CN106747413B - 钛酸铜钙纳米单晶粉体及其制备方法 - Google Patents

钛酸铜钙纳米单晶粉体及其制备方法 Download PDF

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CN106747413B
CN106747413B CN201710098560.9A CN201710098560A CN106747413B CN 106747413 B CN106747413 B CN 106747413B CN 201710098560 A CN201710098560 A CN 201710098560A CN 106747413 B CN106747413 B CN 106747413B
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慕春红
任和
宋远强
邓凯
罗建军
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Sichuan Huantan Technology Co ltd
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Abstract

本发明公开了一种钛酸铜钙纳米单晶粉体及其制备方法。该纳米单晶粉体包括以下重量份的组分：铜盐2.5~20份、钙盐1~9份、钛酸丁酯3.5~16份、有机粘合剂5~25份、弱酸1.5~6份以及溶剂55~75份；其制备方法为：（1）按配方将铜盐、钙盐、钛酸丁酯、酸液和溶剂混合，超声后搅拌，得溶液Ⅰ；（2）将有机粘合剂加入溶液Ⅰ中，搅拌溶解，得溶液Ⅱ；（3）将溶液Ⅱ加入喷雾干燥机中处理，得无机/有机粉末，再将无机/有机粉末置于烧结炉中烧结，得钛酸铜钙纳米单晶粉体。本发明可有效提升钛酸铜钙纳米单晶粉体的生产效率，降低生产成本。

