CN111606693A - 一种高温负温度系数热敏电阻材料的制备方法 - Google Patents
一种高温负温度系数热敏电阻材料的制备方法 Download PDFInfo
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- CN111606693A CN111606693A CN202010481653.1A CN202010481653A CN111606693A CN 111606693 A CN111606693 A CN 111606693A CN 202010481653 A CN202010481653 A CN 202010481653A CN 111606693 A CN111606693 A CN 111606693A
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Abstract
本发明涉及热敏电阻材料制备领域,具体关于一种高温负温度系数热敏电阻材料的制备方法;本发明的一种高温负温度系数热敏电阻材料的制备方法,本方法将一种金属掺杂球型二氧化铈纳米粉体材料结合纳米二氧化锰粉体和二氧化硅纳米粒,采用固相合成法制备出一种负温度系数热敏电阻材料,该材料具备高温物理、化学、电气性能稳定,尤其电阻对高温直流负荷随时间变化小的高温负温度系数热敏电阻材料;该材料在使用范围内无相变;该材料具有的适用温度范围广,高温条件下灵敏度合适,室温电阻率和材料常数可控、高温老化系数低的特点。
Description
技术领域
本发明涉及热敏电阻材料制备领域,尤其是一种高温负温度系数热敏电阻材料的制备方法。
背景技术
负温度系数热敏电阻又称NTC热敏电阻,是一类电阻值随温度增大而减小的一种传感器电阻。广泛用于各种电子原件中,如温度传感器、可复式保险丝及自动调节的加热器等。
201910235582.4涉及一种符合制备具有电阻负温度系数(NTC)热敏电阻的材料。本发明的NTC热敏电阻材料以氧化锌为主要成分组成,通过改变所述成分组成中各元素的含量达到调节热敏电阻元件的室温电阻率和材料常数B值的目的,实现宽范围室温电阻值和材料常数B值的调节。该发明涉的NTC热敏电阻材料具有原料来源广、原料成本低、室温电阻率值和材料常数可调控的特点,适合制备热敏陶瓷电阻元件、厚膜热敏电阻元件、薄膜热敏电阻元件。该发明的NTC热敏电阻适用于温度测量、温度控制、抑制浪涌、线路补偿和红外探测等应用领域。
201811242010.0 公开了一种负温度系数珠状热敏电阻的制备方法。采用三氧化二钴、四氧化三锰、氧化镍、三氧化二铁和氧化镁为原材料,经过球磨法制备五元系氧化物热敏电阻粉体材料;采用有机溶剂配制热敏电阻浆料;采用点胶机定量控制珠状成型;经过高温烧结、焊接外引线后,采用无机高温胶封装、焊接测试线后制得珠状热敏电阻。该发明制备的热敏电阻适用于高温,材料常数B25℃/50℃为3500K±5%,温度0℃时电阻值为45kΩ±10%,温度900℃,高温老化200h后R0℃阻值变化率小于±4%。该发明制备的高温热敏电阻高温性能稳定,一致性好,老化性能稳定,适用于航空航天、汽车领域温度测量与控制。
201711185209.X公开了一种负温度系数的PPS热敏电阻的制备方法,该发明所得产品制备的NTC热敏电阻元件的性能稳定高、可靠性高,所述热敏电阻本发明所得产品具有聚苯硫醚(PPS)复合材料,导电率较高,在高温环境和潮湿环境中,性能温度。
