甘氨酸对固相法合成钛酸钡粉体的影响

doi:10.19964/j.issn.1006-4990.2022-0559

摘要/Abstract

摘要：

以BaCO₃和TiO₂为原料、甘氨酸为添加剂，采用固相法合成钛酸钡（BT）粉体。研究了不同合成温度和甘氨酸添加量对BT粉体性能的影响，利用XRD、BET、SEM、DSC、TG等手段对合成的BT粉体进行表征。结果表明，添加甘氨酸可以促进BaCO₃在650 ℃附近分解，使BT粉体的合成温度降低50 ℃，在900 ℃就能得到纯相BT，在1 000 ℃可以得到四方率（c/a）>1.010的BT粉体，但添加过量的甘氨酸使粉体粒径急剧增大反而会降低其性能；添加15%的甘氨酸在1 000 ℃保温2 h可以得到c/a=1.010 3、平均粒径为520 nm、k=9.00的BT粉体，其性能整体优于平均粒径为600 nm的商业BT粉。将二者在1 280 ℃烧结2 h得到的陶瓷进行介电性能对比发现，商业粉室温和居里点介电常数略大于添加15%甘氨酸的合成粉，但室温下正交-四方的相变峰使介电损耗急剧增大。

关键词: BaTiO₃, 甘氨酸, 四方率, k值, 介电性能

Abstract:

Barium titanate（BT） powders were synthesized by solid-state reaction using BaCO₃ and TiO₂ as raw materials and glycine as additive.The effects of different synthesis temperatures and glycine addition on the properties of BT powder were studied.The synthesized BT powders were characterized by XRD，BET，SEM，DSC and TG.The results showed that the addition of glycine could promote the decomposition of BaCO₃ near 650 ℃ and reduce the synthesis temperature of BT powder by 50 ℃.After adding glycine，pure phase BT could be obtained at 900 ℃，and BT powder with c/a>1.010 could be obtained at 1 000 ℃.However，the addition of excessive glycine made the particle size increase sharply，which would deteriorate the performance of BT powder.The BT powder with c/a=1.010 3，average particle size of 520 nm and k=9.00 could be obtained by adding 15% glycine at 1 000 ℃ for 2 h，and its performance was better than that of commercial BT powder with 600 nm.BT ceramics were obtained by sintering commercial powder and synthetic powder with 15% glycine at 1 280 ℃，respectively.Comparing the dielectric properties of the two ceramics，it was found that the dielectric constants of the former at room temperature and Curie point were slightly larger than those of the latter，but the dielectric loss was increased obviously due to the orthorhombic-tetragonal phase transition peak at room temperature.

Key words: BaTiO₃, glycine, tetragonality, k-factor, dielectric properties

中图分类号:

TQ132.35

李雪梅, 黄福祥, 龙敏, 田中青, 孟范成, 罗晓阳. 甘氨酸对固相法合成钛酸钡粉体的影响[J]. 无机盐工业, 2023, 55(7): 65-69.

LI Xuemei, HUANG Fuxiang, LONG Min, TIAN Zhongqing, MENG Fancheng, LUO Xiaoyang. Effect of glycine on solid-state synthesis of barium titanate powder[J]. Inorganic Chemicals Industry, 2023, 55(7): 65-69.

