CN116655367A - 一种负温度系数热敏陶瓷材料及其制备方法 - Google Patents
一种负温度系数热敏陶瓷材料及其制备方法 Download PDFInfo
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- 239000000463 material Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 9
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
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Abstract
本发明属于电子陶瓷材料领域,具体涉及一种负温度系数热敏陶瓷材料及其制备方法。所述陶瓷材料的成分包括0.69(Bi1‑xMgx)FeO3‑0.31BaTiO3,其中x=0.1%~5.0%。陶瓷材料的配方原料包括含有以下元素的氧化物、无机盐或有机盐:Bi、Fe、Ba、Ti、Mg金属元素;例如包括Bi2O3、Fe2O3、BaCO3、TiO2及MgO粉末。本发明的宽温区高温热敏电阻材料具有良好的致密性,同时具有优秀的热敏性能,在0~700℃范围内具有明显的负温度系数特性,适合制备宽温区高温热敏电阻器。
Description
技术领域
本发明涉及半导体热敏电阻领域,具体是一种负温度系数热敏电阻陶瓷材料及其制备方法。
背景技术
敏感元件和传感器是电子信息产业的支柱之一,具有广阔的发展前景,对电子工业的发展具有举足轻重的作用。温度系数(Negative Temperature Coefficient,NTC)热敏电阻是一种电阻值随温度增大而减小的电阻。其具有结构简单,体积较小、灵敏度高、成本低等优点,被广泛应用于测温控温、电子产品的过流保护及温度的补偿等,已成为医疗电器、汽车工业、家用电器甚至航空航天等诸多家用及工业领域不可缺少的电子元器件之一。然而传统的过渡金属氧化物组成的尖晶石热敏电阻陶瓷通常只能应用于300℃以下,无法满足高温环境下的使用,这就给新型高温NTC热敏陶瓷材料的开发提出新挑战。
高温NTC热敏陶瓷是指能在300℃以上场合应用的NTC热敏陶瓷。在目前研究中,一般通过两种方法实现在高温环境下的使用:一种是将NTC热敏陶瓷与高阻陶瓷混合,以实现提高材料高温稳定性的作用;另一种是对具有高温稳定性的钙钛矿型热敏陶瓷进行改性,通常是通过掺杂对钙钛矿结构中A、B位元素进行替换,改变其电特性,使其能在高温区域稳定应用,并具有适用的NTC性能。铁酸铋-钛酸钡陶瓷材料属于钙钛矿陶瓷,其具有高温稳定性好的特点,被广泛研究于高温电子陶瓷的领域。目前基于铁酸铋-钛酸钡陶瓷制备NTC热敏电阻的研究还鲜有报道,因此对其作为NTC热敏电阻的潜力还有待研究。
发明内容
为了解决现有技术存在的问题,本发明提供一种适用于高温NTC热敏陶瓷材料及其制备方法,制备的0.69(Bi1-xMgx)FeO3-0.31BaTiO3宽温区高温热敏电阻材料具有良好的致密性,同时具有优秀的热敏性能,在0~700℃范围内具有明显的负温度系数特性,适合制备宽温区高温热敏电阻器。
本发明的负温度系数热敏陶瓷材料,其成分包括0.69(Bi1-xMgx)FeO3-0.31BaTiO3,其中x=0.1%~5.0%。
优选地,x的取值为:x=0.5%,或x=1.0%,或x=1.5%,或x=2.0%。
优选地,所述陶瓷材料的配方原料包括含有以下元素的氧化物、无机盐或有机盐:Bi、Fe、Ba、Ti、Mg金属元素。
进一步优选地,所述陶瓷材料的配方原料包括Bi2O3、Fe2O3、BaCO3、TiO2及MgO粉末。
本发明的负温度系数热敏陶瓷材料的制备方法,包括如下步骤:
步骤(1)、按配方计算,称取配方原料;
步骤(2)、将步骤(1)中称取的配方原料混合,以去离子水为混合介质,将原料混合研磨若干小时,并烘干;
步骤(3)、对步骤(2)烘干后得到的粉体,进行预烧后得到粉末;