Description

钛酸铜钙纳米单晶粉体及其制备方法
技术领域
本发明属于电子陶瓷粉体制备技术领域，具体涉及一种钛酸铜钙纳米单晶粉体及其制备方法。
背景技术
随着电子科技的进步，电子整机的集成化、高速化发展对所用元器件在小型化、片式化、高品质因数方面的要求进一步提高；小型化多层片式陶瓷电容器以其高可靠性、高品质因数的优点已在很多场合取代了电解电容器，多层片式陶瓷电容器生产制造过程中所采用的介质浆料决定了所制备的电容器的性能指标，介质浆料一般由陶瓷微粉配以适量的有机溶剂、分散剂等组成；其中，陶瓷微粉的材料体系组成、结晶状态、粒径大小、粒径分布等因素决定了烧结多层片式器件的性能指标，一般来讲，在材料体系既定的前提下，陶瓷微粉颗粒的结晶越完整、粒径分布越均匀，则烧结后的电子陶瓷综合电气性能越好。
在电子陶瓷微粉工业生产过程中，通过混料、预烧后得到的介质陶瓷粉一般为多晶或无定形态微米级颗粒，经过一定工序形成器件生坯后经过二次高温共烧或烧结成元器件，过程中其结晶度得到进一步提高；若能够采用纳米级单晶超细粉体作为生坯用的介质浆料陶瓷粉，则将导致烧结器件内部晶粒融合更加完整，烧结体更加致密，气孔更少，因此共烧工艺和产品性能将得到大大改善。
钛酸铜钙（CaCu3Ti4O12，简称CCTO）化合物已被实验证实具有巨介电常数（ε≈104-105）和较低的损耗（tgδ≈0.03），是性能优异的介质电容器用介质陶瓷材料，依据传统的片式元器件工艺，通常采用常规粉体工艺和固相反应法制备CCTO预烧粉体，然后配制成陶瓷浆料，该途径获得的CCTO陶瓷粉多为尺寸为微米级的多晶颗粒，且含有大量无定形杂相，容易在后续烧结陶瓷块体中引入大量气孔、缺陷，导致最终得到的介质陶瓷块体介电常数降低，损耗增加，限制了CCTO电容器的综合品质提升和应用。
有文献报道采用移动浮区法制备CCTO单晶体，但其工艺成本高，且与电子陶瓷粉体工艺不兼容，难以得到产业化应用；另有报道采用熔盐法制备出CCTO纳米晶粉体，但是熔盐法容易引入杂质离子和形成杂相，且需要后续清洗工序，生产效率低；因此，开发一种简便的、低成本的、可量产的CCTO单晶微/纳粉体的制备工艺对产业化开发高性能CCTO介质电容器具有重要意义。
发明内容
针对现有技术中的上述不足，本发明提供一种钛酸铜钙纳米单晶粉体及其制备方法，有效解决现有生产方法成本高、效率低的问题。
为解决上述的技术问题，本发明采用的技术方案为：
一种钛酸铜钙纳米单晶粉体，包括以下重量份的组分：
铜盐2.5~20份、钙盐1~9份、钛酸丁酯3.5~16份、有机粘合剂5~25份、弱酸1.5~6份以及溶剂55~75份。
进一步地，铜盐5份、钙盐2份、钛酸丁酯9.5份、有机粘合剂9份、弱酸3.8份以及溶剂63份。
进一步地，铜盐为硝酸铜、氯化铜或醋酸铜。
进一步地，钙盐为硝酸钙、碳酸钙、磷酸钙或氯化钙。
进一步地，有机粘合剂为聚乙烯醇、聚乙烯吡咯烷酮、甲基纤维素、羟丙基甲基纤维素、羧甲基纤维素钠、羧乙基纤维素、聚丙烯酰胺、聚氧化乙烯或聚丙烯酸。
进一步地，酸液为冰醋酸、盐酸或硝酸。
进一步地，溶剂为水、乙醇、甲醇、乙二醇甲醚或丙酮。
上述钛酸铜钙纳米单晶粉体的制备方法，包括以下步骤：
（1）按配方将铜盐、钙盐、钛酸丁酯、酸液和溶剂混合，于50~200W功率超声15~60min，再搅拌30~120min，形成溶液Ⅰ；
（2）将有机粘合剂加入溶液Ⅰ中，于40~80℃搅拌溶解3~12h，得溶液Ⅱ；
（3）将溶液Ⅱ加入150~300℃、压力为0.1~0.5MPa的喷雾干燥机中处理，得无机/有机粉末，再将无机/有机粉末置于Ar/O2氛围的烧结炉中，于850~1200℃烧结2~10h，得粒径为160~360nm的钛酸铜钙纳米单晶粉体。
进一步地，步骤（3）中O2与Ar体积比为1~5:1~5。
进一步地，步骤（3）中O2与Ar体积比为1:5。
本发明的有益效果为：
（1）本发明得到的钛酸铜钙纳米单晶为超细粉体，粒径在160~360nm范围可调，并且晶粒呈现完整的单晶结晶状态；此种钛酸铜钙超细粉体在先进电子陶瓷浆料和介质电容器领域具有广阔的应用前景。
（2）本发明提供的钛酸铜钙纳米单晶超细粉体的制备方法，整个过程经历化学溶液、无机/有机超细微粉和钛酸铜钙超细粉的物理化学转变，可以通过前期配制化学溶液时精确的调控钙、铜、钛离子的及无机盐的总体浓度，从而控制钛酸铜钙纳米晶的粒径。
（3）整个工艺过程所用到的设备结构简单，反应条件常规，工艺过程简单，工艺成本低，易规模化生产。
（4）在150~300℃时，溶液Ⅱ在喷雾过程中形成的微液滴中的溶剂能够迅速挥发掉，避免发生多个微液滴的团聚，便于形成粒径细微的无机/有机粉末。
附图说明
图1为本发明提供的钛酸铜钙纳米单晶粉体的XRD图谱，其中用“*”标出的为钛酸铜钙的特征衍射峰；
图2为本发明提供的钛酸铜钙纳米单晶粉体的扫描电镜图；
图3为本发明提供的钛酸铜钙纳米单晶粉体的透射电镜图；
图4为本发明提供的钛酸铜钙纳米单晶粉体的高分辨率透射电镜图；
图5为本发明提供的钛酸铜钙纳米单晶粉体颗粒的透射电子显微镜SEAD单晶衍射图。
具体实施方式
下面对本发明的具体实施方式进行描述，以便于本技术领域的技术人员理解本发明，但应该清楚，本发明不限于具体实施方式的范围，对本技术领域的普通技术人员来讲，只要各种变化在所附的权利要求限定和确定的本发明的精神和范围内，这些变化是显而易见的，一切利用本发明构思的发明创造均在保护之列。
实施例1
一种钛酸铜钙纳米单晶粉体，包括以下重量份的组分：
