CN107140977B - 钡掺杂铬酸镧包覆钇稳定氧化锆负温度系数热敏复合陶瓷材料的制备方法 - Google Patents

钡掺杂铬酸镧包覆钇稳定氧化锆负温度系数热敏复合陶瓷材料的制备方法 Download PDF

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CN107140977B
CN107140977B CN201710350950.0A CN201710350950A CN107140977B CN 107140977 B CN107140977 B CN 107140977B CN 201710350950 A CN201710350950 A CN 201710350950A CN 107140977 B CN107140977 B CN 107140977B
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stabilized zirconia
barium
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doped lanthanum
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张惠敏
陈明星
刘婷
姜辉
常爱民
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

本发明涉及一种钡掺杂铬酸镧包覆钇稳定氧化锆负温度系数热敏复合陶瓷材料的制备方法，该方法内部核是具有高电阻值的高阻相钇稳定氧化锆（YSZ）材料，外部壳是具有低电阻率和低热敏常数的低阻相LaBaCrO材料，核和壳分别通过以氧氯化锆的八水化合物、硝酸钇的六水化合物、氨水；三氧化二镧、三氧化二铬和碳酸钡为原料，经过研磨、煅烧、研磨、复合压块成型、冷等静压成型、高温烧结，即可得到LaBaCrO‑YSZ包覆结构的热敏陶瓷，其材料常数B‑75℃/‑50℃的范围为(1700‑3500)×(1±2%)K，温度‑50℃电阻值的范围为(15‑3132)×(1±2%)Ω。采用本发明制备的钡掺杂的铬酸镧包覆氧化钇稳定氧化锆热敏陶瓷材料具有负温度系数特性，电性能稳定，一致性较好，适合制造中低温下宽温区环境中的热敏电阻器。

Description

钡掺杂铬酸镧包覆钇稳定氧化锆负温度系数热敏复合陶瓷材 料的制备方法
技术领域
本发明涉及一种钡掺杂铬酸镧包覆钇稳定氧化锆负温度系数复合材料的制备方法，该热敏陶瓷材料在-196-50℃温度范围内具有明显的负温度系数特性，是一种适用于制造中低温下宽温区热敏电阻器的新型陶瓷材料，该包覆结构具有在较宽范围内调节热敏电阻阻值的特征，属于半导体传感器领域。
背景技术
敏感材料与元器件是国家确定的电子信息产业的三大支柱之一，现已被认为是最具有发展前途的电子技术产品，发展敏感器件对提升我国电子工业在国际上地位有举足轻重的作用。热敏电阻具有可靠性好、灵敏度高、价格低廉等特点，已被广泛应用于日常生活用电器和工业设备的温度传感与控制。NTC热敏电阻主要的应用包括：抑制浪涌电流、温度补偿、温度测量与控制。为满足航空工业和日常生活的测量宽温区应用需求，宽温区热敏电阻材料已成为NTC热敏电阻领域新的发展趋势和研究热点。
LaCrO3具有很高的熔点(2400℃)，并具有耐化学腐蚀等优良特点，已被广泛用于耐火材料，加热材料及燃料电池等领域。通过Ba2+离子的掺杂，调节LaCrO3的电阻率ρ及其热敏常数B，可获得具有低ρ和低B的陶瓷材料；YSZ具有化学性质稳定、耐腐蚀、高阻值等特征。
