CN110451960A - 一种钕掺杂的白钨矿结构负温度系数热敏电阻材料及其制备方法 - Google Patents

一种钕掺杂的白钨矿结构负温度系数热敏电阻材料及其制备方法 Download PDF

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CN110451960A
CN110451960A CN201910909120.6A CN201910909120A CN110451960A CN 110451960 A CN110451960 A CN 110451960A CN 201910909120 A CN201910909120 A CN 201910909120A CN 110451960 A CN110451960 A CN 110451960A
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张惠敏
李晓卉
常爱民
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

本发明涉及一种钕掺杂的白钨矿结构负温度系数热敏电阻材料及其制备方法，该材料以CaCO3、CeO2、Nb2O5、WO3和Nd2O3为原料，经过混合研磨、煅烧、研磨、冷等静压成型、高温烧结，即可得到Ca1‑xNdxCeNbWO8热敏电阻陶瓷材料，其中0≤x≤0.9，其电性能参数为：B25℃/50℃=4052‑6563K±6%,ρ25℃=0.102‑1.76×109Ω·cm±7%，500℃高温老化500h后阻值变化率在±6.19%以内。采用本发明制备的钕掺杂的白钨矿结构负温度系数热敏电阻材料在温度区间0℃‑600℃内具有明显的负温度系数特性，材料体系电性能稳定，一致性较好，老化性能稳定，是一种适合制造用于宽温区热敏电阻器的新型热敏电阻材料。

