CN114920555A - 一种锰掺杂锆酸钙高温负温度系数热敏电阻材料的制备方法 - Google Patents
一种锰掺杂锆酸钙高温负温度系数热敏电阻材料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种锰掺杂锆酸钙高温负温度系数热敏电阻材料的制备方法，该方法以碳酸钙，二氧化锆，二氧化锰为原料，通过传统固相法合成，该热敏电阻材料具有温区宽、灵敏度高的特点。采用固相法预烧不同锰掺杂量的的粉体，然后在15MPa的压力下单轴挤压成圆片，再将圆片在300MPa的压力下等静压180秒，在1500℃下保温10h，得到热敏电阻陶瓷，然后在陶瓷的两面均匀涂抹铂浆，以铂丝做引线，在温度900℃下退火30min，电阻值在200‑1200℃的温度范围内测量，即得B值和ρ800分别在19521‑9526 K，1.84×106‑2.63×103Ω·cm之间的具有宽温区的NTC热敏电阻材料，这些电性能参数表明该热敏电阻具有良好的应用潜力，可应用于高温负温度系数热敏电阻传感器领域。
Description
技术领域
本发明涉及一种锰掺杂锆酸钙高温负温度系数热敏电阻材料的制备方法。
背景技术
材料具有负温度系数热敏特性的发现时间比较久，由此制成的热敏电阻器件可用来制作精确的温度测量传感器,用于医疗、航天、军事等领域。传统的NTC热敏电阻材料是以过渡族金属为基础来制作薄膜传感器和热敏电阻器件，然而由这种材料制成的热敏电阻器件温区较窄，限制了使用的范围。因此，开发高温区使用的热敏电阻是有非常有必要的。CaZrO3(CZO)就是一种ABO3型钙钛矿材料,电性能具有NTC效应，熔点是2345℃，有两种多晶型，即低温时的正交结构(Pnma)和高温时的立方钙钛矿结构(Pm3m)。CaZrO3(CZO)陶瓷材料具有良好的的高温稳定，但材料的孔隙率高、密度低。电阻值在兆欧级别，阻值很大，材料常数B的值达到20000K以上，这对材料的电性能产生了影响。但是，对钙钛矿A位和B位的掺杂却能很好的改善材料的性能，降低B值和空隙率。Mn元素是尖晶石NTC热敏电阻中常用元素，对尖晶石类材料的电性能有着重要影响，因而选择锰元素掺杂CaZrO3(CZO)。本发明中通过锰元素掺杂CaZrO3(CZO)材料，可以有效的降低CaZrO3(CZO)陶瓷材料的B值和空隙率，提高其导电性。
发明内容
本发明的目的在于，提供一种锰掺杂锆酸钙高温负温度系数热敏电阻材料的制备方法，该方法按CaMnxZr(1-x)O3其中0<x<0.15通过固相法制成，利用Mn掺杂可明显增加锆酸钙的导电性，降低纯相的气孔率和减少晶粒的团聚。采用固相法预烧不同Mn掺杂量的的粉体，然后在15MPa的压力下单轴挤压成圆片，再将圆片在300MPa的压力下等静压，得到热敏电阻陶瓷片，然后在陶瓷片的两面均匀涂抹铂浆，以铂丝做引线，在温度900℃下退火30min，电阻值在200-1200℃的温度范围内测量，即得到B值和ρ800分别在19521-9526K，1.84×106-2.63×103Ω·cm之间的锰掺杂锆酸钙高温负温度系数热敏电阻材料。该热敏电阻材料在900℃下老化300小时，其老化系数不超过4.3％。由电性能参数表明：该热敏电阻具有良好的应用潜力，可应用于高温NTC传感器领域。
本发明所述的一种锰掺杂锆酸钙高温负温度系数热敏电阻材料的制备方法，按下列步骤进行：
a、按化学式CaMnxZr(1-x)O3，其中0<x<0.15的重量百分比，将原料碳酸钙，二氧化锆，二氧化锰进行混合，在研钵中研磨6h；
b、将步骤a研磨后的粉体以2℃/min的速率升温，在200℃时保温2h，再升温到1250℃，并保温3h，以2℃/min的速率降温，得到的粉末，再次研磨3h，得到粉末；
