CN114773034A - 一种高稳定负温度系数热敏陶瓷材料的制备方法 - Google Patents
一种高稳定负温度系数热敏陶瓷材料的制备方法 Download PDFInfo
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Abstract
本发明涉及一种高稳定负温度系数热敏陶瓷材料的制备方法,该方法以通过以Mn2O3、Co2O3、NiO为初始氧化物原料,并掺杂特定化学计量比的Al2O3与Ho2O3,经过研磨、煅烧、研磨、压块成型、冷等静压成型、高温烧结即可得到高稳定负温度系数热敏陶瓷,其材料常数B25/50℃的范围为3561‑3998K,温度0℃电阻率的范围为10703‑12847Ω·cm,采用本发明制备的高稳定负温度系数热敏陶瓷材料具有明显的负温度系数特性,材料体系稳定性高,线性度好,其晶粒具有凸起的表面形貌,适合制造用于高稳定的NTC热敏电阻器。
Description
技术领域
本发明涉及一种高稳定负温度系数热敏陶瓷材料的制备方法,属于半导体传感器领域。
背景技术
要培育壮大核心电子元器件,积极促进全国各地电子信息制造行业发展,敏感材料与元器件作为国家确定的电子信息产业的三大支柱之一,加强相关产品研发与制造技术的创新,有利于提升我国电子工业在国际上的地位。热敏电阻器作为常见的敏感材料与元器件,其产品本身具有高灵敏度、高精度、宽温域,价格低廉等特点,已广泛应用于日常生活电器、工业设备、航空航天和深海探测等方方面面的温度传感与控制。对于精密测温的高精度NTC热敏电阻器来说,测温精度要高于0.05 ℃,它自身的稳定性至关重要,如果自身稳定性不佳,就难以应用在高精度温度测量上。所以为了满足NTC热敏电阻特别是高灵敏高精度热敏电阻的应用需求,对热敏电阻器稳定性的研发和创新一直是该领域的研究热点。
稀土金属钬能与碳、氢、氧、氮、磷、硫和卤素元素形成极为稳定的化合物,其中Ho2O3的相对分子量为377.86g/mol,是一种重型稀土氧化物,Ho3+的离子半径为90.1pm,能与钍、镉、锌、镁、汞、锆等多种金属形成固溶体,且可以和其他非稀土金属形成多达3000余种的金属间化合物,其中与传统NTC材料中的金属元素Mn、Co、Ni就形成了多达200余种的金属间化合物;同时有研究表明稀土元素能填补晶格缺陷和细化晶粒,这些因素都能帮助提升NTC 热敏电阻器的稳定性。
本发明运用高能球磨法制造出高活性纳米氧化物粉末,首次通过将Ho3+离子和Al3 +离子以特定的化学计量比掺入Mn-Co-Ni尖晶石结构的晶格中,烧结体晶粒具有凸起的表面形貌,可在保持原有NTC特性不变的同时,极大地提升材料的稳定性,获得的热敏电阻材料体系适用于制造高稳定热敏电阻。
发明内容
本发明的目的在于,提供一种高稳定负温度系数热敏陶瓷材料的制备方法,该方法以通过以Mn2O3、Co2O3、NiO为初始氧化物原料,并掺杂特定化学计量比的Al2O3与Ho2O3,经过研磨、煅烧、研磨、压块成型、冷等静压成型、高温烧结即可得到高稳定负温度系数热敏陶瓷,其材料常数B25/50℃的范围为3561-3998K,温度0℃电阻率的范围为10703-12847Ω·cm,在高温烧结的过程中,掺杂的部分Ho3+离子和Al3+离子会固溶到尖晶石结构的基体中,由于掺杂元素具有拖曳效应,元素倾向于在晶界处聚集,细化了尖晶石晶粒,同时由于凸起的晶粒表面形貌,会减少老化过程中晶界与空气的接触面积,降低了晶界阳离子空位向晶粒内部的迁移,让材料具有很高的稳定性。采用本发明制备的高稳定负温度系数热敏陶瓷材料具有明显的负温度系数特性,材料体系稳定性高,线性度好,其晶粒具有凸起的表面形貌,适合制造用于高稳定的NTC热敏电阻器。
本发明所述的一种高稳定负温度系数热敏陶瓷材料的制备方法,该方法中涉及的初始氧化物原料主要为Mn2O3、Co2O3、NiO并掺杂特定化学计量比的Al2O3与Ho2O3,在 2000r/min-4200r/min的条件下经过高能搅拌球磨后得到混合纳米粉体,具体操作按下列步骤进行:
a、按摩尔比30-40:6-7:14-16:5-6:0.2-1将原料Mn2O3、Co2O3、NiO、Al2O3、Ho2O3准确称量,置于高能球磨机中研磨7-10h,球磨介质为氧化锆陶瓷微珠,粉体及球磨介质的质量比为1:1.5-3,经80目的分子筛过筛,在温度80-120℃下烘干后得到混合均匀的块体;
b、将步骤a中得到的块体置于玛瑙研钵研磨2-3h得到混合均匀的粉体;
c、将步骤b中得到的粉体放置于温度920-1000℃的马弗炉中煅烧2-4h,得到MnxCoyNizAlwHovO4粉体,其中x+y+z+w+v=3;
d、将步骤b得到的MnxCoyNizAlwHovO4,加入质量比1-2%的分散剂三乙醇胺、聚乙二醇辛基苯基醚或聚丙烯酸胺,再次置于高能球磨机中均匀混合研磨4-6h,得到材料粉体;
e、将步骤d得到的粉体称取0.4g倒入直径为10mm的磨具中,液压机采用20-40MPa保压时间50-70秒,压制成圆片生坯;
f、将步骤e中得到的圆片生坯进行抽真空处理,然后放入冷等静压机中,压力为300-350MPa,保压时间为180-240s;
g、将步骤f得到的生坯材料放入马弗炉中烧结2-4h,烧结温度为1230℃-1260℃,升温速率为2-4℃/min,在250℃下保温2h,降温速率为1-2℃/min;
h、将步骤g得到的陶瓷片放入容器中,加入去离子水,将容器放入超声清洗池中5min,如此操作往复3次,将得到的热敏陶瓷材料表面水分烘干,正反两面用丝网印刷银浆电极,于温度850℃-900℃下烧渗10min,即得到高稳定负温度系数热敏陶瓷材料。
本发明所述的一种高稳定负温度系数热敏陶瓷材料的制备方法,该方法采用高能球磨法,制备过程是分别将原料Mn2O3、Co2O3、NiO、Al2O3、Ho2O3按摩尔比30-40:6-7:14-16:5-6:0.2-1 准确称量,置于高能球磨机中研磨7-10h,得到混合均匀的高活性粉体材料,于温度920- 1000℃的马弗炉中煅烧2-4h,再次置于高能球磨机中研磨4-6h,得到材料粉体。最后将材料粉体倒入磨具中,液压机下采用20-40MPa保压时间50-70秒,压制成型为圆片生坯,再将成型的圆片生坯进行冷等静压,最后对生坯进行高温烧结得到陶瓷圆片,再涂覆银浆电极即获得电阻圆片,该陶瓷电阻具有很高的电学稳定性。其材料常数B25/50℃的范围为3561-3998K,温度0℃电阻率的范围为10703-12847Ω·cm。采用本发明制备的高稳定负温度系数热敏陶瓷材料具有负温度系数特性,材料体系电性能稳定,线性度良好,适合制造高稳定的热敏电阻器,为高稳定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。
本发明所述的高稳定负温度系数热敏陶瓷材料,其创新点主要如下:
将Al2O3和Ho2O3共同掺杂到Mn-Co-Ni体系的NTC热敏陶瓷材料中,形成了多边形凸起的晶粒,细化了尖晶石晶粒,将材料的电阻漂移率提升至0.1%以下,实现了高稳定NTC热敏电阻器的设计和制造。
该热敏陶瓷材料是一种Al2O3和Ho2O3掺杂Mn-Co-Ni的五元材料体系,在0-100℃温度范围内有着明显的负温度系数特性,经过长达1000小时125℃的高温加速老化,其电阻漂移率小于0.1%,是一种具有高稳定性的新型陶瓷材料。
附图说明
图1为本发明具有多边形凸起结构的二维SEM晶粒形貌;
图2为本发明具有多边形凸起结构的三维AFM晶粒形貌;
图3为本发明具有单一尖晶石结构的X射线衍射图谱;
图4为本发明的热敏电阻阻温特性曲线。
具体实施方式
实施例1
a、按摩尔比35:6:14:5:0.2将原料Mn2O3、Co2O3、NiO、Al2O3和Ho2O3准确称量,置于高能球磨机中研磨7h,球磨介质为氧化锆陶瓷微珠,粉体与球磨介质的质量比为1:1.5,经80目的分子筛过筛,在温度120℃下烘干后得到混合均匀的块体;
b、将步骤a中得到的材料块体置于玛瑙研钵研磨2h得到混合均匀的粉体;
