织构PNN-PZT陶瓷的光固化成型制备及其电学性能研究

doi:10.11949/0438-1157.20220245

摘要/Abstract

摘要：

为高效制备织构压电陶瓷，以球状Pb(Ni_1/3Nb_2/3)O₃-PbZrO₃-PbTiO₃ (PNN-PZT) 为基体粉体，片状BaTiO₃ （BT）为模板粉体，采用光固化成型技术代替传统流延技术制备织构压电陶瓷。研究了粉体形貌对打印浆料流动性的影响、浆料的光敏参数以及不同BT含量织构陶瓷的晶体结构和电学性能。结果表明，球状粉体浆料具有低黏度的特性，能够有效提高打印浆料的固含量，最大固含量可达86%（质量）。此时陶瓷浆料的临界曝光量与透射深度分别为127.5 mJ/cm²和21.1 μm。打印后的PNN-PZT-BT陶瓷沿[00l]_c方向生长，BT模板粉体含量从1%增长到5%，陶瓷的织构度由42%增到92%。当BT含量为3%时，样品具有最高的压电常数d₃₃=1047 pC/N。与传统的流延法相比，SLA技术的工艺优势在于制备周期短，稳定性高，能够有效降低织构陶瓷的制备难度。

关键词: 织构陶瓷, 光固化, 高固含浆料, 压电陶瓷

Abstract:

Textured Pb(Ni_1/3Nb_2/3)O₃-PbZrO₃-PbTiO₃ (PNN-PZT) ceramics which were using spherical PNN-PZT powders as matrix and plate-like BaTiO₃ (BT) powders as template were prepared by stereo lithography apparatus (SLA) method. The impact of powder morphology on the fluidity of printing paste, as well as the crystal structure, electrical properties of textured ceramics with different BaTiO₃ contents were investigated. The results show that the spherical powder slurry is characterized by low viscosity, which can effectively increase the solid content of the printing slurry and the maximum solid content is 86%(mass). At this time, the critical energy density and curing depth of the ceramic slurry are 127.5 mJ/cm² and 21.1 μm respectively. Using BT as template can effectively promote the growth of PNN-PZT-BT ceramics along the [00l]_c direction, with the BT content increasing from 1% to 5%, the texture degree of ceramic texture increasing from 42% to 92%. The sample has the highest piezoelectric constant d₃₃=1047 pC/N when the BT content is 3%. Compared with the traditional casting method, the process advantages of SLA technology are that the preparation cycle is short and the stability is high, which can effectively reduce the difficulty of preparing textured ceramics.

Key words: textured ceramics, stereolithography, high solid content slurry, piezoelectric ceramics

中图分类号:

TM 282

陆遥, 董杰, 孙大为, 谢乐天, 卢家勇, 杜晓宁. 织构PNN-PZT陶瓷的光固化成型制备及其电学性能研究[J]. 化工学报, 2022, 73(8): 3768-3775.

Yao LU, Jie DONG, Dawei SUN, Letian XIE, Jiayong LU, Xiaoning DU. Fabrication and electrical properties of textured PNN-PZT ceramics by stereolithography technology[J]. CIESC Journal, 2022, 73(8): 3768-3775.

图/表 6

图1 片状模板粉体与球状基体粉体SEM照片

Fig.1 SEM images of plate-like template particles and spherical matrix particles

图2 浆料的流变特性曲线(a)不同粉体含量浆料的流变曲线; (b)剪切速率60 s-1下浆料的相对黏度随固含量的变化关系

Fig.2 Rheological features of slurry(a) the rheological curves of slurry with different powder content; (b) relation between relative viscosity and solid content of slurry at shear rate 60 s-1

图3 光引发剂含量对浆料的光敏特性的影响(a) 不同光引发剂含量下浆料单层固化厚度随曝光时间的变化曲线; (b) 曝光能量与固化厚度的变化关系

Fig.3 Effect of photoinitiator concentration on photosensitive properties of the paste(a) variation curves of curing depth with exposure time under different photoinitiator content; (b) variation curves of exposure energy and curing depth

图4 不同BT模板含量PNN-PZT-xBT织构陶瓷的XRD衍射谱图及织构度变化曲线

Fig.4 XRD patterns of PNN-PZT-xBT textured ceramics with different BT template contents (insert: variation curve of lotgering factor )

图5 不同BT模板含量PNN-PZT-xBT陶瓷的电学性能(a) 介电温度谱图; (b) 电滞回线; (c) 矫顽场强Ec, 剩余极化强度Pr, 饱和极化强度Psat的变化曲线

Fig.5 Electrical properties of PNN-PZT-xBT textured ceramics with different BT template content(a) dielectric temperature spectra; (b) P-E hysteresis loops; (c) variations of the coercive field Ec, remanent polarization Pr and saturation polarization Psat

表1 室温下PNN-PZT-xBT陶瓷与其他铅基织构陶瓷的电学性能

Table 1 Electrical properties of PNN-PZT-xBT ceramics and other Pb-based textured ceramics at room temperature

Material	F₍₀₀₁₎ /%	T/℃	d₃₃/(pC/N)	T_C/℃	ε_r	tanδ
this work
PNN-PZT-0BT	0	1200	740	117	7125	0.035
PNN-PZT-1BT	42	1200	996	122	5035	0.032
PNN-PZT-3BT	73	1200	1047	123	4527	0.030
PNN-PZT-5BT	92	1200	752	125	6218	0.029
other Pb-based textured ceramics
PNN-PZT^[34]	82	1250	1210	103	7200	0.031
PMN-PZT^[35]	90	1150	1100	204	2310	—
PMN-PT^[36]	98	1150	1000	160	2591	0.006
PIN-PMN-PT^[37]	97	1200	927	200	2425	0.013
PIN-PMN-PT^[38]	95	1240	780	225	2850	—

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