醋酸铜（Cu(CH3COO)2·H2O）2.5份、硝酸钙（Ca(NO3)2·4H2O）1份、聚乙烯吡咯烷酮（PVP，K90）5份、钛酸丁酯3.5份、冰醋酸1.5份以及无水乙醇75份。
上述钛酸铜钙纳米单晶粉体的制备方法，包括以下步骤：
（1）按配方将醋酸铜、硝酸钙、钛酸丁酯、冰醋酸和无水乙醇混合，于90W功率超声30min，再磁力搅拌120min至充分溶解，形成溶液Ⅰ；
（2）将聚乙烯吡咯烷酮加入溶液Ⅰ中，于45℃磁力搅拌溶解8h至充分溶解，得溶液Ⅱ；
（3）将溶液Ⅱ加入200℃、0.1MPa的喷雾干燥机中处理，得无机/有机粉末，再将无机/有机粉末置于Ar/O2（V:V=5:1）氛围的烧结炉中，于900℃烧结4h，得钛酸铜钙纳米单晶粉体。
实施例2
一种钛酸铜钙纳米单晶粉体，包括以下重量份的组分：
醋酸铜（Cu(CH3COO)2·H2O）5份、硝酸钙（Ca(NO3)2·4H2O）2份、聚乙烯吡咯烷酮（PVP，K90）9份、钛酸丁酯9.5份、冰醋酸3.8份以及无水乙醇63份。
上述钛酸铜钙纳米单晶粉体的制备方法，包括以下步骤：
（1）按配方将醋酸铜、硝酸钙、钛酸丁酯、冰醋酸和无水乙醇混合，于50W功率超声15min，再磁力搅拌30min至充分溶解，形成溶液Ⅰ；
（2）将聚乙烯吡咯烷酮加入溶液Ⅰ中，于40℃磁力搅拌溶解3h至充分溶解，得溶液Ⅱ；
（3）将溶液Ⅱ加入150℃、0.25MPa的喷雾干燥机中处理，得无机/有机粉末，再将无机/有机粉末置于Ar/O2（V:V=1:1）氛围的烧结炉中，于880℃烧结3h，得钛酸铜钙纳米单晶粉体。
实施例3
一种钛酸铜钙纳米单晶粉体，包括以下重量份的组分：
醋酸铜（Cu(CH3COO)2·H2O）5份、硝酸钙（Ca(NO3)2·4H2O）2份、聚乙烯吡咯烷酮（PVP，K90）5份、钛酸丁酯9.5份、冰醋酸3.8份以及无水乙醇63份。
上述钛酸铜钙纳米单晶粉体的制备方法，包括以下步骤：
（1）按配方将醋酸铜、硝酸钙、钛酸丁酯、冰醋酸和无水乙醇混合，于200W功率超声60min，再磁力搅拌120min至充分溶解，形成溶液Ⅰ；
（2）将聚乙烯吡咯烷酮加入溶液Ⅰ中，于80℃磁力搅拌溶解12h至充分溶解，得溶液Ⅱ；
（3）将溶液Ⅱ加入300℃、0.15MPa的喷雾干燥机中处理，得无机/有机粉末，再将无机/有机粉末置于Ar/O2（V:V=1:5）氛围的烧结炉中，于900℃烧结3h，得钛酸铜钙纳米单晶粉体。
实施例4
一种钛酸铜钙纳米单晶粉体，包括以下重量份的组分：
硝酸铜（Cu(NO3)2·3H2O）7.66份、硝酸钙（Ca(NO3)2·4H2O）2.5份、聚乙烯吡咯烷酮（PVP，K90）5.5份、钛酸丁酯12份、冰醋酸5份以及乙二醇甲醚63.5份。
上述钛酸铜钙纳米单晶粉体的制备方法，包括以下步骤：
（1）按配方将硝酸铜、硝酸钙、钛酸丁酯、冰醋酸和乙二醇甲醚混合，于90W功率超声30min，再磁力搅拌120min至充分溶解，形成溶液Ⅰ；
（2）将聚乙烯吡咯烷酮加入溶液Ⅰ中，于45℃磁力搅拌溶解8h至充分溶解，得溶液Ⅱ；
（3）将溶液Ⅱ加入200℃、0.2MPa的喷雾干燥机中处理，得无机/有机粉末，再将无机/有机粉末置于Ar/O2（V:V=4:1）氛围的烧结炉中，于1000℃烧结3h，得钛酸铜钙纳米单晶粉体。
实施例5
一种钛酸铜钙纳米单晶粉体，包括以下重量份的组分：
硝酸铜（Cu(NO3)2·3H2O）5份、硝酸钙（Ca(NO3)2·4H2O）8.144份、聚乙烯吡咯烷酮（PVP，K30）8.74份、钛酸丁酯3.92份、冰醋酸1.6份以及乙二醇甲醚55份。
上述钛酸铜钙纳米单晶粉体的制备方法，包括以下步骤：
（1）按配方将硝酸铜、硝酸钙、钛酸丁酯、冰醋酸和乙二醇甲醚混合，于90W功率超声30min，再磁力搅拌120min至充分溶解，形成溶液Ⅰ；
（2）将聚乙烯吡咯烷酮加入溶液Ⅰ中，于45℃磁力搅拌溶解8h至充分溶解，得溶液Ⅱ；
（3）将溶液Ⅱ加入200℃、0.5MPa的喷雾干燥机中处理，得无机/有机粉末，再将无机/有机粉末置于Ar/O2（V:V=5:1）氛围的烧结炉中，于1100℃烧结2h，得钛酸铜钙纳米单晶粉体。
实施例6
一种钛酸铜钙纳米单晶粉体，包括以下重量份的组分：
硝酸铜（Cu(NO3)2·3H2O）20份、硝酸钙（Ca(NO3)2·4H2O）9份、聚乙烯醇25份、钛酸丁酯16份、冰醋酸6份以及丙酮55份。
上述钛酸铜钙纳米单晶粉体的制备方法，包括以下步骤：
（1）按配方将硝酸铜、硝酸钙、钛酸丁酯、冰醋酸和丙酮混合，于90W功率超声30min，再磁力搅拌120min至充分溶解，形成溶液Ⅰ；
（2）将聚乙烯醇加入溶液Ⅰ中，于45℃磁力搅拌溶解8h至充分溶解，得溶液Ⅱ；
（3）将溶液Ⅱ加入200℃、0.35MPa的喷雾干燥机中处理，得无机/有机粉末，再将无机/有机粉末置于Ar/O2（V:V=5:1）氛围的烧结炉中，于1080℃烧结2h，得钛酸铜钙纳米单晶粉体。
实验例
对实施例3所得钛酸铜钙纳米单晶粉体进行检测，其检测图谱见图1~5。
如图1所示，有的XRD衍射峰均与类钙钛矿结构钛酸铜钙的标准衍射峰相吻合，说明所提供的纳米颗粒为典型的类钙钛矿结构的钛酸铜钙相，没有其他杂相形成，另外在图中虚线所示处出现非晶包，说明所提供粉末有纳米级尺寸的晶粒。
图2显示颗粒尺寸在100~200纳米范围。
图3清晰的显示了所提供纳米粉末颗粒的外形，颗粒尺寸范围为100~250nm。
如图4所示，经测量得到晶面间距为3.23Å，对应钛酸铜钙的（211）晶面。
图5中的衍射图案为周期性亮点，为典型的单晶衍射特征，有效证明了所提供钛酸铜钙粉末的单晶特性。