c、将步骤b中得到的粉体放置于温度920℃的马弗炉中煅烧2h,得到 Mn1.97Co0.33Ni0.39Al0.28Ho0.03O4粉体;
d、将步骤b得到的Mn1.97Co0.33Ni0.39Al0.28Ho0.03O4,加入质量比1%的分散剂三乙醇胺,再次置于高能球磨机中均匀混合研磨4h,得到材料粉体;
e、将步骤d得到的粉体称取0.4g倒入直径为10mm的磨具中,液压机采用20MPa保压时间50秒,压制成圆片生坯;
f、将步骤e中得到的圆片生坯进行抽真空处理,然后放入冷等静压机中,压力为300MPa,保压时间为180s;
g、将步骤f得到的生坯材料放入马弗炉中烧结2h,烧结温度为1230℃,升温速率为2℃/min,在温度250℃下保温2h,降温速率为1℃/min;
h、将步骤g得到的陶瓷片放入容器中,加入去离子水,将容器放入超声清洗池中5min,如此操作往复3次,将得到的热敏陶瓷材料表面水分烘干,正反两面用丝网印刷银浆电极,于温度850℃下烧渗10min,即得到高稳定负温度系数热敏陶瓷。
通过该方法获得的热敏电阻材料在温度为0℃下电阻率为10703Ω·cm,材料常数为 B25/50℃=3997K。
实施例2
a、按摩尔比32:6:15:5:0.4将原料Mn2O3、Co2O3、NiO、Al2O3和Ho2O3准确称量,置于高能球磨机中研磨8h,球磨介质为氧化锆陶瓷微珠,粉体及球磨介质的质量比为1:1.5,经80目的分子筛过筛,在温度90℃下烘干后得到混合均匀的块体;
b、将步骤a中得到的材料块体置于玛瑙研钵研磨3h得到混合均匀的粉体;
c、将步骤b中得到的粉体材料放置于温度925℃的马弗炉中煅烧2.5h,得到 Mn1.8 8Co0.36Ni0.43Al0.30Ho0.03O4粉体;
d、将步骤b得到的Mn1.88Co0.36Ni0.43Al0.30Ho0.03O4,加入质量比1.2%的分散剂聚乙二醇辛基苯基醚,再次置于高能球磨机中均匀混合研磨5h,得到材料粉体;
e、将步骤d得到的粉体称取0.4g倒入直径为10mm的磨具中,液压机采用25MPa保压时间50秒,压制成圆片生坯;
f、将步骤e中得到的圆片生坯进行抽真空处理,然后放入冷等静压机中,压力为310MPa,保压时间为180s;
g、将步骤f得到的生坯材料放入马弗炉中烧结3h,烧结温度为1235℃,升温速率为3℃/min,在温度250℃下保温2h,降温速率为2℃/min;
h、将步骤g得到的陶瓷片放入容器中,加入去离子水,将容器放入超声清洗池中5min,如此操作往复3次,将得到的热敏陶瓷材料表面水分烘干,正反两面用丝网印刷银浆电极,于温度850℃下烧渗10min即得到高稳定负温度系数热敏陶瓷。
通过该方法获得的热敏电阻材料在温度为0℃下电阻率为11523Ω·cm,材料常数为 B25/50℃=3989K。
实施例3
a、按摩尔比35:7:16:6:0.3将原料Mn2O3、Co2O3、NiO、Al2O3和Ho2O3准确称量,置于高能球磨机中研磨9h,球磨介质为氧化锆陶瓷微珠,粉体及球磨介质的质量比为1:1.5,经80目的分子筛过筛,在温度110℃下烘干后得到混合均匀的块体;
b、将步骤a中得到的材料块体置于玛瑙研钵研磨3h得到混合均匀的粉体;
c、将步骤b中得到的粉体放置于温度950℃的马弗炉中煅烧3h,得到Mn1.87Co0.37Ni0.43Al0.31Ho0.02O4粉体;
d、将步骤b得到的Mn1.87Co0.37Ni0.43Al0.31Ho0.02O4,加入质量比1%的分散剂聚丙烯酸胺,再次置于高能球磨机中均匀混合研磨5h,得到材料粉体;
e、将步骤d得到的粉体称取0.4g倒入直径为10mm的磨具中,液压机采用30MPa保压时间50-70秒,压制成圆片生坯;
f、将步骤e中得到的圆片生坯进行抽真空处理,然后放入冷等静压机中,压力为350MPa,保压时间为240s;
g、将步骤f得到的生坯材料放入马弗炉中烧结4h,烧结温度为1250℃,升温速率为4℃/min,在温度250℃下保温2h,降温速率为2℃/min;
