CN112694325A - 一种ptc热敏电阻陶瓷材料及其制备方法、应用 - Google Patents

一种ptc热敏电阻陶瓷材料及其制备方法、应用 Download PDF

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CN112694325A
CN112694325A CN202011527368.5A CN202011527368A CN112694325A CN 112694325 A CN112694325 A CN 112694325A CN 202011527368 A CN202011527368 A CN 202011527368A CN 112694325 A CN112694325 A CN 112694325A
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ptc thermistor
oxide
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朱兴文
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Jiangsu Jun Porcelain Technology Co ltd
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Abstract

本发明公开了一种PTC热敏电阻陶瓷材料及其制备方法、应用，由基于钛酸铅钡的基础陶瓷粉料和添加材料组成，所述添加材料包括：Si的氧化物，Al的氧化物，Mn的氧化物和Mn的碳酸盐中的任一种或任两种；本发明提供的提供一种电阻非线性系数在5‑49％范围内可控可调的PTC热敏电阻材料。

Description

一种PTC热敏电阻陶瓷材料及其制备方法、应用
技术领域
本发明涉及电子材料技术领域，具体涉及一种PTC热敏电阻陶瓷材料及其制备方法、应用。
背景技术
PTC陶瓷一般是指具有正的电阻温度系数(Positive Temperature CoefficientResistance)的热敏电阻材料或元器件。PTC陶瓷具有温敏、节能、无明火和安全等优点，已广泛应用于汽车、家电、通信、自动化控制等领域。以PTC作为恒温发热体制作的发热器，可靠性、安全性高，发热量可随环境温度变化自动调节。在限流、温度传感等领域，由于PTC独特的电阻随温度变化而突跳的特性，而使这些器件具有体积小、结构简单、可靠性高等特点。
近年来，工业上对PTC材料加热元件及限流、热保护等元器件的性能要求逐渐提高，特别是体现在温度响应及性能可靠性方面。对PTC加热元件，使用一段时间后，其室温电阻会呈现不同程度的增加，加热功率下降，即所谓的老化现象，急需改善；对限流和热保护用PTC元件，要求其动作时间更短、恢复时间更快。这些要求均与PTC热敏电阻材料的关键性能-电阻温度非线性特性(以下简称温度系数α)-有关。
PTC材料作为加热元件，长时间工作后电阻上升，导致工作温度下移，发热量减少，发热功率下降。对空调辅助加热的PTC加热器，要求干烧1000小时功率下降＜8％，目前实际均在8～10％。因此就要求PTC材料电阻上升同样的幅度，但温度变化区间要小；对PTC限流元件和热保护元件，其动作时间和恢复时间是一对矛盾，动作时间越快，恢复越慢，这就要求PTC材料在很窄的温度区间阻值有很大的变化。这些要求均指向PTC材料的关键特性-电阻非线性系数，如何实现PTC材料的电阻非线性系数可控可调成为目前研发人员研究的热点。
发明内容
为解决上述技术问题，本发明的目的在于提供一种电阻非线性系数在5-49％范围内可控可调的PTC热敏电阻材料。
为达到上述目的，本发明的技术方案如下：
一种PTC热敏电阻陶瓷材料，由基于钛酸铅钡的基础陶瓷粉料和添加材料组成，所述添加材料包括：Si的氧化物，Al的氧化物，Mn的氧化物和Mn的碳酸盐中的任一种或任两种。
本发明提供的提供一种电阻非线性系数在5-49％范围内可控可调的PTC热敏电阻材料。
在上述技术方案的基础上，本发明还可以作如下改进：
