CN112430083B - 一种ptc热敏电阻陶瓷的制备方法 - Google Patents

一种ptc热敏电阻陶瓷的制备方法 Download PDF

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CN112430083B
CN112430083B CN202011443101.8A CN202011443101A CN112430083B CN 112430083 B CN112430083 B CN 112430083B CN 202011443101 A CN202011443101 A CN 202011443101A CN 112430083 B CN112430083 B CN 112430083B
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李明阳
张路路
宋涛
王玉宝
陈学江
魏华阳
张永翠
徐先豹
王浩然
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Shandong Industrial Ceramics Research and Design Institute Co Ltd
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Abstract

本发明公开了一种PTC热敏电阻陶瓷的制备方法，本申请采用三段烧结并分别控制气氛(氧化‑还原‑氧化)。其中第二段制造密闭环境，并利用碳粉消耗氧气制造还原气氛，使烧结得到的瓷体室温电阻低，电阻起跳性小，工艺流程简单，节省材料，可有效提高成品的PTC特性和居里温度，还能提高设备的利用率，并进一步提高样品的生产效率。

Description

一种PTC热敏电阻陶瓷的制备方法
技术领域
本发明主要涉及一种陶瓷电阻材料的制备方法，特别涉及一种 PTC热敏电阻陶瓷的制备方法。
背景技术
目前所使用的热敏陶瓷材料，制备工艺冗杂，制备成本高；同时存在启动电流大，居里温度低，性能不稳定等的缺点，要提高居里温度，需要达到预定的PTC性能，主要取决于还原温度、还原时间；
而现有的制备工艺均采用成型烧结的同时提供还原气氛，成型烧结的同时提供还原气氛，目的是为了减少了坯体的转移，提高批量化生产过程中的效率，但是由于以下几点原因降低PTC热敏电阻陶瓷烧结的成品率：
1、坯体的还原时间和还原温度受制于成型温度，容易出现还原不到位或还原过度的现象；
2、还原性气氛要求比较高，需要控制多个变量，对容器的要求比较高，限制了容器的体积，一次烧结的坯体数量有限，反而降低了批量化生产过程中的效率；
3、成型烧结需要的时间较长，需要在整个成型烧结过程中严格控制还原气氛所述的各个变量，不同坯体所需的还原温度不同，若烧结过程中，还原气氛控制不当，尤其是烧结初期在还原气氛下烧结容易使坯体出现裂缝甚至开裂，大大降低了产品的成型率。
发明内容
为了解决现有技术的问题，本发明旨在提供一种居里点高、制备方法简单、生产效率高的PTC热敏电阻陶瓷及其制备方法。
一种PTC热敏电阻陶瓷的制备方法，包括以下步骤：
(1)制备PTC陶瓷坯体；
(2)对所述PTC陶瓷坯体进行预成型烧结；
(3)将预成型烧结后的PTC陶瓷坯体进行还原气氛烧结；
(4)将还原性气氛烧结后的PTC陶瓷坯体进行重氧化烧结得到PTC 热敏电阻陶瓷。
通过第一步的预烧结成型，以增大体积密度，降低气孔率，与还原气氛烧结需要控制多个变量不同，第一步的的预烧对容器等的要求低，可以将大量坯体一起烧结，使之成型，并将成型失败的样品剔除，提高了第二步还原制备的成品率，使第二步的还原烧结气氛易于控制。
进一步的，还原气氛烧结时，以200℃/h的升温速率升1230-1260℃，保温30-60min后，以180-280℃/h的降温速率降到室温。
在还原气氛下，晶界处存在大量的氧空位，钡空位减少，钡空位在晶粒边界的数量以及进入晶粒体内的扩散深度均有所减少，从而钡空位晶界高阻层势垒降低，样品电阻降低。
进一步的，还原气氛烧结时，将所述成型烧结后的PTC陶瓷坯体和碳粉置于密闭容器中，所述碳粉与PTC陶瓷坯体用隔块隔离。
将碳粉与坯体隔离，有利于氧空位的扩散从而使钡空位晶界高阻层势垒降低，以降低样品电阻。
通过制造密闭环境，利用消耗氧气制造还原性气氛，使烧结得到的瓷体室温电阻低，电阻起跳性小，居里温度高。
进一步的，所述制备PTC陶瓷坯体的PTC陶瓷粉料的成分包括：主料和添加剂；所述主料包括BaTiO3、La2O3、SiO2；添加剂包括Al2O3、 PbTiO3中一种或两种。主料中的BaTiO3、La2O3、SiO2用以产生坯体的PTC特性，添加剂的Al2O3、PbTiO3用以稳定坯体的PTC特性。
进一步的，所述成型烧结过程为：将所述PTC陶瓷坯体在 1280-1350℃的，保温30-60min。
由于预烧结以后坯体的体积有一定的收缩，可以节省密闭空间的体积，可以更加优化密闭容器内坯体的排布。
进一步的，所述重氧化烧结过程为：将所述将还原性气氛烧结后的 PTC陶瓷坯体置于700-800℃空气氛围，保温40-180min。在700-800的温度范围内可以在容器内统一加热，简化了工艺步骤，不需对单个坯体的进行还原性气氛控制。
进一步的，在所述PTC热敏电阻陶瓷表面涂覆银浆并固化。
进一步的，所述固化条件为在500℃条件下保温20min。