Claims (7)

1.一种钛酸铜钙纳米单晶粉体的制备方法，其特征在于，包括以下步骤：
（1）按配方将铜盐、钙盐、钛酸丁酯、酸液和溶剂混合，于50~200W功率超声15~60min，再搅拌30~120min，形成溶液Ⅰ；所述配方包括以下重量份的组分：
铜盐2.5~20份、钙盐1~9份、钛酸丁酯3.5~16份、有机粘合剂5~25份、酸液1.5~6份以及溶剂55~75份；
所述铜盐为 硝酸铜、氯化铜或醋酸铜；所述钙盐为硝酸钙或氯化钙；
（2）将有机粘合剂加入溶液Ⅰ中，于40~80℃搅拌溶解3~12h，得溶液Ⅱ；
（3）将溶液Ⅱ加入150~300℃、压力为0.1~0.5MPa的喷雾干燥机中处理，得无机/有机粉末，再将无机/有机粉末置于Ar/O2氛围的烧结炉中，于850~1200℃烧结2~10h，得粒径为160~360nm的钛酸铜钙纳米单晶粉体。
2.根据权利要求1所述的钛酸铜钙纳米单晶粉体的制备方法，其特征在于，所述配方包括以下重量份的组分：
铜盐5份、钙盐2份、钛酸丁酯9.5份、有机粘合剂9份、酸液3.8份以及溶剂63份。
3.根据权利要求1或2所述的钛酸铜钙纳米单晶粉体的制备方法，其特征在于，所述有机粘合剂为聚乙烯醇、聚乙烯吡咯烷酮、甲基纤维素、羟丙基甲基纤维素、羧甲基纤维素钠、羧乙基纤维素、聚丙烯酰胺、聚氧化乙烯或聚丙烯酸。
4.根据权利要求1或2所述的钛酸铜钙纳米单晶粉体的制备方法，其特征在于，所述酸液为冰醋酸、盐酸或硝酸。
5.根据权利要求1或2所述的钛酸铜钙纳米单晶粉体的制备方法，其特征在于，所述溶剂为水、乙醇、甲醇、乙二醇甲醚或丙酮。
6.根据权利要求1所述的钛酸铜钙纳米单晶粉体的制备方法，其特征在于，步骤（3）中所述O2与Ar体积比为1~5:1~5。
7.根据权利要求1所述的钛酸铜钙纳米单晶粉体的制备方法，其特征在于，步骤（3）中所述O2与Ar体积比为1:5。
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