40wt%、CaO10~30wt%、MgO5~20wt%、SiO210~20wt%以及B20310~45wt%。
6.如权利要求1所述的低温烧结C0G特性微波介质材料,其特征在于,所述改性添加剂和烧结助剂元素的组成形式为氧化物,碳酸盐和/或氧化物与碳酸盐的混合物。
7.一种低温烧结C0G特性微波介质材料的制备方法,其特征在于,包括:
按照化学计量配比主料,按摩尔比CaMgSi2O6,CaCO3:Mg(OH)2:SiO2=1:1:2,在1100~1200℃煅烧2~4小时;
按照化学计量配比副料BaZrO3,按摩尔比BaCO3:ZrO2=1:1~1:1.02,在1100~1200℃煅烧3~5小时;
按照化学计量配比烧结助剂,重量百分比是Li2O10~40wt%、CaO10~30wt%、MgO5~20wt%、SiO210~20wt%、B20310~45wt%,将配比后氧化物混合后以去离子水为介质球磨4~8小时后,出料烘干过筛后,再在700~850℃煅烧1~2个小时,然后冷却粉碎;
按化学计量比例加入主料50~58wt%,副料21~26wt%,改性添加剂3%~8wt%,包括MnO0.1~0.3wt%,Al2O30.5~3wt%,Co3O40.1~1wt%,ZnO0.5~5wt%,烧结助剂12~22wt%。按照粉料、介质重量与去离子水重量比1:4:4混合后球磨6~8个小时;干燥后获得所制备的微波介质陶瓷粉末。
8.根据权利要求7所述的低温烧结C0G特性微波介质材料的制备方法,其特征在于,所述助熔剂元素的组成形式为氧化物,碳酸盐和/或氧化物与碳酸盐的混合物。
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