作为优选方案，所述基于钛酸铅钡的基础陶瓷粉料通式为：
(Ba1-x-y-z PbxCayREz)(Ti1-wMEw)O3+aTiO2 (1)
在通式(1)中，所述RE为Y、Sb、Bi、La、Ce、Er、Sm和Nd中任一种元素或任几种元素；
在通式(1)中，所述ME为Nb、Ta和V中的中任一种元素或任几种元素；
在通式(1)中，x是0≤x≤0.6mol；
通式(1)中，y是0≤y≤0.12mol；
通式(1)中，z、w是0.0005≤z+w≤0.0055mol；
通式(1)中，a是0.002≤a≤0.03mol。
作为优选方案，通式(1)中A位的Ba和Ca的总量(1-x)mol中，(0.980-x)～(0.997-x)mol是以碳酸盐的形式加入，剩余0.003～0.020mol的Ba和Ca以硫酸盐的形式加入。
作为优选方案，以1mol含Ti元素的氧化物为基准，所述Si的氧化物添加含量为小于0.03mol并且大于0mol。
作为优选方案，以1mol含Ti元素的氧化物为基准，所述Al的氧化物添加含量为小于0.015mol并且大于0mol。
作为优选方案，以1mol含Ti元素的氧化物为基准，所述Mn的氧化物和碳酸盐的添加含量为小于0.002mol并且大于0mol。
本发明还公开一种基于钛酸铅钡的基础陶瓷粉料的制备方法，其特征在于，将含Ba元素的碳酸盐和硫酸盐、含Ca元素的碳酸盐和硫酸盐、含Pb元素的氧化物,含Ti元素的氧化物,含RE的氧化物和含Me的氧化物作为原材料，进行球磨混合、干燥、合成、粉碎，制备获得基于钛酸铅钡的基础陶瓷粉料。
本发明还公开一种PTC热敏电阻陶瓷材料的制备方法，其特征在于，包括以下制备步骤：
1)分别称取基于钛酸铅钡的基础陶瓷粉料，Si的氧化物，Al的氧化物，Mn的氧化物和Mn的碳酸盐中的任一种或任两种这些成分,将这些分别称取的成分在去离子水中球磨混合得到混合料；
2)干燥加粘合剂造粒、并以5MPa～15MPa的压力压制成素坯；
3)将压制好的素坯在1240～1330℃温度下，保温25分钟～35分钟进行烧结得到烧结后的陶瓷片；
4)在烧结后的陶瓷片的表面涂覆电极浆料，并在480～580℃、保温6～30min进行烧制，将电极固化，最终获得PTC热敏电阻陶瓷片。
作为优选方案，步骤4)中的所述电极浆料为Ag电极浆料或Zn电极浆料中的任一种或任两种。
本发明还公开所述的PTC热敏电阻陶瓷材料在限流、定温加热器和温控器及过热温度传感器中的应用。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
除非特别指明，以下实施例中所用的试剂均可从正规渠道商购获得，以下实施例中所用的试剂均为化学纯及以上。
为了达到本发明的目的，本发明所公开的一种PTC热敏电阻陶瓷材料是一种以1mol的TiO2为基准，由摩尔数按下列通式(1)计算的组分为主要成分的陶瓷烧结体。
(Ba1-x-y-z PbxCayREz)(Ti1-wMEw)O3+aTiO2 (1)
其中，RE为Y、Sb、Bi、La、Ce、Er、Sm和Nd中的至少一种元素，作为施主元素在ABO3型钙钛矿结构中置换A位，以实现材料的半导化；所述ME为Nb、Ta和V中的至少一种元素，它(们)同样作为施主置换B位，多施主共掺杂有抑制晶粒长大的效果。
通式(1)中的Pb和Ca元素置换部分A位的Ba，Pb的置换可以连续调节PTC材料的居里温度(调节PTC材料的居里温度范围为120～320℃)；Ca的置换可以调节材料的晶粒大小；
A位和B位的置换数量(摩尔数)x、y、z、w和a满足下列通式(2)～(5)：
0≤x≤0.6 (2)
0≤y≤0.12 (3)
0.0005≤z+w≤0.0055 (4)
0.002≤a≤0.03 (5)
通式(1)中A位的Ba和Ca的总量(1-x)mol中，(0.980-x)～(0.997-x)mol是以碳酸盐的形式加入，剩余0.003～0.020mol的Ba和Ca以硫酸盐的形式加入。由于硫酸盐在高温时会分解生成SO3，SO3是强氧化剂，烧结时会促进晶界氧化，从而能提高电阻非线性系数，更优选0.006～0.010mol的Ba和Ca硫酸盐加入量，在此范围内材料的PTC性能更优异，室温电阻不超过104Ωcm，电阻非线性系数在25％以上；
