CN110655400A - 大通流容量氧化锌压敏电阻陶瓷材料、其制备方法及其电阻器的制备方法 - Google Patents

大通流容量氧化锌压敏电阻陶瓷材料、其制备方法及其电阻器的制备方法 Download PDF

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CN110655400A
CN110655400A CN201910942758.XA CN201910942758A CN110655400A CN 110655400 A CN110655400 A CN 110655400A CN 201910942758 A CN201910942758 A CN 201910942758A CN 110655400 A CN110655400 A CN 110655400A
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zinc oxide
mol
ceramic material
flow capacity
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李经仁
林康
邹海雄
张军志
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XIAMEN SONGYUAN ELECTRONICS CO Ltd
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Abstract

本发明公开了大通流容量氧化锌压敏电阻陶瓷材料，包括主材料和改性剂，所述的主材料由以下摩尔百分比的原料组成：氧化锌92～95 mol%，氧化铋0.8～1.5 mol%，氧化锑1.2～1.5 mol%，三氧化二钴1.0～1.5 mol%，碳酸锰1.0～1.5 mol%，三氧化二镍0.5～1.0 mol%，氧化铬0.5～1.0 mol%，改性剂为由占主材料的质量百分比为以下比例的原料组成：钨酸盐0.2～1%，铟化物0.2～0.5%，九水合销酸铝0.01～0.05%。本发明还公开了大通流容量氧化锌压敏电阻陶瓷材料的制备方法，以及大通流容量氧化锌压敏电阻器的制备方法，本发明通过在氧化锌压敏电阻陶瓷材料的主材料内添加改性剂，形成了晶粒分布均匀，完整致密的陶瓷结构，极大的提高了通流容量，提升了产品的可靠性和安全性。

