CN104402038A - 一种单分散纳米ZnO压敏陶瓷粉体的制备方法 - Google Patents

一种单分散纳米ZnO压敏陶瓷粉体的制备方法 Download PDF

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CN104402038A
CN104402038A CN201410582462.9A CN201410582462A CN104402038A CN 104402038 A CN104402038 A CN 104402038A CN 201410582462 A CN201410582462 A CN 201410582462A CN 104402038 A CN104402038 A CN 104402038A
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sensitive ceramic
powder
zno
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王茂华
束静
马小玉
江雯
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CHANGZHOU CHUANGJIE LIGHTNING PROTECTION Co Ltd
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Abstract

本发明涉及纳米氧化锌，特指一种单分散纳米ZnO压敏陶瓷粉体的制备方法，属于电子陶瓷制备及应用技术领域。本发明主要采用十二烷基磺酸钠(SDS)作为分散剂合成纳米复合ZnO粉体，从而制得高性能的ZnO压敏陶瓷材料；采用十二烷基磺酸钠(SDS)作为分散剂合成纳米复合ZnO，得到的粉体颗粒尺寸较小、形貌均一、物相分散均匀、粉体纯度高，有效的提高了ZnO压敏陶瓷的电性能。

Description

一种单分散纳米ZnO压敏陶瓷粉体的制备方法
技术领域
  本发明涉及纳米氧化锌，特指一种单分散纳米ZnO压敏陶瓷粉体的制备方法，属于电子陶瓷制备及应用技术领域。
背景技术
氧化锌(ZnO)是一种n-型直接宽带隙金属氧化物半导体材料(3.36V)，具有高的激子结合能(60meV)，良好的化学和热稳定性；ZnO掺杂微量的Bi、Pr、Co、Cr、Mn等元素制备的压敏陶瓷具有超常的非线性特性；氧化锌压敏陶瓷工作原理是基于所具有的伏安(I-V)非线性特性，即当电压低于某一临界值时，压敏陶瓷的阻值非常高，相当于绝缘体，当电压超过这一临界值时，电阻急剧减小，接近于导体，因为这种效应的存在，压敏电阻器被广泛应用于过压保护和稳压方面；随着工业化步伐的加快，对电力***的需求增多、要求提高，高层建筑和大型工业设备的增多，对高压ZnO压敏电阻的需求量逐年上升，同时对其性能也提出了更高的要求；高压ZnO压敏电阻的优点是电压梯度高、大电流特性好，但能量容量小，容易损坏，解决这一问题的有效方法是开发高压高能型压敏电阻；ZnO压敏电阻电性能的提高主要取决于ZnO粉体的形貌尺寸，以及颗粒的分散程度, 因此制备形貌均一，颗粒尺寸小，分散性好的纳米复合ZnO粉体是生产过程的关键所在。
目前制备ZnO压敏陶瓷材料除了固相法以外，主要采用液相法，液相法主要包括沉淀法，水热法，溶胶凝胶法，微乳液法等；在这些方法中沉淀法应用最为普遍，因为沉淀法具有便于操作，工艺简单，适用于大型工业生产等优点；但是通常情况下在不采用额外辅助手段时，沉淀法制备得到的纳米ZnO粉体分散性较差，产物产率较低，颗粒大小不均；因此，目前研究的重点是探讨一种新的方法