以上发明以及现有专利制备的负温度系数热敏电阻材料大多都是尖晶石结构的负温度系数热敏电阻材料,这种材料在高于300℃时非常容易发生严重的重排,稳定性极差,限制了负温度系数热敏电阻材料在汽车尾气温度控制,石油和地质钻探等领域的应用。
发明内容
为了解决上述问题,本发明提供了一种高温负温度系数热敏电阻材料的制备方法。
一种高温负温度系数热敏电阻材料的制备方法,其操作步骤为:
按照质量份数,将15-34份的金属掺杂球型二氧化铈纳米粉体,24-38份的二氧化锰粉体,3-8份的二氧化硅纳米粒和120-180份的水加入球磨罐中,然后球磨2-8h,完成后将得到的浆料在80-120℃烘干,粉碎后在马弗炉中控温900-1000℃煅烧1-5h,冷却后加入2-8份的石墨烯改性MQ树脂,混合均匀后造粒,然后在150-260MPa的压力下干法成型制成直径5-10mm,厚0.5-2mm厚的圆片,然后控温500-600℃煅烧1-3h,然后升温到1100-1200℃煅烧4-8h,完成后将得到的陶瓷片打磨光滑,清洗干净后印刷银浆,烘干后在800-860℃保温10-30min,冷却后即可得到一种高温负温度系数热敏电阻材料。
所述的金属掺杂球型二氧化铈纳米粉体,按照以下方案制备:
按照质量份数,将13-35份的硝酸铈铵,0.18-2.3份的硝酸钙,0.32-4.2份的硝酸镍,0.27-0.51份的硝酸铜加入到200-400份的纯水中,混合搅拌均匀后,加入50-200份的乙二醇和1-10份的聚乙烯吡咯烷酮,混合搅拌30-60min后加入5-20份的柠檬酸,继续搅拌10-20min,然后将反应液转移到水热反应釜中,控温150-200℃,反应10-30h,完成反应后冷却至室温,离心过滤得到沉淀物,用纯水和乙醇洗涤,随后于90-100℃干燥5-10h,即可得到所述的金属掺杂球型二氧化铈纳米粉体。
所述的石墨烯改性MQ树脂,使用丙烯酸镍作为共聚单体;
所述的石墨烯改性MQ树脂,使用丙基硅烷接枝的石墨烯作为共聚单体;
所述的石墨烯改性MQ树脂,使用烯丙基硅烷接枝的石墨烯,乙烯基三乙氧基硅烷,亚油酰胺共聚合制备;
所述的石墨烯改性MQ树脂,其制备方法如下:
步骤1:按照质量份数,将200-300份乙醇和5-12份氧化石墨烯,12-30份的乙烯基三乙氧基硅烷混合,在搅拌和超声下分散,然后加入10-20份水合肼及20-80份氨水,控温50℃-100℃进行还原,反应2-5h,完成后抽滤,洗涤,干燥, 得到烯丙基硅烷接枝的石墨烯。
其部分反应机理示意为:
步骤2:按照质量份数,4-10份烯丙基硅烷接枝的石墨烯,10-22份乙烯基MQ树脂,100-220份甲苯混合,加入1-5份丙烯酸镍,0.3-1.5份过氧化苯甲酰,0.4-1.6份明胶在氮气保护条件下于60℃-83℃下反应2-6小时后,减压蒸馏除去甲苯溶剂,回收的溶剂循环使用,用乙醇洗涤,烘干,即得石墨烯改性MQ树脂。
其部分反应机理示意为:
所述的乙烯-乙酸乙烯酯共聚物树脂的醋酸乙烯含量为25%-41%。
所述的金属掺杂球型二氧化铈纳米粉体平均粒径为50-100nm。
所述的粘结剂为聚乙烯醇或丁苯乳胶或水性聚丙烯酸乳液。
所述的球磨珠与粉料的质量比为1.5-2.8:1。
本发明的一种高温负温度系数热敏电阻材料的制备方法,本方法将一种金属掺杂球型二氧化铈纳米粉体材料结合纳米二氧化锰粉体和二氧化硅纳米粒,使用使用烯丙基硅烷接枝的石墨烯,乙烯基三乙氧基硅烷,亚油酰胺共聚合采用固相合成法石墨烯改性MQ树脂作为粘结剂,制备出一种负温度系数热敏电阻材料,该材料具备高温物理、化学、电气性能稳定,尤其电阻对高温直流负荷随时间变化小的高温负温度系数热敏电阻材料;该材料在使用范围内无相变;该材料具有的适用温度范围广,高温条件下灵敏度合适,室温电阻率和材料常数可控、高温老化系数低的特点。