本发明首次通过将低阻相的LaBaCrO材料包覆高阻相的钇稳定氧化锆(YSZ)，获得LaBaCrO-YSZ复合相热敏材料体系，可在较宽范围内调节材料的电阻值且对材料的B值影响较小，获得的复合热敏电阻材料体系适用于制造中低温下宽温区环境应用的热敏电阻。
发明内容
本发明的目的在于，提供一种钡掺杂铬酸镧包覆钇稳定氧化锆负温度系数热敏复合陶瓷材料的制备方法，该方法内部核是具有高电阻值的高阻相钇稳定氧化锆(YSZ)材料，外部壳是具有低电阻率和低热敏常数的低阻相LaBaCrO材料，核和壳分别通过以氧氯化锆的八水化合物、硝酸钇的六水化合物、氨水；三氧化二镧、三氧化二铬和碳酸钡为原料，经过研磨、煅烧、研磨、复合压块成型、冷等静压成型、高温烧结，即可得到LaBaCrO-YSZ包覆结构的热敏陶瓷，其材料常数B-75℃/-50℃的范围为(1700-3500)×(1±2％)K，温度-50℃电阻值的范围为(15-3132)×(1±2％)Ω。采用本发明制备的钡掺杂的铬酸镧包覆氧化钇稳定氧化锆热敏陶瓷电阻具有负温度系数特性，材料体系电性能稳定，一致性较好，适合制造用于中低温下宽温区环境中使用的热敏电阻器。
本发明所述的一种钡掺杂铬酸镧包覆钇稳定氧化锆负温度系数热敏复合陶瓷材料的制备方法，该方法中涉及的材料结构由内核钇稳定氧化锆(1)和外壳LaBaCrO(2)组成，具体操作按下列步骤进行：
a、将原料La2O3、BaCO3和Cr2O3，按摩尔比La:Ba:Cr＝30-50:1-30:40-50准确称量，置于玛瑙研钵研磨5-8h，得到混合均匀的粉体材料；
b、将步骤a中得到的粉体材料于温度1200-1400℃煅烧5-8h，再次研磨6-10h，得到钡掺杂的铬酸镧粉体(2)；
c、将原料ZrOCl2·8H2O和Y(NO3)3·6H2O按摩尔比Zr:Y＝84-96:4-16准确称量，分别加入去离子水中配置成0.2-0.5mol/L的溶液，备用；
d、准确量取浓氨水，再将浓氨水溶于去离子水中，配置成10-12mol/L的溶液，备用；
e、将步骤c中所得到的两种溶液混合，然后逐滴滴入步骤d配置的氨水中，边滴边搅拌，至白色絮状物完全析出，进行洗涤、过滤，并于温度70-80℃烘干，得到粉体；
f、将步骤e中得到的粉体于温度600-900℃煅烧4-6h，再次研磨6-10h，得到钇稳定氧化锆的粉体；
g、将步骤f得到的粉体材料以3-6Kg/cm2的压力进行压块成型，保压1min，得到直径为2-15mm的核钇稳定氧化锆(1)圆片生坯；
h、将步骤g得到的核钇稳定氧化锆(1)生坯置于步骤b中得到的铬酸镧粉体(2)中，以30-60Kg/cm2的压力进行压块成型，保压1-3min，得到直径为5-20mm的圆片生坯，将成型的块体材料进行冷等静压，在压强为200-400MPa下保压1-4min，后将块体材料于温度1400-1700℃烧结4-7h，即可得钡掺杂铬酸镧包覆钇稳定氧化锆热敏陶瓷材料；
i、将步骤h得到的热敏陶瓷材料正反两面涂覆银浆电极，于温度850℃下烧渗2h，即得到钡掺杂铬酸镧包覆钇稳定氧化锆的负温度系数热敏复合陶瓷材料。