Description

一种钕掺杂的白钨矿结构负温度系数热敏电阻材料及其制备 方法
技术领域
本发明涉及一种钕掺杂的白钨矿结构负温度系数热敏电阻材料及其制备方法，该热敏电阻材料在0℃-600℃范围内具有明显的负温度系数特性，是一种适用于制造宽温热敏电阻器的新型热敏电阻，属于半导体传感器领域。
背景技术
敏感元件和传感器是国家确定的电子信息产业的三大支柱之一，现已被认为是最具发展前途的电子技术产品，发展敏感元器件对提升我国电子工业在国际上的地位具有举足轻重的作用。其中，宽温区热敏电阻器无论是在传统的家电、信息行业，还是医疗、汽车、地质勘探等行业都具有广阔的应用前景，是替代工业用金属传感器的理想产品。传统的尖晶石结构NTC具有一定局限性，使用温度区间范围较窄为-50℃-300℃，且尖晶石结构组成的多元系陶瓷材料的稳定性较差，烧结后材料处于非平衡状态，造成材料电学特性改变，限制其发展。现代材料科学的关键挑战之一就是开发新的化合物并在此基础上改性优化，因此，开发一种可实现宽温区温度测量并且较高温度下性能稳定的新型热敏电阻材料具有重要意义。
适用于高温区温度测量的白钨矿结构CaCeNbWO8具有高B值和高熔点，并具有优良的高温力学性能和高温稳定性。向CaCeNbWO8材料掺入一定比例的稀土氧化物Nd2O3，从而得到新型的低B值高阻值负温度系数热敏电阻材料。本发明在0℃-600℃范围内具有明显负温度系数特性，材料体系性能稳定，一致性好，老化性能稳定，适于制造宽温区使用热敏电阻器。
发明内容
本发明的目的在于，提供一种钕掺杂的白钨矿结构负温度系数热敏电阻材料及其制备方法，该材料以CaCO3、CeO2、Nb2O5、WO3和Nd2O3为原料，经过混合研磨、煅烧、研磨、冷等静压成型、高温烧结，即可得到Ca1-xNdxCeNbWO8热敏电阻陶瓷材料，其中0≤x≤0.9，其电性能参数为：B25℃/50℃＝4052-6563K±6％,ρ25℃＝0.102-1.76×109Ω·cm±7％，温度500℃高温老化500h后阻值变化率在±6.19％以内。采用本发明制备的钕掺杂的白钨矿结构负温度系数热敏电阻材料具有负温度系数特性，材料体系电性能稳定，一致性较好，老化性能稳定，适合制造用于高温环境中的热敏电阻器的新型热敏电阻材料。
本发明所述的一种钕掺杂的白钨矿结构负温度系数热敏电阻材料，该热敏电阻材料的化学通式为：Ca1-xNdxCeNbWO8，其中0≤x≤0.9，由原料CaCO3、CeO2、Nb2O5、WO3和Nd2O3配制而成。
所述钕掺杂的白钨矿结构负温度系数热敏电阻材料的制备方法，按下列步骤进行：
a、以CaCO3、CeO2、Nb2O5、WO3和Nd2O3为原料，其化学通式为Ca1-xNdxCeNbWO8，将原料按摩尔比CaCO3:CeO2:Nb2O5:WO3:Nd2O3＝0.04-0.4:0.4:0.2:0.4:0-0.18称量，置于玛瑙研钵中研磨，时间6-8h，将其充分混合均匀，得到粉体；
b、将步骤a中得到的粉体在温度1100℃-1200℃煅烧3-5h，再研磨4-6h，此过程重复两遍，即得热敏电阻粉体；
c、将步骤b得到的热敏电阻粉体以30-40Kg/cm2的压力进行压块成型，时间为1-3min，将成型的块体进行冷等静压，在压强为200-300MPa保压1-3min，然后将块体在温度1250℃-1350℃下烧结3-9h，即得钕掺杂白钨矿结构钙铈铌钨陶瓷材料；
d、将步骤c得到的钙铈铌钨陶瓷材料正反两面涂覆铂浆电极，然后在温度1100℃-1200℃下退火1-2h，即得到电性能参数为：B25℃/50℃＝4052-6563K±6％,ρ25℃＝0.102-1.76×109Ω·cm±7％的钕掺杂的白钨矿结构负温度系数热敏电阻材料。
本发明所述的一种钕掺杂的白钨矿结构负温度系数热敏电阻材料及其制备方法，采用固相法将分析纯碳酸钙，分析纯二氧化铈，分析纯五氧化二铌，分析纯三氧化钨和分析纯三氧化二钕进行混合研磨、煅烧、再研磨，将此过程重复两次即得负温度系数热敏电阻粉体材料，再将该粉体片式冷等静压成型，高温烧结后正反两面涂烧铂浆电极获得热敏电阻，该热敏材料为单一白钨矿结构，其电性能参数为：B25℃/50℃＝4052-6563K±6％,ρ25℃＝0.102-1.76×109Ω·cm±7％，温度500℃高温老化500h后阻值变化率在±6.19％以内。
本发明所述的一种钕掺杂的白钨矿结构负温度系数热敏电阻材料及其制备方法，利用钕掺杂白钨矿结构CaCeNbWO8制备了钕掺杂的白钨矿结构热敏电阻材料，其创新点主要有：
(1)CaCeNbWO8材料是高熔点材料，在高温环境中性能稳定，且具有负温度特性，将其作为基体材料，掺杂Nd3+离子使其四方性发生改变，可获得工作温度范围较宽的(0℃-600℃)负温度系数热敏电阻。
(2)Nd3+离子掺杂CaCeNbWO8材料，取代部分Ca2+离子，使载流子浓度增加，实现了CaCeNbWO8材料电性能调节。
该材料具有明显的负温度系数特性，材料体系电性能稳定，一致性较好，老化性能稳定，适合制造用于宽温环境的热敏电阻。
附图说明
图1为本发明的X射线衍射图谱，其中—◆—为CaWO4；
图2为本发明的扫描电镜图。
具体实施方式
实施例1