进一步的，所述PTC热敏电阻陶瓷居里温度为180-280℃，电阻率500-650Ω·cm，升阻比为4.0-5.0Log(ρmix/ρmin)。本发明制备的 PTC热敏电阻陶瓷居里温度相较于传统工艺明显提高，各项参数明显得到优化。
进一步的，所述PTC热敏电阻陶瓷根据权利要求1-9任一所述的制备方法制备。
本发明还具有如下的有益效果：
1.在还原烧结前进行独立的预成型烧结，将还原过程与成型过程分离，在成型过程中不设置还原性气氛，使还原气氛单独控制，还原时间和还原温度不再受制于成型温度，使还原过程的反应条件更加适当，更易控制，还原效果更加充分，大大提高了坯体的成品率。
2.预成型烧结过程中坯体有一定程度的收缩，增大了体积密度，在第二步的还原中，可优化样品在密闭容器中的排布，使可以放置更多样品，提高设备的利用率，并进一步提高样品的生产效率。
3.由于预烧结过程中的坯体收缩，在坯体收缩过程中坯体排出一部分氧气，在下一步的还原过程中，使还原性气体能更好地对坯体进行还原，使氧气压和还原气氛气压更好地达到平衡，进一步提高了还原效率，从而提高了烧结成品的质量。
具体实施方式
为了更好的了解本发明的技术方案，下面结合具体实施例对本发明作进一步说明。
实施例1:
首先按摩尔百分比84.65％的BaTiO3、0.21％的La2O3、2％的SiO2、0.23％的Al2O3、15.91％的PbTiO3陶瓷配方配料得到混合物B，然后按质量比为 1:1:2的比例将混合物B、去离子水和球加入球磨罐进行球磨20min，所得料浆在90℃烘干，进行造粒、成型坯体。
然后将成型后的坯体在1280℃的氧化气氛下保温30min，随后随炉降温至室温。
将烧结成型的坯体至于碳粉营造的还原气氛中进行陶瓷还原。还原气氛的制备通过将3.5g的碳粉置于50ml的密闭的耐烧容器中。密闭容器从室温以200℃/h的升温速率升到1230℃，保温30min，再以180℃/h 的降温速率降到室温，即得到半导化的陶瓷样品；
将具有半导性的陶瓷样品在空气中于700℃下再氧化40min，使晶界得到氧化而形成晶界势垒得到PTC热敏电阻陶瓷电阻材料。
最后在所述PTC热敏电阻陶瓷表面涂覆银浆并在500℃保温20min的条件下固化。
实施例2:
1.首先按摩尔百分比72.65％BaTiO3、0.14％La2O3、5％SiO2、0.21％Al2O3 21％PbTiO3的陶瓷配方配料得到混合物B，然后按质量比为1:1:2的比例将混合物B、去离子水和球加入球磨罐进行球磨20min，所得料浆在90℃烘干，进行造粒、成型坯体。
然后将成型后的坯体在1320℃的氧化气氛下保温45min，随后随炉降温至室温。
将烧结成型的坯体至于碳粉营造的还原气氛中进行陶瓷还原。还原气氛通过3g的碳粉置于50ml的密闭的耐烧容器中。密闭容器从室温以 200℃/h的升温速率升到1250℃，保温40min，再以230℃/h的降温速率降到室温，即得到半导化的陶瓷样品；
将具有半导性的陶瓷样品在空气中于750℃下再氧化120min，使晶界得到氧化而形成晶界势垒得到PTC热敏电阻陶瓷电阻材料。
最后在所述PTC热敏电阻陶瓷表面涂覆银浆并在500℃保温20min的条件下固化。
实施例3:
首先按摩尔百分比92％BaTiO3 0.14％La2O3 7.65％SiO2 0.21％Al2O3的陶瓷配方配料得到混合物C，然后按质量比为1:1:2的比例将混合物C、去离子水和球加入球磨罐进行球磨20min，所得料浆在90℃烘干，进行造粒、成型坯体。
然后将成型后的坯体在1350℃的氧化气氛下保温60min，随后随炉降温至室温。
将烧结成型的坯体至于碳粉营造的还原气氛中进行陶瓷还原。还原气氛通过4g的碳粉置于50ml的密闭的耐烧容器中。密闭容器从室温以200℃/h的升温速率升到1250℃，保温40min，再以280℃/h的降温速率降到室温，即得到半导化的陶瓷样品。
将具有半导性的陶瓷样品在空气中于800℃下再氧化180min，使晶界得到氧化而形成晶界势垒得到高居里点无铅PTC热敏电阻陶瓷电阻材料。
最后在所述PTC热敏电阻陶瓷表面涂覆银浆并在500℃保温20min的条件下固化。
实施例4:
首先按摩尔百分比87％BaTiO3 0.16％La2O3 12.5％SiO2 0.34％Al2O3的陶瓷配方配料得到混合物D，然后按质量比为1:1:2的比例将混合物D、去离子水和球加入球磨罐进行球磨20min，所得料浆在90℃烘干，进行造粒、成型坯体。
然后将成型后的坯体在1250℃的氧化气氛下保温30min，随后随炉降温至室温。
将烧结成型的坯体至于碳粉营造的还原气氛中进行陶瓷还原。还原气氛通过5g的碳粉置于50ml的密闭的耐烧容器中。密闭容器从室温以 200℃/h的升温速率升到800℃，保温30min，再以300℃/h的降温速率降到室温，即得到半导化的陶瓷样品；
将具有半导性的陶瓷样品在空气中于700℃下再氧化40min，使晶界得到氧化而形成晶界势垒得到高居里点无铅PTC热敏电阻陶瓷电阻材料。
最后在所述PTC热敏电阻陶瓷表面涂覆银浆并在500℃保温20min 的条件下固化。
对比例：
下表为本申请与传统工艺的具体量化参数对比
Figure BDA0002823232450000061
以上描述仅为本申请的较佳实施例以及对所运用技术原理的说明。本领域技术人员应当理解，本申请中所涉及的发明范围，并不限于上述技术特征的特定组合而成的技术方案，同时也应涵盖在不脱离所述发明构思的情况下，由上述技术特征或其等同特征进行任意组合而形成的其它技术方案。例如上述特征与本申请中公开的(但不限于)具有类似功能的技术特征进行互相替换而形成的技术方案。

