CN113087495B - 一种ntc热敏材料及其制备方法与应用 - Google Patents
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Abstract
本发明提供了一种NTC热敏材料及其制备方法与应用。本发明NTC热敏材料包括以下质量百分含量的组分:Mn3O4 33‑58%、Co3O4 25‑50%、Ni2O3 10‑25%、Al2O3 2‑8%、ZrO2 0.5‑2%、Cr2O3 0.5‑2%、Y2O3 0.1‑1%、Bi2O3 2‑5%、H3BO3 1‑1.5%。本发明NTC热敏材料具有烧结温度低、瓷体强度高、热稳定性好的特点,用于制备片式NTC热敏电阻器时,烧结温度仅需1080℃,并且1080℃烧结所得片式NTC热敏电阻器电阻率为2450Ω·cm以上,B值在4200以上,最大抗弯曲强度在2mm以上,150℃下老化1000h后△R25/R25≤2%。
Description
技术领域
本发明属于热敏电阻领域,具体涉及一种NTC热敏材料及其制备方法与应用。
背景技术
随着电子产品应用环境更加多元化,加之小型化设计让电路板的耐温要求更高,以往电子零件的125℃操作温度已经逐渐不符合客户的需求。近年来电子元器件的更新换代和技术进步非常快,为符合市场发展趋势,片式NTC(负的温度系数)电阻产品已朝着高可靠性、高精度方向发展,高可靠片式NTC热敏电阻器主要体现在具有高的机械强度、耐热性,长期高温环境工作下阻值漂移小。
目前同行中已将片式NTC产品使用温度由125℃提高到150℃,使之在不同条件的工作环境下提供过温保护或温度控制。因此,开发一种在高温工作条件下性能变化率低(即稳定性好)、机械强度好,满足150℃高温工作的NTC热敏电阻陶瓷粉料迫在眉睫。
发明内容
本发明的目的在于克服现有技术存在的不足之处而提供一种NTC热敏材料及其制备方法与应用,以使NTC热敏材料制得的NTC电阻产品具有非常好的机械强度的同时,在150℃等高温工作环境下性能稳定性好。
为实现上述目的,第一方面,本发明提供了一种NTC热敏材料,包括以下质量百分含量的组分:Mn3O4 33-58%、Co3O4 25-50%、Ni2O3 10-25%、Al2O3 2-8%、ZrO2 0.5-2%、Cr2O3 0.5-2%、Y2O3 0.1-1%、Bi2O3 2-5%、H3BO3 1-1.5%。
作为本发明NTC热敏材料的优选实施方式,所述NTC热敏材料包括以下质量百分含量的组分:Mn3O4 33.9-38.6%、Co3O4 33.8-41.6%、Ni2O3 11.3-16.9%、Al2O3 2.9-5.3%、ZrO2 1.1-1.4%、Cr2O3 1.0-1.4%、Y2O3 0.8%、Bi2O3 3.3%、H3BO3 1.4%。
作为本发明NTC热敏材料的优选实施方式,所述NTC热敏材料包括以下质量百分含量的组分:Mn3O4 33.9%、Co3O4 41.6%、Ni2O3 11.3%、Al2O3 5.3%、ZrO2 1.2%、Cr2O31.2%、Y2O3 0.8%、Bi2O3 3.3%、H3BO3 1.4%
作为本发明NTC热敏材料的优选实施方式,所述NTC热敏材料包括以下质量百分含量的组分:Mn3O4 36.7%、Co3O4 38.6%、Ni2O3 12.6%、Al2O3 3.8%、ZrO2 1.4%、Cr2O31.4%、Y2O3 0.8%、Bi2O3 3.3%、H3BO3 1.4%。
作为本发明NTC热敏材料的优选实施方式,所述NTC热敏材料包括以下质量百分含量的组分:Mn3O4 38.6%、Co3O4 33.8%、Ni2O3 16.8%、Al2O3 2.9%、ZrO2 1.4%、Cr2O31.0%、Y2O3 0.8%、Bi2O3 3.3%、H3BO3 1.4%。
