CN113800901B - 低温环境下低损耗钛酸铜镧钙介电陶瓷材料及其制备方法 - Google Patents

低温环境下低损耗钛酸铜镧钙介电陶瓷材料及其制备方法 Download PDF

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CN113800901B
CN113800901B CN202111157600.5A CN202111157600A CN113800901B CN 113800901 B CN113800901 B CN 113800901B CN 202111157600 A CN202111157600 A CN 202111157600A CN 113800901 B CN113800901 B CN 113800901B
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张建花
郭斯琪
卢文敏
陈子成
王大伟
郭向阳
郝嵘
雷志鹏
李媛媛
田慕琴
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Taiyuan University of Technology
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Abstract

本发明公开一种低介电损耗钛酸铜镧钙介电陶瓷材料及其制备方法。本陶瓷材料的组成为Ca1‑xLaxCu3Ti4O12+0.5x(0<x<1)。该粉体用溶胶凝胶法合成。具体工艺为：以硝酸铜、硝酸钙、硝酸镧、钛酸四丁酯为原料，按照计量比进行称量配料；以无水乙醇为溶剂；将上述溶胶置于水浴锅中，不断搅拌至形成干凝胶；利用电炉和马弗炉除去干凝胶中的有机物，形成CLCTO前驱体粉末；之后进行加胶、研磨、压片，制成陶瓷胚体，再把胚体放入马弗炉内烧结；在炉内自然冷却至室温，得到CLCTO介电陶瓷。该陶瓷的介电损耗可在20℃降低至0.008，在低温环境下（‑100℃），50 Hz时介电损耗更是可以降低至0.003以下，在低温环境下具有广泛的应用前景。

