CN112645693B - 一种复合负温度系数热敏陶瓷材料的制备方法 - Google Patents
一种复合负温度系数热敏陶瓷材料的制备方法 Download PDFInfo
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Abstract
本发明涉及一种复合负温度系数热敏陶瓷材料的制备方法,将镍、钴、锌和锰的氧化物混合均匀后,与磨介材料和分散剂一起球磨,将得到的粉末干燥后煅烧,然后二次球磨,烘干后过筛,得到粉料;将粉料加入硝酸银溶液中,搅拌均匀后,干燥并过筛,得到的复合粉体加入到硼氢化钠溶液中,搅拌均匀后,分别用去离子水和乙醇离心洗涤,干燥后加入粘合剂进行造粒,然后模压成型,将成型后的坯体煅烧,最后冷却,即得。本发明制得的负温度系数热敏陶瓷材料具有致密性好、稳定性高、精度高、导电性能优良、适合工业化生产等特点,室温电阻率为15.25~542.52Ω·cm,B值为3000~3531K,适合用于低温测量等技术领域。
Description
技术领域
本发明涉及一种热敏电阻材料的制备方法,尤其是一种复合负温度系数热敏陶瓷材料的制备方法。
背景技术
负温度系数(NTC)热敏陶瓷具有测温精度高、互换性好、可靠性高等特点,在温度测量、控制、补偿等方面应用十分广泛。通常NTC热敏陶瓷材料由通式为AB2O4的锰系过渡金属尖晶石氧化物组成,随着科技的发展,对这类材料的低阻值和高B值提出了更高的要求,而通常的情况是当材料的电阻率较高时,B值也高,反之亦然。因此,需要通过掺杂或复合其他材料调节其电学性能。研究表明仅掺杂铜离子能使其室温电阻率降至100Ω·cm以下,然而由于铜离子价态转变及离子与空位迁移等因素导致此类材料电学性能稳定性较差,通常阻值漂移大于10%,例如,Ni0.5Mn2.5O4陶瓷的室温电阻率为2900Ω·cm,老化值为1.9%,添加少量Cu离子时,Cu0.2Ni0.5Mn2.3O4陶瓷的室温电阻率降低两个数量级,为70Ω·cm,而老化值却增加了一个数量级,为14.9%;Ni0.66Mn2.34O4陶瓷的室温电阻率为2037Ω·cm,添加少量Cu离子时,Cu0.2Ni0.66Mn2.14O4陶瓷的室温电阻率降低两个数量级,为42Ω·cm,而老化值却高达12.6%。通过与低阻相氧化物材料复合制备的复合热敏陶瓷材料性能有所改善,然而由于两相材料中原子能够互相固溶,易导致材料组分偏析等问题,不适合广泛应用。
因此,探索新的复合材料制备低阻值高稳定性的NTC热敏材料迫在眉睫。
发明内容
本发明的目的在于针对现有技术的负温度系数热敏陶瓷材料存在的不足,提供一种复合负温度系数热敏陶瓷材料的制备方法,制得的负温度系数热敏陶瓷材料具有低阻值和高B值,并且稳定性高。
技术方案
一种复合负温度系数热敏陶瓷材料的制备方法,包括如下步骤:
(1)将镍、钴、锌和锰的氧化物混合均匀后,得到混合物,将混合物与磨介材料和分散剂按重量比1:(1~3):(1~3)装入球磨罐球磨6~24h,将得到的粉末干燥后进行煅烧,然后二次球磨6~24h,烘干后过筛,得到粉料;
(2)取硝酸银溶于去离子水,得到硝酸银溶液,将步骤(1)得到的粉料加入硝酸银溶液中,搅拌均匀后,干燥并过筛,得到复合粉体;
(3)将复合粉体加入到硼氢化钠溶液中,搅拌均匀后,分别用去离子水和乙醇离心洗涤,然后干燥,得到粉体;