本发明的PTC热敏电阻陶瓷材料采用A、B位双施主掺杂(RE、ME元素，各选其中的一种或多种)，掺杂总量(z+w)优选为0.0009～0.0035mol。双施主掺杂有利于促进材料的半导化，室温电阻下降，同时掺杂后晶格内A、B位缺陷平衡，晶粒生长均匀，材料的耐电压强度上升；
以上述将含Ba元素的碳酸盐和硫酸盐、含Ca元素的碳酸盐和硫酸盐、含Pb元素的氧化物,含Ti元素的氧化物,含RE的氧化物和含Me的氧化物作为原材料，进行球磨混合、干燥、合成、粉碎等陶瓷制作工艺，制备获得基础陶瓷粉料。
本发明获得这些特性的理由，是通过材料组分调整来促进烧结过程中的晶界氧化而实现的。PTC热敏电阻材料，在某一温度以上(居里温度，Tc)，其电阻会上升2～6个数量级。电阻上升的机理主要是由于居里温度以上晶界势垒上升引起，而晶界势垒的高低与烧结过程中陶瓷晶界氧化和受主杂质(如Mn等)吸附有关。晶界上杂质离子的氧化(如Mn、Ce等由低价氧化为高价)，以及高温烧结时碳酸盐和硫酸盐的分解形成的氧化剂促进了晶界的氧化是获得这些特性的主因。但是，本发明获得这些特性的机理并不限定于此。
进一步，在上述基础陶瓷粉料中，以1mol的Ti为基准，优选添加含量0.035mol以下的Si的氧化物。进一步地，优选0.30mol以下的Si的氧化物，因为高于0.035mol的Si会导致电阻有增大的趋势。Si的氧化物与通式(1)中的TiO2在烧结过程中形成低共融玻璃相而存在于晶界，有降低烧结温度的效果；同时，该玻璃相会吸附部分有害杂质，有降低室温电阻率的效果；优选Si的氧化物，因为这些化合物会部分高温分解，有利于增加烧结活性和均匀分散，有一定程度提高电阻非线性系数的效果；
进一步，在上述基础陶瓷粉料中，以1mol的Ti的氧化物为基准，优选添加总含量0.015mol以下的Al的氧化物，Al2O3与SiO2和TiO2一起形成低共熔玻璃相有降低烧结温度、调节电阻非线性系数的效果；
另外，在上述基础陶瓷粉料中，以1mol的Ti的氧化物为基准，优选添加含量0.002mol以下的Mn的氧化物和碳酸盐，有调节室温电阻、提高非线性的效果。进一步，优选0.0015mol以下且在0.0005mol以上的Mn的碳酸盐，该组分的材料电阻率低于104Ωcm，且材料的电阻非线性系数高；
本发明提供的PTC热敏电阻陶瓷材料，通过通式(1)的化合物合成后，再添加Si的氮化物、碳化物或碳氢化物、Al的氧化物、Mn的氧化物和碳酸盐后，经过球磨混合、干燥、加粘合剂后造粒并成型，脱胶烧结后得到。
本发明PTC热敏电阻陶瓷材料的性能测试是通过PTC热敏电阻陶瓷片进行检测的；PTC热敏电阻陶瓷片通过以下制备步骤获得：PTC热敏电阻陶瓷材料在压制烧结后的陶瓷片经过表面丝网涂覆Ag/Zn电极浆料，并经500～580℃，0.5小时烧结，将电极固化，制备获得PTC热敏电阻陶瓷片。
另外，本发明PTC热敏电阻陶瓷材料的性能，如PTC升阻比(突跳)、电阻非线性系数α15等按下式(6)～(7)计算获得：
PTC突跳＝log10(Rmax/Rmin)(单位：无) (6)
α15＝2.303×log10(RTc+15/RTc)/15(单位：％) (7)
式中，Rmax是电阻-温度特性中最大的电阻，Rmin是最小的电阻；Tc是材料的居里温度，它是2倍最小电阻值对应的温度；RTc+15是温度(Tc+15℃)所对应的电阻值，RTc是居里温度时的电阻值。PTC材料在通电后的工作点一般在其居里温度15℃左右，在此温度范围内材料的性能是其关键指标，因此本发明以α15来标定PTC的关键性能。
另外，将上述陶瓷片以2℃/分钟的升温速度进行电阻-温度(R-T)特性测试，测试温度范围25～330℃。
另外，以50Vac/分钟的速率进行加载电压测试，直至击穿，记录其击穿电压值。将10片陶瓷片并联以导热硅胶粘合在铝波纹条上并通电固化后制成PTC加热器，在25±1℃的环境中220Vac电压下以2.5米/秒的风速测试其功率P1，然后在220Vac电压下无风通电1000小时(干烧)，再以同样条件测试发热功率P2，计算干烧前后的功率变化率：
ΔP＝(P2-P1)/P1×100％ (8)