步骤(4)、将步骤(3)预烧得到的粉末进行研磨,再次以去离子水为介质,研磨若干小时并烘干;
步骤(5)、将步骤(4)烘干后得到的粉末造粒;
步骤(6)、将步骤(5)造粒后的粉末过筛;
步骤(7)、将步骤(6)筛选后的粉体装入模具中,施加高压,压制成型;
步骤(8)、将步骤(7)压制出的坯体放入高温炉中排胶;
步骤(9)、将步骤(8)排胶后的坯体置于坩埚中,然后进行烧结,冷却。
与现有技术相比,本发明取得的技术效果包括:
1、本发明采用Bi2O3、Fe2O3、BaCO3、TiO2、MgO粉末为原料,通过固相烧结法得到的铁酸铋-钛酸钡基高温NTC热敏陶瓷材料,即0.69(Bi1-xMgx)FeO3-0.31BaTiO3陶瓷材料,具有良好的致密性,同时具有优秀的热敏性能,在1020℃的烧结温度下,100℃时电阻率ρ100为2.2×106Ω·cm~4.7×104Ω·cm,100℃至600℃的热敏常数B100/600值为4430K~6421K;在0~700℃范围内具有明显的负温度系数特性,适合制备宽温区高温热敏电阻器。
本发明通过球磨、预烧、二次球磨、造粒、成型、烧结等步骤,即可制备0.69(Bi1- xMgx)FeO3-0.31BaTiO3宽温区高温热敏电阻材料。
2、本发明热敏陶瓷材料的成分简单、制备工艺简单,且通过调节元素含量,可以大范围地调节热敏电阻元件的电阻值,且保持较高的材料热敏常数B。
3、本发明的热敏电阻材料的成分配方,实际应用过程中可以根据需求,调整生产工艺,具有一定的灵活性。例如,原料可以选用含有关键元素的氧化物、无机盐或有机盐。
附图说明
图1为本发明实施例1、2、3、4制得的高温NTC陶瓷的X射线衍射图谱。
图2为本发明实施例2制得的高温NTC热敏陶瓷的表面SEM图。
图3是本发明实施例1、2、3、4制得高温NTC陶瓷的电阻-温度特征图,以表明实施例具有典型的NTC特性。
具体实施方式
本发明提供了一种适用于高温NTC热敏陶瓷材料及其制备方法,以下结合附图及实施例所示对本发明做进一步说明,但本发明的实施方式并不限于此。
本发明为一种适用于高温的NTC热敏陶瓷材料,NTC热敏电阻的成分组成包括0.69(Bi1-xMgx)FeO3-0.31BaTiO3,其中x=0.1%~5.0%;即配方中含有Bi、Fe、Ba、Ti、Mg元素,其原料可以是含有这些元素的氧化物、无机盐或有机盐。
本发明所采用的固相烧结工艺流程,包括如下步骤:
步骤(1)、按配方计算,称取配方原料,如Bi2O3、Fe2O3、BaCO3、TiO2、MgO粉末;
步骤(2)、将步骤(1)中称取的原料混合,以去离子水为混合介质,采用行星球磨机将原料混合球磨12小时,并烘干;
步骤(3)、将步骤(2)烘干后得到的粉体,装入刚玉坩埚中,放入马弗炉中以800℃预烧得到粉末,保温4小时;
步骤(4)、将步骤(3)预烧得到的粉末进行研磨,再次以去离子水为介质,在行星球磨机中球磨12小时,并烘干;
步骤(5)、将步骤(4)烘干后得到的粉末造粒;造粒时选用聚乙烯醇(PVA)为粘合剂,粘合剂的加入量为粉体质量的10%;
步骤(6)、将步骤(5)造粒后的粉末过筛,选用100目筛网;
步骤(7)、将步骤(6)筛选后的粉体装入专用模具中,施加5MPa高压,压制成型;
步骤(8)、将步骤(7)压制出的坯体放入高温电炉中排胶,排胶温度为600℃,保温2小时;
步骤(9)、将步骤(8)排胶后的坯体置于坩埚中,放入马弗炉中进行烧结;升温速率为3℃/分钟,烧结温度为1020℃,保温3小时,烧结后随炉冷却;
步骤(10)、选用1000目砂纸打磨,将步骤(9)烧结得到的陶瓷打磨表面,并使用超声清洗,随后采用丝网印刷法在材料两面印刷上电极。
下面以不同的x取值,举几个实施例对本发明的技术方案做进一步详细描述。
实施例1
本实施例制备x=0.5%的铁酸铋-钛酸钡NTC热敏陶瓷电阻材料。
