CN106927814A - 一种氧化锌压敏电阻器介质材料及其应用 - Google Patents

一种氧化锌压敏电阻器介质材料及其应用 Download PDF

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CN106927814A
CN106927814A CN201710192788.4A CN201710192788A CN106927814A CN 106927814 A CN106927814 A CN 106927814A CN 201710192788 A CN201710192788 A CN 201710192788A CN 106927814 A CN106927814 A CN 106927814A
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嵇名奥
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Abstract

本发明提供了一种氧化锌压敏电阻器介质材料及其应用，该氧化锌压敏电阻器介质材料按摩尔份数计，其组成为：主成分ZnO 92‑100份，添加剂成分Sb2O3 1‑3份、Bi2O3 1.5‑2.5份、TiO2 0.2‑0.8份、MnO2 0.8‑2份、Co2O3 0.1‑0.5份、Cr2O3 0.05‑0.5份、MoO3 0.05‑0.3份、CeO2 0.02‑0.3份、AgNO3 0.05‑0.2份，本发明氧化锌压敏电阻器介质材料以氧化锌为主原料，采用无铅配方添加Sb2O3、Bi2O3、TiO2、MnO2、Co2O3、Cr2O3、MoO3、CeO2、AgNO39种添加剂，可在低温下进行烧结，不仅满足了环保的要求，同时制备工艺简单，大大降低了生产成本，由本发明制得的氧化锌压敏电阻器介质材料的压敏电压为562‑582V/mm，非线性系数α＞50，漏电流IL＜10μA，综合性能优良。