第二方面,本发明提供了上述NTC热敏材料的制备方法包括以下步骤:
(1)将Mn3O4、Co3O4、Ni2O3、Al2O3、ZrO2、Cr2O3和Y2O3混合后预烧,得到1#烧后料;
(2)将Bi2O3和H3BO3混合后预烧,得到2#烧后料;
(3)将所述1#烧后料和所述2#烧后料混合分散均匀,即得所述NTC热敏材料。
作为本发明制备方法的优选实施方式,所述步骤(1)中,预烧温度为850℃~980℃;所述步骤(2)中,预烧温度为500℃~600℃。
作为本发明制备方法的优选实施方式,所述步骤(3)中,分散方式为湿法研磨,研磨后还需进行干燥处理。
作为本发明制备方法的优选实施方式,所述步骤(1)~(2)中,都在预烧后对所得烧后料进行研磨分散。
第三方面,本发明还提供了一种片式NTC热敏电阻器,其主要由上述NTC热敏材料制备而成。
相比现有技术,本发明的有益效果在于:本发明NTC热敏材料具有烧结温度低、瓷体强度高、热稳定性好的特点,用于制备片式NTC热敏电阻器时,烧结温度仅需1080℃,并且1080℃烧结所得片式NTC热敏电阻器电阻率为2450Ω·cm以上,B值在4200以上,最大抗弯曲强度在2mm以上,150℃下老化1000h后△R25/R25≤2%。
附图说明
图1为最大抗弯曲强度测试示意图。
具体实施方式
为更好的说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明作进一步说明。
Mn-Co-Ni-Al体系热敏陶瓷属于典型的尖晶石结构,本发明的NTC热敏材料通过在该体系中添加高焓值、稳定性强的ZrO2、Cr2O3和Y2O3来提高体系的热稳定性,其中Zr主要是以施主掺杂于晶界中,提高了P型半导体的晶界势垒,材料电阻率明显增大,但也使材料的烧结温度(指的是NTC热敏材料制备NTC热敏电阻器时的烧结温度)有所提高;再掺杂Bi2O3和H3BO3作为助烧剂来降低烧结温度(指的是NTC热敏材料制备NTC热敏电阻器时的烧结温度),同时Bi2O3和H3BO3在高温烧结过程中,一部分熔化形成玻璃相,附着在晶界表面,一方面提高了材料的电阻率,改善了瓷体的致密性,提高了瓷强度,另一方面形成的玻璃相使晶界处的阳离子空位迁移浓度与晶粒内部相近,使所得NTC热敏电阻在150℃环境条件下,阳离子迁移不明显,从而提高了产品的热稳定性。上述NTC热敏材料制备NTC热敏电阻器时的烧结温度仅需1080℃,如1080℃烧结所得片式NTC热敏电阻器电阻率为2450Ω·cm以上,B值在4200以上,最大抗弯曲强度在2mm以上,150℃下老化1000h后△R25/R25≤2%。具体而言,NTC热敏材料包括以下质量百分含量的组分:Mn3O4 33-58%、Co3O4 25-50%、Ni2O3 10-25%、Al2O3 2-8%、ZrO2 0.5-2%、Cr2O3 0.5-2%、Y2O3 0.1-1%、Bi2O3 2-5%、H3BO3 1-1.5%。研究发现,对于本发明的NTC热敏电阻器,Bi2O3和H3BO3对提高其B值、最大抗弯曲强度以及150℃环境条件下的热稳定性具有协同增效的作用。
