CN111517778B - 一种低温烧结氧化锌压敏陶瓷及其制备方法 - Google Patents

一种低温烧结氧化锌压敏陶瓷及其制备方法 Download PDF

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CN111517778B
CN111517778B CN202010429853.2A CN202010429853A CN111517778B CN 111517778 B CN111517778 B CN 111517778B CN 202010429853 A CN202010429853 A CN 202010429853A CN 111517778 B CN111517778 B CN 111517778B
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卢振亚
肖淼淼
杨凤金
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South China University of Technology SCUT
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Abstract

本发明公开了一种低温烧结氧化锌压敏陶瓷及其制备方法，将氧化锌、烧结助剂B4C和改性添加剂混合并球磨，干燥后得粉料；改性添加剂含有Bi2O3、Sb2O3、Co3O4、锰的氧化物和Ni2O3；得到的粉料加PVA胶，造粒过筛，压片排胶；于900‑950℃烧结2‑3h，获得黑色致密的压敏陶瓷片；再将压敏陶瓷片的两面分别涂覆银浆，升温至500℃‑550℃，保温20‑30分钟后冷却，得到两面均印有电极的压敏陶瓷。本发明通过采用B4C作为烧结助剂，将烧结温度从传统的1100‑1200℃降至950℃以下的同时也保证了压敏陶瓷具备良好的综合电性能，整体工艺节能降耗，绿色环保，简便易行且可工业化推广。

Description

一种低温烧结氧化锌压敏陶瓷及其制备方法
技术领域
本发明涉及一种低温烧结氧化锌压敏陶瓷及其制备方法，属于压敏电阻材料技术领域。
背景技术
ZnO压敏电阻器以其优异的非线性电流电压特性和高的能量吸收能力，被广泛应用于电子电路和电力***中，作为稳压和浪涌保护器件。随着电子电路朝着集成化和微型化发展，对相应的保护元件也有了体积上的要求，而可以用于表面贴装的多层压敏电阻器则大大缩小了器件的尺寸。
通常ZnO压敏陶瓷的烧结温度范围为1100-1200℃，在如此高的温度下常用具有高熔点的银钯合金作为内电极，以实现内电极和压敏陶瓷层的高温共烧。但在高温共烧过程中压敏陶瓷层中的Bi2O3和内电极中的Pd会发生界面反应，使得多层压敏电阻器的电性能恶化。如果可以把共烧温度也即压敏陶瓷的烧结温度降低至Ag的熔点(约为960℃)以下，就可以使用纯银电极替代银钯内电极，避免了电性能劣化的同时也降低了成本。通过添加低熔点的烧结助剂，在较低温度下形成液相而促进烧结是一种被公认的经济、高效的降低烧结温度的方法，常用的烧结助剂有B2O3、硼基玻璃料等。
流延成型法是制备多层压敏电阻器的重要工艺，而传统流延成型的浆料大多以有机溶剂为基体，缺陷是有毒，会造成环境污染，因此研究绿色环保，无毒安全的以水性溶剂为基体的水基流延工艺成为了主要趋势。当在陶瓷基料中添加B2O3、硼基玻璃料作为烧结助剂时，在配制浆料时可溶于水的B2O3、HBO3和微溶于水的硼基玻璃料会和浆料中带有羟基或氨基的有机粘结剂以及分散剂反应形成络合物，影响浆料的流变性和化学均匀性，进而影响到了水基流延浆料的制备和生坯膜的性能。浆料制备是流延工艺的首要环节，粘结剂和分散剂又是浆料的基本组成中不可或缺的部分，故选用化学性质稳定的烧结助剂成为了能否采用水基流延工艺制备多层压敏电阻器的关键。
