硅酸盐学报

La₂O₃掺杂对光固化增材制造锆钛酸铅压电陶瓷成形与电学性能的影响

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贺俊超 ² , 段文俊 ² , 李轩 ² , 周士翔 ³ , 龚小龙 ² , 陈鹏 ² , 陈安南 ⁵ , 吴甲民 ⁴ , 闫春泽 ⁴ , 孙华君 ¹ , 刘凯 ¹^,² , 史玉升 ⁴

硅酸盐学报 | 研究论文 2026,54(9): 2974-2988

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硅酸盐学报 |研究论文 2026 , 54 (9) : 2974 -2988

La₂O₃掺杂对光固化增材制造锆钛酸铅压电陶瓷成形与电学性能的影响

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贺俊超², 段文俊², 李轩², 周士翔³, 龚小龙², 陈鹏², 陈安南⁵, 吴甲民⁴, 闫春泽⁴, 孙华君¹, 刘凯¹^,², 史玉升⁴

作者信息

^1．武汉理工大学，硅酸盐科学与先进建材全国重点实验室，中国武汉 430070

^2．武汉理工大学材料科学与工程学院，中国武汉 430070

^3．武汉理工大学交通与物流工程学院，中国武汉 430070

^4．华中科技大学材料科学与工程学院，材料成形与模具技术全国重点实验室，中国武汉 430074

^5．香港城市大学机械工程系，中国香港 999007

通讯作者:

刘凯（1987—），男，博士，教授。

作者简介:

贺俊超（1996—），男，博士研究生。

Effect of La₂O₃ Doping on Forming and Electrical Properties of PZT Piezoelectric Ceramics Fabricated via Photopolymerization Additive Manufacturing

Junchao HE², Wenjun DUAN², Xuan LI², Shixiang ZHOU³, Xiaolong GONG², Peng CHEN², Annan CHEN⁵, Jiamin WU⁴, Chunze YAN⁴, Huajun SUN¹, Kai LIU¹^,², Yusheng SHI⁴

Affiliations

^1.State Key Laboratory of Silicate Science and Advanced Building Materials, Wuhan University of Technology, Wuhan 430070, China

^2.School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, China

^3.School of Transportation and Logistics Engineering, Wuhan University of Technology, Wuhan 430070, China

^4.School of Materials Science and Engineering, Huazhong University of Science and Technology; State Key Laboratory of Materials Processing and Die & Mould Technology, Wuhan 430074, China

^5.Department of Mechanical Engineering, City University of Hong Kong, Hong Kong 999007, China

Corresponding Author:

{LIU} Kai (1987-), male, Ph.D., Professor. E-mail: liukai19870222@163.com

HE Junchao (1996-), male, Doctoral candidate. E-mail: 335016@whut.edu.cn

出版时间: 2026-08-18 doi: 10.14062/j.issn.0454-5648.20260119

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摘要

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针对光固化增材制造PZT压电陶瓷在成形困难与电学性能不足方面的挑战，本工作提出前驱体光固化-固相反应协同优化策略。以ZrO₂-TiO₂-PbCO₃-La₂O₃为前驱体配制浆料，通过光固化成形后在1270 ℃进行固相反应烧结，实现成形质量与电学性能的同步提升。结果表明，在相同曝光条件下，前驱体浆料的单层固化厚度约为80 μm，较预烧PZT粉体浆料（约25 μm）提高约2.2倍。引入La₂O₃后，光斑半宽w₀降低约20%，横向过曝得到有效抑制。3%（摩尔分数）La₂O₃掺杂样品的剩余极化强度P_r与压电系数d₃₃分别达到32.78 μC·cm^-2和350.6 pC·N^-1，相较未掺杂样品分别提升约6.6倍与70%，并表现出扩散度γ≈1.85的介电弛豫特征。La₂O₃在固化阶段通过增强局域光吸收抑制线宽扩展，在烧结阶段通过晶粒与畴结构调控提升铁电与压电响应。基于该策略，本工作制备了最小杆径约450 μm的桁架结构PZT压电陶瓷，为光固化增材制造高性能复杂结构PZT器件的应用奠定了理论基础。