附图说明
图1为实施例2制备的石墨烯改性MQ树脂样品的傅里叶红外光谱图;
在1094cm-1附近存在硅氧的反对称伸缩吸收峰,在2916cm-1附近存在碳氢的伸缩吸收峰,说明乙烯基MQ树脂参与了反应;在2150cm-1附近存在硅氢的伸缩吸收峰,在753cm-1附近存在硅碳的伸缩吸收峰,说明烯丙基硅烷接枝石墨烯参与了反应;在1724cm-1附近存在羧基的羰基的伸缩吸收峰,在922cm-1附近存在羧基的羟基的面外弯曲吸收峰,说明亚油酰胺参与了反应;在1641cm-1附近无明显的碳碳双键吸收峰,说明双键均已参与反应。
具体实施方式
下面通过具体实施例对该发明作进一步说明:
按照GBT1550-1997 非本征半导体材料导电类型测试方法测定制备的材料的室温(25℃)电阻率和高温电阻率(600℃);将材料于500°C 老化200h后的老化系数。
所述乙烯基MQ树脂为市售产品,如成都晨光博达橡塑有限公司生产的乙烯基MQ硅树脂产品,
实施例1
一种高温负温度系数热敏电阻材料的制备方法,其操作步骤为:
将15g金属掺杂球型二氧化铈纳米粉体,24g二氧化锰粉体,3g二氧化硅纳米粒和120g水加入球磨罐中,然后球磨2h,完成后将得到的浆料在80℃烘干,粉碎后在马弗炉中控温900℃煅烧1h,冷却后加入2g的石墨烯改性MQ树脂,混合均匀后造粒,然后在150MPa的压力下干法成型制成直径5mm,厚0.5mm厚的圆片,然后控温500℃煅烧1h,然后升温到1100℃煅烧4h,完成后将得到的陶瓷片打磨光滑,清洗干净后印刷银浆,烘干后在800℃保温10min,冷却后即可得到一种高温负温度系数热敏电阻材料。
所述的金属掺杂球型二氧化铈纳米粉体,按照以下方案制备:
将13g硝酸铈铵,0.18g硝酸钙,0.32g硝酸镍,0.27g硝酸铜加入到200g纯水中,混合搅拌均匀后,加入50g乙二醇和1g聚乙烯吡咯烷酮,混合搅拌30min后加入5g柠檬酸,继续搅拌10min,然后将反应液转移到水热反应釜中,控温150℃,反应10h,完成反应后冷却至室温,离心过滤得到沉淀物,用纯水和乙醇洗涤,随后于90℃干燥5h,即可得到所述的金属掺杂球型二氧化铈纳米粉体。
所述的烯丙基硅烷接枝的石墨烯,其制备方法如下:
步骤1:将200g乙醇和5g氧化石墨烯,12g的乙烯基三乙氧基硅烷混合,在搅拌和超声下分散,然后加入10g水合肼及20g氨水,控温50℃进行还原,反应2h,完成后抽滤,洗涤,干燥,得到烯丙基硅烷接枝的石墨烯。
所述的石墨烯改性MQ树脂的制备方法为:4g烯丙基硅烷接枝的石墨烯,10g乙烯基MQ树脂,100g甲苯混合,加入1g丙烯酸镍,0.3g过氧化苯甲酰,0.4g明胶在氮气保护条件下于60℃下反应2小时后,减压蒸馏除去甲苯溶剂,回收的溶剂循环使用,用乙醇洗涤,烘干,即得石墨烯改性MQ树脂。
所述的金属掺杂球型二氧化铈纳米粉体平均粒径为50nm。
所述的球磨珠与粉料的质量比为1.5:1。
所制备的材料的室温电阻率为2.1×105Ωcm,高温电阻率为87.2Ωcm,老化系数为1.57%。
实施例2
一种高温负温度系数热敏电阻材料的制备方法,其操作步骤为:
将23g金属掺杂球型二氧化铈纳米粉体,31g二氧化锰粉体,5g二氧化硅纳米粒和150g水加入球磨罐中,然后球磨5h,完成后将得到的浆料在100℃烘干,粉碎后在马弗炉中控温950℃煅烧3h,冷却后加入6g的石墨烯改性MQ树脂,混合均匀后造粒,然后在210MPa的压力下干法成型制成直径7mm,厚1mm厚的圆片,然后控温550℃煅烧2h,然后升温到1150℃煅烧6h,完成后将得到的陶瓷片打磨光滑,清洗干净后印刷银浆,烘干后在830℃保温20min,冷却后即可得到一种高温负温度系数热敏电阻材料。
所述的金属掺杂球型二氧化铈纳米粉体,按照以下方案制备:
将24g硝酸铈铵,1.4g硝酸钙,2.3g硝酸镍,0.34g硝酸铜加入到300g纯水中,混合搅拌均匀后,加入120g乙二醇和3g聚乙烯吡咯烷酮,混合搅拌45min后加入12g柠檬酸,继续搅拌15min,然后将反应液转移到水热反应釜中,控温180℃,反应20h,完成反应后冷却至室温,离心过滤得到沉淀物,用纯水和乙醇洗涤,随后于95℃干燥8h,即可得到所述的金属掺杂球型二氧化铈纳米粉体。
所述的烯丙基硅烷接枝的石墨烯,其制备方法如下:
步骤1:将232g乙醇和7g氧化石墨烯,18g的乙烯基三乙氧基硅烷混合,在搅拌和超声下分散,然后加入15g水合肼及60g氨水,控温70℃进行还原,反应3h,完成后抽滤,洗涤,干燥,得到烯丙基硅烷接枝的石墨烯。
所述的石墨烯改性MQ树脂的制备方法为:6g烯丙基硅烷接枝的石墨烯,15g乙烯基MQ树脂,174g甲苯混合,加入3g丙烯酸镍,0.8g过氧化苯甲酰,0.7g明胶在氮气保护条件下于68℃下反应3小时后,减压蒸馏除去甲苯溶剂,回收的溶剂循环使用,用乙醇洗涤,烘干,即得石墨烯改性MQ树脂。
所述的金属掺杂球型二氧化铈纳米粉体平均粒径为80nm。
所述的球磨珠与粉料的质量比为2.2:1。
所制备的材料的室温电阻率为2.4×105Ωcm,高温电阻率为94.5Ωcm,老化系数为1.41%。
实施例3
一种高温负温度系数热敏电阻材料的制备方法,其操作步骤为:
将34g金属掺杂球型二氧化铈纳米粉体,38g二氧化锰粉体,8g二氧化硅纳米粒和180g水加入球磨罐中,然后球磨8h,完成后将得到的浆料在120℃烘干,粉碎后在马弗炉中控温1000℃煅烧5h,冷却后加入8g的石墨烯改性MQ树脂,混合均匀后造粒,然后在260MPa的压力下干法成型制成直径10mm,厚2mm厚的圆片,然后控温600℃煅烧3h,然后升温到1200℃煅烧8h,完成后将得到的陶瓷片打磨光滑,清洗干净后印刷银浆,烘干后在860℃保温30min,冷却后即可得到一种高温负温度系数热敏电阻材料。
所述的金属掺杂球型二氧化铈纳米粉体,按照以下方案制备:
将35g硝酸铈铵,2.3g硝酸钙,4.2g硝酸镍,0.51g硝酸铜加入到400g纯水中,混合搅拌均匀后,加入200g乙二醇和10g聚乙烯吡咯烷酮,混合搅拌60min后加入20g柠檬酸,继续搅拌20min,然后将反应液转移到水热反应釜中,控温200℃,反应30h,完成反应后冷却至室温,离心过滤得到沉淀物,用纯水和乙醇洗涤,随后于100℃干燥10h,即可得到所述的金属掺杂球型二氧化铈纳米粉体。
所述的烯丙基硅烷接枝的石墨烯,其制备方法如下:
步骤1:将300g乙醇和12g氧化石墨烯,30g的乙烯基三乙氧基硅烷混合,在搅拌和超声下分散,然后加入20g水合肼及80g氨水,控温100℃进行还原,反应5h,完成后抽滤,洗涤,干燥, 得到烯丙基硅烷接枝的石墨烯。
所述的石墨烯改性MQ树脂的制备方法为:10g烯丙基硅烷接枝的石墨烯,22g乙烯基MQ树脂,220g甲苯混合,加入5g丙烯酸镍,1.5g过氧化苯甲酰,1.6g明胶在氮气保护条件下于83℃下反应6小时后,减压蒸馏除去甲苯溶剂,回收的溶剂循环使用,用乙醇洗涤,烘干,即得石墨烯改性MQ树脂。