以下通过实施例及比较例来进一步具体说明本发明，但是本发明完全不限定于以下的实施例。
本发明的PTC热敏电阻陶瓷材料是基于，但是完全不限定于以下的基础陶瓷粉料(合成料)，在具体说明实施例前，先制备基础陶瓷粉料。作为起始原料准备化学纯及以上纯度的TiO2,BaCO3,CaCO3,BaSO4,CaSO4,PbO,以及RE和Me的氧化物(如La2O3,Nb2O5等)，按表1的比例称取各原料，采用球磨(水介质)混合，干燥后在1050℃温度环境下，2～4小时合成，获得基础陶瓷粉料(合成料)。
表1、基础陶瓷粉料配方表
Figure BDA0002851210110000071
Figure BDA0002851210110000081
实施例一
在制取SB系列基础陶瓷粉料(合成料)后，按表2分别称取SiO2,Al2O3,MnO2,在去离子水中球磨混合，然后干燥加粘合剂造粒、并以10MPa的压力压片制成尺寸为24×15×2.9mm的方形素坯，在空气气氛中，将压制好的方形素坯1280～1330℃温度下，保温30分钟烧结，使方形素坯充分烧结和实现固相反应，对烧结后得到的陶瓷表面进行研磨，使其厚度保持为2.4mm，然后在陶瓷片表面涂覆Ag和Zn电极浆料，并在480～520℃、保温8min进行烧制，将电极固化，最终获得PTC热敏电阻陶瓷片1，并测试其性能，PTC热敏电阻陶瓷片1的性能见表2。
实施例一的结果示于表2中。
表2：实施例一的样品组成与性能列表。
Figure BDA0002851210110000082
Figure BDA0002851210110000091
由表2可知，配方中碳酸钙含量增加，室温电阻有所上升，特别是Ca含量y大于0.06mol时，电阻上升幅度大。从耐压的角度看，y值含量在0.03mol左右时，耐压较高。
对比样品SB-2-1和SB-3-2，增加外加TiO2含量，耐压上升明显，温度系数及老化有向好的趋势。
另外，MnO2含量增加，电阻上升，当含量增至0.0018mol时，电阻接近104ΩCm，不优选；当含量低于0.0005时，电阻低，耐压低至180Vac/mm，不优选。
对比样品SB-6-1，SB-7-1和SB-8-1，BaSO4含量增加，温度系数明显上升，1000H功率变化率下降。
实施例二
在制取SB系列基础陶瓷粉料(合成料)后，按表3分别称取SiO2,Al2O3,MnO2,MnCO3,在去离子水中球磨混合，然后干燥加粘合剂造粒、并以10MPa的压力压片制成尺寸为24×15×2.9mm的方形素坯。在空气气氛中，将压制好的方形素坯1270～1310℃下，保温30分钟烧结，使方形素坯充分烧结和实现固相反应。对烧结后得到的陶瓷表面进行研磨，使其厚度保持为2.4mm，然后在陶瓷片表面涂覆Ag和Zn电极浆料，并在480～520℃、保温8min进行烧制，将电极固化，最终获得PTC热敏电阻陶瓷片2，并测试其性能，PTC热敏电阻陶瓷片2的性能见表3。
实施例二的结果示于表3中。
表3：实施例二的样品组成与性能列表。
Figure BDA0002851210110000101
Figure BDA0002851210110000111
由表3可知，配方中以MnCO3替代MnO2，室温电阻减小，电阻非线性系数增大，耐压性能上升，功率老化趋好，因此优选MnCO3作为PTC性能调节剂。
从调整施主掺杂量对比的两组样品可以看出，添加含量增加，耐压性能提升明显。但是，当同时BaSO4含量较高(＞0.009mol)时，室温电阻已超出实用范围。
对比实施例二的两组样品，随BaSO4含量增加，温度系数明显上升，1000H功率变化率下降。
实施例三
在制取SB系列基础陶瓷粉料(合成料)后，按表4分别称取SiO2,Al2O3,MnCO3,在去离子水中球磨混合，然后干燥加粘合剂造粒、并以10MPa的压力压片制成尺寸为24×15×2.9mm的方形素坯。在空气气氛中，将压制好的方形素坯1240～1290℃下，保温30分钟烧结，使方形素坯充分烧结和实现固相反应。对烧结后得到的陶瓷表面进行研磨，使其厚度保持为2.4mm，然后在陶瓷片表面涂覆Ag和Zn电极浆料，并在480～520℃、保温8min进行烧制，将电极固化，最终获得PTC热敏电阻陶瓷片3，并测试其性能，PTC热敏电阻陶瓷片3的性能见表3。
