镧掺杂PMN-PT陶瓷在准同型相界处的相组成调控

摘要/Abstract

摘要： 采用两步预烧工艺制备Pb_{0.962 5}La_0.025(Mg_1/3Nb_2/3)_1-zTi_zO₃(z=0.28、0.29、0.30、0.31)陶瓷,其准同型相界(MPB)的化学组成位于PbTiO₃含量为0.29 mol和0.30 mol附近。选取准同型相界两侧的化学组成,制备四方晶相Pb(Mg_1/3Nb_2/3)_0.66Ti_0.34O₃和三方晶相Pb_1-1.5xLa_x(Mg_1/3Nb_2/3)_1-yTi_yO₃(x=0.083 3~0.041 7,y=0.206 7~0.273 3)陶瓷粉体。将两种晶相粉体按照设计比例(三方晶相摩尔分数w=0.3、0.4、0.5、0.6)混合,干压成型,烧结成化学组成相同、晶相占比不同的Pb_{0.962 5}La_0.025(Mg_1/3Nb_2/3)_0.70Ti_0.30O₃陶瓷。研究了晶相组成对陶瓷压电性能、介电性能、铁电性能的影响。结果表明,高温烧结后,陶瓷中的三方晶相和四方晶相占比与配料比基本一致。当w=0.5时,1 250 ℃烧结陶瓷中三方晶相与四方晶相含量占比分别为0.47、0.53,晶粒平均尺寸为(5.24±0.23) μm,相对密度为96.76%。陶瓷的压电应变常数d₃₃、径向机电转换系数k_p、厚度机电转换系数k_t、相对介电常数ε_r、剩余极化强度P_r和场致应变系数S(1 Hz、3.5 kV/mm)分别为1 014 pC/N、0.67、0.64、10 955、24 μC/cm²和0.21%。该方法可人为调控化学组成位于准同型相界的陶瓷的晶相占比。

关键词: PLMN-PT陶瓷, 压电陶瓷, 镧掺杂, 准同型相界, 压电性能, 介电性能, 铁电性能

Abstract: The Pb_{0.962 5}La_0.025(Mg_1/3Nb_2/3)_1-zTi_zO₃ (z=0.28, 0.29, 0.30, 0.31) piezoelectric ceramics were synthesized by two-step pre-sintering process. The morphotropic phase boundary (MPB) of ceramics was found at 0.29 mol and 0.30 mol of PbTiO₃.Selecting the chemical composition on both sides of morphotropic phase boundary, and the tetragonal phase Pb(Mg_1/3Nb_2/3)_0.66Ti_0.34O₃ powder and rhombohedral phase Pb_1-1.5xLa_x(Mg_1/3Nb_2/3)_1-yTi_yO₃ (x=0.083 3~0.041 7, y=0.206 7~0.273 3) powder rhombohedral phase were prepared, respectively. Two crystal phase powders (rhombohedral phase mole fraction w=0.3, 0.4, 0.5, 0.6) were mixed and pressed into disks. The ceramics with the same chemical compositionand different crystal phase proportion of Pb_{0.962 5}La_0.025(Mg_1/3Nb_2/3)_0.70Ti_0.30O₃ were sintered. The effect of crystal phase ratio on the piezoelectric, dielectric, and ferroelectric properties of ceramics were investigated. The results show that the rhombohedral and tetragonal phase ratios of ceramics are pasically the same as the proportion of ingredients. For the sample with w=0.5, the rhombohedral and tetragonal phase ratios of ceramics sintered at 1 250 ℃ is about 0.47, 0.53, respectly. The average grain size is (5.24±0.23) μm. The relative density of ceramics is 96.76%. The piezoelectric constant d₃₃, planner electromechanical coefficient k_p, thickness electromechanical coefficient k_t, relative permittivity ε_r, remnant polarization P_r, and field-induced strain S (1 Hz, 3.5 kV/mm) of ceramics are 1 014 pC/N, 0.67, 0.64, 10 955, 24 μC/cm², and 0.21%, respectively. For the chemical composition near MPB, the rhombohedral and tetragonal phase ratios of ceramics could be tuned artificially via this method.