Description

一种氧化锌压敏电阻器介质材料及其应用
技术领域
本发明涉及压敏电阻材料领域，具体涉及一种氧化锌压敏电阻器介质材料及其应用。
背景技术
随着电子工业的飞速发展，尤其是电子集成化和微型化的迫切需要，对压敏电阻电子陶瓷材料提出了更加严格的要求。压敏陶瓷材料的低压化、低漏电流、高非线性系数、低成本和高可靠性的性是压敏陶瓷材料获得广泛应用的大趋势。其中氧化锌压敏陶瓷是以氧化锌为主体，适当添加Bi2O3、Sb2O3、Co2O3、NiO、MnO2等氧化物而制备的功能电子陶瓷。氧化物添加剂除少量与ZnO固溶，在烧结过程中使ZnO半导化外，其余主要在ZnO晶粒之间形成高阻晶界，由于晶界的存在，使其表现出优良的非线性性能，广泛用于制造各种半导体器件的过电压保护、电子设备的雷击流通涌保护、各种负荷开关的浪涌吸收、各种装置中的瞬间脉冲抑制等电子保护装置。
目前，市场上的氧化锌压敏电阻器介质中，主要成分氧化锌所占比例为87-93％，其他成分一般占重量比例为7-13％。氧化锌是氧化锌压敏电阻器介质的基础材料，而氧化锌压敏器介质中其它成分的熔点大多低于氧化锌，目前行业中氧化锌压敏电阻器瓷介材料主要是九元系配方，氧化锌压敏电阻器芯片烧结一般在高温1250-1300℃、保温2.5h左右的条件下烧成，能耗较高。中国专利CN1564270A“低温烧结ZnO多层片式压敏电阻器及其制造方法”，公开了一种低温烧结添加剂(主要由Bi2O3、Sb2O3、B2O3、TiO2组成)来降低压敏电阻器陶瓷烧结温度的方法，但TiO2会减小压敏电阻的非线性系数及增加压敏电阻的漏流，劣化压敏电阻的性能。同时无铅化、低毒化是国际环境保护的必然趋势，因此有必要开发出低温烧结的、综合性能良好的无铅化ZnO压敏陶瓷材料及其制备技术。
发明内容
为了克服现有技术中存在的问题，本发明提供了一种氧化锌压敏电阻器介质材料。
为实现以上目的，本发明通过以下技术方案予以实现：
一种氧化锌压敏电阻器介质材料，按摩尔份数计，其组成为：主成分ZnO 92-100份，添加剂成分Sb2O3 1-3份、Bi2O3 1.5-2.5份、TiO2 0.2-0.8份、MnO2 0.8-2份、Co2O3 0.1-0.5份、Cr2O3 0.05-0.5份、MoO3 0.05-0.3份、CeO2 0.02-0.3份、AgNO3 0.05-0.2份。
优选地，所述氧化锌压敏电阻器介质材料按摩尔份数计，其组成为：主成分ZnO 96份，添加剂成分Sb2O3 1.8份、Bi2O3 2.2份、TiO2 0.5份、MnO2 1.6份、Co2O3 0.4份、Cr2O3 0.3份、MoO3 0.18份、CeO2 0.12份、AgNO3 0.12份。
优选地，所述氧化锌压敏电阻器介质材料由以下方法制备得到：
(1)按配方比称取各原料；
(2)将主成分ZnO与Sb2O3、Bi2O3、TiO2、MnO2、Co2O3、Cr2O3、MoO3、CeO2、AgNO3 9种添加剂原料混合均匀后置于高能球磨机中进行湿法球磨，球磨结束后经干燥得混合料粉；
(3)将所得混合料粉按照常规制备工艺，经过造粒压片制得素坯，再将素坯在880-920℃烧结，即得所述氧化锌压敏电阻器介质材料。
优选地，所述步骤(2)中：采用氧化锆磨球，在高能球磨机中以乙醇作为介质进行湿法球磨，球磨时间为6-8h，其中总原料量∶氧化锆磨球∶乙醇的质量比为1∶15-20∶3-6。
优选地，所述步骤(2)中高能球磨机的转速为300-500转/min。
优选地，所述步骤(3)中的烧结时间为2-3.5h。
本发明的有益效果是：本发明氧化锌压敏电阻器介质材料以氧化锌为主原料，采用无铅配方添加Sb2O3、Bi2O3、TiO2、MnO2、Co2O3、Cr2O3、MoO3、CeO2、AgNO3 9种添加剂，可在(880-920℃)低温下进行烧结，不仅满足了环保的要求，同时制备工艺简单，大大降低了氧化锌压敏电阻器介质材料的生产成本。由本发明制得的氧化锌压敏电阻器介质材料的压敏电压为562-582V/mm，非线性系数α＞50，漏电流IL＜10μA，综合性能优良。
具体实施方式
下面结合具体实施例进一步说明本发明的技术解决方案，实施例不能理解为是对技术解决方案的限制。
实施例1：
一种氧化锌压敏电阻器介质材料，按摩尔份数计，其组成为：主成分ZnO 96份，添加剂成分Sb2O3 1.8份、Bi2O3 2.2份、TiO2 0.5份、MnO2 1.6份、Co2O3 0.4份、Cr2O3 0.3份、MoO3 0.18份、CeO2 0.12份、AgNO3 0.12份。
上述氧化锌压敏电阻器介质材料由以下方法制备得到：
(1)按配方比称取各原料；
(2)将主成分ZnO与Sb2O3、Bi2O3、TiO2、MnO2、Co2O3、Cr2O3、MoO3、CeO2、AgNO3 9种添加剂原料混合均匀后置于高能球磨机中，采用氧化锆磨球，并以乙醇作为介质进行湿法球磨，球磨时间为8h，高能球磨机的转速为300转/min；其中总原料量∶氧化锆磨球∶乙醇的质量比为1∶20∶6；球磨结束后经干燥得混合料粉；
(3)将所得混合料粉按照常规制备工艺，经过造粒压片制得素坯，再将素坯在900℃烧结3h，即得所述氧化锌压敏电阻器介质材料。
经检测分析可知上述氧化锌压敏电阻器介质材料的压敏电压为582V/mm，非线性系数α为55，漏电流I L为6.8μA。
实施例2：
一种氧化锌压敏电阻器介质材料，按摩尔份数计，其组成为：主成分ZnO 100份，添加剂成分Sb2O3 2份、Bi2O3 2.5份、TiO2 0.6份、MnO2 2份、Co2O3 0.25份、Cr2O3 0.2份、MoO30.05份、CeO2 0.02份、AgNO3 0.2份。
上述氧化锌压敏电阻器介质材料由以下方法制备得到：
(1)按配方比称取各原料；
(2)将主成分ZnO与Sb2O3、Bi2O3、TiO2、MnO2、Co2O3、Cr2O3、MoO3、CeO2、AgNO3 9种添加剂原料混合均匀后置于高能球磨机中，采用氧化锆磨球，并以乙醇作为介质进行湿法球磨，球磨时间为6h，高能球磨机的转速为500转/min；其中总原料量∶氧化锆磨球∶乙醇的质量比为1∶18∶5；球磨结束后经干燥得混合料粉；
(3)将所得混合料粉按照常规制备工艺，经过造粒压片制得素坯，再将素坯在880℃烧结3.5h，即得所述氧化锌压敏电阻器介质材料。
经检测分析可知上述氧化锌压敏电阻器介质材料的压敏电压为564V/mm，非线性系数α为51，漏电流I L为8μA。
实施例3：
一种氧化锌压敏电阻器介质材料，按摩尔份数计，其组成为：主成分ZnO 92份，添加剂成分Sb2O3 1份、Bi2O3 2.2份、TiO2 0.2份、MnO2 1.4份、Co2O3 0.5份、Cr2O3 0.5份、MoO30.15份、CeO2 0.3份、AgNO3 0.05份。
上述氧化锌压敏电阻器介质材料由以下方法制备得到：
(1)按配方比称取各原料；
(2)将主成分ZnO与Sb2O3、Bi2O3、TiO2、MnO2、Co2O3、Cr2O3、MoO3、CeO2、AgNO3 9种添加剂原料混合均匀后置于高能球磨机中，采用氧化锆磨球，并以乙醇作为介质进行湿法球磨，球磨时间为7h，高能球磨机的转速为400转/min；其中总原料量∶氧化锆磨球∶乙醇的质量比为1∶15∶3；球磨结束后经干燥得混合料粉；
(3)将所得混合料粉按照常规制备工艺，经过造粒压片制得素坯，再将素坯在920℃烧结2h，即得所述氧化锌压敏电阻器介质材料。
经检测分析可知上述氧化锌压敏电阻器介质材料的压敏电压为562V/mm，非线性系数α为51，漏电流I L为9.1μA。
实施例4：
一种氧化锌压敏电阻器介质材料，按摩尔份数计，其组成为：主成分ZnO 94份，添加剂成分Sb2O3 3份、Bi2O3 1.5份、TiO2 0.8份、MnO2 0.8份、Co2O3 0.1份、Cr2O3 0.05份、MoO30.3份、CeO2 0.8份、AgNO3 0.16份。
上述氧化锌压敏电阻器介质材料的制备方法同实施例1。
经检测分析可知上述氧化锌压敏电阻器介质材料的压敏电压为568V/mm，非线性系数α为52，漏电流I L为8μA。
实施例5：
一种氧化锌压敏电阻器介质材料，按摩尔份数计，其组成为：主成分ZnO 92份，添加剂成分Sb2O3 3份、Bi2O3 2.5份、TiO2 0.6份、MnO2 1.2份、Co2O3 0.18份、Cr2O3 0.25份、MoO3 0.15份、CeO2 0.3份、AgNO3 0.2份。
上述氧化锌压敏电阻器介质材料的制备方法同实施例1。
经检测分析可知上述氧化锌压敏电阻器介质材料的压敏电压为574V/mm，非线性系数α为52，漏电流I L为7.8μA。
实施例6：
一种氧化锌压敏电阻器介质材料，按摩尔份数计，其组成为：主成分ZnO 98份，添加剂成分Sb2O3 1.5份、Bi2O3 2份、TiO2 0.5份、MnO2 0.8份、Co2O3 0.5份、Cr2O3 0.5份、MoO30.25份、CeO2 0.02份、AgNO3 0.15份。
上述氧化锌压敏电阻器介质材料的制备方法同实施例2。
经检测分析可知上述氧化锌压敏电阻器介质材料的压敏电压为580V/mm，非线性系数α为53，漏电流I L为7μA。
以上为对本发明实施例的描述，通过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 (7)