a、以CaCO3、CeO2、Nb2O5、WO3和Nd2O3为原料，其化学通式为CaCeNbWO8，将原料按摩尔比CaCO3:CeO2:Nb2O5:WO3＝0.4:0.4:0.2:0.4称量，置于玛瑙研钵中研磨，时间6h，将其充分混合均匀，得到粉体；
b、将步骤a中得到的粉体在温度1100℃煅烧3h，再研磨4h，此过程重复两遍，即得热敏电阻粉体；
c、将步骤b得到的粉体以30Kg/cm2的压力进行压块成型，时间为1min，将成型的块体进行冷等静压，在压强为200MPa保压1min，然后将块体在1350℃下烧结3h，即得钕掺杂白钨矿结构钙铈铌钨陶瓷材料；
d、将步骤c得到的陶瓷材料正反两面涂覆铂浆电极，然后在温度1200℃下退火2h，即得到钕掺杂的白钨矿结构负温度系数热敏电阻材料；
通过该方法获得的热敏电阻材料电学参数为B25/50＝6563K±4.6％，ρ25℃＝1.76×109Ω·cm±6％，温度500℃高温老化500h后阻值变化率在±4.27％以内。
实施例2
a、以CaCO3、CeO2、Nb2O5、WO3和Nd2O3为原料，其化学通式为Ca0.9Nd0.1CeNbWO8，将原料按摩尔比CaCO3:CeO2:Nb2O5:WO3:Nd2O3＝0.36:0.4:0.2:0.4:0.02称量，置于玛瑙研钵中研磨，时间7h，将其充分混合均匀，得到粉体；
b、将步骤a中得到的粉体在温度1200℃煅烧3h，再研磨5h，此过程重复两遍，即得热敏电阻粉体；
c、将步骤b得到的热敏电阻粉体以40Kg/cm2的压力进行压块成型，时间为2min，将成型的块体进行冷等静压，在压强为300MPa保压2min，然后将块体在1300℃下烧结6h，即得钕掺杂白钨矿结构钙铈铌钨陶瓷材料；
d、将步骤c得到的陶瓷材料正反两面涂覆铂浆电极，然后在温度1100℃下退火2h，即得到钕掺杂的白钨矿结构负温度系数热敏电阻材料；
通过该方法获得的热敏电阻材料电学参数为B25/50＝5633K±5.6％，ρ25℃＝2.59×108Ω·cm±6％，温度500℃高温老化500h后阻值变化率在±4.13％以内。
实施例3
a、以CaCO3、CeO2、Nb2O5、WO3和Nd2O3为原料，其化学通式为Ca0.8Nd0.2CeNbWO8，将原料按摩尔比CaCO3:CeO2:Nb2O5:WO3:Nd2O3＝0.32:0.4:0.2:0.4:0.04称量，置于玛瑙研钵中研磨，时间7h，将其充分混合均匀，得到粉体；
b、将步骤a中得到的粉体在温度1200℃煅烧4h，再研磨6h，此过程重复两遍，即得热敏电阻粉体；
c、将步骤b得到的热敏电阻粉体以40Kg/cm2的压力进行压块成型，时间为2min，将成型的块体进行冷等静压，在压强为300MPa保压3min，然后将块体在1300℃下烧结9h，即得钕掺杂白钨矿结构钙铈铌钨陶瓷材料；
d、将步骤c得到的陶瓷材料正反两面涂覆铂浆电极，然后在温度1100℃下退火2h，即得到钕掺杂的白钨矿结构热敏电阻材料；
通过该方法获得的热敏电阻材料电学参数为B25/50＝5146K±5.3％，ρ25℃＝1.89×108Ω·cm±5.8％，温度500℃高温老化500h后阻值变化率在±4.97％以内。
实施例4
a、以CaCO3、CeO2、Nb2O5、WO3和Nd2O3为原料，其化学通式为Ca0.4Nd0.6CeNbWO8，将原料按摩尔比CaCO3:CeO2:Nb2O5:WO3:Nd2O3＝0.16:0.4:0.2:0.4:0.12称量，置于玛瑙研钵中研磨，时间8h，将其充分混合均匀，得到粉体；
b、将步骤a中得到的粉体在温度1200℃煅烧5h，再研磨6h，此过程重复两遍，即得热敏电阻粉体；
c、将步骤b得到的热敏电阻粉体以40Kg/cm2的压力进行压块成型，时间为3min，将成型的块体进行冷等静压，在压强为300MPa保压3min，然后将块体在1250℃下烧结3h，即得钕掺杂白钨矿结构钙铈铌钨陶瓷材料；
d、将步骤c得到的陶瓷材料正反两面涂覆铂浆电极，然后在温度1100℃下退火1h，即得到钕掺杂的白钨矿结构热敏电阻材料；
通过该方法获得的热敏电阻材料电学参数为B25/50＝4651K±6％，ρ25℃＝1.79×108Ω·cm±7％，温度500℃高温老化500h后阻值变化率在±6.19％以内。
实施例5
a、以CaCO3、CeO2、Nb2O5、WO3和Nd2O3为原料，其化学通式为Ca0.1Nd0.9CeNbWO8，将原料按摩尔比CaCO3:CeO2:Nb2O5:WO3:Nd2O3＝0.04:0.4:0.2:0.4:0.18称量，置于玛瑙研钵中研磨，时间6h，将其充分混合均匀，得到粉体；
b、将步骤a中得到的粉体在温度1100℃煅烧5h，再研磨5h，此过程重复两遍，即得热敏电阻粉体；
c、将步骤b得到的热敏电阻粉体以30Kg/cm2的压力进行压块成型，时间为3min，将成型的块体进行冷等静压，在压强为300MPa保压2min，然后将块体在1250℃下烧结3h，即得钕掺杂白钨矿结构钙铈铌钨陶瓷材料；
d、将步骤c得到的陶瓷材料正反两面涂覆铂浆电极，然后在温度1100℃下退火1h，即得到钕掺杂的白钨矿结构热敏电阻材料；
通过该方法获得的热敏电阻材料电学参数为B25/50＝4052K±5％，ρ25℃＝1.02×108Ω·cm±6.8％，温度500℃高温老化500h后阻值变化率在±6.04％以内。