Key words: PLMN-PT ceramics, piezoelectric ceramics, lanthanum doping, morphotropic phase boundary, piezoelectric property, dielectric property, ferroelectric property

中图分类号:

TQ174

包国翠, 李坤, 杨光, 崔佳宁, 施东良, 林国豪, 方必军. 镧掺杂PMN-PT陶瓷在准同型相界处的相组成调控[J]. 硅酸盐通报, 2022, 41(10): 3647-3657.

BAO Guocui, LI Kun, YANG Guang, CUI Jianing, SHI Dongliang, LAM Kwokho, FANG Bijun. Phase Composition Tuning of Lanthanum-Doped PMN-PT Ceramics at Morphotropic Phase Boundary[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2022, 41(10): 3647-3657.

参考文献

[1] SMOLENSKY G. Ferroelectrics with diffuse phase transition[J]. Ferroelectrics, 1984, 53(1): 129-135.
[2] SWARTZ S L, SHROUT T R, SCHULZE W A, et al. Dielectric properties of lead-magnesium niobate ceramics[J]. Journal of the American Ceramic Society, 1984, 67(5): 311-314.
[3] CROSS L E, JANG S J, NEWNHAM R E, et al. Large electrostrictive effects in relaxor ferroelectrics[J]. Ferroelectrics, 1980, 23(1): 187-191.
[4] FU H X, COHEN R E. Polarization rotation mechanism for ultrahigh electromechanical response in single-crystal piezoelectrics[J]. Nature, 2000, 403(6767): 281-283.
[5] CROSS L E. Relaxorferroelectrics: an overview[J]. Ferroelectrics, 1994, 151(1): 305-320.
[6] NOMURA S, UCHINO K. Electrostrictive effect in Pb(Mg_1/3Nb_2/3)O₃-type materials[J]. Ferroelectrics, 1982, 41(1): 117-132.
[7] NOMURA S, UCHINO K. Recent applications of PMN-based electrostrictors[J]. Ferroelectrics, 1983, 50(1): 197-202.
[8] 殷德政,张学勤,张可强,等.基于增材制造的陶瓷材料点阵结构研究现状与挑战[J].硅酸盐学报,2021,49(9):1786-1809.
YIN D Z, ZHANG X Q, ZHANG K Q, et al. Development on ceramic lattice structures via additive manufacturing[J]. Journal of the Chinese Ceramic Society, 2021, 49(9): 1786-1809 (in Chinese).
[9] CHEN Y, UCHINO K, VIEHLAND D. Substituent effects in 0.65Pb(Mg_1/3Nb_2/3)O₃0.35PbTiO₃ piezoelectric ceramics[J]. Journal of Electroceramics, 2001, 6: 13-19.
[10] LEJEUNE M, BOILOT J P. Ceramics of perovskite lead magnesium niobate[J]. Ferroelectrics, 1984, 54(1): 191-194.
[11] SAHA D, SEN A, MAITI H S. Solid-state synthesis of precursor MgNb₂O₆ for the preparation of Pb(Mg_1/9Nb_2/9)O₉[J]. Journal of Materials Science Letters, 1994, 13(10): 723-724.
[12] GUHA J P, HONG D J, ANDERSON H U. Effect of excess PbO on the sintering characteristics and dielectric properties of Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃-based ceramics[J]. Journal of the American Ceramic Society, 1988, 71(3): 152.
[13] LIOU Y C. Stoichiometric perovskite PMN-PT ceramics produced by reaction-sintering process[J]. Materials Science and Engineering: B, 2003, 103(3): 281-284.
[14] JAYASINGH E M, PRABHAKARAN K, SOORAJ R, et al. Synthesis of pyrochlore free PMN-PT powder by partial oxalate process route[J]. Ceramics International, 2009, 35(2): 591-596.