在一些实施方式中,NTC热敏材料包括以下质量百分含量的组分:Mn3O4 33.9-55%、Co3O4 24.4-41.6%、Ni2O3 11.3-16.9%、Al2O3 2.2-5.3%、ZrO2 0.5-1.4%、Cr2O31.0-1.4%、Y2O3 0.8-1%、Bi2O3 3.3%、H3BO3 1.4%。如NTC热敏材料包括以下质量百分含量的组分:Mn3O4 33.9%、Co3O4 41.6%、Ni2O3 11.3%、Al2O3 5.3%、ZrO2 1.2%、Cr2O31.2%、Y2O3 0.8%、Bi2O3 3.3%、H3BO3 1.4%,或者NTC热敏材料包括以下质量百分含量的组分:Mn3O4 36.7%、Co3O4 38.6%、Ni2O3 12.6%、Al2O3 3.8%、ZrO2 1.4%、Cr2O3 1.4%、Y2O3 0.8%、Bi2O3 3.3%、H3BO3 1.4%,或者NTC热敏材料包括以下质量百分含量的组分:Mn3O4 38.6%、Co3O4 33.8%、Ni2O3 16.8%、Al2O3 2.9%、ZrO2 1.4%、Cr2O3 1.0%、Y2O30.8%、Bi2O3 3.3%、H3BO3 1.4%。
本发明的NTC热敏材料的制备方法包括以下步骤:
(1)将Mn3O4、Co3O4、Ni2O3、Al2O3、ZrO2、Cr2O3和Y2O3混合后预烧,得到1#烧后料;
(2)将Bi2O3和H3BO3混合后预烧,得到2#烧后料;
(3)将1#烧后料和2#烧后料混合分散均匀,即得NTC热敏材料。
在一些实施方式中,步骤(1)中,预烧温度为850℃~980℃;步骤(2)中,预烧温度为500℃~600℃。
在一些实施方式中,步骤(3)中,分散方式为研磨,这里的研磨方式可选择湿法研磨,湿法研磨后还需对物料进行干燥处理。另外,这里的研磨可选择球磨、砂磨。步骤(3)中研磨分散完,通常会进行过筛处理,当然也可以不用过筛。
在一些实施方式中,步骤(1)~(2)中,都在预烧后对所得烧后料进行研磨分散,这里的研磨分散可选择湿法研磨,湿法研磨后还需对物料进行干燥处理。另外,这里的研磨可选择球磨。步骤(1)~(2)中研磨分散完,通常会进行过筛处理,当然也可以不用过筛。
实施例1
本实施例提供了一种NTC热敏材料。本实施例NTC热敏材料包括以下质量百分含量的组分:Mn3O4 33.9%、Co3O4 41.6%、Ni2O3 11.3%、Al2O3 5.3%、ZrO2 1.2%、Cr2O3 1.2%、Y2O3 0.8%、Bi2O3 3.3%、H3BO3 1.4%。
本实施例NTC热敏材料的制备方法包括以下步骤:
(1)精确称取Mn3O4、Co3O4、Ni2O3、Al2O3、ZrO2、Cr2O3和Y2O3,总重500g(各组分的质量百分含量分别为:Mn3O4 35.6%、Co3O4 43.7%、Ni2O3 11.9%、Al2O3 5.6%、ZrO2 1.2%、Cr2O3 1.2%、Y2O3 0.8%),倒入装有1500gΦ7.5mm锆球的聚胺脂球磨罐中,加去离子水500g,用转速320r/min行星式球磨机上湿磨6h,将磨好的料倒入不锈钢盘中,放入150℃的烘箱中烘干,用40目筛网过筛,用箱式炉在900℃下预烧2.5小时,预烧后用40目筛网过筛得到1#烧后料;
(2)精确称取Bi2O3和H3BO3,总重100g(各组分的质量百分含量分别为:H3BO3 30%、Bi2O3 70%),倒入装有300gΦ7.5mm锆球的聚胺脂球磨罐中,加去离子水100g,用转速320r/min行星式球磨机上湿磨6h,将磨好的料倒入不锈钢盘中,放入150℃的烘箱中烘干,用40目筛网过筛,用箱式炉在500℃下预烧2.5小时,预烧后用40目筛网过筛得到2#烧后料;
(3)将1#烧后料和2#烧后料按1#烧后料:2#烧后料=100:5的质量配比进行混合,按粉料重量:锆球重量:纯水的重量=1:3:1.2的配比进行球磨,球磨8h后得到均匀、颗粒在0.6μm以下的粉料,然后干燥、过筛,得到该NTC热敏材料。
