CN108863344B - 一种高性能ZnO压敏陶瓷的制备工艺 - Google Patents

一种高性能ZnO压敏陶瓷的制备工艺 Download PDF

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CN108863344B
CN108863344B CN201811177527.6A CN201811177527A CN108863344B CN 108863344 B CN108863344 B CN 108863344B CN 201811177527 A CN201811177527 A CN 201811177527A CN 108863344 B CN108863344 B CN 108863344B
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庞驰
赵文英
方超
费自豪
施斌
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Guiyang Hi Tec Yige Electronic Co ltd
Guizhou University
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Guizhou University
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Abstract

本发明公开了一种高性能ZnO压敏陶瓷的制备工艺，包括如下步骤：1)取ZnO压敏陶瓷掺杂料原料；2)将ZnO压敏陶瓷掺杂料原料装入球磨罐充分混合球磨，将球磨后得到的浆料放置在干燥箱中烘干，得粉体；3)向粉体加入水，再加入氨水、柠檬酸或草酸中的一种或任意几种的组合物，然后加热进行水热处理，水热处理后的粉末烘干，得ZnO压敏陶瓷掺杂料；4)将步骤3)制得的ZnO压敏陶瓷掺杂料与ZnO粉体混合得ZnO压敏陶瓷原料粉体，将ZnO压敏陶瓷原料粉体采用传统ZnO压敏陶瓷的处理工艺处理，得高性能ZnO压敏陶瓷。本发明具有制得的ZnO压敏陶瓷性能好，原料用量少，成本低，污染小，工艺更加简单，工艺稳定性好的特点。