Description

低温环境下低损耗钛酸铜镧钙介电陶瓷材料及其制备方法
技术领域
本发明属于电介质陶瓷合成技术领域，具体涉及一种低温环境下低介电损耗钛酸铜镧钙介电陶瓷材料及其制备方法。
背景技术
CaCu3Ti4O12（简称CCTO）陶瓷材料是一种具有高介电常数以及高热稳定性的新型介电陶瓷，在科研领域中受到了广泛关注。CCTO陶瓷具有巨大的介电常数、良好的频率稳定性和温度稳定性，突出的非欧姆特性（J-E曲线非线性），这使得CCTO陶瓷在大容量电容器小型化方面充满了潜力。然而，CCTO陶瓷还伴随着相对较高的介电损耗，不利于其作为电子材料的应用，应用范围被限制。若可以保持CCTO的巨介电常数以及良好的温度稳定性，对其进行取代或掺杂改性，降低介电损耗，便可使其更好的在实际应用中发挥作用。针对于低温环境下介电陶瓷的研究还很少。
目前，国内外的许多研究结果表明：室温下，CCTO的介电损耗较高，普遍在0.05以上（王行行，蔡会武. (2018). CaCu3Ti4O12（CCTO）陶瓷的研究进展. Applied ChemicalIndustry, 47(9), 5.）。有报道，CCTO的介电常数达到5.9×104，同时1 kHz下，其介电损耗为0.06 （Zhao, J., Liu, J., & Ma, G. (2012). Preparation, characterization anddielectric properties of CaCu3Ti4O12 ceramics. Ceramics International, 38(2),1221-1225. ）。另外，一种钛酸铜钠镉铋陶瓷Na1/3Cd1/3Bi1/3Cu3Ti4O12的介电常数达到了1.5×104，同时其介电损耗降低至0.04（Peng, Z., Wang, J., Liang, P., Zhu, J., Zhou,X., Chao, X., et al. (2020). A new perovskite-related ceramic with colossalpermittivity and low dielectric loss. Journal of the European CeramicSociety, 40(12), 4010-4015.）。而溶胶-凝胶法法制备的CaCu2.5Zn0.5Ti4O12陶瓷的介电损耗降低至0.017，但其击穿场强仅有1763 V/cm（Jakkree Boonlakhorn, P. K., BunditPutasaeng, Prasit Thongbai. (2020 ). Significantly improved non-Ohmic andgiant dielectric properties of CaCu3-xZnxTi4O12 ceramics by enhancing grainboundary response. Materials Research Express, 7(6), 066301-066312.）。从目前的研究可以看出，室温下，介电损耗的值可以降低至0.05以下，但关于低温环境下，CCTO陶瓷的介电性能研究还很少。
因此，若可以在低温环境下保持高介电常数的同时，降低介电损耗，就可以使CCTO陶瓷在更大范围得以应用，比如南北极以及太空等低温环境。
发明内容
针对上述CCTO产品在低温环境下介电常数、介电损耗等应用的技术问题，本发明提供了一种在低温环境下低介电损耗钛酸铜镧钙(CLCTO)介电陶瓷材料，并且提供了该CLCTO介电陶瓷的制备方法，可在保持介电常数仍处于较高水平时，再较宽温度范围内降低CCTO陶瓷的介电损耗。
为达到以上目的，本发明所述一种低温环境下低介电损耗钛酸铜镧钙介电陶瓷材料，其化学式为：Ca1-xLaxCu3Ti4O12+0.5x，其中0＜x＜1。
本发明所述的一种低温环境下低介电损耗钛酸铜镧钙介电陶瓷材料的制备方法是采取如下技术方案予以实现：
（1） CLCTO陶瓷前驱体粉末的制备。根据Ca1-xLaxCu3Ti4O12+0.5x（0<x<1）的化学计量比称取硝酸铜、硝酸钙、硝酸镧与柠檬酸原料，为得到最佳络合效果，柠檬酸物质的量为硝酸铜、硝酸钙、硝酸镧和钛酸四丁酯中金属阳离子（Ca2+、Cu2+、Ti4+，La3+）摩尔数之和的1.5倍。将称好的原料倒入无水乙醇中，不断搅拌使原料充分溶解后将称好的钛酸四丁酯倒入混合液中；加入少量PVA（聚乙二醇）增强分散性，搅拌得到溶胶。为获得大小均匀的陶瓷颗粒，对溶胶进行85 ℃恒温水浴且搅拌，且中途不断测试其pH值。为使得杂相最少，需加入少量氨水调节使其pH值保持稳定在2左右，直至形成凝胶。形成凝胶后， 继续85 ℃水浴保温12 h，确保酒精挥发完全以及凝胶足够干燥。将凝胶放入到蒸发皿中，用电炉对其进行去除有机物处理，进行此操作时不断翻搅，保证样品受热的均匀性。将产物放入研钵，均匀研磨10 min后，放入马弗炉中高温预烧，形成CLCTO陶瓷前驱体粉末。
（2） CLCTO陶瓷的制备。把前驱体粉末倒入玛瑙研钵中，并加入前驱体粉末5%质量的PVA粘合剂搅拌均匀后放入烧杯中，在烘箱中适度干燥后，称取制得的适量粉末放入磨具中压片，制得CLCTO陶瓷胚体。将胚体放入干燥箱中70 ℃完全干燥后放入马弗炉中，为得到最佳微观形貌，在1040 ℃保温烧结。烧结结束后，在炉内自然冷却至室温。
本发明采用溶胶凝胶法制备与CCTO结构及性能相近的CLCTO介电陶瓷，制备方法操作简单、重复性好、成品率高，实验制备得到的样品均匀性好，致密化程度高，所述组分以及步骤（1）中各个加料步骤、水浴步骤、步骤（2）中的干燥、烧结等步骤，都对最终产品性能起到了重要的作用，所制备的CLCTO陶瓷的介电损耗室温下可降低至0.008，同时介电常数在1 kHz时为5900~8900，具有低介电损耗与高介电常数的特点。特别是，CLCTO-06（即x=0.06）样品在低温环境下（-100 ℃）获得非常低的介电损耗（<0.003），证明这些材料有在低温环境下应用的潜能。
附图说明
图1为不同配比的CLCTO介电陶瓷试样的XRD图；
图2为不同配比的CLCTO介电陶瓷试样的介电常数频谱图；
图3为不同配比的CLCTO介电陶瓷试样的介电常数温谱图；
图4为不同配比的CLCTO介电陶瓷试样的介电损耗温谱图。
具体实施方式
下面结合具体实施方式对本发明进一步说明。下述说明仅仅是实例性的，而不限制本发明的范围。
实施例1
根据Ca1-xLaxCu3Ti4O12+0.5x中，x取值0.04，称取硝酸钙、硝酸镧、硝酸铜、柠檬酸分别为9.2054 g、0.6998 g、29.2848 g、76.0306 g，将其倒入装有300 ml无水乙醇的烧杯中，不断搅拌使其充分溶解，用烧杯称取55.5624 g钛酸四丁酯倒入混合液中，然后向此烧杯中加入100 ml的无水乙醇，最后加入1.5 ml的PVA增强分散性，使样品更加均匀，搅拌使其充分溶解，形成溶胶，然后把溶胶放到85 ℃的水浴锅中，保持搅拌棒200~250 rpm进行搅拌，搅拌过程中不断进行pH值矫正，保持pH值为2，不断搅拌形成凝胶。形成凝胶后，在水浴锅中85 ℃继续保温12 h，确保酒精挥发完全以及凝胶足够干燥。把凝胶倒入蒸发皿中再放到电炉上保持400~450 ℃除去凝胶中的有机物；然后再放入到马弗炉中800 ℃高温预烧，形成CLCTO陶瓷前驱体粉末。
把CLCTO陶瓷前驱体粉末放入玛瑙研钵中，并加入前驱体粉末5%质量的PVA粘合剂，在烘箱中干燥10 min；称取0.32 g粉体放入模具中，用100 MPa压强压制成圆片。把压好的圆片放入干燥箱中70 ℃干燥12 h再放入马弗炉中内，先以5 ℃/min的升温速率上升到200 ℃保温10 min进行除湿干燥，然后以相同的升温速率上升到700 ℃保温1 h进行排胶，最后以10 ℃/min的升温速率上升到1040 ℃保温12 h进行烧结。烧结结束后，取出样品在空气中自然冷却至室温，得到CLCTO陶瓷。
在烧结好的CLCTO陶瓷样品表面用十字交叉法均匀涂上银浆，在马弗炉内650 ℃保温0.5 h完成镀银，即可进行介电性能的测量。得到了低介电损耗CLCTO介电陶瓷材料，20℃时其介电损耗低至0.014，同时介电常数在1kHz时为8928。-100 ℃，50Hz时其介电损耗低至0.005。如表1所示。
实施例2
根据Ca1-xLaxCu3Ti4O12+0.5x中，x取值0.06，称取硝酸钙、硝酸镧、硝酸铜、柠檬酸分别为9.0316 g、1.0497 g、29.2848 g、76.0306 g，其他步骤与实施例1相同，得到了低介电损耗CLCTO介电陶瓷材料，20 ℃时其介电损耗低至0.008，同时介电常数在1kHz时为7122。-100 ℃，50Hz时其介电损耗低至0.002。如表1所示。
实施例3
根据Ca1-xLaxCu3Ti4O12+0.5x中，x取值0.08，称取硝酸钙、硝酸镧、硝酸铜、柠檬酸分别为8.8219 g、1.3996 g、29.2848 g、76.0306 g，其他步骤与实施例1相同，得到了低介电损耗CLCTO介电陶瓷材料，20 ℃时其介电损耗低至0.016，同时介电常数在1kHz时为5940。-100 ℃，50Hz时其介电损耗低至0.005。如表1所示。
实施例4
根据Ca1-xLaxCu3Ti4O12+0.5x中，x取值0.10，称取硝酸钙、硝酸镧、硝酸铜、柠檬酸分别为8.6309 g、1.7495 g、29.2848 g、76.0306 g，其他步骤与实施例1相同，得到了低介电损耗CLCTO介电陶瓷材料，20 ℃是其介电损耗低至0.010，同时介电常数在1kHz时为6148。-100 ℃，50Hz时其介电损耗低至0.004。如表1所示。
Figure DEST_PATH_IMAGE001
。