图/表 8

图1

表1

图2

表2

图3

表3

图4

图5

参考文献 16

1	LIU Jinpeng， YOU Xiaoqiang， CHEN Nan，et al.Fabrication of BaTiO₃/epoxy composites exhibiting large dielectric constant，low dielectric loss and high flexural strength［J］.Journal of Wuhan University of Technology（Mater.Sci.Ed.），2019，34（6）：1266-1273.
2	WANG Hongxian， LIU Baibo， WANG Xiaohui.Effects of dielectric thickness on energy storage properties of surface modified BaTiO₃ multilayer ceramic capacitors［J］.Journal of Alloys and Compo- unds，2020，817：152804.
3	HUANG Yongan， LU Biao， ZOU Yixuan，et al.Grain size effect on dielectric，piezoelectric and ferroelectric property of BaTiO₃ ceramics with fine grains［J］.Journal of Inorganic Materials，2018，33（7）：767-772.
4	邹清栎，邹建新.钛酸钡基电子陶瓷材料的改性进展［J］.无机盐工业，2022，54（6）：46-54.
	ZOU Qingli， ZOU Jianxin.Modification progress on barium titanate-based electronic ceramic materials［J］.Inorganic Chemicals Industry，2022，54（6）：46-54.
5	韩淑芬，陈伟伟，于洁.钛酸钡纳米复合材料制备与性能研究［J］.无机盐工业，2016，48（12）：19-22.
	HAN Shufen， CHEN Weiwei， YU Jie.Study on synthesis and properties of barium titanate nano-composites［J］.Inorganic Chemicals Industry，2016，48（12）：19-22.
6	TSAI H Y， CHANG S J， YANG Tingyi，et al.Distinct dispersion stability of various TiO₂ nanopowders using ammonium polyacrylate as dispersant［J］.Ceramics International，2018，44（5）：5131-5138.
7	SONG E， KIM D H， JEONG E J，et al.Effects of particle size and polymorph type of TiO₂ on the properties of BaTiO₃ nanopowder prepared by solid-state reaction［J］.Environmental Research，2021， 202：111668.
8	MOGHTADA A， HEIDARY MOGHADAM A， ASHIRI R.Tetragonality enhancement in BaTiO₃ by mechanical activation of the starting BaCO₃ and TiO₂ powders：Characterization of the contribution of the mechanical activation and postmilling calcination phenomena［J］.International Journal of Applied Ceramic Technology，2018，15（6）：1518-1531.
9	ZHANG Lei， WEN Jiaxin， ZHANG Zixi，et al.Enhanced dielectric properties of BaTiO₃ based on ultrafine powders by two-step calcination［J］.Physica B：Condensed Matter，2019，560：155-161.
10	BEAUGER A， MUTIN J C， NIEPCE J C.Synthesis reaction of metatitanate BaTiO₃：Part 1，Effect of the gaseous atmosphere
	upon the thermal evolution of the system BaCO₃-TiO₂ ［J］.Journal of Materials Science，1983，18（10）：3041-3046.
11	BEAUGER A， MUTIN J C， NIEPCE J C.Synthesis reaction of metatitanate BaTiO₃：Part 2，Study of solid-solid reaction interfaces［J］.Journal of Materials Science，1983，18（12）：3543-3550.
12	ANDO C， TSUZUKU K， KOBAYASHI T，et al.Function of glycine during solid-state reaction toward well-crystallized fine particulate barium titanate［J］.Journal of Materials Science：Materials in Electronics，2009，20（9）：844-850.
13	OGUCHI H， ANDO C， CHAZONO H，et al.Effects of glycine on the solid-state synthesis of barium titanate micro-particles with high tetragonality［J］.Journal De Physique Ⅳ（Proceedings），2005，128：33-39.
14	钱浩宇，朱归胜，徐华蕊，等.甘氨酸辅助微波固相合成四方相钛酸钡［J］.电子元件与材料，2019，38（12）：48-53.
	QIAN Haoyu， ZHU Guisheng， XU Huarui，et al.Glycine-assisted microwave solid phase synthesis of tetragonal barium titanate［J］.Electronic Components and Materials，2019，38（12）：48-53.
15	ZHU Chaoqiong， ZHAO Qiancheng， CAI Ziming，et al.High reliable non-reducible ultra-fine BaTiO₃-based ceramics fabricated via solid-state method［J］.Journal of Alloys and Compounds，2020，829：154496.
16	SHERLIN VINITA V， GOWRI SHANKAR RAO R， SAMUEL J，et al.Structural，Raman and optical investigations of barium titanate nanoparticles［J］.Phosphorus，Sulfur，and Silicon and the Related Elements，2022，197（3）：169-175.

样品编号	质量损失率/%
样品编号	约200 ℃	400~600 ℃	700~960 ℃
GL-0	—	—	14.9
GL-2.5	0.1	—	14.9
GL-5	0.4	0.6	14.7
GL-7.5	2.0	2.2	14.4
GL-10	2.6	3.3	13.1
GL-15	4.5	5.6	12.6
GL-20	5.2	5.4	12.9
GL-25	6.0	5.3	13.0

样品编号	950 ℃		1 000 ℃		1 050 ℃		1 100 ℃
样品编号	c/a	k	c/a	k	c/a	k	c/a	k
GL-0	1.005 4	1.35	1.008 3	1.83	1.009 9	7.81	1.009 9	7.76
GL-2.5	1.006 9	1.17	1.008 1	1.74	1.009 8	5.36	1.009 5	6.07
GL-5	1.006 9	1.44	1.009 1	3.19	1.009 9	11.27	1.010 2	9.26
GL-7.5	1.008 3	1.36	1.008 9	3.23	1.010 1	13.73	1.010 3	11.76
GL-10	1.006 8	1.56	1.009 7	5.93	1.009 9	7.92	1.010 6	11.76
GL-15	1.008 4	1.68	1.010 3	9.00	1.010 3	9.00	1.010 5	13.85
GL-20	1.008 2	1.69	1.009 6	6.06	1.010 1	9.59	1.010 0	11.58
GL-25	1.008 8	1.82	1.009 7	4.97	1.009 9	8.09	1.010 3	12.68

样品编号	粒径/nm
样品编号	1 000 ℃	1 050 ℃	1 100 ℃
GL-0	390	410	470
GL-2.5	410	470	630
GL-5	440	520	730
GL-7.5	480	590	740
GL-10	500	610	750
GL-15	520	650	760
GL-20	540	710	830
GL-25	570	740	860

[1]	李亦易,孙峤昳,马琳鸽,卓锦德,宋卫国. 甘氨酸盐捕集二氧化碳后的矿化解吸与再生研究[J]. 无机盐工业, 2021, 53(2): 38-41.
[2]	欧阳林虹,王文倩,王文伟,吴洁茹,薛昊. 二氧化硅掺杂钛酸锶钡陶瓷的介电性能与电卡效应[J]. 无机盐工业, 2020, 52(3): 39-44.
[3]	韩淑芬, 陈伟伟, 于洁. 钛酸钡纳米复合材料制备与性能研究[J]. 无机盐工业, 2016, 48(12): 19-.

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会