CN101786866B - 一种抗还原性铜内电极高频低温烧结陶瓷介质材料 - Google Patents
一种抗还原性铜内电极高频低温烧结陶瓷介质材料 Download PDFInfo
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Abstract
本发明公开了一种抗还原铜内电极高频低温烧结陶瓷介质材料,可用于铜内电极多层陶瓷电容器制作。由主晶相、改性添加剂、烧结助熔剂组成,主晶相的结构式是MgxBa(1-x)ZrySi(1-y)O3,其中0.8≤x≤0.95,0.05≤y≤0.2,所述的改性添加剂是MnO2、CaO、Li2O、Bi2O3、TiO2中的一种或几种;所述的烧结助熔剂是B2O3、SiO2、ZnO、CuO、K2O、BaO中的一种或几种。上述陶瓷介质材料满足EIA标准COG特性,且材料具备均一、粒度分布均匀、分散性高、成型工艺好的特点,符合环保要求,介电特性优良。
Description
技术领域
本发明涉及陶瓷介质材料及所得元器件的制备方法,尤其涉及一种符合COG特性,且能与铜内电极匹配的高频低温烧结的陶瓷介质材料。
背景技术
随着产品高性能、低成本的市场需求,迫使陶瓷电容器制造商不断寻找既能降低生产成本又能满足更高性能要求的替代材料,是制造商们面临的重大挑战之一。目前的多层片式陶瓷电容器,以下简称MLCC,已基本实现用贱金属化,80%以上的MLCC使用贱金属内电极材料(以镍为主)取代钯银内电极材料,可有效降低约40%的生产成本。更进一步的研究,铜电极的使用被提上日程,相对于其他贱金属而言,铜不仅具有价格上的优势,同时更重要的是在高频领域,铜的电气性能更为优秀。不过铜比镍更容易氧化,且铜的熔点(1083℃)比镍的(1453℃)低,而目前通用瓷料的烧结温度很高,与铜电极难以匹配,从而影响MLCC的电性能。若要使用铜作为内电极材料,首先必然要获得满足要求的陶瓷介质材料。
发明内容
本发明需解决的技术问题是提供一种符合COG瓷介特性、材料分散性高、成型工艺好、满足RoSH条例要求、抗还原铜内电极电容器用陶瓷介质材料。
为解决上述技术问题,本发明提供的技术方案是:一种抗还原铜内电极高频低温烧结陶瓷介质材料,由主晶相、改性添加剂、烧结助熔剂组成,主晶相的结构式是MgxBa(1-x)ZrySi(1-y)O3,其中0.8≤x≤0.95,0.05≤y≤0.2,所述的改性添加剂是MnO2、CaO、Li2O、Bi2O3、TiO2中的一种或几种;所述的烧结助熔剂是B2O3、SiO2、ZnO、CuO、K2O、BaO中的一种或几种。
进一步:上述抗还原铜内电极高频陶瓷介质材料,其特征在于:按摩尔百分比计,主晶相80~95mol%、,改性添加剂1.2~10mol%、烧结助熔剂2.5~18mol%。按摩尔百分比计,改性添加剂在整个抗还原铜内电极陶高频陶瓷介质材料中的组成是MnO2 0.2~0.5mol%、CaO 0~1.0mol%、Li2O 1.0~3.0mol%、Bi2O3 0~5.0mol%、TiO2 0~1.0mol%。按摩尔百分比计,所述的烧结助熔剂在整个抗还原铜内电极高频低温烧结陶瓷介质材料中的组成是B2O3 1.0~3.0mol%、SiO2 0~6.0mol%、ZnO 1.5~6.0mol%、CuO 0~1.0mol%、K2O 0~1.0mol%、BaO 0~1.0mol%。所述的主晶相由Mg(OH)2、SiO2、BaCO3和ZrO2球磨混合均匀后,在1050~1170℃温度预煅烧制得。
上述组成中,主成分选择具有良好高频性能的复合物MgxBa(1-x)ZrySi(1-y)O3,该复合物介电常数较低,较低的介质损耗角正切值,和近乎线性的介电-温度特性,这些都能从主材料上保证了本发明材料制作成MLCC具有优良的电性能。改性添加剂材料的加入,能够使材料的介电常数保持在10左右,并且很好的调节陶瓷介质材料的温度系数,使介电-温度特性近乎线性;同时还能抑制瓷体晶粒的异常生长,使晶粒生长均匀,这对提高介质材料的耐压强度起到很好的作用,并最终使本发明获得的MLCC具有高可靠性。烧结助熔剂的一个主要作用是降低本发明陶瓷材料的烧结温度,使材料能在小于1100℃的温度下进行致密烧结,烧结后的陶瓷体晶粒生长均匀,具有高致密度,进一步保证了制成的MLCC具有高可靠性。本发明采用了还原气氛烧结的MgxBa(1-x)ZrySi(1-y)O3体系的非铁电性铜电极介质陶瓷,烧结温度低于1100℃,瓷料可与铜(Cu)内电极浆料匹配,瓷料性能优越。