所述的金属掺杂球型二氧化铈纳米粉体平均粒径为100nm。
所述的球磨珠与粉料的质量比为2.8:1。
所制备的材料的室温电阻率为2.5×105Ωcm,高温电阻率为102.4Ωcm,老化系数为1.21%。
对比例1
一种高温负温度系数热敏电阻材料的制备方法,其操作步骤为:
将24g二氧化锰粉体,3g二氧化硅纳米粒和120g水加入球磨罐中,然后球磨2h,完成后将得到的浆料在80℃烘干,粉碎后在马弗炉中控温900℃煅烧1h,冷却后加入2g的石墨烯改性MQ树脂,混合均匀后造粒,然后在150MPa的压力下干法成型制成直径5mm,厚0.5mm厚的圆片,然后控温500℃煅烧1h,然后升温到1100℃煅烧4h,完成后将得到的陶瓷片打磨光滑,清洗干净后印刷银浆,烘干后在800℃保温10min,冷却后即可得到一种高温负温度系数热敏电阻材料。
所述的烯丙基硅烷接枝的石墨烯,其制备方法如下:
步骤1:将200g乙醇和5g氧化石墨烯,12g的乙烯基三乙氧基硅烷混合,在搅拌和超声下分散,然后加入10g水合肼及20g氨水,控温50℃进行还原,反应2h,完成后抽滤,洗涤,干燥,得到烯丙基硅烷接枝的石墨烯。
所述的石墨烯改性MQ树脂的制备方法为:4g烯丙基硅烷接枝的石墨烯,10g乙烯基MQ树脂,100g甲苯混合,加入1g丙烯酸镍,0.3g过氧化苯甲酰,0.4g明胶在氮气保护条件下于60℃下反应2小时后,减压蒸馏除去甲苯溶剂,回收的溶剂循环使用,用乙醇洗涤,烘干,即得石墨烯改性MQ树脂。
所述的球磨珠与粉料的质量比为1.5:1。
所制备的材料的室温电阻率为1.47×105Ωcm,高温电阻率无法测出,老化系数无法测出。
对比例2
一种高温负温度系数热敏电阻材料的制备方法,其操作步骤为:
将15g金属掺杂球型二氧化铈纳米粉体,24g二氧化锰粉体,3g二氧化硅纳米粒和120g水加入球磨罐中,然后球磨2h,完成后将得到的浆料在80℃烘干,粉碎后在马弗炉中控温900℃煅烧1h,冷却后加入2g的石墨烯改性MQ树脂,混合均匀后造粒,然后在150MPa的压力下干法成型制成直径5mm,厚0.5mm厚的圆片,然后控温500℃煅烧1h,然后升温到1100℃煅烧4h,完成后将得到的陶瓷片打磨光滑,清洗干净后印刷银浆,烘干后在800℃保温10min,冷却后即可得到一种高温负温度系数热敏电阻材料。
所述的金属掺杂球型二氧化铈纳米粉体,按照以下方案制备:
将13g硝酸铈铵,0.32g硝酸镍,0.27g硝酸铜加入到200g纯水中,混合搅拌均匀后,加入50g乙二醇和1g聚乙烯吡咯烷酮,混合搅拌30min后加入5g柠檬酸,继续搅拌10min,然后将反应液转移到水热反应釜中,控温150℃,反应10h,完成反应后冷却至室温,离心过滤得到沉淀物,用纯水和乙醇洗涤,随后于90℃干燥5h,即可得到所述的金属掺杂球型二氧化铈纳米粉体。
所述的烯丙基硅烷接枝的石墨烯,其制备方法如下:
步骤1:将200g乙醇和5g氧化石墨烯,12g的乙烯基三乙氧基硅烷混合,在搅拌和超声下分散,然后加入10g水合肼及20g氨水,控温50℃进行还原,反应2h,完成后抽滤,洗涤,干燥,得到烯丙基硅烷接枝的石墨烯。
所述的石墨烯改性MQ树脂的制备方法为:4g烯丙基硅烷接枝的石墨烯,10g乙烯基MQ树脂,100g甲苯混合,加入1g丙烯酸镍,0.3g过氧化苯甲酰,0.4g明胶在氮气保护条件下于60℃下反应2小时后,减压蒸馏除去甲苯溶剂,回收的溶剂循环使用,用乙醇洗涤,烘干,即得石墨烯改性MQ树脂。