Claims (2)

1.一种钕掺杂的白钨矿结构负温度系数热敏电阻材料，其特征在于，该热敏电阻材料的化学通式为：Ca1-xNdxCeNbWO8，其中0≤x≤0.9，由原料CaCO3、CeO2、Nb2O5、WO3和Nd2O3配制而成。
2.根据权利要求1所述的钕掺杂的白钨矿结构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、以CaCO3、CeO2、Nb2O5、WO3和Nd2O3为原料，其化学通式为Ca1-xNdxCeNbWO8，将原料按摩尔比CaCO3:CeO2:Nb2O5:WO3:Nd2O3=0.04-0.4:0.4:0.2:0.4:0-0.18称量，置于玛瑙研钵中研磨，时间6-8h，将其充分混合均匀，得到粉体；
b、将步骤a中得到的粉体在温度1100℃-1200℃煅烧3-5h，再研磨4-6h，此过程重复两遍，即得热敏电阻粉体；
c、将步骤b得到的热敏电阻粉体以30-40Kg/cm2的压力进行压块成型，时间为1-3min，将成型的块体进行冷等静压，在压强为200-300MPa保压1-3min，然后将块体在温度1250℃-1350℃下烧结3-9h，即得钕掺杂白钨矿结构钙铈铌钨陶瓷材料；
d、将步骤c得到的钙铈铌钨陶瓷材料正反两面涂覆铂浆电极，然后在温度1100℃-1200℃下退火1-2h，即得到电性能参数为：B25℃/50℃=4052-6563K±6%,ρ25℃=0.102-1.76×109Ω·cm±7%的钕掺杂的白钨矿结构负温度系数热敏电阻材料。
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110903087A (zh) * 2019-11-22 2020-03-24 中科立民新材料（扬州）有限公司 一种低b高阻型宽温区高温热敏电阻材料及其制备方法和应用
CN111484327A (zh) * 2020-04-23 2020-08-04 中国科学院新疆理化技术研究所 一种温区和b值可调的锶、铈、铌和钨四元系热敏电阻材料及其制备方法
CN111704462A (zh) * 2020-07-03 2020-09-25 中国科学院新疆理化技术研究所 适用于通用航空尾气排放测温的复合负温度系数热敏电阻及其制备方法
CN112759391A (zh) * 2020-12-31 2021-05-07 中科立民新材料（扬州）有限公司 一种镱掺杂ntc型高温热敏电阻陶瓷材料及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001143907A (ja) * 1999-08-30 2001-05-25 Nippon Soken Inc サーミスタ素子
CN101186497A (zh) * 2007-12-07 2008-05-28 华南理工大学 一种提高铋层结构压电铁电陶瓷材料高温电阻率的方法
CN103011811A (zh) * 2012-12-07 2013-04-03 华中科技大学 一种高温负温度系数热敏电阻材料的制备方法
CN104692802A (zh) * 2015-03-27 2015-06-10 中国科学院新疆理化技术研究所 一种三氧化二钇掺杂的宽温区热敏电阻材料及其制备方法
CN109297608A (zh) * 2018-09-19 2019-02-01 北京科技大学 基于掺杂钛酸锶基氧化物的微区热扰动双向锁定探测方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001143907A (ja) * 1999-08-30 2001-05-25 Nippon Soken Inc サーミスタ素子
CN101186497A (zh) * 2007-12-07 2008-05-28 华南理工大学 一种提高铋层结构压电铁电陶瓷材料高温电阻率的方法
CN103011811A (zh) * 2012-12-07 2013-04-03 华中科技大学 一种高温负温度系数热敏电阻材料的制备方法
CN104692802A (zh) * 2015-03-27 2015-06-10 中国科学院新疆理化技术研究所 一种三氧化二钇掺杂的宽温区热敏电阻材料及其制备方法
CN109297608A (zh) * 2018-09-19 2019-02-01 北京科技大学 基于掺杂钛酸锶基氧化物的微区热扰动双向锁定探测方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
赵长江: "Y2O3掺杂Ca-Ce-Nb-W-O热敏材料研究及元器件研制", 《中国优秀硕士学位论文全文数据库》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110903087A (zh) * 2019-11-22 2020-03-24 中科立民新材料（扬州）有限公司 一种低b高阻型宽温区高温热敏电阻材料及其制备方法和应用
CN110903087B (zh) * 2019-11-22 2022-03-08 中科立民新材料（扬州）有限公司 一种低b高阻型宽温区高温热敏电阻材料及其制备方法和应用
CN111484327A (zh) * 2020-04-23 2020-08-04 中国科学院新疆理化技术研究所 一种温区和b值可调的锶、铈、铌和钨四元系热敏电阻材料及其制备方法
CN111704462A (zh) * 2020-07-03 2020-09-25 中国科学院新疆理化技术研究所 适用于通用航空尾气排放测温的复合负温度系数热敏电阻及其制备方法
CN112759391A (zh) * 2020-12-31 2021-05-07 中科立民新材料（扬州）有限公司 一种镱掺杂ntc型高温热敏电阻陶瓷材料及其制备方法和应用

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