综上所述，一方面要降低烧结温度，实现压敏陶瓷层和纯银电极的低温共烧，节能降耗；另一方面要能采用水基流延工艺制备多层片式压敏电阻器，以响应国家绿色环保号召。故探索合适的烧结助剂，对多层片式氧化锌压敏电阻的低温烧结方向的研究有重大意义。
发明内容
本发明的目的是针对现有多层片式压敏陶瓷的制备技术中存在的烧结温度过高、内电极和陶瓷层共烧时发生反应等问题，提供一种低温烧结氧化锌压敏陶瓷及其制备方法。
本发明的目的通过以下技术方案实现：
一种低温烧结氧化锌压敏陶瓷的制备方法，包括如下步骤：
(1)将氧化锌、烧结助剂和改性添加剂按比例混合，并球磨，干燥后得粉料；所述烧结助剂为B4C，改性添加剂含有Bi2O3、Sb2O3、Co3O4、锰的氧化物和Ni2O3；
(2)得到的粉料加PVA胶，造粒过筛，压制成型，随后将得到的陶瓷生坯片进行排胶处理；
(3)将排完胶的陶瓷坯片进行烧结，烧结温度900-950℃，烧结时间2-3小时，获得黑色致密的压敏陶瓷片；
(4)将压敏陶瓷片的两面用常规丝网印刷工艺，分别涂覆银浆，升温至500℃-550℃，保温20-30分钟后冷却，得到两面均印有电极的压敏陶瓷。
优选地，步骤(1)所述ZnO和Bi2O3、Sb2O3、Co3O4、锰的氧化物、Ni2O3的摩尔百分比为(95.3-98.6)：(0.5-1.5)：(0.5-1.5)：(0.2-0.5)：(0.1-0.7)：(0.1-0.5)，并满足各组分含量之和为100％；所述B4C和ZnO的质量比为(0.2-1)：100。
优选地，所述B4C和ZnO的质量比为0.5：100。
优选地，所述改性添加剂中还含有Cr2O3、Al(NO3)·9H2O和SiO2，所述Cr2O3、Al(NO3)·9H2O、SiO2和ZnO的质量比为(0.1-1)：(0.01-0.1)：(0.1-1)：100。
优选地，步骤(3)所述烧结是以4-6℃每分钟的升温速率升至烧结温度，所述烧结温度为900-910℃，烧结时间2.5-3小时。
优选地，步骤(2)中所述PVA胶为聚乙烯醇溶液，其加入量为ZnO的10-12wt％。
优选地，所述排胶温度为600-650℃，保温时间1-1.5h。
优选地，步骤(1)所述粉料放入球磨罐中，加水混合，球磨40-60分钟，所述粉料、球和水的质量比为1.5：1：1。
优选地，所述的改性添加剂中锰的氧化物为Mn3O4或MnO2。
优选地，步骤(3)中的压制成型的压力为80-100MPa，保压时间3-5秒。
与现有技术相比，本发明的有益效果在于：
本发明工艺简单，采用传统固相合成法，使用B4C作为烧结助剂，实现了氧化锌压敏陶瓷的低温烧结，将烧结温度从传统的1100-1200℃降至900-950℃。B4C化学性质稳定，常温下不会和其他添加剂反应影响浆料制备，在600℃左右便氧化分解生成B2O3玻璃相，并均匀分布于基体中，协助富Bi液相润湿ZnO晶粒，加快传质，促进烧结，在降低烧结温度的同时也能保证晶粒的充分发育，并且B4C中B元素有着高达78％的百分含量，单位 B4C转化的B2O3量高。烧结过程中部分B2O3玻璃相和ZnO结合生成硼酸锌相，起到了和尖晶石类似的钉扎作用，从而阻碍晶粒异常长大，提高了压敏陶瓷的电位梯度。
本发明结合了水基流延工艺制备多层片式压敏电阻和低温烧结，满足了替换多层片式压敏电阻中的银钯电极为纯银内电极的需求。所制备的氧化锌压敏陶瓷的电位梯度介于1200-1300V/mm之间，非线性系数在20-30之间，漏电流控制在10μA左右，综合电性能良好，微观结构均匀。
本发明绿色环保，节能降耗，适合工业化推广应用。
附图说明
图1是本发明所述对比样的氧化锌压敏陶瓷的SEM图谱。