从而制得高性能的ZnO压敏陶瓷材料。
    本发明主要采用十二烷基磺酸钠(SDS)作为分散剂合成纳米复合ZnO粉体，从而制得高性能的ZnO压敏陶瓷材料；十二烷基磺酸钠(SDS)是一种典型的阴离子表面活性剂，其结构同时包含亲水性基团磺酸基和亲油性基团十二烷基，这种不对称的两亲结构基团赋予十二烷基磺酸钠在溶液中的特殊性能，十二烷基磺酸钠(SDS)在水中活性增强易受外界因素的影响而诱发化学反应，这种变化可以使表面活性剂活性增强，其亲油基和亲水基在溶液中更容易体现其亲水能力，增强表面活性剂降低表面张力的能力；采用十二烷基磺酸钠(SDS)作为分散剂合成纳米复合ZnO，得到的粉体颗粒尺寸较小、形貌均一、物相分散均匀、粉体纯度高，有效的提高了ZnO压敏陶瓷的电性能。
发明内容
本发明的目的在于提供一种ZnO压敏陶瓷材料的制备方法，克服传统固相法和液相法制备纳米复合ZnO粉体存在的缺点，和解决当前ZnO压敏陶瓷材料制备粉体颗粒尺寸较大，且得到的氧化锌形貌不均匀，颗粒大小不一的问题，根据选用合适分散剂来改善ZnO粉体微观结构，提高ZnO压敏陶瓷材料的电性能。
本发明所采用的方法涉及到许多因素，如反应物的配比、反应温度、反应时间等，它包括以下步骤：
1、纳米复合ZnO粉体的制备
（1）以分析纯的Zn(NO3)2·6H2O，Bi(NO3)2·5H2O，Co(NO3)2·6H2O，SbCl3, 
MnCl2·4H2O, Cr(NO3)3·9H2O为原料，分别配置Zn(NO3)2、Bi(NO3)2、Co(NO3)2、SbCl3、 MnCl2 和Cr(NO3)3水溶液，以摩尔百分含量计算，按照97%的ZnO，1%的Sb2O3，0.5%的Bi2O3 ，0.5%的Co3O4，0.5%的CrO3和0.5%的MnO的配比混合，搅拌均匀。
（2）配置十二烷基磺酸钠水溶液，将十二烷基磺酸钠水溶液加入配制好的混合溶液中，加热搅拌均匀，SDS与Zn(NO3)2·6H2O的物质量之比为1~10:1。
（3）量取适量的NaOH溶液，快速加入混合溶液中，得到沉淀物，加热搅拌均匀，氢氧化钠与Zn(NO3)2·6H2O的物质量之比为2~4:1。
（4）最后将得到的粉体抽滤，并用去离子水和乙醇充分洗涤去除杂质，最后在真空干燥箱中干燥。
  所述步骤1中配置的Zn(NO3)2·6H2O，Bi(NO3)2·5H2O，Co(NO3)2·6H2O，SbCl3，MnCl2·4H2O水溶液浓度均为1mol/L。
  所述步骤2中配置十二烷基磺酸钠水溶液的浓度为4mol/L。 
  所述步骤2中加热温度为60~90℃，搅拌时间为30min。
  所述步骤3中配置氧化钠溶液为4mol/L，加热温度为60~90℃，搅拌时间为2h。
  所述步骤4中的干燥指于80℃下干燥6h。
2、ZnO压敏陶瓷的制备
（1）配制质量分数为5%的聚乙烯醇( PVA)溶液，加入纳米复合ZnO粉体中，在研钵中研磨，用200目的筛子过筛造粒，在30~80MPa下压制成片状。
（2）将步骤(1)制得的片状素坯在1050~1200℃下烧结，于空气气氛下保温2h，升降温速率均为5℃/min，降温至200℃后，室温下自然冷却，得到ZnO压敏陶瓷。
（3）将步骤(2)制得的ZnO压敏陶瓷表面打磨，抛光，被银，制作电极。
本发明提供的材料配方和制备方法所制得的纳米复合ZnO粉体为棕色，ZnO压敏陶瓷片为黑灰色固体，收缩率8%~15%，压敏电压V1mA为400~500V/mm，漏电流JLeak为1.25±0.09μA，非线性系数α为(42.16 ± 0.56)；由于电位梯度相对较高，可以用于制造高压、超高压电力***的过电压保护产品等。
本发明采用上述技术方案的优点是：
该方法制备的纳米复合ZnO颗粒尺寸较小，形貌均一，分散性好。