选取纯度高于99%的Bi2O3、Fe2O3、BaCO3、TiO2、MgO粉末为配方原料,按化学式0.69(Bi0.995Mg0.005)FeO3-0.31BaTiO3的化学计量比例称取原料。以去离子水为球磨介质,氧化锆小球为磨球,球磨罐材质为聚四氟乙烯。按原料、磨球、去离子水为1:1:1的质量比放入行星球磨机,进行球磨混合12小时,出料后放入烘箱,在110℃烘干。将烘干的粉料以3℃/分钟的升温速率从室温升至800℃进行预烧,保温4小时。将预烧后的中间体研磨后,以去离子水为球磨介质进行二次球磨12小时,烘干,加入质量浓度为10%的聚乙烯醇水溶液作为粘合剂,进行造粒,并过100目筛。在5MPa的压力下,在模具中压制成直径为12mm,厚度为1.0mm的圆片。随后在烧结炉中将陶瓷片从室温加热5h升温至600℃,并保温2h进行排胶,以除去PVA。将排胶后的陶瓷坯片以3℃/分钟的升温速率升温至1020℃进行烧结,保温3小时,随炉自然冷却至室温。将烧结后的陶瓷片表面用1000目砂纸打磨平整,采用丝网印刷工艺,在陶瓷片两面被银,并在800℃烧银保温20分钟,形成电极。最后进行电性能测试。经测试,实施例为钙钛矿结构,没有杂相生成,陶瓷致密,没有气孔,电性能方面,在100℃时电阻率ρ100为2.2×106Ω·cm,100℃至600℃的热敏常数B100/600为6421K。
实施例2
本实施例制备x=1.0%的铁酸铋-钛酸钡NTC热敏陶瓷电阻材料。
选取纯度高于99%的Bi2O3、Fe2O3、BaCO3、TiO2、MgO粉末为配方原料,按化学式0.69(Bi0.99Mg0.01)FeO3-0.31BaTiO3的化学计量比例称取原料。以去离子水为球磨介质,氧化锆小球为磨球,球磨罐材质为聚四氟乙烯。按原料、磨球、去离子水为1:1:1的质量比放入行星球磨机,进行球磨混合12小时,出料后放入烘箱,在110℃烘干。将烘干的粉料以3℃/分钟的升温速率从室温升至800℃进行预烧,保温4小时。将预烧后的中间体研磨后,以去离子水为球磨介质进行二次球磨12小时,烘干,加入质量浓度为10%的聚乙烯醇水溶液作为粘合剂,进行造粒,并过100目筛。在5MPa的压力下,在模具中压制成直径为12mm,厚度为1.0mm的圆片。随后在烧结炉中将陶瓷片从室温加热5h升温至600℃,并保温2h进行排胶,以除去PVA。将排胶后的陶瓷坯片以3℃/分钟的升温速率升温至1020℃进行烧结,保温3小时,随炉自然冷却至室温。将烧结后的陶瓷片表面用1000目砂纸打磨平整,采用丝网印刷工艺,在陶瓷片两面被银,并在800℃烧银保温20分钟,形成电极。最后进行电性能测试。经测试,实施例为钙钛矿结构,没有杂相生成,陶瓷致密,没有气孔,电性能方面,在100℃时电阻率ρ100为4.0×105Ω·cm,100℃至600℃的热敏常数B100/600为5502K。
实施例3
本实施例制备x=1.5%的铁酸铋-钛酸钡NTC热敏陶瓷电阻材料。
选取纯度高于99%的Bi2O3、Fe2O3、BaCO3、TiO2、MgO粉末为配方原料,按化学式0.69(Bi0.985Mg0.015)FeO3-0.31BaTiO3的化学计量比例称取原料。以去离子水为球磨介质,氧化锆小球为磨球,球磨罐材质为聚四氟乙烯。按原料、磨球、去离子水为1:1:1的质量比放入行星球磨机,进行球磨混合12小时,出料后放入烘箱,在110℃烘干。将烘干的粉料以3℃/分钟的升温速率从室温升至800℃进行预烧,保温4小时。将预烧后的中间体研磨后,以去离子水为球磨介质进行二次球磨12小时,烘干,加入质量浓度为10%的聚乙烯醇水溶液作为粘合剂,进行造粒,并过100目筛。在5MPa的压力下,在模具中压制成直径为12mm,厚度为1.0mm的圆片。随后在烧结炉中将陶瓷片从室温加热5h升温至600℃,并保温2h进行排胶,以除去PVA。将排胶后的陶瓷坯片以3℃/分钟的升温速率升温至1020℃进行烧结,保温3小时,随炉自然冷却至室温。将烧结后的陶瓷片表面用1000目砂纸打磨平整,采用丝网印刷工艺,在陶瓷片两面被银,并在800℃烧银保温20分钟,形成电极。最后进行电性能测试。经测试,实施例为钙钛矿结构,没有杂相生成,陶瓷致密,没有气孔,电性能方面,在100℃时电阻率ρ100为7.6×104Ω·cm,100℃至600℃的热敏常数B100/600为4592K。