[15] KONG L B, MA J, ZHU W, et al. Preparation of PMN-PT ceramics via a high-energy ball milling process[J]. Journal of Alloys and Compounds, 2002, 336(1/2): 242-246.
[16] CHU R Q, LI Y, GONG S W, et al. Pyrochlore free 0.67PMN-0.33PT ceramics prepared by particle-coating method[J]. Materials Science and Engineering: B, 2012, 177(14): 1170-1177.
[17] GHASEMIFARD M, HOSSEINI S M, KHORRAMI G H. Synthesis and structure of PMN-PT ceramic nanopowder free from pyrochlore phase[J]. Ceramics International, 2009, 35(7): 2899-2905.
[18] MOETAKEF P, NEMATI Z A. Synthesis of PMN pyrochlore free ceramics via a modified mixed oxide method[J]. Journal of Electroceramics, 2007, 19(2): 207-213.
[19] RAVINDRANATHAN P, KOMARNENI S, BHALLA A S, et al. Synthesis and dielectric properties of solution sol-gel-derived 0.9Pb(Mg_1/3Nb_2/3)O₃-0.1PbTiO₃ ceramics[J]. Journal of the American Ceramic Society, 1991, 74(12): 2996-2999.
[20] 谈鸿恩,庄志强.锰掺杂对PMN-PT陶瓷介电和压电特性的影响[J].材料导报,2007,21(s3):345-347.
TAN H E, ZHUANG Z Q. Effect of Mn dopant on dielectric and piezoelectric properties of PMN-PT ceramics[J]. Materials Review, 2007, 21(s3): 345-347 (in Chinese).
[21] 李涛,刘敬松,李惠琴,等.Sm₂O₃掺杂对铌镁酸铅铁电陶瓷介电性能的影响[J].电子元件与材料,2011,30(5):1-4.
LI T, LIU J S, LI H Q, et al. Influences of Sm₂O₃-doping on the dielectric properties of lead magnesium niobate ferroelectric ceramics[J]. Electronic Components and Materials, 2011, 30(5): 1-4 (in Chinese).
[22] LI H Q, LIU J S, YU H T, et al. Relaxor behavior and Raman spectra of CuO-doped Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ ferroelectric ceramics[J]. Journal of Advanced Ceramics, 2014, 3(3): 177-183.
[23] CAO L H, YAO X, XU Z, et al. Research on dielectric and piezoelectric properties of Ta-doped 0.68Pb(Mg_1/3Nb_2/3)O₃-0.32PbTiO₃ ceramics[J]. Ceramics International, 2004, 30(7): 1373-1376.
[24] 尹慧娟,徐志军,初瑞清,等.La掺杂对0.75PMN-0.25PT压电陶瓷结构及其性能的影响[J].硅酸盐通报,2013,32(6):1067-1071.
YIN H J, XU Z J, CHU R Q, et al. Effects of La-doping on the structure and electrical properties of 0.75PMN-0.25PT piezoelectric ceramics[J]. Bulletin of the Chinese Ceramic Society, 2013, 32(6): 1067-1071 (in Chinese).
[25] ZHOU Z L, WEN B S, MA J H. Effects of lanthanum doping on dielectric and electrostrictive properties of lead magnesium niobate-lead titanate ceramics[J]. Ferroelectrics, 1997, 196(1): 81-84.
[26] YOU R Y, ZHANG D M, FU L, et al. Dielectric relaxation and electromechanical degradation of Gd-doped PMN-29PT ferroelectric ceramics with ultrahigh piezoelectricity[J]. Journal of Vibration Engineering & Technologies, 2022, 10(2): 639-647.
[27] LI F, LIN D B, CHEN Z B, et al. Ultrahigh piezoelectricity in ferroelectric ceramics by design[J]. Nature Materials, 2018, 17(4): 349-354.
[28] QIAN K, FANG B J, DU Q B, et al. Phase development and electrical properties of Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ ceramics prepared by partial oxalate route[J]. Physica Status Solidi (a), 2013, 210(6): 1149-1156.