本发明所述的钡掺杂铬酸镧包覆钇稳定氧化锆负温度系数热敏复合陶瓷材料的制备方法，该方法内部核钇稳定氧化锆(YSZ)的制备采用共沉淀法，外部壳LaBaCrO的制备采用氧化物固相法。钇稳定氧化锆(YSZ)粉体制备是分别将ZrOCl2·8H2O和Y(NO3)3·6H2O水解为0.2-0.5mol/L等摩尔浓度的溶液，然后将两种溶液混合，在以摩尔浓度10-12mol/L的氨水为沉淀剂，使混合溶液的白色絮状物沉淀完全，在进行洗涤、烘干和煅烧即可得到YSZ粉体；LaBaCrO粉体制备以La2O3、Cr2O3和BaCO3为原料，进行混合、研磨、煅烧、再研磨即得到LaBaCrO粉体。将YSZ粉体进行压块成型，然后包覆LaBaCrO粉体再一次进行压块成型，再将复合成型的块体进行冷等静压成型，得到生坯，最后对生坯进行高温烧结。在涂覆银浆电极即获得电阻圆片，该陶瓷电阻属于复合陶瓷的一种表现形式。其材料常数B-75℃/-50℃范围为(1700-3500)×(1±2％)K，温度-50℃电阻值范围为(15-3132)×(1±2％)Ω。采用本发明制备的钡掺杂的铬酸镧包覆钇稳定氧化锆热敏复合陶瓷材料，呈现高阻、低B的负温度系数特性，该陶瓷电阻的电性能稳定，一致性较好，适用于中低温下的宽温区的测量，为负温度系数热敏陶瓷材料的制备提供了一种新颖的制备方法。
本发明利用一种物理包覆的形式进行了LaBaCrO-YSZ热敏陶瓷，其创新点主要有以下两方面。
(1)首次将物理包覆形式应用于NTC热敏陶瓷材料研究中，以高阻相的钇稳定氧化锆(YSZ)为核，低阻低B的LaBaCrO为壳，实现了电阻值在较宽范围的调节。
(2)本发明的热敏陶瓷具有化学性质和电学性质稳定、耐腐蚀等特性，并且可以应用于测量液氮至50℃的宽温区。
附图说明
图1为本发明的复合陶瓷结构示意图；
图2为本发明的X射线衍射图谱，其中(a)钇稳定氧化锆(YSZ)；(b)LaBaCrO；(c)复合陶瓷材料LaBaCrO-YSZ；
图3为本发明的复合陶瓷材料接界处扫描电镜图。
具体实施方式
实施例1
a、将原料La2O3、BaCO3和Cr2O3，按摩尔比La:Ba:Cr＝30:30:40计算出所需原料的质量并准确称量，置于玛瑙研钵研磨8h，得到混合均匀的粉体材料；
b、将步骤a中得到的粉体材料于温度1400℃煅烧5h，再次研磨6h即得到钡掺杂的铬酸镧粉体LaBaCrO 2；
c、将原料ZrOCl2·8H2O和Y(NO3)3·6H2O按摩尔比Zr:Y＝84:16计算出所需原料的质量并准确称量，分别加入去离子水中配置成0.5mol/L的溶液，备用；
d、准确量取浓氨水，再将浓氨水溶于去离子水中，配置成12mol/L的溶液，备用；
e、将c中所得到的两种溶液混合，然后逐滴滴入步骤d配置的氨水溶液，边滴边搅拌，至白色絮状物完全析出，进行洗涤、过滤，并于温度70℃烘干，得到粉体；
f、将步骤e中得到的粉体于温度600℃煅烧6h，再次研磨6h即得到钇稳定氧化锆的粉体；
g、将步骤f得到的粉体材料以3Kg/cm2的压力进行压块成型，保压1min，得到直径为2mm的钇稳定氧化锆1圆片生坯；
h、将步骤g得到的钇稳定氧化锆1生坯置于步骤b中得到的钡掺杂铬酸镧的粉体LaBaCrO2中，以30Kg/cm2的压力进行压块成型，保压1min，得到直径为5mm的圆片生坯，将成型的块体材料进行冷等静压，在压强为200MPa下保压4min，后将块体材料于温度1400℃烧结7h，即可得钡掺杂铬酸镧包覆钇稳定氧化锆热敏陶瓷材料；
i、将步骤h得到的热敏陶瓷材料正反两面涂覆银浆电极，于温度850℃下烧渗2h，即得到钡掺杂铬酸镧包覆钇稳定氧化锆的负温度系数热敏复合陶瓷材料。
通过该方法获得的热敏电阻材料在温度为-50℃下电阻为15.0×(1±2％)Ω，材料常数为B-75℃/-50℃＝1700×(1±2％)K。
实施例2
a、将原料La2O3、BaCO3和Cr2O3，按摩尔比La:Ba:Cr＝37:20:43计算出所需原料的质量并准确称量，置于玛瑙研钵研磨7h，得到混合均匀的粉体材料；