实施例4
本实施例制备x=2.0%的铁酸铋-钛酸钡NTC热敏陶瓷电阻材料。
选取纯度高于99%的Bi2O3、Fe2O3、BaCO3、TiO2、MgO粉末为配方原料,按化学式0.69(Bi0.985Mg0.015)FeO3-0.31BaTiO3的化学计量比例称取原料。以去离子水为球磨介质,氧化锆小球为磨球,球磨罐材质为聚四氟乙烯。按原料、磨球、去离子水为1:1:1的质量比放入行星球磨机,进行球磨混合12小时,出料后放入烘箱,在110℃烘干。将烘干的粉料以3℃/分钟的升温速率从室温升至800℃进行预烧,保温4小时。将预烧后的中间体研磨后,以去离子水为球磨介质进行二次球磨12小时,烘干,加入质量浓度为10%的聚乙烯醇水溶液作为粘合剂,进行造粒,并过100目筛。在5MPa的压力下,在模具中压制成直径为12mm,厚度为1.0mm的圆片。随后在烧结炉中将陶瓷片从室温加热5h升温至600℃,并保温2h进行排胶,以除去PVA。将排胶后的陶瓷坯片以3℃/分钟的升温速率升温至1020℃进行烧结,保温3小时,随炉自然冷却至室温。将烧结后的陶瓷片表面用1000目砂纸打磨平整,采用丝网印刷工艺,在陶瓷片两面被银,并在800℃烧银,保温20分钟,形成电极。最后进行电性能测试。经测试,实施例为钙钛矿结构,没有杂相生成,陶瓷致密,没有气孔,电性能方面,在100℃时电阻率ρ100为4.7×104Ω·cm,100℃至600℃的热敏常数B100/600为4430K。
本发明制备的适用于高温的NTC热敏材料在保证基本致密的基础上,具有良好的NTC热敏性能。在1020℃的烧结温度下,100℃时电阻率ρ100为2.2×106Ω·cm~4.7×104Ω·cm,100℃至600℃的热敏常数B100/600值为4430K~6421K。在0~700℃范围内具有明显的负温度系数特性,适合制备宽温区高温热敏电阻器。上述实施例1-4制得的高温NTC陶瓷的X射线衍射图谱如图1所示;实施例2制得的高温NTC热敏陶瓷的表面SEM图如图2所示;实施例1-4制得高温NTC陶瓷的电阻-温度特征图如图3所示,以表明实施例具有典型的NTC特性。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (6)
1.一种负温度系数热敏陶瓷材料,其特征在于,所述陶瓷材料的成分包括0.69(Bi1- xMgx)FeO3-0.31BaTiO3,其中x=0.1%~5.0%。
2.根据权利要求1所述的负温度系数热敏陶瓷材料,其特征在于,x的取值为:x=0.5%,或x=1.0%,或x=1.5%,或x=2.0%。
3.根据权利要求1或2所述的负温度系数热敏陶瓷材料,其特征在于,所述陶瓷材料的配方原料包括含有以下元素的氧化物、无机盐或有机盐:Bi、Fe、Ba、Ti、Mg金属元素。
4.根据权利要求3所述的负温度系数热敏陶瓷材料,其特征在于,所述陶瓷材料的配方原料包括Bi2O3、Fe2O3、BaCO3、TiO2及MgO粉末。
5.一种权利要求1-4中任一项所述负温度系数热敏陶瓷材料的制备方法,其特征在于,包括如下步骤:
步骤(1)、按配方计算,称取配方原料;
步骤(2)、将步骤(1)中称取的配方原料混合,以去离子水为混合介质,将原料混合研磨若干小时,并烘干;
步骤(3)、对步骤(2)烘干后得到的粉体,进行预烧后得到粉末;
步骤(4)、将步骤(3)预烧得到的粉末进行研磨,再次以去离子水为介质,研磨若干小时并烘干;
步骤(5)、将步骤(4)烘干后得到的粉末造粒;
步骤(6)、将步骤(5)造粒后的粉末过筛;
步骤(7)、将步骤(6)筛选后的粉体装入模具中,施加高压,压制成型;
步骤(8)、将步骤(7)压制出的坯体放入高温炉中排胶;
步骤(9)、将步骤(8)排胶后的坯体置于坩埚中,然后进行烧结,冷却。
6.根据权利要求5所述的制备方法,其特征在于,还包括:
步骤(10)、将步骤(9)烧结得到的陶瓷表面打磨平整,并超声清洗后,在材料两面印刷上电极。
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