Description

一种高性能ZnO压敏陶瓷的制备工艺
技术领域
本发明涉及一种陶瓷掺杂料的处理方法，特别是一种高性能ZnO压敏陶瓷的制备工艺。
背景技术
压敏陶瓷是指电阻值随着外加电压变化有一显著的非线性变化的半导体陶瓷，具有非线性伏安特性，在某一临界电压下，压敏电阻陶瓷电阻值非常高，几乎没有电流，但当超过这一临界电压时，电阻将急剧变化，并有电流通过，随电压的少许增加，电流会很快增大。
ZnO压敏陶瓷，其主要原料氧化锌占90％左右，其粒度大致在0.5微米，而掺杂料包括氧化铋、氧化钴、氧化锰、氧化镍等，占10％左右，粒度大致在几～几十微米。如何将少量加入的大颗粒掺杂料均匀分散到陶瓷中，是提高压敏陶瓷性能的关键因素。
现目前，在ZnO压敏陶瓷的实际生产过程中，通常是将原料采用球磨法来处理，但球磨的方法仅仅能将原料球磨至1微米左右，虽然满足了大多数应用的要求，但是在一些高端的应用场合下，使用这些原料的陶瓷的性能还达不到客户的要求。最近几年有采用化学共沉淀、溶解-凝胶法、冷冻干燥法等手段来合成超细原料氧化物，从而提升陶瓷的性能。但是，仍然没有得到理想的效果。而水热法是目前针对陶瓷原料处理的一种新的方法，能够进一步提高原料的处理效果。但是，现目前的水热法仍然存在缺陷，主要体现在：1、现目前的水热法必须利用原料的可溶性盐(主要为硝酸盐)为原料，与碱进行反应，最终制得氧化物，但可溶性盐的价格比氧化物的价格昂贵得多，增加了陶瓷的原料成本；2、原料的可溶性盐最终制得的氧化物的量只是可溶性盐的量的一小部分(以氧化钴的可溶性硝酸盐-六水合硝酸钴为例，处理完成后氧化钴为26％，其余74％为硝酸根和结晶水)，因此，制备氧化物时需要大量的可溶性盐和碱进行反应，进一步增加了陶瓷的原料成本，同时，废液中含有大量的酸根，对环境污染较大；3、可溶性盐与碱的反应体系更加复杂，条件更加苛刻，处理过程中的工艺的稳定性较难把握。
发明内容
本发明的目的在于，提供一种高性能ZnO压敏陶瓷的制备工艺。本发明具有制得的ZnO压敏陶瓷性能好，原料用量少，成本低，污染小，工艺更加简单，工艺稳定性好的特点。
本发明的技术方案：一种高性能ZnO压敏陶瓷的制备工艺，包括如下步骤：
1)取Bi2O3、Sb2O3、Co3O4、Mn3O4、NiO和Cr2O3进行混合，得ZnO压敏陶瓷掺杂料原料；
2)将ZnO压敏陶瓷掺杂料原料装入球磨罐，加入酒精后将掺杂料原料充分混合球磨，将球磨后得到的浆料放置在干燥箱中烘干，得粉体；
3)向粉体加入水，再加入氨水、柠檬酸或草酸中的一种或任意几种的组合物，然后加热进行水热处理，水热处理后的粉末在干燥箱中烘干，得ZnO压敏陶瓷掺杂料；
4)将步骤3)制得的ZnO压敏陶瓷掺杂料与ZnO粉体混合得ZnO压敏陶瓷原料粉体，将ZnO压敏陶瓷原料粉体采用传统ZnO压敏陶瓷的处理工艺处理，得高性能ZnO压敏陶瓷。
前述的高性能ZnO压敏陶瓷的制备工艺，步骤2)中，所述浆料是在60-120℃的干燥箱中烘干。
前述的高性能ZnO压敏陶瓷的制备工艺，所述浆料是在70℃的干燥箱中烘干。
前述的高性能ZnO压敏陶瓷的制备工艺，步骤3)中，所述水热处理的反应体系中，氨水、柠檬酸或草酸中的一种或任意几种的组合物的浓度为0.5-2mol/L。
前述的高性能ZnO压敏陶瓷的制备工艺，所述水热处理的反应体系中，氨水、柠檬酸或草酸中的一种或任意几种的组合物的浓度为1mol/L。
前述的高性能ZnO压敏陶瓷的制备工艺，步骤3)中，所述水热处理的处理温度为200-400℃；所述水热处理的处理时间为5-25h。
前述的高性能ZnO压敏陶瓷的制备工艺，所述水热处理的处理温度为300℃；所述水热处理的处理时间为15h。
前述的高性能ZnO压敏陶瓷的制备工艺，步骤3)中，所述水热处理后的粉末是在60-80℃的干燥箱中烘干。
前述的高性能ZnO压敏陶瓷的制备工艺，所述水热处理后的粉末是在70℃的干燥箱中烘干。
本发明的有益效果
1、本发明通过先处理掺杂料，制得的掺杂料分布更均匀、粉体粒径更小、粒度分布范围更窄、比表面积更多、活性更强，掺杂后制得的ZnO压敏陶瓷的性能更好。
2、本发明通过直接利用氧化物作为原料进行处理，与采用可溶性盐作为原料相比，其原料成本得到了极大的降低；同时，由于是直接将氧化物进行处理得到氧化物，几乎没有原料的损失，而是需要多少掺杂料的量就用多少原料进行处理即可，大大减少了材料的用量，进一步降低了成本；另外，本发明处理过程中处理剂用量少，产生的废液少，大大降低了对环境的污染程度；此外，本发明直接利用氧化物进行处理，工艺更加简单，工艺的稳定性更好。
为进一步说明本发明的有益效果，申请人设计了以下实验：
实验例