采用本发明制备的ZnO压敏陶瓷，非线性系数较大，漏电流小，符合高压电力***的过电压保护产品的要求。
附图说明
   图1 是本发明所制得纳米复合ZnO粉体的TEM图，从图中可以看出纳米ZnO粉体颗粒大小均一，分散性较好，粉体颗粒大小为20~30nm。
   图2 是本发明所制得的ZnO压敏陶瓷的SEM图，图中的ZnO压敏陶瓷材料致密性良好，形貌均一，颗粒大小为7~9μm。
  图3（a),(b)分别为是本发明所制得的ZnO粉体和ZnO压敏陶瓷的XRD图，从图中可以看出在后期热处理后，有新的尖晶石相产生即Zn7Sb2O12相。
具体实施方式
下面结合附图和实施例，对本发明做进一步的描述，但绝不限制本发明的范围：
实施例1
1、纳米复合ZnO粉体的制备
（1）配置Zn(NO3)2、Bi(NO3)2、Co(NO3)2、SbCl3、 MnCl2 和Cr(NO3)3水溶液，(溶液浓度均为1M）以摩尔百分含量计算，按照97%的ZnO,1%的Sb2O3,0.5%的Bi2O3 ，Co3O4，CrO3，MnO的配比混合，搅拌均匀。
（2）量取20mL十二烷基磺酸钠(SDS)水溶液，加入配制好的混合溶液中，90 ℃加热搅拌30min。
（3）配制4M 的NaOH溶液，量取30mL快速加入混合溶液中，得到沉淀物，90℃水浴加热，继续快速搅拌2h。
（4）将得到的粉体抽滤，并用去离子水和乙醇充分洗涤去除杂质，最后在真空干燥箱中80℃干燥6h。
2、ZnO压敏陶瓷的制备
(1)配置质量分数为5%的聚乙烯醇( PVA)，加入纳米复合ZnO粉体中，在研钵中研磨，用200目的筛子过筛造粒，在50MPa下压制成片。
(2)将步骤(1)制得的片状素坯在1050℃下烧结，于空气气氛下保温2h，升降温速率5℃/min，降温至200℃后，室温下自然冷却，得到ZnO压敏陶瓷。
实施例2
本实施例中，制备纳米复合ZnO粉体时，各组份重量与实施例1一样，加入20mL十二烷基磺酸钠(SDS)水溶液，80 ℃加热搅拌, 30min后快速加入30mL4M的NaOH溶液，80℃水浴加热，继续快速搅拌2h，将上述所得沉淀物抽滤洗涤去除杂质，最后在真空干燥箱中80℃干燥6h；上述材料采用与实施例1相同的工艺步骤，制备成ZnO压敏陶瓷，其不同之处在于陶瓷烧结温度为1100℃。
实施例3
本实施例中，制备纳米复合ZnO粉体时，各组份重量与实施例1一样，加入20mL十二烷基磺酸钠(SDS) 水溶液，70 ℃加热搅拌, 30min后快速加入30mL4M的NaOH溶液，70℃水浴加热，继续快速搅拌2h，将上述所得沉淀物抽滤洗涤去除杂质，最后在真空干燥箱中80℃干燥6h；上述材料采用与实施例1相同的工艺步骤，制备成ZnO压敏陶瓷，其不同之处在于陶瓷烧结温度为1150℃。
实施例4
本实施例中，制备纳米复合ZnO粉体时，各组份重量与实施例1一样，加入20mL十二烷基磺酸钠(SDS) 水溶液,60 ℃加热搅拌，30min后快速加入30mL4M的NaOH溶液，60℃水浴加热，继续快速搅拌2h，将上述所得沉淀物抽滤洗涤去除杂质，最后在真空干燥箱中80℃干燥6h；上述材料采用与实施例1相同的工艺步骤，制备成ZnO压敏陶瓷，其不同之处在于陶瓷烧结温度为1050℃。
实施例5
本实施例中，制备纳米复合ZnO粉体时，各组份重量与实施例1一样，加入20mL十二烷基磺酸钠(SDS) 水溶液，90 ℃加热搅拌, 30min后快速加入30mL4M的NaOH溶液，90℃水浴加热，继续快速搅拌2h，将上述所得沉淀物抽滤洗涤去除杂质，最后在真空干燥箱中80℃干燥6h；上述材料采用与实施例1相同的工艺步骤，制备成ZnO压敏陶瓷，其不同之处在于陶瓷烧结温度为1200℃。