Claims (7)

1.一种PTC热敏电阻陶瓷的制备方法，其特征在于，包括以下步骤：
（1）制备PTC陶瓷坯体；
（2）对所述PTC陶瓷坯体进行预成型烧结；
（3）将预成型烧结后的PTC陶瓷坯体进行还原气氛烧结；
（4）将还原性气氛烧结后的PTC陶瓷坯体进行重氧化烧结得到PTC热敏电阻陶瓷；
其中，所述成型烧结过程为：将所述PTC陶瓷坯体在1280-1350℃的含氧条件下，保温30-60min；
还原气氛烧结时，将所述成型烧结后的PTC陶瓷坯体和碳粉置于密闭容器中，所述碳粉与PTC陶瓷坯体用隔块隔离使之相互不接触；
所述制备PTC陶瓷坯体的PTC陶瓷粉料的成分包括：主料和添加剂；所述主料包括BaTiO3、La2O3、SiO2；添加剂包括Al2O3、PbTiO3中的一种或两种。
2.由权利要求1所述的一种PTC热敏电阻陶瓷的制备方法，其特征在于，还原气氛烧结时，以200℃/h的升温速率升1230-1260℃，保温30-60min后，以180-280℃/h的降温速率降到室温。
3.由权利要求1所述的一种PTC热敏电阻陶瓷的制备方法，其特征在于，所述重氧化烧结过程为：将所述还原性气氛烧结后的PTC陶瓷坯体置于700-800℃空气氛围，保温40-180min。
4.由权利要求1所述的一种PTC热敏电阻陶瓷的制备方法，其特征在于，在所述PTC热敏电阻陶瓷表面涂覆银浆并固化。
5.由权利要求4所述的一种PTC热敏电阻陶瓷的制备方法，其特征在于，所述固化条件为在500℃条件下保温20min。
6.由权利要求1所述的一种PTC热敏电阻陶瓷的制备方法，其特征在于，所述PTC热敏电阻陶瓷居里温度为180-280℃，电阻率500-650Ω•cm，升阻比为4.0-5.0 Log(ρmix/ρmin)。
7.一种PTC热敏电阻陶瓷，其特征在于，所述PTC热敏电阻陶瓷根据权利要求1-6任一所述的制备方法制备。
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