b、将步骤a中得到的粉体于温度1350℃煅烧6h，再次研磨7h即得到钡掺杂的铬酸镧粉体LaBaCrO 2；
c、将原料ZrOCl2·8H2O和Y(NO3)3·6H2O按摩尔比Zr:Y＝88:12计算出所需原料的质量并准确称量，分别加入去离子水中配置成0.4mol/L的溶液，备用；
d、准确量取浓氨水，再将浓氨水溶于去离子水中，配置成11mol/L的溶液，备用；
e、将c中所得到的两种溶液混合，然后逐滴滴入步骤d配置的氨水，边滴边搅拌，至白色絮状物完全析出，进行洗涤、过滤，并于温度75℃烘干，得到粉体；
f、将步骤e中得到的粉体于温度700℃煅烧5h，再次研磨7h即得到钇稳定氧化锆的粉体；
g、将步骤f得到的粉体材料以4Kg/cm2的压力进行压块成型，保压1min，得到直径为5mm的钇稳定氧化锆1圆片生坯；
h、将步骤g得到的钇稳定氧化锆1生坯置于步骤b中得到的钡掺杂铬酸镧的粉体LaBaCrO2中，以40Kg/cm2的压力进行压块成型，保压2.5min，得到直径为10mm的圆片生坯，将成型的块体材料进行冷等静压，在压强为270MPa下保压3min，后将块体材料于温度1500℃烧结6h，即可得钡掺杂铬酸镧包覆钇稳定氧化锆热敏陶瓷材料；
i、将步骤h得到的热敏陶瓷材料正反两面涂覆银浆电极，于温度850℃下烧渗2h，即得到钡掺杂铬酸镧包覆钇稳定氧化锆的负温度系数热敏复合陶瓷材料。
通过该方法获得的热敏电阻材料在温度为-50℃下电阻为245.0×(1±2％)Ω，材料常数为B-75℃/-50℃＝2010×(1±2％)K。
实施例3
a、将原料La2O3、BaCO3和Cr2O3，按摩尔比La:Ba:Cr＝42:12:46计算出所需原料的质量并准确称量，置于玛瑙研钵研磨6h，得到混合均匀的粉体材料；
b、将步骤a中得到的粉体于温度1300℃煅烧7h，再次研磨8.5h即得到钡掺杂的铬酸镧粉体LaBaCrO 2；
c、将原料ZrOCl2·8H2O和Y(NO3)3·6H2O按摩尔比Zr:Y＝92:8计算出所需原料的质量，分别加入去离子水中配置成0.3mol/L的溶液，备用；
d、准确量取浓氨水，再将浓氨水溶于去离子水中，配置成11mol/L的溶液，备用；
e、将c中所得到的两种溶液混合，然后逐滴滴入步骤d配置的氨水，边滴边搅拌，至白色絮状物完全析出，进行洗涤、过滤，并于温度80℃烘干，得到粉体；
f、将步骤e中得到的粉体于温度800℃煅烧4.5h，再次研磨8.5h即得到钇稳定氧化锆的粉体；
g、将步骤f得到的粉体材料以5Kg/cm2的压力进行压块成型，保压1min，得到直径为10mm的钇稳定氧化锆1圆片生坯；
h、将步骤g得到的钇稳定氧化锆1生坯置于步骤b中得到的钡掺杂铬酸镧的粉体LaBaCrO2中，以50Kg/cm2的压力进行压块成型，保压2.5min，得到直径为15mm的圆片生坯，将成型的块体材料进行冷等静压，在压强为320MPa下保压2min，后将块体材料于1600℃烧结5h，即可得钡掺杂铬酸镧包覆钇稳定氧化锆热敏陶瓷材料；
i、将步骤h得到的热敏陶瓷材料正反两面涂覆银浆电极，于温度850℃下烧渗2h，即得到钡掺杂铬酸镧包覆钇稳定氧化锆的负温度系数热敏复合陶瓷材料。
通过该方法获得的热敏电阻材料在温度为-50℃下电阻为1968.0×(1±2％)Ω，材料常数为B-75℃/-50℃＝2860×(1±2％)K。
实施例4
a、将原料La2O3、BaCO3和Cr2O3，按摩尔比La:Cr＝49:1:50计算出所需原料的质量并准确称量，置于玛瑙研钵研磨5h，得到混合均匀的粉体材料；
