CN105801099B - 一种具有居里点温度敏感性的MnZn铁氧体以及制备方法 - Google Patents

一种具有居里点温度敏感性的MnZn铁氧体以及制备方法 Download PDF

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CN105801099B
CN105801099B CN201610129753.1A CN201610129753A CN105801099B CN 105801099 B CN105801099 B CN 105801099B CN 201610129753 A CN201610129753 A CN 201610129753A CN 105801099 B CN105801099 B CN 105801099B
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龙克文
颜天宝
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Sanqiao Hui (Foshan) New Materials Co., Ltd.
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Abstract

本发明属于铁氧体材料领域,具体公开了一种具有居里点温度敏感性的MnZn铁氧体,包括以下重量份组分:氧化锰、氧化锌、二硫化钼粉、纳米二氧化钛、聚乙二醇、石墨烯、白炭黑、羰基铁粉、氧化钴、三氧化二钴等。本发明借助于具有大表面积比颗粒粒径小的物质和内部含水分子结构的物质配合多次球磨构建了烧结混合料,该混合料能够达到微观均匀,烧结时内部氧化活性高,热量传播均匀,能够促进形成内部孔隙小、体密度高,晶粒纯度高密度均匀细致的锰锌铁氧体的形成,同时,所加的白炭黑迁移率高、具有良好的载流子电导率,能够促进提高锰锌铁氧体的温度敏感性,增加锰锌铁氧体的新应用。