[29] HILCZER B. Influence of lattice defects on the properties of ferroelectrics[J]. Key Engineering Materials, 1995, 101/102: 95-128.
[30] WEI X Y, FENG Y J, YAO X. Dielectric relaxation behavior in barium stannate titanate ferroelectric ceramics with diffused phase transition[J]. Applied Physics Letters, 2003, 83(10): 2031-2033.
[31] SHVARTSMAN V V, KLEEMANN W, DEC J, et al. Diffuse phase transition in BaTi_1-xSn_xO₃ ceramics: an intermediate state between ferroelectric and relaxor behavior[J]. Journal of Applied Physics, 2006, 99(12): 124111.
[32] 董昌,梁瑞虹,周志勇,等.Sm掺杂增强PZT基弛豫型铁电陶瓷压电性能研究[J].无机材料学报,2021,36(12):1270-1276.
DONG C, LIANG R H, ZHOU Z Y, et al. Piezoelectric property of PZT-based relaxor-ferroelectric ceramics enhanced by Sm doping[J]. Journal of Inorganic Materials, 2021, 36(12): 1270-1276 (in Chinese).
[33] UDOMKAN N, LIMSUWAN P, TUNKASIRI T. Effect of rare-earth (Re=La, Nd, Ce and Gd) doping on the piezoelectric of PZT(52:48) ceramics[J]. International Journal of Modern Physics B, 2007, 21(26): 4549-4559.
[34] ZHANG S J, LI F, JIANG X N, et al. Advantages and challenges of relaxor-PbTiO₃ ferroelectric crystals for electroacoustic transducers: a review[J]. Progress in Materials Science, 2015, 68: 1-66.
[35] WANG H F, JIANG B, SHROUT T R, et al. Electromechanical properties of fine-grain, 0.7Pb(Mg(_1/3)Nb(_2/3))O₃-0.3PbTiO₃ ceramics[J]. IEEE Transactions on Ultrasonics, Ferroelectrics, and Frequency Control, 2004, 51(7): 908-912.
[36] CAO W W, RANDALL C A. Grain size and domain size relations in bulk ceramic ferroelectric materials[J]. Journal of Physics and Chemistry of Solids, 1996, 57(10): 1499-1505.
[37] LEE H J, ZHANG S J, LUO J, et al. Thickness dependent properties of relaxor-PbTiO₃ ferroelectrics for ultrasonic transducers[J]. Advanced Functional Materials, 2010, 20(18): 3154-3162.
[38] ZUO R Z, LIU Y, SU S, et al. Phase transformation behavior and electrical properties of Pb(Zr_0.56Ti_0.44)O₃-Bi(Zn_0.5Ti_0.5)O₃ solid solution ceramics[J]. Journal of the American Ceramic Society, 2011, 94(12): 4340-4344.
[39] HAUN M J, FURMAN E, JANG S J, et al. Thermodynamic theory of the lead zirconate-titanate solid solution system, part I: phenomenology[J]. Ferroelectrics, 1989, 99(1): 13-25.
[40] WANG D W, CAO M S, ZHANG S J. Investigation of ternary system Pb(Sn, Ti)O₃-Pb(Mg_1/3Nb_2/3)O₃ with morphotropic phase boundary compositions[J]. Journal of the European Ceramic Society, 2012, 32(2): 441-448.
[41] LI Y, YUAN J, WANG D W, et al. Effects of Nb, Mn doping on the structure, piezoelectric, and dielectric properties of 0.8Pb(Sn_0.46Ti_0.54)O₃-0.2Pb(Mg_1/3Nb_2/3)O₃ piezoelectric ceramics[J]. Journal of the American Ceramic Society, 2013, 96(11): 3440-3447.