(4)往步骤(3)的粉体中加入粘合剂进行造粒,然后模压成型,将成型后的坯体煅烧,最后冷却,即得复合负温度系数热敏陶瓷材料。
进一步,步骤(1)中,所述镍、钴、锌和锰的氧化物的配比按原子百分比:镍18~20%、钴13.33~33.33%、锌0~2%、锰46.67~66.67%。
进一步,步骤(1)中,所述分散剂为无水乙醇。
进一步,步骤(1)中,所述煅烧温度为950~1050℃,时间为2~4h。
进一步,步骤(2)中,所述硝酸银用量按金属银来计算,金属银的用量为粉料质量的3~20%。
进一步,步骤(3)中,所述硼氢化钠的用量为硝酸银摩尔量的1.2倍。
进一步,步骤(4)中,所述粘合剂为浓度为5~8wt%的聚乙烯醇溶液,粘合剂与粉体的质量比为(5~8):(95~92)。
进一步,步骤(4)中,所述煅烧温度为1000~1150℃,时间为4~8h。
有益效果:本发明先以镍、钴、锌和锰的氧化物为原料,通过氧化物固相法制备尖晶石结构的氧化物粉末,然后以硝酸银和硼氢化钠为原料,通过化学还原法制备金属银颗粒填料,最后采用陶瓷制备工艺法制备出新型负温度系数热敏陶瓷材料。本发明制得的负温度系数热敏陶瓷材料具有致密性好、稳定性高、精度高、导电性能优良、适合工业化生产等特点,室温电阻率为15.25~542.52Ω·cm,B值为3000~3531K,适合用于低温测量等技术领域。
具体实施方式
下面结合具体实施例对本发明的技术方案作进一步说明。
实施例1
一种复合负温度系数热敏陶瓷材料的制备方法,包括如下步骤:
(1)以分析纯的NiO、ZnO、Co3O4、MnO2为原料,按原子百分比Ni:Zn:Co:Mn=20:0:33.33:46.67准确称取后混合均匀,得到混合物,将混合物与磨介材料玛瑙球和分散剂无水乙醇按重量比1:2:3装入球磨罐球磨12h,将得到的粉末干燥后进行煅烧(1000℃煅烧2h),然后二次球磨12h,烘干后过80目筛,得到粉料;
(2)取硝酸银(金属银的用量占粉料质量的15%)溶于去离子水,得到硝酸银溶液,将步骤(1)得到的粉料加入硝酸银溶液中,搅拌均匀后,干燥并过80目筛,得到复合粉体;
(3)将复合粉体加入到硼氢化钠溶液(硼氢化钠摩尔量为硝酸银摩尔量的1.2倍)中,搅拌均匀后,分别用去离子水和乙醇离心洗涤数次,然后干燥,得到粉体;
(4)往步骤(3)的粉体中加入粘合剂(5wt%的聚乙烯醇溶液)进行造粒,粘合剂与粉体的质量比为8:92,然后在10MPa压力下模压成直径为12mm的圆片,将成型后的坯体1100℃煅烧5h,最后冷却,即得复合负温度系数热敏陶瓷材料。
将制得的复合负温度系数热敏陶瓷材料进行电学性能测试,测试方法:先将复合负温度系数热敏陶瓷材料进行表面抛光,抛光介质为金刚砂,随后在两个表面上涂覆一层均匀的银浆,烘干后,在电阻炉中750℃烧银并保温15min,被银后的陶瓷样品将侧面抛光后进行电学性能测试。
电阻测量:被银后的陶瓷片样品加焊上银电极引线。使用PROVA-901数字多用表测试电阻值,在甲基硅油中分别测量25℃、85℃时的电阻R25和R85,根据式计算电阻率:
式中:ρ为样品的电阻率,Ω·cm;R为样品的电阻,Ω;S为样品的面积,cm2;L为样品的厚度,cm。
B值计算:
式中,R1和R2分别为在25℃和85℃温度下样品的电阻值。