关键词

光固化增材制造 / 锆钛酸铅压电陶瓷 / 成形精度 / 电学性能

Abstract

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Introduction

Lead zirconate titanate (PZT) piezoceramics are widely used in sensors, actuators, and energy harvesters because of their intense electromechanical coupling. As device designs shift toward porous structures, curved parts, and lattice architectures, conventional ceramic processing becomes less practical due to the brittleness, tooling limits, and mold cost. Vat photopolymerization (VPP) additive manufacturing can produce high-resolution parts with a good surface quality, yet PZT printing is often limited by poor curing. Pre-sintered PZT powders can absorb and scatter UV light, which reduces curing depth, weakens interlayer bonding, and causes lateral overcuring that blurs feature edges.

To mitigate these issues, this study was to introduce an integrated "inorganic-precursor photopolymerization + solid-state reaction" route. ZrO₂-TiO₂-PbCO₃-based precursors could replace presintered PZT to improve optical penetration and curing stability during VPP. Meanwhile, La₂O₃ served as a multifunctional dopant to favor sharpen printed features via limiting lateral curing spread, promoted densification, refined grains, and tuned tetragonal-rhombohedral coexistence toward an MPB-adjacent state during sintering. This study could provide a practical way to improve both printability and ferroelectric/piezoelectric performance.

Methods

Pb_1-_xLa_xZr_0.53Ti_0.47O₃(i.e., x=0、0.01、0.02、0.03、0.04、0.05) precursor powders were prepared via stoichiometric mixing of ZrO₂, TiO₂, PbCO₃ and La₂O₃ and subsequent grinding to ensure the homogeneity. The photocurable slurries with 82% solids were formulated by a TMPTA/PEG400/modified epoxy/HDDA resin system (in a mass ratio of 3∶3∶3∶1), TPO photoinitiator (3% relative to resin), and dispersant (2% relative to powders). The VPP printing was conducted at 12 mW·mm^-2 with an exposure for 3.5 s per layer. The printed parts were subjected to a staged debinding-calcination-sintering, including debinding in N₂ to 350 ℃ for 2 h and 600 ℃ for 2 h under slow heating to mitigate cracking, followed by air burnout/calcination with holds at 600 ℃ and 850 ℃ and final sintering at 1270 ℃ for 2 h. Silver electrodes were screen-printed, and the samples were poled in an oil bath under 3 kV·mm^-1 at 140 ℃ for 15 min. The curing depth and lateral linewidth were quantified via the Beer-Lambert and Gaussian beam fitting. The density/porosity, scanning electron microscopy (SEM) images, X-ray diffraction (XRD) patterns (rietveld refinement), P-E loops, dielectric spectroscopy, d₃₃, and the relaxor diffuseness parameter γ were employed to establish the process-structure-property relationships.

Results and discussion

Once presintered PZT powders are replaced by inorganic precursors, the most immediate change appears in curing robustness. Under identical exposure conditions, the single-layer curing thickness increases from 25 μm to 80-85 μm, while the optical penetration depth D_p increases from 9.94 μm to 28-30 μm. With much weaker attenuation in the curing band, the chronic issues of insufficient through-thickness curing and limited interlayer bonding are substantially relieved. A stronger curing does not occur at the cost of poorer fidelity. Lateral broadening becomes easier to restrain. The effective beam half-width w_o decreases from 44 μm in a conventional slurry to 15.0 μm in the precursor system, and further decreases to 13.7 μm after La₂O₃ addition, making the linewidth less sensitive to exposure energy and reducing overcuring-driven edge blurring.

La₂O₃ affects printing and sintering, but its sintering benefit appears only within a limited range. The densification improves as La₂O₃ increases, and then declines as the dopant is excessive. The relative density increases from 94.1 to 99.8% and decreases to 97.6% when La₂O₃ exceeds 3%. In parallel, La₂O₃ strongly refines the microstructure, keeping grains with the sizes of 1.27-2.30 μm, while undoped PZT reaches 8-10 μm under the same conditions, indicating a suppressed abnormal grain growth. The Rietveld refinement shows a single perovskite phase for all the compositions, with MPB-type tetragonal-rhombohedral coexistence. The rhombohedral fraction increases to t 22.4% as x = 0.03 (tetragonal of 77.6%) and then decreases at a higher x, indicating an optimal coexistence as x = 0.03.