Description

一种具有居里点温度敏感性的MnZn铁氧体以及制备方法
技术领域
本发明属于铁氧体材料领域,具体地说是涉及一种具有居里点温度敏感性的MnZn铁氧体以及制备方法。
背景技术
锰锌铁氧体是现在电子工业以及信息产业的基础材料,随着社会的进步和通讯技术、计算机技术的不断发展,锰锌铁氧体扮演着越来越重要的角色,对高性能锰锌铁氧体也提出了越来越高的要求,要求其晶粒内部气孔少,整体密度高,晶粒纯度高、无缺陷、杂质,内应力小,晶粒大小、尺寸、外观及性能都达到最佳。
石墨烯是一种二维平面碳原子薄膜材料,物理尺寸小,比表面大,同时具有单原子层厚度、机械硬度高、载流子迁移率高、柔韧性和透光性好、电导率可调节等特点。
发明内容
本发明针对高性能MnZn铁氧体的发展,提出一种具有居里点温度敏感性的MnZn铁氧体以及制备方法。
为达到上述目的,本发明所采取的技术方案为:
一种具有居里点温度敏感性的MnZn铁氧体,包括以下重量份组分:氧化锰60-70、氧化锌58-66、二硫化钼粉18-24、纳米二氧化钛23-25、聚乙二醇100-110、石墨烯20-30、白炭黑21-29、羰基铁粉13-19、氧化钴16-24、三氧化二钴12-16、五氧化二钒8-12、CuSO4·5H2O35-45、Ni(NO3)2·6H2O 26-30、(NH42C2O4·H2O 15-21、适量的浓度10%的硝酸。
一种具有居里点温度敏感性的MnZn铁氧体的制备方法,包括以下步骤:
(1)初步处理:将氧化锰、氧化锌、二硫化钼粉、纳米二氧化钛、氧化钴、三氧化二钴、五氧化二钒混合以及总重量10-12倍的浓度10%的硝酸,在100℃加热搅拌20-30min,停止加热,采用磁力配合200W超声处理30-40min至均匀分散,得浆液,在之后球磨罐中球磨该浆液4-5h,得细化浆液备用;
(2)将细化浆液与800-900℃惰性气体环境中煅烧10-12h,之后球磨2-3h,得混合料备用;
(3)将混合料、石墨烯、白炭黑、羰基铁粉、聚乙二醇混合搅拌均匀置于电加热炉中,与300-400℃惰性气体环境中煅烧10-12h,之后球磨1.2-1.6h,得大表面积比的混合料备用;
(4)将大表面积比的混合料、CuSO4·5H2O、Ni(NO3)6H2O、(NH4)2C2O4·H2O混合,放在带搅拌装置的电热炉中,在50-60℃下边加热边搅拌6-7h,得到可以保证湿度的混合料备用,之后,趁热在放入行星式球磨机中混合研磨1.4-1.8h,到的微观均匀的混合料备用;
(5)将微观均匀的混合料放在磨具中压制成所需形状坯块,然后连同模具转入带程序升温功能的惰性气体气氛的窑炉中烧结,烧结时,温度以3-4℃/min的升温速率从室温加热到1200-1300℃,保温3-4h,随后在惰性气氛下自然降温冷却至室温,得到所述高热阻敏感度和热磁敏感度纳米晶锰锌铁氧体。
本发明的有益效果:
本发明以氧化锰、氧化锌、二硫化钼粉、纳米二氧化钛、氧化钴、三氧化二钴、五氧化二钒为材料,借助于具有大表面积比颗粒粒径小的石墨烯、白炭黑、羰基铁粉物质和内部含水分子结构的CuSO4·5H2O、Ni(NO3)2·6H2O、(NH42C2O4·H2O,配合多次球磨构建了烧结混合料,该混合料能够达到微观均匀,烧结时内部氧化活性高,热量传播均匀,能够促进形成内部孔隙小、体密度高,晶粒纯度高密度均匀细致的锰锌铁氧体的形成,同时,所加的白炭黑迁移率高、具有良好的载流子电导率,能够促进提高锰锌铁氧体的温度敏感性,增加锰锌铁氧体的新应用。
具体实施方式
下面结合具体实施例对本发明所述技术方案作进一步的说明。
实施例1:
一种具有居里点温度敏感性的MnZn铁氧体,包括以下重量(kg)组分:氧化锰60、氧化锌58、二硫化钼粉18、纳米二氧化钛23、聚乙二醇110、石墨烯30、白炭黑29、羰基铁粉19、氧化钴20、三氧化二钴14、五氧化二钒10、CuSO4·5H2O 35、Ni(NO3)2·6H2O 26、(NH4)2C2O4·H2O 15、适量的浓度10%的硝酸。
一种具有居里点温度敏感性的MnZn铁氧体的制备方法,包括以下步骤:
(1)初步处理:将氧化锰、氧化锌、二硫化钼粉、纳米二氧化钛、氧化钴、三氧化二钴、五氧化二钒混合以及总重量11倍的浓度10%的硝酸,在100℃加热搅拌20min,停止加热,采用磁力配合200W超声处理30min至均匀分散,得浆液,在之后球磨罐中球磨该浆液4h,得细化浆液备用;
(2)将细化浆液与800℃惰性气体环境中煅烧10h,之后球磨2h,得混合料备用;
(3)将混合料、石墨烯、白炭黑、羰基铁粉、聚乙二醇混合搅拌均匀置于电加热炉中,与300℃惰性气体环境中煅烧10h,之后球磨1.2h,得大表面积比的混合料备用;
(4)将大表面积比的混合料、CuSO4·5H2O、Ni(NO3)2·6H2O、(NH42C2O4·H2O混合,放在带搅拌装置的电热炉中,在50℃下边加热边搅拌6h,得到可以保证湿度的混合料备用,之后,趁热在放入行星式球磨机中混合研磨1.4h,到的微观均匀的混合料备用;
(5)将微观均匀的混合料放在磨具中压制成所需形状坯块,然后连同模具转入带程序升温功能的惰性气体气氛的窑炉中烧结,烧结时,温度以3-4℃/min的升温速率从室温加热到1200℃,保温3h,随后在惰性气氛下自然降温冷却至室温,得到所述高热阻敏感度和热磁敏感度纳米晶锰锌铁氧体。
实施例2:
一种具有居里点温度敏感性的MnZn铁氧体,包括以下重量(kg)组分:氧化锰65、氧化锌62、二硫化钼粉20、纳米二氧化钛24、聚乙二醇105、石墨烯25、白炭黑25、羰基铁粉16、氧化钴20、三氧化二钴14、五氧化二钒10、CuSO4·5H2O 40、Ni(NO3)2·6H2O 28、(NH42C2O4·H2O 18、适量的浓度10%的硝酸。
一种具有居里点温度敏感性的MnZn铁氧体的制备方法,包括以下步骤:
(1)初步处理:将氧化锰、氧化锌、二硫化钼粉、纳米二氧化钛、氧化钴、三氧化二钴、五氧化二钒混合以及总重量11倍的浓度10%的硝酸,在100℃加热搅拌25min,停止加热,采用磁力配合200W超声处理35min至均匀分散,得浆液,在之后球磨罐中球磨该浆液4.5h,得细化浆液备用;
(2)将细化浆液与850℃惰性气体环境中煅烧11h,之后球磨2.5h,得混合料备用;
(3)将混合料、石墨烯、白炭黑、羰基铁粉、聚乙二醇混合搅拌均匀置于电加热炉中,与350℃惰性气体环境中煅烧11h,之后球磨1.4h,得大表面积比的混合料备用;
(4)将大表面积比的混合料、CuSO4·5H2O、Ni(NO3)2·6H2O、(NH42C2O4·H2O混合,放在带搅拌装置的电热炉中,在55℃下边加热边搅拌6.5h,得到可以保证湿度的混合料备用,之后,趁热在放入行星式球磨机中混合研磨1.6h,到的微观均匀的混合料备用;
(5)将微观均匀的混合料放在磨具中压制成所需形状坯块,然后连同模具转入带程序升温功能的惰性气体气氛的窑炉中烧结,烧结时,温度以3-4℃/min的升温速率从室温加热到1250℃,保温3.5h,随后在惰性气氛下自然降温冷却至室温,得到所述高热阻敏感度和热磁敏感度纳米晶锰锌铁氧体。
实施例3:
一种具有居里点温度敏感性的MnZn铁氧体,包括以下重量(kg)组分:氧化锰70、氧化锌66、二硫化钼粉24、纳米二氧化钛5、聚乙二醇100、石墨烯20、白炭黑21、羰基铁粉13、氧化钴20、三氧化二钴14、五氧化二钒10、CuSO4·5H2O 45、Ni(NO3)2·6H2O 30、(NH42C2O4·H2O 21、适量的浓度10%的硝酸。
一种具有居里点温度敏感性的MnZn铁氧体的制备方法,包括以下步骤:
(1)初步处理:将氧化锰、氧化锌、二硫化钼粉、纳米二氧化钛、氧化钴、三氧化二钴、五氧化二钒混合以及总重量12倍的浓度10%的硝酸,在100℃加热搅拌30min,停止加热,采用磁力配合200W超声处理40min至均匀分散,得浆液,在之后球磨罐中球磨该浆液5h,得细化浆液备用;
(2)将细化浆液与900℃惰性气体环境中煅烧12h,之后球磨3h,得混合料备用;
(3)将混合料、石墨烯、白炭黑、羰基铁粉、聚乙二醇混合搅拌均匀置于电加热炉中,与400℃惰性气体环境中煅烧12h,之后球磨1.6h,得大表面积比的混合料备用;
(4)将大表面积比的混合料、CuSO4·5H2O、Ni(NO3)2·6H2O、(NH42C2O4·H2O混合,放在带搅拌装置的电热炉中,在60℃下边加热边搅拌7h,得到可以保证湿度的混合料备用,之后,趁热在放入行星式球磨机中混合研磨1.8h,到的微观均匀的混合料备用;
(5)将微观均匀的混合料放在磨具中压制成所需形状坯块,然后连同模具转入带程序升温功能的惰性气体气氛的窑炉中烧结,烧结时,温度以3-4℃/min的升温速率从室温加热到1300℃,保温4h,随后在惰性气氛下自然降温冷却至室温,得到所述高热阻敏感度和热磁敏感度纳米晶锰锌铁氧体。
对实施例1-3所得的MnZn铁氧体进行了居里点温度敏感性测试,发现实施例1-3的MnZn铁氧体的居里点以及居里点温度敏感程度分别如下:
表1 实施例1-3所得的MnZn铁氧体居里点温度敏感性测试结果
实施例1 实施例2 实施例3
居里温度(℃) 26.8 29 28.4
居里点温度敏感程度(℃) 0.11 0.03 0.08
密度( g/cm³) 4.9 4.8 5.1