将本实施例NTC热敏材料制备片式NTC热敏电阻器,具体步骤如下:将该NTC热敏材料中添加PVB树脂、醋酸正丙脂、增塑剂、分散剂、无水乙醇等制成浆,并通过干法流延成膜片,将膜片按0805片式NTC厚度尺寸叠成巴块,并通过等水静水压将巴块层压致密,将巴块按0805长、宽尺寸切割成NTC生坯,在450-490℃保温5-10小时条件下进行排胶,在1080℃-1190℃保温5小时条件下烧成,然后经倒角、玻璃层包封、封端、烧端、电镀制成片式NTC热敏电阻器。测试所得片式NTC热敏电阻器的相关性能,结果见表1。
实施例2
本实施例提供了一种NTC热敏材料,该NTC热敏材料包括以下质量百分含量的组分:Mn3O4 36.7%、Co3O4 38.6%、Ni2O3 12.6%、Al2O3 3.8%、ZrO2 1.4%、Cr2O3 1.4%、Y2O30.8%、Bi2O3 3.3%、H3BO3 1.4%。
本实施例NTC热敏材料的制备方法包括以下步骤:
(1)精确称取Mn3O4、Co3O4、Ni2O3、Al2O3、ZrO2、Cr2O3和Y2O3,总重500g(各组分的质量百分含量分别为Mn3O4 38.5%、Co3O4 40.5%、Ni2O3 13.2%、Al2O3 4%、ZrO2 1.5%、Cr2O31.5%、Y2O3 0.8%),倒入装有1500gΦ7.5mm锆球的聚胺脂球磨罐中,加去离子水500g,用转速320r/min行星式球磨机上湿磨6h,将磨好的料倒入不锈钢盘中,放入150℃的烘箱中烘干,用40目筛网过筛,用箱式炉在900℃下预烧2.5小时,预烧后用40目筛网过筛得到1#烧后料;
(2)精确称取Bi2O3和H3BO3,总重100g(各组分的质量百分含量分别为:H3BO3 30%、Bi2O3 70%),倒入装有300gΦ7.5mm锆球的聚胺脂球磨罐中,加去离子水100g,用转速320r/min行星式球磨机上湿磨6h,将磨好的料倒入不锈钢盘中,放入150℃的烘箱中烘干,用40目筛网过筛,用箱式炉在500℃下预烧2.5小时,预烧后用40目筛网过筛得到2#烧后料;
(3)将1#烧后料和2#烧后料按1#烧后料:2#烧后料=100:5的质量配比进行混合,按粉料重量:锆球重量:纯水的重量=1:3:1.2的配比进行球磨,球磨8h后得到均匀、颗粒在0.6μm以下的粉料,然后干燥、过筛,得到该NTC热敏材料。
将本实施例NTC热敏材料用于制备片式NTC热敏电阻器,方法步骤以及工艺参数均同实施例1。测试所得片式NTC热敏电阻器的相关性能,结果见表1。
实施例3
本实施例提供了一种NTC热敏材料,该NTC热敏材料包括以下质量百分含量的组分:Mn3O4 38.6%、Co3O4 33.8%、Ni2O3 16.8%、Al2O3 2.9%、ZrO2 1.4%、Cr2O3 1.0%、Y2O30.8%、Bi2O3 3.3%、H3BO3 1.4%。
该NTC热敏材料的制备方法包括以下步骤:
(1)精确称取Mn3O4、Co3O4、Ni2O3、Al2O3、ZrO2、Cr2O3和Y2O3,总重500g(各组分的质量百分含量分别为Mn3O4 40.5%、Co3O4 35.5%、Ni2O3 17.7%、Al2O3 3%、ZrO2 1.5%、Cr2O31%、Y2O3 0.8%),倒入装有1500gΦ7.5mm锆球的聚胺脂球磨罐中,加去离子水500g,用转速320r/min行星式球磨机上湿磨6h,将磨好的料倒入不锈钢盘中,放入150℃的烘箱中烘干,用40目筛网过筛,用箱式炉在900℃下预烧2.5小时,预烧后用40目筛网过筛得到1#烧后料;
(2)精确称取Bi2O3和H3BO3,总重100g(各组分的质量百分含量分别为:H3BO3 30%、Bi2O3 70%),倒入装有300gΦ7.5mm锆球的聚胺脂球磨罐中,加去离子水100g,用转速320r/min行星式球磨机上湿磨6h,将磨好的料倒入不锈钢盘中,放入150℃的烘箱中烘干,用40目筛网过筛,用箱式炉在500℃下预烧2.5小时,预烧后用40目筛网过筛得到2#烧后料;