实施例三的结果示于表4中。
表4：实施例三的样品组成与性能列表。
Figure BDA0002851210110000112
Figure BDA0002851210110000121
从表4结果可以看出，CaSO4和BaSO4的添加均可以显著调高PTC的电阻非线性系数，两者的调整效果基本相同。但是，CaSO4对室温电阻的影响较大，高含量(≥0.009mol)的组分不优选。CaSO4添加对功率老化的改善作用要优于BaSO4，但其耐压性能稍低。
本发明提供的提供一种电阻非线性系数在5-49％范围内可控可调的PTC热敏电阻材料。
以上所述的仅是本发明的优选实施方式，应当指出，对于本领域的普通技术人员来说，在不脱离本发明创造构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。

Claims (10)

1.一种PTC热敏电阻陶瓷材料，其特征在于，由基于钛酸铅钡的基础陶瓷粉料和添加材料组成，所述添加材料包括：Si的氧化物，Al的氧化物，Mn的氧化物和Mn的碳酸盐中的任一种或任两种。
2.根据权利要求1所述的PTC热敏电阻陶瓷材料，其特征在于，所述基于钛酸铅钡的基础陶瓷粉料通式为：
(Ba1-x-y-z PbxCayREz)(Ti1-wMEw)O3+aTiO2 (1)
在通式(1)中，所述RE为Y、Sb、Bi、La、Ce、Er、Sm和Nd中任一种元素或任几种元素；
在通式(1)中，所述ME为Nb、Ta和V中的中任一种元素或任几种元素；
在通式(1)中，x是0≤x≤0.6mol；
通式(1)中，y是0≤y≤0.12mol；
通式(1)中，z、w是0.0005≤z+w≤0.0055mol；
通式(1)中，a是0.002≤a≤0.03mol。
3.根据权利要求2所述的PTC热敏电阻陶瓷材料，其特征在于，通式(1)中A位的Ba和Ca的总量(1-x)mol中，(0.980-x)～(0.997-x)mol是以碳酸盐的形式加入，剩余0.003～0.020mol的Ba和Ca以硫酸盐的形式加入。
4.根据权利要求1所述的PTC热敏电阻陶瓷材料，其特征在于，以1mol含Ti元素的氧化物为基准，所述Si的氧化物添加含量为小于0.03mol并且大于0mol。
5.根据权利要求1所述的PTC热敏电阻陶瓷材料，其特征在于，以1mol含Ti元素的氧化物为基准，所述Al的氧化物添加含量为小于0.015mol并且大于0mol。
6.根据权利要求1所述的PTC热敏电阻陶瓷材料，其特征在于，以1mol含Ti元素的氧化物为基准，所述Mn的氧化物和碳酸盐的添加含量为小于0.002mol并且大于0mol。
7.根据权利要求1-6中任一项所述的基于钛酸铅钡的基础陶瓷粉料的制备方法，其特征在于，将含Ba元素的碳酸盐和硫酸盐、含Ca元素的碳酸盐和硫酸盐、含Pb元素的氧化物,含Ti元素的氧化物,含RE的氧化物和含Me的氧化物作为原材料，进行球磨混合、干燥、合成、粉碎，制备获得基于钛酸铅钡的基础陶瓷粉料。
8.根据权利要求1-6中任一项所述的PTC热敏电阻陶瓷材料在限流、定温加热器和温控器及过热温度传感器中的应用。
9.一种PTC热敏电阻陶瓷材料的制备方法，其特征在于，包括以下制备步骤：
1)分别称取基于钛酸铅钡的基础陶瓷粉料，Si的氧化物，Al的氧化物，Mn的氧化物和Mn的碳酸盐中的任一种或任两种这些成分,将这些分别称取的成分在去离子水中球磨混合得到混合料；
2)干燥加粘合剂造粒、并以5MPa～15MPa的压力压制成素坯；
3)将压制好的素坯在1240～1330℃温度下，保温25分钟-35分钟进行烧结得到烧结后的陶瓷片；
4)在烧结后的陶瓷片的表面涂覆电极浆料，并在480～580℃、保温6～30min进行烧制，将电极固化，最终获得PTC热敏电阻陶瓷片。
10.根据权利要求9所述的PTC热敏电阻陶瓷材料的制备方法，其特征在于，步骤4)中的所述电极浆料为Ag电极浆料或Zn电极浆料中的任一种或任两种。
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