在用上述高频低温烧结陶瓷介质材料制备MLCC产品的方法中,按常规瓷料生产工艺流程制作MLCC瓷料,包括瓷浆制备、制作介质膜片、交替叠印内电极和介质层、坯块干燥、层压、切割、排胶、烧结、倒角、封端、烧端工艺。即按片式MLCC的制作流程加入有机粘合剂和乙醇等溶剂,从而形成浆料,把浆料流延制作成薄膜片,在膜片上印刷铜Cu内电极,交替层叠所需层数,形成生坯MLCC芯片,然后在200~300℃温度热处理生坯MLCC芯片,以排除有机粘合剂和溶剂,在1000~1100℃温度烧结2.5~5小时MLCC芯片,然后,经表面处理,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830~900℃温度范围内热处理外电极,再经电镀处理等工艺,即可得到MLCC产品。该制备方法中,产品烧结温度低,对工艺设备的要求简单,陶瓷介质材料粒度分布均匀,烧结中瓷体晶粒生长均匀、致密,MLCC产品电气性能优良。
具体实施方式
本发明的主旨是采用MgxBa(1-x)ZrySi(1-y)O3体系为材料主晶相,加入改性添加剂调节性能,并加入烧结助熔剂帮助降低烧结温度,采用常规的工艺制成所需粉体,得到一种符合COG瓷介特性、材料分散性高、成型工艺好的低温烧结陶瓷介质材料,且在制作MLCC产品时,烧结温度低、晶粒生长均匀、致密,产品无缺陷或缺陷小。下面结合实施例对本发明的内容作进一步详述,实施例中所提及的内容并非对本发明的限定,材料配方选择可因地制宜而对结果无实质性的影响。
首先,简述本发明材料配方的基本方案:一种抗还原铜高频低温烧结陶瓷介质材料,由主晶相、改性添加剂、烧结助熔剂组成,主晶相的结构式是MgxBa(1-x)ZrySi(1-y)O3其中0.8≤x≤0.95,0.05≤y≤0.2,所述的改性添加剂是MnO2、CaO、Li2O、Bi2O3、TiO2中的一种或几种;所述的烧结助熔剂是B2O3、SiO2、ZnO、CuO、K2O、BaO中的一种或几种。
实施例1
一种抗还原铜内电极高频低温烧结陶瓷介质材料,采用纯度为99.5%以上的原材料,以0.8mol Mg(OH)2、0.8mol SiO2、0.2mol BaCO3和0.2molZrO2的混合比例,球磨均匀,在1150℃温度下煅烧该混合物3小时,即得主晶相为Mg0.8Ba0.2Si0.8Zr0.2O3材料。然后按预定比例添加如表1所示的改性添加剂和烧结助剂。
表1:主晶相、改性添加剂、烧结助熔剂配方组成
按本领域技术人员常用的瓷料生产工艺流程制作陶瓷介质瓷料,然后按常用的MLCC的制作流程加入有机粘合剂和乙醇等溶剂,从而形成浆料,把浆料流延制作成薄膜片,在膜片上印刷铜Cu内电极,交替层叠所需层数,形成生坯MLCC芯片,然后在200~300℃温度热处理生坯MLCC芯片,以排除有机粘合剂和溶剂。在1000~1100℃温度烧结2.5~5小时MLCC芯片,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830~900℃温度范围内热处理外电极。再经电镀处理等工艺,即可得到MLCC产品。该MLCC产品具有容量稳定、性能好的特点。在室温25℃时,利用HP4278电桥,在1MHz,1.0V(AC)下测试本MLCC产品容量、损耗;利用SF2512快速绝缘机,施加100V的DC额定电压10秒,测试绝缘电阻;利用高低温箱,在-55~+125℃之间,测试介电常数-温度系数;利用HP4991A测试本MLCC产品频率特性等;产品性能测试参数如表2的1~10号材料配方对应的MLCC测试参数。
表2:根据上述陶瓷介质材料制得的MLCC产品性能参数
发明材料编号 | 介电常数 | 介电损耗DF(×10-4) | 温度系数-55~+125℃(ppm/℃) | 绝缘电阻(Ω) |
1 | 10.1 | 0.9 | -10~20 | >1011 |
2 | 9.8 | 0.7 | 5~15 | >1011 |
3 | 9.5 | 0.9 | 13~20 | >1011 |
4 | 8.9 | 0.9 | -6~17 | >1011 |
5 | 9.7 | 1.2 | 5~13 | >1011 |
6 | 9.1 | 1.1 | 6~9 | >1011 |
7 | 10.2 | 0.7 | -2~6 | >1011 |
8 | 11.3 | 0.9 | 8~11 | >1011 |
9 | 10.3 | 1.5 | -5~7 | >1011 |
10 | 9.8 | 1.0 | -8~2 | >1011 |
实施例2
一种抗还原铜内电极高频低温烧结陶瓷介质材料,采用纯度为99.5%以上的原材料,以0.9mol Mg(OH)2、0.9mol SiO2、0.1mol BaCO3和0.1mol ZrO2的混合比例,球磨均匀,在1150℃温度煅烧该混合物3小时,即得主晶相为Mg0.9Ba0.1Si0.9Zr0.1O3材料。然后按预定比例添加如表3所示的改性添加剂和烧结助剂。
表3:主晶相、改性添加剂、烧结助熔剂配方组成
按实施例1的方法制造和测试MLCC的电性能,测试结果如表4所示:
表4:根据上述陶瓷介质材料制得的MLCC产品性能参数
发明材料编号 | 介电常数 | 介电损耗DF(×10-4) | 温度系数-55~+125℃(ppm/℃) | 绝缘电阻(Ω) |
11 | 11.6 | 1.3 | -3~20 | >1011 |
12 | 11.2 | 0.8 | 14~27 | >1011 |
13 | 10.3 | 1.5 | 2~13 | >1011 |
14 | 9.7 | 1.0 | -8~16 | >1011 |
15 | 9.3 | 0.6 | 10~23 | >1011 |
16 | 10.6 | 0.8 | 4~26 | >1011 |
17 | 9.2 | 0.9 | -10~22 | >1011 |
18 | 8.9 | 1.1 | 3~17 | >1011 |
19 | 9.5 | 0.7 | -5~17 | >1011 |
20 | 10.1 | 1.0 | 6~15 | >1011 |
实施例3
一种抗还原铜内电极高频低温烧结陶瓷介质材料,采用纯度为99.5%以上的原材料,以0.95mol Mg(OH)2、0.95mol SiO2、0.05mol BaCO3和0.05molZrO2的混合比例,球磨均匀,在1150℃温度煅烧该混合物3小时,即得主晶相为Mg0.95Ba0.05Si0.95Zr0.05O3材料。然后按预定比例添加如表5所示的改性添加剂和烧结助剂。
表5:主晶相、改性添加剂、烧结助熔剂配方组成
按实施例1的方法制造和测试MLCC的电性能,测试结果如表6所示:
表6:根据上述陶瓷介质材料制得的MLCC产品性能参数
发明材料编号 | 介电常数 | 介电损耗DF(×10-4) | 温度系数-55~+125℃(ppm/℃) | 绝缘电阻(Ω) |
21 | 8.9 | 0.7 | -12~22 | >1011 |
22 | 9.1 | 0.8 | 4~16 | >1011 |
23 | 9.2 | 0.6 | 11~23 | >1011 |
24 | 9.5 | 1.0 | -8~19 | >1011 |
25 | 9.7 | 1.2 | 10~23 | >1011 |
26 | 10.0 | 1.1 | 5~16 | >1011 |
27 | 10.4 | 0.8 | -5~20 | >1011 |
28 | 10.7 | 1.3 | 3~19 | >1011 |
29 | 11.2 | 1.2 | -5~17 | >1011 |
30 | 11.5 | 1.0 | -6~15 | >1011 |
Claims (6)
1.一种抗还原铜内电极高频低温烧结陶瓷介质材料,由主晶相、改性添加剂、烧结助熔剂组成,其特征在于:主晶相的结构式是MgxBa(1-x)ZrySi(1-y)O3其中0.8≤x≤0.95,0.05≤y≤0.2,所述的改性添加剂是MnO2、CaO、Li2O、Bi2O3、TiO2中的一种或几种;所述的烧结助熔剂是B2O3、SiO2、ZnO、CuO、K2O、BaO中的一种或几种。
2.根据权利要求1所述的抗还原铜内电极高频低温烧结陶瓷介质材料,其特征在于:按摩尔百分比计,主晶相80~95mol%、改性添加剂1.2~10mol%、烧结助熔剂2.5~18mol%。
3.根据权利要求2所述的抗还原铜内电极高频低温烧结陶瓷介质材料,其特征在于:所述的主晶相MgxBa(1-x)ZrySi(1-y)O3,其中0.8≤x≤0.95,0.05≤y≤0.2,由Mg(OH)2、BaCO3、ZrO2、SiO2按比例球磨混合均匀后,在1050℃~1170℃温度预煅烧制得。
4.根据权利要求2所述的抗还原铜内电极高频低温烧结陶瓷介质材料,其特征在于:按摩尔百分比计,改性添加剂在整个抗还原铜内电极陶高频陶瓷介质材料中的组成是MnO2 0.2~0.5mol%、CaO 0~1.0mol%、Li2O 1.0~3.0mol%、Bi2O3 0~5.0mol%、TiO2 0~1.0mol%。
5.根据权利要求2所述的抗还原铜内电极高频低温烧结陶瓷介质材料,其特征在于:按摩尔百分比计,所述的烧结助熔剂在整个抗还原铜内电极高频低温烧结陶瓷介质材料中的组成是B2O3 1.0~3.0mol%、SiO2 0~6.0mol%、ZnO1.5~6.0mol%、CuO 0~1.0mol%、K2O 0~1.0mol%、BaO 0~1.0mol%。
6.根据权利要求1~5中任意一项所述的抗还原铜内电极高频低温烧结陶瓷介质材料,其特征在于:用该陶瓷介质材料制作的陶瓷电容器在还原气氛下烧结,陶瓷电容器内电极材料使用铜,烧结温度1000℃~1100℃,获得的陶瓷电容器电气性能满足高频COG类陶瓷材料特性。
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