The electrical properties follow the same peak behavior. The undoped ceramics show low P_r (i.e., 4.07-4.31 μC·cm^-2) and E_c of 0.78 kV·mm^-1, whereas La doping boosts P_r to 32.87 μC·cm^-2 and E_c to 1.18 kV·mm^-1 as x = 0.03. The dielectric response remains stable from 10² to 10⁵ Hz, with ε_r≈(3.0-3.3) × 10³ and tanδ≈0.03-0.05. The piezoelectric coefficient d₃₃ increases from 205 to 350.6 pC·N^-1 as x = 0.03, then decreaes at a higher x. The relaxor behavior strengthens as well, with γ rising from 1.33 to 1.85 as x = 0.03 (1.86 as x = 0.05). The PFM and TEM images indicate that a moderate La₂O₃ enhances domain switching, while an excess La₂O₃ increases disorder and random-field effects, weakening ferroelectric order and reducing P_r, ε_r, and d₃₃ beyond the optimum.

Conclusions

This work combined precursor-assisted VPP printing with solid-state reaction sintering to improve curing stability, dimensional accuracy, and electromechanical performance in PLZT. The precursor increased curing depth, La₂O₃ limited lateral curing, and the dopant refined grains and supported MPB-adjacent phase coexistence during sintering. The overall performance became optimum as x = 0.03, where P_r, d₃₃, and ε_r increased, while dielectric loss was low, although the more relaxor-like behavior indicated a trade-off between higher response and greater disorder.

Key words

vat photopolymerization additive manufacturing / lead zirconate titanate piezoelectric ceramics / dimensional accuracy / electrical properties

引用本文

贺俊超, 段文俊, 李轩, 周士翔, 龚小龙, 陈鹏, 陈安南, 吴甲民, 闫春泽, 孙华君, 刘凯, 史玉升. La₂O₃掺杂对光固化增材制造锆钛酸铅压电陶瓷成形与电学性能的影响. 硅酸盐学报, 2026 , 54 (9) : 2974 -2988 . DOI: 10.14062/j.issn.0454-5648.20260119

Junchao HE, Wenjun DUAN, Xuan LI, Shixiang ZHOU, Xiaolong GONG, Peng CHEN, Annan CHEN, Jiamin WU, Chunze YAN, Huajun SUN, Kai LIU, Yusheng SHI. Effect of La₂O₃ Doping on Forming and Electrical Properties of PZT Piezoelectric Ceramics Fabricated via Photopolymerization Additive Manufacturing[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (9) : 2974 -2988 . DOI: 10.14062/j.issn.0454-5648.20260119

基金

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国家重点研发计划青年科学家项目(2021YFB3703100)
国家自然科学基金(52202066)
2023年湖北省重大攻关项目（JD）(2023BAA023)

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2026年第54卷第9期

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文章信息

doi: 10.14062/j.issn.0454-5648.20260119

接收时间：2026-02-28
首发时间：2026-10-22
出版时间：2026-08-18

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收稿日期：2026-02-28
修回日期：2026-03-31

基金

国家重点研发计划青年科学家项目(2021YFB3703100)

国家自然科学基金(52202066)

2023年湖北省重大攻关项目（JD）(2023BAA023)

作者信息

^1．武汉理工大学，硅酸盐科学与先进建材全国重点实验室，中国武汉 430070

^2．武汉理工大学材料科学与工程学院，中国武汉 430070

^3．武汉理工大学交通与物流工程学院，中国武汉 430070

^4．华中科技大学材料科学与工程学院，材料成形与模具技术全国重点实验室，中国武汉 430074

^5．香港城市大学机械工程系，中国香港 999007

通讯作者:

刘凯（1987—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20260119

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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