Description

大通流容量氧化锌压敏电阻陶瓷材料、其制备方法及其电阻 器的制备方法
技术领域
本发明涉及电阻材料技术领域，尤其是氧化锌压敏电阻陶瓷材料、其制备方法及氧化锌压敏电阻器的制备方法。
背景技术
氧化锌压敏电阻作为主流的防护器件，随着人类生存生活安全防护意识的提高，其运用越来越广：如在电力系统、电子线路中，用于吸收大气过电压和操作过电压，超导移能中的应用、发电机组灭磁、电器设备、半导体器件及各种电机过压保护等方面都具有广泛的应用前景。
电子电力、通讯、运输设备的安全运行直接影响生存发展，通流容量作为氧化锌压敏电阻器的重要指标，直接决定了产品的可靠性，安全性，因此开发一款具有大通流容量的氧化锌压敏电阻瓷料可以很好的契合市场对高性能压敏电阻的要求。
公布号为105481363A的发明专利公开了一种大通流容量、低残压、高梯度氧化锌压敏电阻陶瓷，其通过添加Ag和Y元素，从而减小泄漏电流，实现大通流容量。
发明内容
本发明的目的在于提供一种氧化锌压敏电阻陶瓷材料、其制备方法及其电阻器的制备方法，以得到晶粒均匀致密的材料，实现其大通流容量。为实现上述目的，本发明采用以下技术方案：
本发明公开了一种大通流容量氧化锌压敏电阻陶瓷材料，包括主材料和改性剂，所述的主材料由以下摩尔百分比的原料组成：氧化锌92～95mol％，氧化铋0.8～1.5mol％，氧化锑1.2～1.5mol％，三氧化二钴1.0～1.5mol％，碳酸锰1.0～1.5mol％，三氧化二镍0.5～1.0mol％，氧化铬0.5～1.0mol％，所述的改性剂为由占主材料的质量百分比为以下比例的原料组成：钨酸盐0.2～1％，铟化物0.2～0.5％，九水合销酸铝0.01～0.05％。
进一步地，所述的改性剂还包括占主材料的质量百分比为以下比例的若干种原料组成：
二氧化锆0～0.5％，二氧化硅0～0.5％，硝酸银0～0.05％，氧化硼0～0.1％。
优选地，所述的钨酸盐为钨酸锌。所述的铟化物为锑化铟。
本发明还公开了大通流容量氧化锌压敏电阻陶瓷材料的制备方法，采用以上大通流容量氧化锌压敏电阻陶瓷材料按照以下步骤制备：
S1.将主材料及改性剂比例称量混合得到原料。
S2.将原料加入球磨机中，往球磨机中加入研磨介质及水，于球磨机内混合至粒径小于1μm后加入粘结剂，混合均匀，得到研磨料；
S3.将研磨料加入喷雾造粒塔进行喷雾造粒得到大通流容量氧化锌压敏陶瓷材料粉末。
优选地，步骤S2中按原料：研磨介质：水＝1:5:0.5的质量比例添加至球磨机中。
其中，所述的研磨介质为氧化锆球磨珠，所述的粘结剂为丙烯酸系粘结剂。
本发明还公开了大通流容量氧化锌压敏电阻器的制备方法，采用上述方法制备得到大通流容量氧化锌压敏电阻陶瓷材料，成型为3.2g/cm3～3.3g/cm3的坯体，在空气气氛下升温至1150℃～1200℃烧结，获得氧化锌压敏电阻器瓷片，再印上银电极，经560℃～580℃还原后获得氧化锌压敏电阻器芯片，焊接包封后制得成品氧化锌压敏电阻器。
由于采用了上述结构，本发明具有如下有益效果：
1、本发明通过在氧化锌压敏电阻陶瓷材料的主材料内添加改性剂，改性剂的添加影响了氧化锌烧结体组成分布和微观结构，因此形成了晶粒分布均匀，完整致密的陶瓷结构，材料缺陷少，极大的提高了通流容量，提升了产品的可靠性和安全性，具有很好的经济效益。
2、添加改性剂钨酸锌，钨酸锌偏析在晶界层中，形成钉扎作用，阻碍晶粒的异常长大，细化晶粒生长，同时进入晶界后有钳制杂质离子能级的作用，提高晶界势垒，提高通流容量。添加改性剂锑化铟，锑化铟中In3+与ZnO晶粒形成填隙固溶体，In3+禁带范围小，电子迁移度大，利于降低晶粒电阻，使晶粒半导化，提高材料通流容量。
附图说明
图1是本发明实施例编号1的测试样大通流容量氧化锌压敏电阻器的表面未处理电镜图。
图2是本发明实施例编号1的对比样氧化锌压敏电阻器的表面未处理电镜图。
图3是本发明实施例编号1的测试样大通流容量氧化锌压敏电阻器的表面处理后的电镜图。
图4是本发明实施例编号1的对比样氧化锌压敏电阻器的表面处理后的电镜图。
具体实施方式
为了使本领域的技术人员更好地理解本发明的技术方案，下面结合附图和具体实施例对本发明作进一步详细的描述。
本实施例公开了一种大通流容量氧化锌压敏电阻陶瓷材料，包括主材料和改性剂，主主材料由以下摩尔百分比的原料组成：氧化锌(ZnO)92～95mol％，氧化铋(Bi2O3)0.8～1.5mol％，氧化锑(Sb2O3)1.2～1.5mol％，三氧化二钴(Co2O3)1.0～1.5mol％，碳酸锰(MnCO3)1.0～1.5mol％，三氧化二镍(Ni2O3)0.5～1.0mol％，氧化铬(Cr2O3)0.5～1.0mol％。以上主材料均可以通过直接购买获得。主材料的配比组成可如表1所示，表1中列出了8种实施方式(M1～M8)的配比方案。
表1大通流容量氧化锌压敏电阻陶瓷材料主材料
Figure BDA0002223359360000031
改性剂为由占主材料的质量百分比为以下比例的原料组成：钨酸盐0.2～1％，铟化物0.2～0.5％，九水合销酸铝(AlNO3.9H2O)0.01～0.05％，二氧化锆(ZrO2)0～0.5％，二氧化硅(SiO2)0～0.5％，硝酸银(AgNO3)0～0.05％，氧化硼(B2O3)0～0.1％。其中钨酸盐可以为钨酸锌(ZnWO4)，钨酸铋(Bi2O12W3)，钨酸钴(CoWO4)，钨酸锰(MnO4W)等，本实施例选用钨酸锌(ZnWO4)。铟化物选用锑化铟(InSb)。改性剂的配比组成可如表2所示，表2列出了16种实施方式。
表2大通流容量氧化锌压敏电阻陶瓷材料
Figure BDA0002223359360000041
本发明公开了上述大通流容量氧化锌压敏电阻陶瓷材料的制备方法，采用以下步骤制备。
S1.按表1和表2将主材料及改性剂比例称量混合得到原料。
S2.将原料加入球磨机中，往球磨机中加入研磨介质及水，按原料：研磨介质：水＝1:5:0.5的质量比例添加至球磨机中，于球磨机内混合至粒径小于1μm。研磨介质选用氧化锆球磨珠，研磨时间大于9H。然后加入粘结剂，粘结剂选用丙烯酸系粘结剂，混合均匀，得到研磨料。
S3.将研磨料加入喷雾造粒塔进行喷雾造粒得到大通流容量氧化锌压敏陶瓷材料粉末。
本发明还公开了大通流容量氧化锌压敏电阻器的制备方法，采用以下步骤制备。
S1-S4.同上制备步骤得到大通流容量氧化锌压敏电阻陶瓷材料。
S5.将制备得到的大通流容量氧化锌压敏电阻陶瓷材料，在6MP的压力下，成型直径16.4mm，厚度2.5mm的圆片型坯体(密度为3.2g/cm3～3.3g/cm3)，在空气气氛下升温至1150℃～1200℃烧结，获得氧化锌压敏电阻器瓷片，再印上直径11mm银电极，经580℃还原后获得氧化锌压敏电阻器芯片，焊接包封后制得成品氧化锌压敏电阻器。
将本发明制备得到的大通流容量氧化锌压敏电阻器进行如下测试。
将本发明制备方法(采用表2的配比原料)按照表3的烧结温度制备得到16组大通流容量氧化锌压敏电阻器测试样，同时增加16组相应对比样，对比样的主材料与表2中的实施例相同，对比样的改性剂未添加钨酸锌(ZnWO4)及锑化铟(InSb)，其余改性剂与表2中的一致。
将16组测试样和16组对比样放在压敏测试仪上测试压敏参数，经M20电涌发生器测试通流容量，10KA冲击一次，得到表3的测试结果。
表3通流容量测试实验
Figure BDA0002223359360000042
Figure BDA0002223359360000051
从表3看出本发明的实施例在1150～1200℃的温度下烧结，产品实现了大通流容量，达到10KA/cm2.满足产品大通流容量的要求。而对比样在1150～1200℃的温度下烧结，在10KA冲击下均炸裂失效。
将表3中的实施例编号1的测试样和对比样放入电子显微镜下观察其结构，得到图1～图4，其中图1、图3为测试样的电镜图，图2、图4为对比样的电镜图。从图中可以看出，本发明制得的大通流容量氧化锌压敏电阻器的瓷样表面晶粒形形貌均匀，一致性好，结构致密度，空洞少。而对比样的表面晶粒大小不一，空洞多，致密性差。由于本发明在配方中增加了改性剂钨酸盐、铟化物，这些改性剂掺杂粒子影响了氧化锌烧结体微观结构，利用掺杂粒子的特性，产生不同的结构分布，通过控制掺杂粒子的配比抑制晶粒的异常长大，得到晶粒分布均匀、晶粒晶界结构完整致密的烧结体，因此本发明的材料配方在1150～1200℃温度烧结，得到了大通流容量达10KA/cm2的氧化锌压敏陶瓷材料。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。