1.一种氧化锌压敏电阻器介质材料，其特征在于，按摩尔份数计，其组成为：主成分ZnO92-100份，添加剂成分Sb2O3 1-3份、Bi2O3 1.5-2.5份、TiO2 0.2-0.8份、MnO2 0.8-2份、Co2O30.1-0.5份、Cr2O3 0.05-0.5份、MoO3 0.05-0.3份、CeO2 0.02-0.3份、AgNO3 0.05-0.2份。
2.根据权利要求1所述的氧化锌压敏电阻器介质材料，其特征在于，按摩尔份数计，其组成为：主成分ZnO 96份，添加剂成分Sb2O3 1.8份、Bi2O3 2.2份、TiO2 0.5份、MnO2 1.6份、Co2O3 0.4份、Cr2O3 0.3份、MoO3 0.18份、CeO2 0.12份、AgNO3 0.12份。
3.根据权利要求1所述的氧化锌压敏电阻器介质材料，其特征在于，所述介质材料由以下方法制备得到：
(1)按配方比称取各原料；
(2)将主成分ZnO与Sb2O3、Bi2O3、TiO2、MnO2、Co2O3、Cr2O3、MoO3、CeO2、AgNO3 9种添加剂原料混合均匀后置于高能球磨机中进行湿法球磨，球磨结束后经干燥得混合料粉；
(3)将所得混合料粉按照常规制备工艺，经过造粒压片制得素坯，再将素坯在880-920℃烧结，即得所述氧化锌压敏电阻器介质材料。
4.根据权利要求3所述的氧化锌压敏电阻器介质材料，其特征在于，所述步骤(2)中：采用氧化锆磨球，在高能球磨机中以乙醇作为介质进行湿法球磨，球磨时间为6-8h，其中总原料量∶氧化锆磨球∶乙醇的质量比为1∶15-20∶3-6。
5.根据权利要求3所述的氧化锌压敏电阻器介质材料，其特征在于，所述步骤(2)中高能球磨机的转速为300-500转/min。
6.根据权利要求3所述的氧化锌压敏电阻器介质材料，其特征在于，所述步骤(3)中的烧结时间为2-3.5h。
7.如权利要求1-6任一项所述的氧化锌压敏电阻器介质材料在压敏电阻器中的应用。
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