(3)将1#烧后料和2#烧后料按1#烧后料:2#烧后料=100:5的质量配比进行混合,按粉料重量:锆球重量:纯水的重量=1:3:1.2的配比进行球磨,球磨8h后得到均匀、颗粒在0.6μm以下的粉料,然后干燥、过筛,得到该NTC热敏材料。
将本实施例NTC热敏材料用于制备片式NTC热敏电阻器,方法步骤以及工艺参数均同实施例1。测试所得片式NTC热敏电阻器的相关性能,结果见表1。
实施例4
本实施例提供了一种NTC热敏材料,该NTC热敏材料包括以下质量百分含量的组分:Mn3O4 55.0%、Co3O4 24.4%、Ni2O3 11.2%、Al2O3 2.2%、ZrO2 0.5%、Cr2O3 1.0%、Y2O31.0%、Bi2O3 3.3%、H3BO3 1.4%。
该NTC热敏材料的制备方法包括以下步骤:
(1)精确称取Mn3O4、Co3O4、Ni2O3、Al2O3、ZrO2、Cr2O3和Y2O3,总重500g(各组分的质量百分含量分别为Mn3O4 57.8%、Co3O4 25.6%、Ni2O3 11.2%、Al2O3 2.3%、ZrO2 0.5%、Cr2O31.0%、Y2O3 1.0%),倒入装有1500gΦ7.5mm锆球的聚胺脂球磨罐中,加去离子水500g,用转速320r/min行星式球磨机上湿磨6h,将磨好的料倒入不锈钢盘中,放入150℃的烘箱中烘干,用40目筛网过筛,用箱式炉在900℃下预烧2.5小时,预烧后用40目筛网过筛得到1#烧后料;
(2)精确称取Bi2O3和H3BO3,总重100g(各组分的质量百分含量分别为:H3BO3 30%、Bi2O3 70%),倒入装有300gΦ7.5mm锆球的聚胺脂球磨罐中,加去离子水100g,用转速320r/min行星式球磨机上湿磨6h,将磨好的料倒入不锈钢盘中,放入150℃的烘箱中烘干,用40目筛网过筛,用箱式炉在500℃下预烧2.5小时,预烧后用40目筛网过筛得到2#烧后料;
(3)将1#烧后料和2#烧后料按1#烧后料:2#烧后料=100:5的质量配比进行混合,按粉料重量:锆球重量:纯水的重量=1:3:1.2的配比进行球磨,球磨8h后得到均匀、颗粒在0.6μm以下的粉料,然后干燥、过筛,得到该NTC热敏材料。
将本实施例NTC热敏材料用于制备片式NTC热敏电阻器,方法步骤以及工艺参数均同实施例1。测试所得片式NTC热敏电阻器的相关性能,结果见表1。
对比例1
本对比例提供了一种NTC热敏材料,该NTC热敏材料包括以下质量百分含量的组分:Mn3O4 64.5%、NiO 11.3%、Co3O4 10.4%、Fe2O3 10.8%、Al2O3 2%、ZnO 1%。将本对比例NTC热敏材料用于制备片式NTC热敏电阻器,方法步骤以及工艺参数均同实施例1。测试所得片式NTC热敏电阻器的相关性能,结果见表1。
对比例2
本对比例提供了一种NTC热敏材料,该NTC热敏材料包括以下质量百分含量的组分:Mn3O4 38.6%、Co3O4 33.8%、Ni2O3 16.8%、Al2O3 2.9%、ZrO2 1.4%、Cr2O3 1.0%、Y2O30.8%、Bi2O3 4.7%。
将本对比例NTC热敏材料用于制备片式NTC热敏电阻器,方法步骤以及工艺参数均同实施例1。测试所得片式NTC热敏电阻器的相关性能,结果见表1。
对比例3
本对比例提供了一种NTC热敏材料,该NTC热敏材料包括以下质量百分含量的组分:Mn3O4 38.6%、Co3O4 33.8%、Ni2O3 16.8%、Al2O3 2.9%、ZrO2 1.4%、Cr2O3 1.0%、Y2O30.8%、H3BO3 4.7%。