Claims (8)

1.大通流容量氧化锌压敏电阻陶瓷材料，其特征在于：包括主材料和改性剂，所述的主材料由以下摩尔百分比的原料组成：
氧化锌92～95 mol%
氧化铋0.8～1.5 mol%
氧化锑1.2～1.5 mol%
三氧化二钴1.0～1.5 mol%
碳酸锰1.0～1.5 mol%
三氧化二镍0.5～1.0 mol%
氧化铬0.5～1.0 mol%
所述的改性剂为由占主材料的质量百分比为以下比例的原料组成：
钨酸盐0.2～1%，铟化物0.2～0.5%，九水合销酸铝 0.01～0.05%。
2.如权利要求1所述的大通流容量氧化锌压敏电阻陶瓷材料，其特征在于：所述的改性剂还包括占主材料的质量百分比为以下比例的若干种原料组成：
二氧化锆 0～0.5%，二氧化硅0～0.5%，硝酸银0～0.05%，氧化硼0～0.1%。
3.如权利要求1所述的大通流容量氧化锌压敏电阻陶瓷材料，其特征在于：所述的钨酸盐为钨酸锌。
4.如权利要求1所述的大通流容量氧化锌压敏电阻陶瓷材料，其特征在于：所述的铟化物为锑化铟。
5.大通流容量氧化锌压敏电阻陶瓷材料的制备方法，其特征在于：采用权利要求1～4任一项所述的大通流容量氧化锌压敏电阻陶瓷材料按照以下步骤制备，
S1. 将主材料及改性剂比例称量混合得到原料，
S2. 将原料加入球磨机中，往球磨机中加入研磨介质及水，于球磨机内混合至粒径小于1μm后加入粘结剂，混合均匀，得到研磨料，
S3. 将研磨料加入喷雾造粒塔进行喷雾造粒得到大通流容量氧化锌压敏陶瓷材料粉末。
6.如权利要求5所述的大通流容量氧化锌压敏电阻陶瓷材料的制备方法，其特征在于：步骤S2中按原料：研磨介质：水=1:5:0.5的质量比例添加至球磨机中。
7.如权利要求5或6所述的大通流容量氧化锌压敏电阻陶瓷材料的制备方法，其特征在于：所述的研磨介质为氧化锆球磨珠，所述的粘结剂为丙烯酸系粘结剂。
8.大通流容量氧化锌压敏电阻器的制备方法，其特征在于：采用权利要求5～7任一项所述的方法制备得到大通流容量氧化锌压敏电阻陶瓷材料，成型为3.2 g/cm3~3.3g/cm3的坯体，在空气气氛下升温至1150℃～1200℃烧结，获得氧化锌压敏电阻器瓷片，再印上银电极，经560℃～580℃还原后获得氧化锌压敏电阻器芯片，焊接包封后制得成品氧化锌压敏电阻器。
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