1、实验方法：本实验例共设置四组实验，第一组为传统工艺制备的ZnO压敏陶瓷片，第二组为本发明实施例1制备的ZnO压敏陶瓷片，第三组为本发明实施例2制备的ZnO压敏陶瓷片，第四组为本发明实施例3制备的ZnO压敏陶瓷片，四组压敏陶瓷片均采用IEC61643-11:2011、UL1449-3rd、GB188022.1-2005和YD1235.1-2002测试标准，分别对四组压敏陶瓷片的最大交流工作电压、最大直流工作电压、标称放电电流、最大放电电流和恒定湿热进行测量。
实验结果：表1为四组陶瓷片实验数据结果对比表，从表1可以看出：经本发明实施例所述方法处理的ZnO压敏陶瓷片的标称放电电流提高了25％，残压比降低了10％，湿热性能提高了200％。说明经本发明处理的氧化物复合粉体在降低了陶瓷成本，减少了环境污染和保证了工艺稳定性的基础上，还较大的提高了所掺杂的陶瓷的性能。
表1：四组陶瓷片实验数据结果对比表
附图说明
附图1为传统固相法和本发明水热法制备的ZnO压敏陶瓷掺杂料粉末的粒度累积分布图；
附图2为传统固相法制备的ZnO压敏陶瓷掺杂料粉末的扫描电镜图；
附图3为本发明水热法制备的ZnO压敏陶瓷掺杂料粉末的扫描电镜图。
具体实施方式
下面结合实施例对本发明作进一步的说明，但并不作为对本发明限制的依据。
本发明的实施例
实施例1：一种高性能ZnO压敏陶瓷的制备工艺，步骤如下：
1)按质量百分比计，取Bi2O3 3％、Sb2O3 2.5％、Co3O4 1.5％、Mn3O4 1％、NiO 1％、Cr2O3 1％和ZnO 90％，首先将Bi2O3、Sb2O3、Co3O4、Mn3O4、NiO和Cr2O3进行混合进行混合，得ZnO压敏陶瓷掺杂料原料；
2)将ZnO压敏陶瓷掺杂料原料装入球磨罐，加入酒精后将掺杂料原料充分混合球磨，将球磨后得到的浆料放置在在70℃的干燥箱中烘干，得粉体；
3)向粉体加入水，再加入氨水，然后加热进行水热处理，水热处理的反应体系中，氨水的浓度为1mol/L，水热处理的处理温度为300℃，水热处理的处理时间为15h，水热处理后的粉末在70℃的干燥箱中烘干，得ZnO压敏陶瓷掺杂料；
4)将步骤3)制得的ZnO压敏陶瓷掺杂料与ZnO粉体混合，得ZnO压敏陶瓷原料粉体，向1kgZnO压敏陶瓷原料粉体中加入1kg去离子水，同时加入浓度10％的聚乙烯醇70g，分散剂8g，消泡剂4g，球磨混合2小时后喷雾造粒，经过成型、排胶、烧结、表面金属化、封装处理，然后得高性能ZnO压敏陶瓷。
实施例2：一种高性能ZnO压敏陶瓷的制备工艺，步骤如下：
1)按质量百分比计，取Bi2O3 3％、Sb2O3 2.5％、Co3O4 1.5％、Mn3O4 1％、NiO 1％、Cr2O3 1％和ZnO 90％，首先将Bi2O3、Sb2O3、Co3O4、Mn3O4、NiO和Cr2O3进行混合进行混合，得ZnO压敏陶瓷掺杂料原料；
2)将ZnO压敏陶瓷掺杂料原料装入球磨罐，加入酒精后将掺杂料原料充分混合球磨，将球磨后得到的浆料放置在在60℃的干燥箱中烘干，得粉体；
3)向粉体加入水，再加入柠檬酸，然后加热进行水热处理，水热处理的反应体系中柠檬酸的浓度为0.5mol/L，水热处理的处理温度为200℃，水热处理的处理时间为25h，水热处理后的粉末在60℃的干燥箱中烘干，得ZnO压敏陶瓷掺杂料；
4)将步骤3)制得的ZnO压敏陶瓷掺杂料与ZnO粉体混合，得ZnO压敏陶瓷原料粉体，向1kgZnO压敏陶瓷原料粉体中加入1kg去离子水，同时加入浓度10％的聚乙烯醇60g，分散剂6g，消泡剂2g，球磨混合1小时后喷雾造粒，经过成型、排胶、烧结、表面金属化、封装处理，然后得高性能ZnO压敏陶瓷。
实施例3：一种高性能ZnO压敏陶瓷的制备工艺，步骤如下：
1)按质量百分比计，取Bi2O3 3％、Sb2O3 2.5％、Co3O4 1.5％、Mn3O4 1％、NiO 1％、Cr2O3 1％和ZnO 90％，首先将Bi2O3、Sb2O3、Co3O4、Mn3O4、NiO和Cr2O3进行混合进行混合，得ZnO压敏陶瓷掺杂料原料；
2)将ZnO压敏陶瓷掺杂料原料装入球磨罐，加入酒精后将掺杂料原料充分混合球磨，将球磨后得到的浆料放置在在120℃的干燥箱中烘干，得粉体；
3)向粉体加入水，再加入草酸，然后加热进行水热处理，水热处理的反应体系中，草酸的浓度为2mol/L，水热处理的处理温度为400℃，水热处理的处理时间为5h，水热处理后的粉末在80℃的干燥箱中烘干，得ZnO压敏陶瓷掺杂料；
4)将步骤3)制得的ZnO压敏陶瓷掺杂料与ZnO粉体混合，得ZnO压敏陶瓷原料粉体，向1kgZnO压敏陶瓷原料粉体中加入1kg去离子水，同时加入浓度10％的聚乙烯醇80g，分散剂10g，消泡剂6g，球磨混合3小时后喷雾造粒，经过成型、排胶、烧结、表面金属化、封装处理，然后得高性能ZnO压敏陶瓷。