b、将步骤a中得到的粉体于温度1200℃煅烧8h，再次研磨10h即得到钡掺杂的铬酸镧粉体LaBaCrO 2；
c、将原料ZrOCl2·8H2O和Y(NO3)3·6H2O按摩尔比Zr:Y＝96:4计算出所需原料的质量，分别加入去离子水中配置成0.2mol/L的溶液，备用；
d、准确量取浓氨水，再将浓氨水溶于去离子水中，配置成10mol/L的溶液，备用；
e、将c中所得到的两种溶液混合，然后逐滴滴入步骤d配置的氨水中，边滴边搅拌，至白色絮状物完全析出，进行洗涤、过滤，并于温度80℃烘干，得到粉体；
f、将步骤e中得到的粉体于温度900℃煅烧4h，再次研磨10h即得到钇稳定氧化锆的粉体；
g、将步骤f得到的粉体材料以6Kg/cm2的压力进行压块成型，保压1min，得到直径为15mm的钇稳定氧化锆1圆片生坯；
h、将步骤g得到的钇稳定氧化锆1生坯置于步骤b中得到的钡掺杂铬酸镧的粉体LaBaCrO2中，以60Kg/cm2的压力进行压块成型，保压3min，得到直径为20mm的圆片生坯，将成型的块体材料进行冷等静压，在压强为400MPa下保压1min，后将块体材料于1700℃烧结4h，即可得铬酸镧包覆钇稳定氧化锆热敏陶瓷材料；
i、将步骤h得到的热敏陶瓷材料正反两面涂覆银浆电极，于温度850℃下烧渗2h，即得到铬酸镧包覆钇稳定氧化锆的负温度系数热敏复合陶瓷材料。
通过该方法获得的热敏电阻材料在温度为-50℃下电阻为3132.0×(1±2％)Ω，材料常数为B-75℃/-50℃＝3500×(1±2％)K。

Claims (1)

1.一种钡掺杂铬酸镧包覆钇稳定氧化锆负温度系数热敏复合陶瓷材料的制备方法，其特征在于该方法中涉及的材料结构由内核钇稳定氧化锆（1）和外壳钡掺杂铬酸镧（2）组成，具体操作按下列步骤进行：
a、将原料La2O3、BaCO3和Cr2O3，按摩尔比La:Ba:Cr =30-50:1-30:40-50准确称量，置于玛瑙研钵研磨5-8h，得到混合均匀的粉体材料；
b、将步骤a中得到的粉体材料于温度1200-1400℃煅烧5-8h，再次研磨6-10h，得到钡掺杂的铬酸镧粉体（2）；
c、将原料ZrOCl2·8H2O和Y(NO3)3·6H2O按摩尔比Zr:Y=84-96:4-16准确称量，分别加入去离子水中配置成0.2-0.5mol/L的溶液，备用；
d、准确量取浓氨水，再将浓氨水溶于去离子水中，配置成10-12mol/L的溶液，备用；
e、将步骤c中所得到的两种溶液混合，然后逐滴滴入步骤d配置的氨水中，边滴边搅拌，至白色絮状物完全析出，进行洗涤、过滤，并于温度70-80℃烘干，得到粉体；
f、将步骤e中得到的粉体于温度600-900℃煅烧4-6h，再次研磨6-10h，得到钇稳定氧化锆的粉体；
g、将步骤f得到的粉体材料以3-6Kg/cm2的压力进行压块成型，保压1min，得到直径为2-15mm的钇稳定氧化锆（1）圆片生坯；
h、将步骤g得到的钇稳定氧化锆（1）生坯置于步骤b中得到的铬酸镧粉体（2）中，以30-60Kg/cm2的压力进行压块成型，保压1-3min，得到直径为5-20mm的圆片生坯，将成型的块体材料进行冷等静压，在压强为200-400MPa下保压1-4min，后将块体材料于温度1400-1700℃烧结4-7h，即可得钡掺杂铬酸镧包覆钇稳定氧化锆热敏陶瓷材料；
i、将步骤h得到的热敏陶瓷材料正反两面涂覆银浆电极，于温度850℃下烧渗2h，即得到钡掺杂铬酸镧包覆钇稳定氧化锆的负温度系数热敏复合陶瓷材料。
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