Claims (1)

1.一种低温环境下低介电损耗钛酸铜镧钙介电陶瓷材料的制备方法，其特征在于，所述制备方法具体包括以下步骤：
（1） CLCTO陶瓷前驱体粉末的制备；根据Ca1-xLaxCu3Ti4O12+0.5x的化学计量比称取硝酸铜、硝酸钙、硝酸镧与柠檬酸原料，柠檬酸物质的量为硝酸铜、硝酸钙、硝酸镧和钛酸四丁酯中金属阳离子摩尔数之和的1.5倍；将称好的原料倒入无水乙醇中，不断搅拌使原料充分溶解后将钛酸四丁酯倒入混合液中，将聚乙二醇加入到混合液中，搅拌至完全溶解形成溶胶；把溶胶放入恒温85℃的水浴锅中不断搅拌，搅拌过程中不断进行pH值矫正，保持pH值为2，使之形成凝胶；将凝胶放入到蒸发皿中，用电炉对其进行去除有机物处理，有机物处理后的凝胶再放入到马弗炉中高温预烧800℃，形成CLCTO陶瓷前驱体粉末；
（2） CLCTO陶瓷的制备；把前驱体粉末倒入玛瑙研钵中，并加入前驱体粉末5%质量的聚乙二醇粘合剂，用电炉适度干燥后，称取制得的适量粉末放入磨具中压片，制得CLCTO陶瓷胚体；把压好的陶瓷胚体放入干燥箱中70℃完全干燥12 h后放入马弗炉中，先以5℃/min的升温速率上升到200℃保温10 min进行除湿干燥，然后以相同的升温速率上升到700℃保温1 h进行排胶，最后以10℃/min的升温速率上升到1040℃保温12 h烧结；烧结结束后，在炉内自然冷却至室温，即可得到Ca1-xLaxCu3Ti4O12+0.5x，其中0.04≤x≤0.10的样品。
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