Claims (7)

1.一种高性能ZnO压敏陶瓷的制备工艺，其特征在于，包括如下步骤：
1)按质量百分比计，取Bi2O3 3％、Sb2O3 2.5％、Co3O4 1.5％、Mn3O4 1％、NiO 1％、Cr2O31％和ZnO 90％，首先将Bi2O3、Sb2O3、Co3O4、Mn3O4、NiO和Cr2O3进行混合，得ZnO压敏陶瓷掺杂料原料；
2)将ZnO压敏陶瓷掺杂料原料装入球磨罐，加入酒精后将掺杂料原料充分混合球磨，将球磨后得到的浆料放置在干燥箱中烘干，得粉体；
3)向粉体加入水，再加入氨水、柠檬酸或草酸中的一种或任意几种的组合物，然后加热进行水热处理，水热处理后的粉末在干燥箱中烘干，得ZnO压敏陶瓷掺杂料；所述水热处理的反应体系中，氨水、柠檬酸或草酸中的一种或任意几种的组合物的浓度为1mol/L；
4)将步骤3)制得的ZnO压敏陶瓷掺杂料与ZnO粉体混合得ZnO压敏陶瓷原料粉体，将ZnO压敏陶瓷原料粉体采用传统ZnO压敏陶瓷的处理工艺处理，得高性能ZnO压敏陶瓷。
2.根据权利要求1所述的高性能ZnO压敏陶瓷的制备工艺，其特征在于：步骤2)中，所述浆料是在60-120℃的干燥箱中烘干。
3.根据权利要求2所述的高性能ZnO压敏陶瓷的制备工艺，其特征在于：所述浆料是在70℃的干燥箱中烘干。
4.根据权利要求1所述的高性能ZnO压敏陶瓷的制备工艺，其特征在于：步骤3)中，所述水热处理的处理温度为200-400℃；所述水热处理的处理时间为5-25h。
5.根据权利要求4所述的高性能ZnO压敏陶瓷的制备工艺，其特征在于：所述水热处理的处理温度为300℃；所述水热处理的处理时间为15h。
6.根据权利要求1所述的高性能ZnO压敏陶瓷的制备工艺，其特征在于：步骤3)中，所述水热处理后的粉末是在60-80℃的干燥箱中烘干。
7.根据权利要求6所述的高性能ZnO压敏陶瓷的制备工艺，其特征在于：所述水热处理后的粉末是在70℃的干燥箱中烘干。
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