将本对比例NTC热敏材料用于制备片式NTC热敏电阻器,方法步骤以及工艺参数均同实施例1。测试所得片式NTC热敏电阻器的相关性能,结果见表1。
表1中,B值采用25℃和50℃两点的热敏电阻计算得到,计算公式如下:
最大抗弯曲强度试验方法如下:在25℃±0.01℃恒温油槽条件下测量电阻器的R25和B值的初始值,然后将元件焊接在测试基板上,按图1所示施加作用力,将弯曲度到达需求值,并保压一定的时间。试验结束后将元件置于常温、常湿的环境下24h后进行外观检验及测量电阻器的R25和B值,计算R25和B值变化率,二者变化率在-5%~5%范围内表示耐弯曲,二者中只要有一个变化率不在-5%~5%范围内就表示不耐弯曲。
表1
由表1可知,对比例1、2所得片式NTC热敏电阻需在1190℃烧结,对比例3抗弯曲强度、耐温方面较差,而实施例1-4所得片式NTC热敏电阻在1080℃烧结即能获得与1190℃烧结相近的性能,并且在抗弯曲强度、耐温方面均优于对比例的样品。
本实施例为最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (9)
1.一种NTC热敏材料,其特征在于,所述NTC热敏材料包括以下质量百分含量的组分:Mn3O4 33.9-38.6%、Co3O4 33.8-41.6%、Ni2O3 11.3-16.9%、Al2O32.9-5.3%、ZrO2 1.2-1.4%、Cr2O3 1.0-1.4%、Y2O3 0.8%、Bi2O3 3.3%、H3BO3 1.4%。
2.根据权利要求1所述的NTC热敏材料,其特征在于,所述NTC热敏材料包括以下质量百分含量的组分:Mn3O4 33.9%、Co3O4 41.6%、Ni2O3 11.3%、Al2O3 5.3%、ZrO2 1.2%、Cr2O31.2%、Y2O3 0.8%、Bi2O3 3.3%、H3BO3 1.4%。
3.根据权利要求1所述的NTC热敏材料,其特征在于,所述NTC热敏材料包括以下质量百分含量的组分:Mn3O4 36.7%、Co3O4 38.6%、Ni2O3 12.6%、Al2O3 3.8%、ZrO2 1.4%、Cr2O31.4%、Y2O3 0.8%、Bi2O3 3.3%、H3BO3 1.4%。
4.根据权利要求1所述的NTC热敏材料,其特征在于,所述NTC热敏材料包括以下质量百分含量的组分:Mn3O4 38.6%、Co3O4 33.8%、Ni2O3 16.8%、Al2O3 2.9%、ZrO2 1.4%、Cr2O31.0%、Y2O3 0.8%、Bi2O3 3.3%、H3BO3 1.4%。
5.如权利要求1~4任一项所述的NTC热敏材料的制备方法,其特征在于,包括以下步骤:
(1)将Mn3O4、Co3O4、Ni2O3、Al2O3、ZrO2、Cr2O3和Y2O3混合后预烧,得到1#烧后料;
(2)将Bi2O3和H3BO3混合后预烧,得到2#烧后料;
(3)将所述1#烧后料和所述2#烧后料混合分散均匀,即得所述NTC热敏材料。
6.根据权利要求5所述的制备方法,其特征在于,所述步骤(1)中,预烧温度为850℃~980℃;所述步骤(2)中,预烧温度为500℃~600℃。
7.根据权利要求5所述的制备方法,其特征在于,所述步骤(3)中,分散方式为湿法研磨,研磨后还需进行干燥处理。
8.根据权利要求5所述的制备方法,其特征在于,所述步骤(1)~(2)中,都在预烧后对所得烧后料进行研磨分散。
9.一种片式NTC热敏电阻器,其特征在于,所述片式NTC热敏电阻器主要由如权利要求1~4任一项所述的NTC热敏材料制备而成。
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