所述的金属掺杂球型二氧化铈纳米粉体平均粒径为50nm。
所述的球磨珠与粉料的质量比为1.5:1。
所制备的材料的室温电阻率为1.92×105Ωcm,高温电阻率为54.7Ωcm,老化系数为3.71%。
对比例3
一种高温负温度系数热敏电阻材料的制备方法,其操作步骤为:
将15g金属掺杂球型二氧化铈纳米粉体,24g二氧化锰粉体,3g二氧化硅纳米粒和120g水加入球磨罐中,然后球磨2h,完成后将得到的浆料在80℃烘干,粉碎后在马弗炉中控温900℃煅烧1h,冷却后加入2g的石墨烯改性MQ树脂,混合均匀后造粒,然后在150MPa的压力下干法成型制成直径5mm,厚0.5mm厚的圆片,然后控温500℃煅烧1h,然后升温到1100℃煅烧4h,完成后将得到的陶瓷片打磨光滑,清洗干净后印刷银浆,烘干后在800℃保温10min,冷却后即可得到一种高温负温度系数热敏电阻材料。
所述的金属掺杂球型二氧化铈纳米粉体,按照以下方案制备:
将13g硝酸铈铵,0.18g硝酸钙加入到200g纯水中,混合搅拌均匀后,加入50g乙二醇和1g聚乙烯吡咯烷酮,混合搅拌30min后加入5g柠檬酸,继续搅拌10min,然后将反应液转移到水热反应釜中,控温150℃,反应10h,完成反应后冷却至室温,离心过滤得到沉淀物,用纯水和乙醇洗涤,随后于90℃干燥5h,即可得到所述的金属掺杂球型二氧化铈纳米粉体。
所述的烯丙基硅烷接枝的石墨烯,其制备方法如下:
步骤1:将200g乙醇和5g氧化石墨烯,12g的乙烯基三乙氧基硅烷混合,在搅拌和超声下分散,然后加入10g水合肼及20g氨水,控温50℃进行还原,反应2h,完成后抽滤,洗涤,干燥,得到烯丙基硅烷接枝的石墨烯。
所述的石墨烯改性MQ树脂的制备方法为:4g烯丙基硅烷接枝的石墨烯,10g乙烯基MQ树脂,100g甲苯混合,加入1g丙烯酸镍,0.3g过氧化苯甲酰,0.4g明胶在氮气保护条件下于60℃下反应2小时后,减压蒸馏除去甲苯溶剂,回收的溶剂循环使用,用乙醇洗涤,烘干,即得石墨烯改性MQ树脂。
所述的金属掺杂球型二氧化铈纳米粉体平均粒径为50nm。
所述的球磨珠与粉料的质量比为1.5:1。
所制备的材料的室温电阻率为1.84×105Ωcm,高温电阻率为42.7Ωcm,老化系数为5.47%。
对比例4
所述的烯丙基硅烷接枝的石墨烯,其制备方法如下:
步骤1:将200g乙醇和5g氧化石墨烯,12g的乙烯基三乙氧基硅烷混合,在搅拌和超声下分散,然后加入10g水合肼及20g氨水,控温50℃进行还原,反应2h,完成后抽滤,洗涤,干燥,得到烯丙基硅烷接枝的石墨烯。
所述的石墨烯改性MQ树脂的制备方法为:4g烯丙基硅烷接枝的石墨烯,10g乙烯基MQ树脂,100g甲苯混合,加入0.3g过氧化苯甲酰,0.4g明胶在氮气保护条件下于60℃下反应2小时后,减压蒸馏除去甲苯溶剂,回收的溶剂循环使用,用乙醇洗涤,烘干,即得石墨烯改性MQ树脂。
其它同实施例1
所制备的材料的室温电阻率为1.91×105Ωcm,高温电阻率为70.8Ωcm,老化系数为1.94%。
对比例5
所述的烯丙基硅烷接枝的石墨烯,其制备方法如下:
步骤1:将200g乙醇和5g氧化石墨烯,12g的乙烯基三乙氧基硅烷混合,在搅拌和超声下分散,然后加入10g水合肼及20g氨水,控温50℃进行还原,反应2h,完成后抽滤,洗涤,干燥,得到烯丙基硅烷接枝的石墨烯。
所述的粘结剂的制备方法为:4g烯丙基硅烷接枝的石墨烯,100g甲苯混合,加入1g丙烯酸镍,0.3g过氧化苯甲酰,0.4g明胶在氮气保护条件下于60℃下反应2小时后,减压蒸馏除去甲苯溶剂,回收的溶剂循环使用,用乙醇洗涤,烘干,即得粘结剂。