h、将步骤g得到的陶瓷片放入容器中,加入去离子水,将容器放入超声清洗池中5min,如此操作往复3次,将得到的热敏陶瓷材料表面水分烘干,正反两面用丝网印刷银浆电极,于温度850℃下烧渗10min即得到高稳定负温度系数热敏陶瓷。
通过该方法获得的热敏电阻材料在温度为0℃下电阻率为11244Ω·cm,材料常数为 B25/50℃=3976K。
实施例4
a、按摩尔比40:7:16:6:1将原料Mn2O3、Co2O3、NiO、Al2O3、Ho2O3准确称量,置于高能球磨机中研磨10h,球磨介质为氧化锆陶瓷微珠,粉体及球磨介质的质量比为1:1.5,经80目的分子筛过筛,在温度120℃下烘干后得到混合均匀的块体;
b、将步骤a中得到的材料块体置于玛瑙研钵研磨3h得到混合均匀的粉体;
c、将步骤b中得到的粉体放置于温度1000℃的马弗炉中煅烧4h,得到 Mn1.94Co0.33Ni0.39Al0.29Ho0.05O4粉体;
d、将步骤b得到的Mn1.94Co0.33Ni0.39Al0.29Ho0.05O4,加入质量比2%的分散剂三乙醇胺,再次置于高能球磨机中均匀混合研磨6h,得到材料粉体;
e、将步骤d得到的粉体称取0.4g倒入直径为10mm的磨具中,液压机采用40MPa保压时间70秒,压制成圆片生坯;
f、将步骤e中得到的圆片生坯进行抽真空处理,然后放入冷等静压机中,压力为350MPa,保压时间为240s;
g、将步骤f得到的生坯材料放入马弗炉中烧结4h,烧结温度为1260℃,升温速率为4℃/min,在温度250℃下保温2h,降温速率为2℃/min;
h、将步骤g得到的陶瓷片放入容器中,加入去离子水,将容器放入超声清洗池中5min,如此操作往复3次,将得到的热敏陶瓷材料表面水分烘干,正反两面用丝网印刷银浆电极,于温度850℃下烧渗10min即得到高稳定负温度系数热敏陶瓷。
通过该方法获得的热敏电阻材料在温度为0℃下电阻率为12847Ω·cm,材料常数为 B25/50℃=3898K。
Claims (1)
1.一种高稳定负温度系数热敏陶瓷材料的制备方法,其特征在于该方法中涉及的初始氧化物原料主要为Mn2O3、Co2O3、NiO并掺杂特定化学计量比的Al2O3与Ho2O3,在2000r/min-4200r/min的条件下经过高能搅拌球磨后得到混合纳米粉体,具体操作按下列步骤进行:
a、按摩尔比30-40:6-7:14-16:5-6:0.2-1将原料Mn2O3、Co2O3、NiO、Al2O3、Ho2O3准确称量,置于高能球磨机中研磨7-10h,球磨介质为氧化锆陶瓷微珠,粉体及球磨介质的质量比为1:1.5-3,经80目的分子筛过筛,在温度80-120℃下烘干后得到混合均匀的块体;
b、将步骤a中得到的块体置于玛瑙研钵研磨2-3h得到混合均匀的粉体;
c、将步骤b中得到的粉体放置于温度920-1000℃的马弗炉中煅烧2-4h,得到MnxCoyNizAlwHovO4粉体,其中x+y+z+w+v=3;
d、将步骤b得到的MnxCoyNizAlwHovO4,加入质量比1-2%的分散剂三乙醇胺、聚乙二醇辛基苯基醚或聚丙烯酸胺,再次置于高能球磨机中均匀混合研磨4-6 h,得到材料粉体;
e、将步骤d得到的粉体称取0.4g倒入直径为10mm的磨具中,液压机采用20-40MPa保压时间50-70秒,压制成圆片生坯;
f、将步骤e中得到的圆片生坯进行抽真空处理,然后放入冷等静压机中,压力为300-350MPa,保压时间为180-240s;
g、将步骤f得到的生坯材料放入马弗炉中烧结2-4h,烧结温度为1230℃-1260℃,升温速率为2-4℃/min,在250℃下保温2h,降温速率为1-2℃/min;
h、将步骤g得到的陶瓷片放入容器中,加入去离子水,将容器放入超声清洗池中5min,如此操作往复3次,将得到的热敏陶瓷材料表面水分烘干,正反两面用丝网印刷银浆电极,于温度850℃-900℃下烧渗10min,即得到高稳定负温度系数热敏陶瓷材料。
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