Claims (2)

1.一种具有居里点温度敏感性的MnZn铁氧体,其特征在于,包括以下重量份组分:氧化锰60-70、氧化锌58-66、二硫化钼粉18-24、纳米二氧化钛23-25、聚乙二醇100-110、石墨烯20-30、白炭黑21-29、羰基铁粉13-19、氧化钴16-24、三氧化二钴12-16、五氧化二钒8-12、CuSO4·5H2O 35-45、Ni(NO3)2·6H2O 26-30、(NH42C2O4·H2O 15-21、适量的浓度10%的硝酸。
2.一种如权利要求1所述的具有居里点温度敏感性的MnZn铁氧体的制备方法,其特征在于,包括以下步骤:
(1)初步处理:将氧化锰、氧化锌、二硫化钼粉、纳米二氧化钛、氧化钴、三氧化二钴、五氧化二钒混合以及总重量10-12倍的浓度10%的硝酸,在100℃加热搅拌20-30min,停止加热,采用磁力配合200W超声处理30-40min至均匀分散,得浆液,在之后球磨罐中球磨该浆液4-5h,得细化浆液备用;
(2)将细化浆液于800-900℃惰性气体环境中煅烧10-12h,之后球磨2-3h,得混合料备用;
(3)将混合料、石墨烯、白炭黑、羰基铁粉、聚乙二醇混合搅拌均匀置于电加热炉中,于300-400℃惰性气体环境中煅烧10-12h,之后球磨1.2-1.6h,得大比表面积的混合料备用;
(4)将大比表面积的混合料、CuSO4·5H2O、Ni(NO3)2·6H2O、(NH42C2O4·H2O混合,放在带搅拌装置的电热炉中,在50-60℃下边加热边搅拌6-7h,得到可以保证湿度的混合料备用,之后,趁热再放入行星式球磨机中混合研磨1.4-1.8h,得到微观均匀的混合料备用;
(5)将微观均匀的混合料放在磨具中压制成所需形状坯块,然后连同模具转入带程序升温功能的惰性气体气氛的窑炉中烧结,烧结时,温度以3-4℃/min的升温速率从室温加热到1200-1300℃,保温3-4h,随后在惰性气氛下自然降温冷却至室温,得到所述具有居里点温度敏感性的MnZn铁氧体。
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