其它同实施例1
所制备的材料的室温电阻率为2.05×105Ωcm,高温电阻率为80.5Ωcm,老化系数为2.42%。
Claims (8)
1.一种高温负温度系数热敏电阻材料的制备方法,其操作步骤为:
按照质量份数,将15-34份的金属掺杂球型二氧化铈纳米粉体,24-38份的二氧化锰粉体,3-8份的二氧化硅纳米粒和120-180份的水加入球磨罐中,然后球磨2-8h,完成后将得到的浆料在80-120℃烘干,粉碎后在马弗炉中控温900-1000℃煅烧1-5h,冷却后加入2-8份的石墨烯改性MQ树脂,混合均匀后造粒,然后在150-260MPa的压力下干法成型制成直径5-10mm,厚0.5-2mm厚的圆片,然后控温500-600℃煅烧1-3h,然后升温到1100-1200℃煅烧4-8h,完成后将得到的陶瓷片打磨光滑,清洗干净后印刷银浆,烘干后在800-860℃保温10-30min,冷却后即可得到一种高温负温度系数热敏电阻材料。
2.根据权利要求1所述的一种高温负温度系数热敏电阻材料的制备方法,其特征在于:所述的石墨烯改性MQ树脂,使用丙烯酸镍作为共聚单体。
3.根据权利要求1所述的一种高温负温度系数热敏电阻材料的制备方法,其特征在于:所述的石墨烯改性MQ树脂,使用烯丙基硅烷接枝的石墨烯作为原料。
4.根据权利要求1所述的一种高温负温度系数热敏电阻材料的制备方法,其特征在于:所述的烯丙基硅烷接枝的石墨烯,其制备方法如下:
步骤1:按照质量份数,将200-300份乙醇和5-12份氧化石墨烯,12-30份的乙烯基三乙氧基硅烷混合,在搅拌和超声下分散,然后加入10-20份水合肼及20-80份氨水,控温50℃-100℃进行还原,反应2-5h,完成后抽滤,洗涤,干燥, 得到烯丙基硅烷接枝的石墨烯。
5.根据权利要求1所述的一种高温负温度系数热敏电阻材料的制备方法,其特征在于:所述的石墨烯改性MQ树脂的制备方法为:按照质量份数,4-10份烯丙基硅烷接枝的石墨烯,10-22份乙烯基MQ树脂,100-220份甲苯混合,加入1-5份丙烯酸镍,0.3-1.5份过氧化苯甲酰,0.4-1.6份明胶在氮气保护条件下于60℃-83℃下反应2-6小时后,减压蒸馏除去甲苯溶剂,回收的溶剂循环使用,用乙醇洗涤,烘干,即得石墨烯改性MQ树脂。
6.根据权利要求1所述的一种高温负温度系数热敏电阻材料的制备方法,其特征在于:所述的金属掺杂球型二氧化铈纳米粉体,按照以下方案制备:
按照质量份数,将13-35份的硝酸铈铵,0.18-2.3份的硝酸钙,0.32-4.2份的硝酸镍,0.27-0.51份的硝酸铜加入到200-400份的纯水中,混合搅拌均匀后,加入50-200份的乙二醇和1-10份的聚乙烯吡咯烷酮,混合搅拌30-60min后加入5-20份的柠檬酸,继续搅拌10-20min,然后将反应液转移到水热反应釜中,控温150-200℃,反应10-30h,完成反应后冷却至室温,离心过滤得到沉淀物,用纯水和乙醇洗涤,随后于90-100℃干燥5-10h,即可得到所述的金属掺杂球型二氧化铈纳米粉体。
7.根据权利要求1所述的一种高温负温度系数热敏电阻材料的制备方法,其特征在于:所述的金属掺杂球型二氧化铈纳米粉体平均粒径为50-100nm。
8.根据权利要求1所述的一种高温负温度系数热敏电阻材料的制备方法,其特征在于:所述的球磨珠与粉料的质量比为1.5-2.8:1。
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