c、将步骤b中的粉末在15MPa单轴挤压成直径为10mm，厚度为2mm的圆片，然后在300MPa的压力下等静压180秒，以2℃/min的速率升温到1500℃下保温10h，再以2℃/min的速率降温，得到陶瓷片；
d、步骤c中的陶瓷片两面均匀涂抹铂浆，以铂丝做引线，在温度900℃下退火30min，并在200-1200℃的温度范围内测量陶瓷的电性能，即得到B值和ρ800分别在19521-9526K，1.84×106-2.63×103Ω·cm之间的锰掺杂锆酸钙高温负温度系数热敏电阻材料。
通过本发明所述方法获得的一种锰掺杂锆酸钙高温负温度系数热敏电阻材料，经电性能的测量：在温度200-1200℃的范围内B值为19521-9526K，ρ800为1.84×106-2.63×103Ω·cm。经老化性能测量，在900℃下老化300小时的老化系数不超过4.3％。这些电性能参数表明该热敏电阻具有良好的应用潜力。
附图说明
图1为本发明的XRD图；
图2为本发明的SEM图；
图3为本发明的电性能图。
具体实施方式
实施例1对比(重量百分比)
a、按照CaZrO3的组成，分别称取44.8％的碳酸钙、55.2％的二氧化锆进行混合，混合后的粉体在研钵中持续研磨6h；
b、将a中研磨后的粉体以2℃/min的速率升温200℃时保温2h，再升温到1250℃，并保温3h，然后以2℃/min的速率降温到50℃，预烧后得到的粉末，再次研磨3h；
c、将步骤b中的粉末在15MPa下单轴挤压成直径为10mm，厚度为2mm的圆片，之后将圆片在300MPa的压力下等静压180秒，所制圆片在温度1500℃下保温10h，然后以2℃/min的速率降温到50℃，得到高温热敏电阻陶瓷片；
d、步骤c中高温热敏电阻陶瓷片两面均匀涂抹铂浆，以铂丝做引线，在温度900℃下退火30min，在温度200-1200℃的范围内测量电性能，即得B值为19521K，ρ800为1.84×106Ω·cm的锆酸钙负温度系数热敏电阻材料。
实施例2(重量百分比)
a、按照CaMn0.05Zr0.95O3的组成，其中x＝0.05，分别称取45.2％的碳酸钙、52.8％的二氧化锆、2％的二氧化锰进行混合，在研钵中研磨6h；
b、将a中研磨后的粉体以2℃/min的速率升温，在200℃时保温2h，之后升温到1250℃，并保温3h，然后以2℃/min的速率降温到50℃，得到的粉末，再次研磨3h；
c、将步骤b中粉末在15MPa下单轴挤压成直径为10mm，厚度为2mm的圆片，之后将圆片在300MPa的压力下等静压180秒，以2℃/min的速率升温到1500℃下保温10h，再以2℃/min的速率降温到50℃，得高温热敏电阻陶瓷片；
d、步骤c中的高温热敏电阻陶瓷片两面均匀涂抹铂浆，以铂丝做引线，在温度900℃下退火30min，在温度200-1200℃的范围内测量电性能，之后在温度900℃下老化300小时测量其老化性能，即得B值为9217K，ρ800为5.13×104Ω·cm，老化系数为3.6％的锰掺杂锆酸钙高温负温度系数热敏电阻材料。
实施例3(重量百分比)
a、按照CaMn0.1Zr0.9O3的组成，其中x＝0.1，分别称取45.6％的碳酸钙、50.5％的二氧化锆、3.9％的二氧化锰进行混合，在研钵中研磨6h；
b、将a中研磨后的粉体以2℃/min的速率升温，在200℃时保温2h，之后再升温到1250℃，并保温3h，以2℃/min的速率降温到50℃，得到的粉末，再次研磨3h；
c、将步骤b中的粉末在15MPa下单轴挤压成直径为10mm，厚度为2mm的圆片，之后将圆片在300MPa的压力下等静压180秒，以2℃/min的速率升温到1500℃下保温10h，再以2℃/min的速率降温到50℃，得到高温热敏电阻陶瓷片；