Claims (8)

1.一种单分散纳米ZnO压敏陶瓷粉体的制备方法，包括配置Zn(NO3)2、Bi(NO3)2、Co(NO3)2、SbCl3、 MnCl2 和Cr(NO3)3水溶液，进行混合得到混合溶液的步骤、将NaOH加入到混合溶液中制备单分散纳米ZnO压敏陶瓷粉体的步骤，其特征在于：在将NaOH加入到混合溶液中之前，将十二烷基磺酸钠加入到混合溶液中，使得后续制备的单分散纳米ZnO压敏陶瓷粉体颗粒尺寸较小，为20~30nm，形貌均一、物相分散均匀。
2.如权利要求1所述的一种单分散纳米ZnO压敏陶瓷粉体的制备方法，其特征在于步骤如下：
（1）分别配置Zn(NO3)2、Bi(NO3)2、Co(NO3)2、SbCl3、 MnCl2 和Cr(NO3)3水溶液，以摩尔百分含量计算，按照97%的ZnO,1%的Sb2O3,0.5%的Bi2O3 ，0.5%的Co3O4，0.5%的CrO3和0.5%的MnO的配比混合，搅拌均匀；
（2）配置十二烷基磺酸钠水溶液，将十二烷基磺酸钠水溶液加入到配制好的混合溶液中，加热搅拌均匀，SDS与Zn(NO3)2·6H2O的物质量之比为1~10:1；
（3）量取适量的NaOH溶液，快速加入混合溶液中，得到沉淀物，加热搅拌均匀，氢氧化钠与Zn(NO3)2·6H2O的物质量之比为2~4:1；
（4）最后将得到的粉体抽滤，并用去离子水和乙醇充分洗涤去除杂质，最后在真空干燥箱中干燥。
3.如权利要求2所述的一种单分散纳米ZnO压敏陶瓷粉体的制备方法，其特征在于：所述步骤1中配置的Zn(NO3)2·6H2O，Bi(NO3)2·5H2O，Co(NO3)2·6H2O，SbCl3，MnCl2·4H2O水溶液浓度均为1mol/L。
4.如权利要求2所述的一种单分散纳米ZnO压敏陶瓷粉体的制备方法，其特征在于： 所述步骤2中配置十二烷基磺酸钠水溶液浓度为4mol/L。
5.如权利要求2所述的一种单分散纳米ZnO压敏陶瓷粉体的制备方法，其特征在于：所述步骤2中加热温度为60~90℃，搅拌时间为30min。
6.如权利要求2所述的一种单分散纳米ZnO压敏陶瓷粉体的制备方法，其特征在于：所述步骤3中配置氧化钠溶液为4mol/L，加热温度为60~90℃，搅拌时间为2h。
7.如权利要求2所述的一种单分散纳米ZnO压敏陶瓷粉体的制备方法，其特征在于：所述步骤4中的干燥指于80℃下干燥6h。
8.采用如权利要求1所述的单分散纳米ZnO压敏陶瓷粉体制备ZnO压敏陶瓷的方法，所述ZnO压敏陶瓷为黑灰色固体，收缩率8%~15%，压敏电压V1mA为400~500V/mm，漏电流JLeak为1.25±0.09μA，非线性系数α为(42.16 ± 0.56)；其特征在于步骤如下：
（1）配制质量分数为5%的聚乙烯醇( PVA)溶液，加入纳米复合ZnO粉体中，在研钵中研磨，用200目的筛子过筛造粒，在30~80MPa下压制成片状；
（2）将步骤(1)制得的片状素坯在1050~1200℃下烧结，于空气气氛下保温2h，升降温速率均为5℃/min，降温至200℃后，室温下自然冷却，得到ZnO压敏陶瓷；
（3）将步骤(2)制得的ZnO压敏陶瓷表面打磨，抛光，被银，制作电极。
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