测得本实施例制得的复合负温度系数热敏陶瓷材料的电学参数为:室温电阻率为80.13±1%Ω·cm,B值为3285±2%K。
将复合负温度系数热敏陶瓷材料放入150℃的烘箱中老化500h后,测得其老化值为2.51±0.2%。
实施例2
一种复合负温度系数热敏陶瓷材料的制备方法,包括如下步骤:
(1)以分析纯的NiO、ZnO、Co3O4、MnO2为原料,按原子百分比Ni:Zn:Co:Mn=18:2:13.33:66.67准确称取后混合均匀,得到混合物,将混合物与磨介材料玛瑙球和分散剂无水乙醇按重量比1:2:2装入球磨罐球磨12h,将得到的粉末干燥后进行煅烧(950℃煅烧2h),然后二次球磨12h,烘干后过80目筛,得到粉料;
(2)取硝酸银(金属银的用量占粉料质量的3%)溶于去离子水,得到硝酸银溶液,将步骤(1)得到的粉料加入硝酸银溶液中,搅拌均匀后,干燥并过80目筛,得到复合粉体;
(3)将复合粉体加入到硼氢化钠溶液(硼氢化钠摩尔量为硝酸银摩尔量的1.2倍)中,搅拌均匀后,分别用去离子水和乙醇离心洗涤数次,然后干燥,得到粉体;
(4)往步骤(3)的粉体中加入粘合剂(5wt%的聚乙烯醇溶液)进行造粒,粘合剂与粉体的质量比为5:95,然后在10MPa压力下模压成直径为12mm的圆片,将成型后的坯体1050℃煅烧5h,最后冷却,即得复合负温度系数热敏陶瓷材料。
测得本实施例制得的复合负温度系数热敏陶瓷材料的电学参数为:室温电阻率为542.52±1%Ω·cm,B值为3531±2%K。
将复合负温度系数热敏陶瓷材料放入150℃的烘箱中老化500h后,测得其老化值为1.25±0.2%。
实施例3
一种复合负温度系数热敏陶瓷材料的制备方法,包括如下步骤:
(1)以分析纯的NiO、ZnO、Co3O4、MnO2为原料,按原子百分比Ni:Zn:Co:Mn=20:0:33.33:46.67准确称取后混合均匀,得到混合物,将混合物与磨介材料玛瑙球和分散剂无水乙醇按重量比1:2:3装入球磨罐球磨12h,将得到的粉末干燥后进行煅烧(1000℃煅烧2h),然后二次球磨12h,烘干后过80目筛,得到粉料;
(2)取硝酸银(金属银的用量占粉料质量的10%)溶于去离子水,得到硝酸银溶液,将步骤(1)得到的粉料加入硝酸银溶液中,搅拌均匀后,干燥并过80目筛,得到复合粉体;
(3)将复合粉体加入到硼氢化钠溶液(硼氢化钠摩尔量为硝酸银摩尔量的1.2倍)中,搅拌均匀后,分别用去离子水和乙醇离心洗涤数次,然后干燥,得到粉体;
(4)往步骤(3)的粉体中加入粘合剂(5wt%的聚乙烯醇溶液)进行造粒,粘合剂与粉体的质量比为8:92,然后在10MPa压力下模压成直径为12mm的圆片,将成型后的坯体1100℃煅烧5h,最后冷却,即得复合负温度系数热敏陶瓷材料。
测得本实施例制得的复合负温度系数热敏陶瓷材料的电学参数为:室温电阻率为103.34±1%Ω·cm,B值为3224±2%K。
将复合负温度系数热敏陶瓷材料放入150℃的烘箱中老化500h后,测得其老化值为2.02±0.2%。
实施例4
一种复合负温度系数热敏陶瓷材料的制备方法,包括如下步骤:
(1)以分析纯的NiO、ZnO、Co3O4、MnO2为原料,按原子百分比Ni:Zn:Co:Mn=18:2:33.33:46.67准确称取后混合均匀,得到混合物,将混合物与磨介材料玛瑙球和分散剂无水乙醇按重量比1:2:3装入球磨罐球磨12h,将得到的粉末干燥后进行煅烧(1000℃煅烧2h),然后二次球磨12h,烘干后过80目筛,得到粉料;
(2)取硝酸银(金属银的用量占粉料质量的20%)溶于去离子水,得到硝酸银溶液,将步骤(1)得到的粉料加入硝酸银溶液中,搅拌均匀后,干燥并过80目筛,得到复合粉体;
(3)将复合粉体加入到硼氢化钠溶液(硼氢化钠摩尔量为硝酸银摩尔量的1.2倍)中,搅拌均匀后,分别用去离子水和乙醇离心洗涤数次,然后干燥,得到粉体;
(4)往步骤(3)的粉体中加入粘合剂(5wt%的聚乙烯醇溶液)进行造粒,粘合剂与粉体的质量比为8:92,然后在10MPa压力下模压成直径为12mm的圆片,将成型后的坯体1100℃煅烧5h,最后冷却,即得复合负温度系数热敏陶瓷材料。
测得本实施例制得的复合负温度系数热敏陶瓷材料的电学参数为:室温电阻率为15.25±1%Ω·cm,B值为3000±2%K。
将复合负温度系数热敏陶瓷材料放入150℃的烘箱中老化500h后,测得其老化值为3.32±0.2%。
Claims (7)
1.一种复合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:
(1)将镍、钴、锌和锰的氧化物混合均匀后,得到混合物,将混合物与磨介材料和分散剂按重量比 1:(1~3):(1~3)装入球磨罐球磨 6~24h,将得到的粉末干燥后进行煅烧,然后二次球磨 6~24 h,烘干后过筛,得到粉料;
(2)取硝酸银溶于去离子水,得到硝酸银溶液,将步骤(1)得到的粉料加入硝酸银溶液中,搅拌均匀后,干燥并过筛,得到复合粉体;
(3)将复合粉体加入到硼氢化钠溶液中,搅拌均匀后,分别用去离子水和乙醇离心洗涤,然后干燥,得到粉体;
(4)往步骤(3)的粉体中加入粘合剂进行造粒,然后模压成型,将成型后的坯体煅烧,最后冷却,即得复合负温度系数热敏陶瓷材料;
步骤(1)中,所述镍、钴、锌和锰的氧化物的配比按原子百分比:镍 18~20%、钴 13.33~33.33%、锌 0~2%、锰 46.67~66.67%。
2.如权利要求1所述复合负温度系数热敏陶瓷材料的制备方法,其特征在于,步骤(1)中,所述分散剂为无水乙醇。
3.如权利要求1所述复合负温度系数热敏陶瓷材料的制备方法,其特征在于,步骤(1)中,所述煅烧温度为 950~1050℃,时间为2~4 h。
4.如权利要求1所述复合负温度系数热敏陶瓷材料的制备方法,其特征在于,步骤(2)中,所述硝酸银用量按金属银来计算,金属银的用量为粉料质量的3~20%。
5.如权利要求1所述复合负温度系数热敏陶瓷材料的制备方法,其特征在于,步骤(3)中,所述硼氢化钠的用量为硝酸银摩尔量的 1.2 倍。
6.如权利要求1所述复合负温度系数热敏陶瓷材料的制备方法,其特征在于,步骤(4)中,所述粘合剂为浓度为 5~8 wt%的聚乙烯醇溶液,粘合剂与粉体的质量比为(5~8):(95~92)。
7.如权利要求1至6任一项所述复合负温度系数热敏陶瓷材料的制备方法,其特征在于,步骤(4)中,所述煅烧温度为1000~1150℃,时间为4~8 h。
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