d、步骤c中的高温热敏电阻陶瓷片两面均匀涂抹铂浆，以铂丝做引线，在温度900℃下退火30min，在温度200-1200℃的范围内测量电性能，之后在温度900℃下老化300小时测量其老化性能，即得B值为9535K，ρ800为1.47×104Ω·cm，老化系数为4.3％的锰掺杂锆酸钙高温负温度系数热敏电阻材料。
实施例4(重量百分比)
a、按照CaMn0.15Zr0.85O3的组成，其中x＝0.15，分别称取46％的碳酸钙、48.1％的二氧化锆、5.9％的二氧化锰进行混合，在研钵中研磨6h；
b、将a中研磨后的粉体以2℃/min的速率升温，在200℃时保温2h，之后再升温到1250℃，并保温3h，以2℃/min的速率降温到50℃，得到的粉末，再次研磨3h；
c、将步骤b中的粉末在15MPa下单轴挤压成直径为10mm，厚度为2mm的圆片，之后将圆片在300MPa的压力下等静压180秒，以2℃/min的速率升温到1500℃下保温10h，再以2℃/min的速率降温到50℃，得待高温热敏电阻陶瓷片；
d、步骤c中的高温热敏电阻陶瓷片两面均匀涂抹铂浆，以铂丝做引线，在温度900℃下退火30min，在温度200-1200℃的范围内测量电性能，之后在温度900℃下老化300小时测量其老化性能，即得B值为9526K，ρ800为2.63×103Ω·cm，老化系数为3.8％的锰掺杂锆酸钙高温负温度系数热敏电阻材料。
实施例5
将实施例2-4获得的任意一种锰掺杂锆酸钙高温负温度系数热敏电阻材料与实施例1相比：
参见图1-3，从图1中可以看出：随着锰掺杂量的增加，所有样品的主相都能很好地匹配CaZrO3的钙钛矿结构，掺杂量小于0.1时为固溶体(PDF#76-2401)，当掺杂量大于0.1时出现第二相为CaMnO3(PDF#76-1132)，这表明它是一种有限固溶体，固溶极限为x＝0.1；
从图2中可以看出：锰掺杂能极大地降低锆酸钙的孔隙率，提高陶瓷的致密性，掺杂后CaMnxZr(1-x)O3(0<x<0.15)陶瓷样品表面晶粒晶界明显，孔隙率低；
从图3中可以看出：电阻率ρ和B值下降明显，在温度200-1200℃范围内陶瓷样品的电阻率随着温度的升高而下降，表现出典型的NTC特性明显，其中的插图是ln(ρ)和1000/T关系图，ln(ρ)和1000/T线性关系良好，小极化子跳跃特征明显，表现出典型的负温度系数特性。
Claims (1)
1.一种锰掺杂锆酸钙高温负温度系数热敏电阻材料的制备方法，其特征在于按下列步骤进行：
a、按化学式CaMnxZr(1-x)O3，其中0<x<0.15的重量百分比，将原料碳酸钙，二氧化锆，二氧化锰进行混合，在研钵中研磨6h；
b、将步骤a研磨后的粉体以2℃/min的速率升温，在200℃时保温2h，再升温到1250℃，并保温3h，以2℃/min的速率降温，得到的粉末，再次研磨3h，得到粉末；
c、将步骤b中的粉末在15MPa单轴挤压成直径为10mm，厚度为2mm的圆片，然后在300MPa的压力下等静压180秒，以2℃/min的速率升温到1500℃下保温10h，再以2℃/min的速率降温，得到陶瓷片；
d、步骤c中的陶瓷片两面均匀涂抹铂浆，以铂丝做引线，在温度900℃下退火30min，并在200-1200℃的温度范围内测量陶瓷的电性能，即得B值和ρ800分别在19521-9526 K，1.84×106-2.63×103Ω·cm之间的锰掺杂锆酸钙高温负温度系数热敏电阻材料。
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