图2是本发明所述的实施例1中的氧化锌压敏陶瓷的SEM图谱。
图3是本发明所述的实施例2中的氧化锌压敏陶瓷的SEM图谱。
图4是本发明所述的实施例3中的氧化锌压敏陶瓷的SEM图谱。
图5是本发明所述的实施例4中的氧化锌压敏陶瓷的SEM图谱。
具体实施方式
下述为结合具体实施例对本发明做进一步详细的描述，应理解，以下实施方式仅是用于帮助技术人员更好理解本发明，而非限制本发明。
实施例1-4
一种低温烧结氧化锌压敏陶瓷的制备方法，具体包括以下步骤：
(1)将氧化锌、烧结助剂和改性添加剂按表1所述的比例混合，混合后的粉料放入球磨罐中，与去离子水混合后于立式行星球磨机中球磨，球磨40分钟，所述粉料、球和水的比为1.5：1：1，球磨结束后将混合均匀的浆料置于烘箱中烘干，得干燥均匀的粉料。
(2)得到的粉料加PVA胶(聚乙烯醇溶液)，加入量为ZnO的10wt％，造粒过筛，压制成型，其中模具为直径约14mm的圆柱形模具，压力为80MPa，保压时间3-5秒，随后将得到的陶瓷生坯片于箱式炉中进行排胶处理，排胶温度为600℃，保温1h后随炉冷却。
(3)将排完胶的陶瓷坯片进行烧结，以5℃每分钟的升温速率升至烧结温度，烧结温度为910℃，保温2.5小时，获得黑色致密的压敏陶瓷片。
(4)将压敏陶瓷片的两面用常规丝网印刷工艺，分别涂覆银浆，升温至550℃，保温20分钟后自然冷却，得到两面均印有电极的压敏陶瓷片。
表1中列出了4种压敏陶瓷各组成材料的配比方案，还包括一组对比样，对比样的主料和改性添加剂的组成与实施例相同，未添加B4C的配比方案。
表2中列出了所测得的4组实施例和一组对比样的电性能参数。可看出未添加B4C的对比样漏电流极大，达到上百微安，而且非线性系数较低，但是电压梯度极高，是由于烧结温度较低，且未添加烧结助剂，所获得的ZnO晶粒细小，发育不完全，综合电性能差。而实施例1-4中加入了B4C之后，在烧结中通过形成液相流动，填充晶粒间的孔隙且加快传质，提高了压敏陶瓷的致密度和改善了电性能。电压梯度稳定在1200-1300V/mm之间，漏电流突降低至10μA左右，非线性系数增至20以上，获得综合电性能较好的压敏陶瓷。
表1
Figure BDA0002500142440000041
表2
Figure BDA0002500142440000042
实施例5
一种低温烧结氧化锌压敏陶瓷的制备方法，具体包括以下步骤：
(1)将氧化锌、烧结助剂和改性添加剂按以下比例混合：ZnO和Bi2O3、Sb2O3、Co3O4、Mn3O4、Ni2O3的摩尔百分比为(97.3)：(1)：(1)：(0.3)：(0.2)：(0.2)；Cr2O3、Al(NO3) ·9H2O、SiO2、B4C和ZnO的质量比为(0.2)：(0.0125)：(0.5)：(0.5):(100)。混合后与去离子水混合后于立式行星球磨机中球磨，球磨40分钟，所述粉料、球和水的比为1.5：1： 1，球磨结束后将混合均匀的浆料置于烘箱中烘干，得干燥均匀的粉料。
(2)得到的粉料加PVA胶(聚乙烯醇溶液)，加入量为ZnO的10wt％，造粒过筛，压制成型，其中模具为直径约14mm的圆柱形模具，压力为80MPa，保压时间3-5秒，随后将得到的陶瓷生坯片于箱式炉中进行排胶处理，排胶温度为600℃，保温1h。
(3)将排完胶的陶瓷坯片进行烧结，以5℃每分钟的升温速率升至烧结温度，烧结温度为900℃，保温2.5小时，获得黑色致密的压敏陶瓷片。
(4)将压敏陶瓷片的两面用常规丝网印刷工艺，分别涂覆银浆，升温至550℃，保温20分钟后自然冷却，得到两面均印有电极的压敏陶瓷片。
测得电压梯度为1214V/mm，非线性系数为26.8，漏电流为5.7μA。
实施例6
一种低温烧结氧化锌压敏陶瓷的制备方法，具体包括以下步骤：
(1)将氧化锌、烧结助剂和改性添加剂按以下比例混合：ZnO和Bi2O3、Sb2O3、Co3O4、MnO2、Ni2O3的摩尔百分比为(96.9)：(1)：(1)：(0.3)：(0.6)：(0.2)；Cr2O3、Al(NO3)· 9H2O、SiO2、B4C和ZnO的质量比为(0.2)：(0.0125)：(0.5)：(0.5)：(100)。混合后与去离子水混合后于立式行星球磨机中球磨，球磨40分钟，所述粉料、球和水的比为1.5：1： 1，球磨结束后将混合均匀的浆料置于烘箱中烘干，得干燥均匀的粉料。
(2)得到的粉料加PVA胶(聚乙烯醇溶液)，加入量为ZnO的10wt％，造粒过筛，压制成型，其中模具为直径约14mm的圆柱形模具，压力为80MPa，保压时间3-5秒，随后将得到的陶瓷生坯片于箱式炉中进行排胶处理，排胶温度为600℃，保温1h。
(3)将排完胶的陶瓷坯片进行烧结，以5℃每分钟的升温速率升至烧结温度，烧结温度为910℃，保温2.5小时，获得黑色致密的压敏陶瓷片。
(4)将压敏陶瓷片的两面用常规丝网印刷工艺，分别涂覆银浆，升温至550℃，保温20分钟后自然冷却，得到两面均印有电极的压敏陶瓷片。
测得电压梯度为1363V/mm，非线性系数为23.4，漏电流为10μA。
本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (8)

1.一种低温烧结氧化锌压敏陶瓷的制备方法，其特征在于，包括如下步骤：
（1）将氧化锌、烧结助剂和改性添加剂混合，并球磨，干燥后得粉料；所述烧结助剂为B4C，改性添加剂含有Bi2O3、Sb2O3、Co3O4、锰的氧化物和Ni2O3；
（2）得到的粉料加PVA胶，造粒过筛，压制成型，随后将得到的陶瓷生坯片进行排胶处理；
（3）将排完胶的陶瓷坯片进行烧结，烧结温度900-950℃，烧结时间2-3小时，获得黑色致密的压敏陶瓷片；
（4）将压敏陶瓷片的两面分别涂覆银浆，升温至500℃-550℃，保温20-30分钟后冷却，得到两面均印有电极的压敏陶瓷；
步骤（1）所述ZnO和Bi2O3、 Sb2O3、Co3O4、锰的氧化物、Ni2O3的摩尔百分比为（95.3-98.6）：（0.5-1.5）：（0.5-1.5）：（0.2-0.5）：（0.1-0.7）：（0.1-0.5），并满足各组分含量之和为100%；所述B4C和ZnO的质量比为（0.2-1）：100；
步骤（1）所述改性添加剂中还含有Cr2O3、Al(NO3)∙9H2O和SiO2，所述Cr2O3、Al(NO3)∙9H2O、SiO2和ZnO的质量比为（0.1-1）：（0.01-0.1）：（0.1-1）：100。
2.根据权利要求1所述的制备方法，其特征在于，所述B4C和ZnO的质量比为0.5：100。
3.根据权利要求1或2所述制备方法，其特征在于，步骤（3）所述烧结是以4-6℃每分钟的速率升至烧结温度，所述烧结温度为900-910℃，烧结时间2.5-3小时。
4.根据权利要求1或2所述制备方法，其特征在于，步骤（2）中所述PVA胶为聚乙烯醇溶液，其加入量为ZnO的10-12wt%。
5.根据权利要求1或2所述制备方法，其特征在于，步骤（2）所述排胶温度为600-650℃，保温时间1-1.5h。
6.根据权利要求1或2所述制备方法，其特征在于，步骤（1）所述粉料放入球磨罐中，加水混合，球磨40-60分钟，所述粉料、球和水的质量比为1.5：1：1；所述的改性添加剂中锰的氧化物为Mn3O4或MnO2。
7.根据权利要求1或2所述制备方法，其特征在于，步骤（3）中的压制成型的压力为80-100MPa，保压时间3-5秒。
8.权利要求1~7任意一项所述方法制备的氧化锌压敏陶瓷。
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