Investigations on phase coexistence and functional properties of BCZT lead-free piezoceramic


  • Jirapa Tangsritrakul Department of Materials and Textile Technology, Faculty of Science and Technology, Thammasat University, Pathum Thani, 12120, Thailand
  • Thiyanee Sonkami Department of Materials and Textile Technology, Faculty of Science and Technology, Thammasat University, Pathum Thani, 12120, Thailand
  • Chumpon Wichittanakom Department of Physics, Faculty of Science and Technology, Thammasat University, Pathum Thani, 12120, Thailand
  • Chotiros Dokkhan National Metal and Materials Technology Center, Thailand Science Park, Pathum Thani 12120, Thailand
  • Panithi Wiroonpochit National Metal and Materials Technology Center, Thailand Science Park, Pathum Thani 12120, Thailand



Lead-free piezoceramics, Phase coexistence, Rietveld refinement, Ferroelectric properties, Barium Titanate


Large piezoelectric properties was observed in (1-x)BZT-(x)BCT where x=0.5 or Ba0.85Ca0.15Ti0.9Zr0.1O3 (denoted as BCZT), leading to a promising candidate for lead-free piezoelectric materials. However, phase formation of the BCZT is controversial and still unclear since various phase coexistences were identified in the literatures, for instances, the mixed phases of rhombohedral-tetragonal (R-T), ortho-rhombic-tetragonal (O-T) or rhombohedral-orthorhombic-tetragonal (R-O-T). Additionally, it is well known that the crystal structure plays a crucial role on the occurrence of polarization in the piezoceramics. Therefore, this work aims to investigate the coexistence of phase formation at room temperature for the BCZT powder and ceramic. Moreover, the electrical properties as a function of temperature, frequency and electric field were observed in order to evaluate the extrinsic contribution of piezoelectric response. It was found that, according to the results from temperature-dependent dielectric properties as well as Rietveld refinement of XRD profiles, the coexistence of O-T phase was observed in the BCZT powder and ceramic. Furthermore, the enhancement of Ca2+ substitution into Ba2+ site in BCZT ceramic caused the shrinkage of unit cell, leading to the shift of XRD profile and Raman spectra. In addition, it was found that the applications of frequency and electric field can influence on changes of domain-wall motion and micro-polar cluster in the BCZT piezoceramic.


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G.H. Haertling, "Ferroelectric Ceramics: History and Technology," Journal American Ceramic Society, vol. 82, pp. 797-818, 1999.

J. Rödel, and J.-F. Li, "Lead-free piezoceramics: Status and perspectives," MRS Bulletin, vol. 43(8), pp. 576-580, 2018.

C-H. Hong, H-P Kim, B-Y. Choi, H-S. Han, J.S. Son, C.W. Ahn, and W. Jo, "Lead-free piezoceramics – Where to move on?," Journal of Materiomics, vol. 2(1), pp. 1-24, 2016.

J. Rödel, K.G. Webber, R. Dittmer, W. Jo, M. Kimura, and D. Damjanovic, "Transferring lead-free piezoelectric ceramics into application," Journal of the European Ceramic Society, vol. 35(6), pp. 1659-1681, 2015.

W. Liu, and X. Ren, "Large piezoelectric effect in Pb-free ceramics," Physical Review Letters, vol. 103(25), pp. 257602, 2009.

M. Acosta, N. Novak, V. Rojas, S. Patel, R. Vaish, J. Koruza, G.A. Rossetti Jr, and J. Rödel "BaTiO3-based piezoelectrics: Fundamentals, current status, and perspectives," Applied Physics Reviews, vol. 4(4), pp. 041305, 2017.

D.S. Keeble, F. Benabdallah, P.A. Thomas, M. Maglione, and J. Kreisel, "Revised structural phase diagram of (Ba0.7Ca0.3TiO3)-(BaZr0.2Ti0.8O3)," Applied Physics Letters, vol. 102(9), pp. 092903, 2013.

A. Bjørnetun Haugen, J.S. Forrester, D. Damjanovic, B. Li, K.J. Bowman, and J.L. Jones, "Structure and phase transitions in 0.5(Ba0.7Ca0.3TiO3)-0.5(BaZr0.2Ti0.8O3) from −100°C to 150°C," Journal of Applied Physics, vol. 113(1), pp. 014103, 2013.

D. Tuan, V. Thanh Tung, L. Tu, and T. Chuong, "Synthesis and Investigation of the Physical Properties of Lead-Free BCZT Ceramics," in Perovskite and Piezoelectric Materials, 2019.

X. Ji, C. Wang, S. Li, S. Zhang, R. Tu, Q. Shen, J. Shi, and L. Zhang, "Structural and electrical properties of BCZT ceramics synthesized by sol–gel process," Journal of Materials Science: Materials in Electronics, vol. 29(9), pp. 7592-7599, 2018.

P. Mishra, Sonia, and P. Kumar, "Effect of sintering temperature on dielectric, piezoelectric and ferroelectric properties of BZT–BCT 50/50 ceramics," Journal of Alloys and Compounds, vol. 545, pp. 210-215, 2012.

Z. Hanani, D. Mezzane, M’barek Amjoud, Y. Gagou, K. Hoummada, C. Perrin, A.G. Razumnaya, Z. Kutnjak, A. Bouzina, M. El Marssi, M. Gouné, and B. Rožič, "Structural, dielectric, and ferroelectric properties of lead-free BCZT ceramics elaborated by low-temperature hydrothermal processing," Journal of Materials Science: Materials in Electronics, vol. 31(13), pp. 10096-10104, 2020.

M.B. Abdessalem, S. Aydi, A. Aydi, N. Abdelmoula, Z. Sassi, and H. Khemakhem, "Polymorphic phase transition and morphotropic phase boundary in Ba1-xCaxTi1-yZr­yO3 ceramics," Applied Physics A, vol. 123(9), pp. 583, 2017.

W. Wang, W. L. Li, D. Xu, W.P. Cao, Y.F. Hou, and W.D. Fei, "Phase transitions in (1-x)BaZr0.2Ti0.8O3-xBa0.7Ca0.3TiO3 powders and ceramic pellets," Ceramics International, vol. 40(3), pp. 3933-3937, 2014.

X. Wang, B.H. Zhang, Y.Y. Li, Y.C. Shi, L.Y. Sun, G. Feng, C.L. Li, Y.F. Liang, Y.P. Zheng, S.Y. Shang, J. Shang, and Y. Hu, "Structure, dielectric, and ferroelectric properties of Ba0.85Ca0.15Zr0.1Ti0.9O3 ceramics sintered at various temperatures," Journal of Materials Science-Materials in Electronics, vol. 31(6), pp. 4732-4742, Mar 2020.

D.A. Ochoa Guerrero, G. Esteves, T. Iamsasri, F. Rubio-Marcos, J.F. Fernández Lozano, J.E. Garcia, and J.L. Jones,

"Extensive domain wall contribution to strain in a (K,Na) NbO3-based lead-free piezoceramics quantified from high energy X-ray diffraction," Journal of the European Ceramic Society, vol. 36(10), pp. 2489-2494, 2016.

B.H. Toby, and R.B. Von Dreele, "GSAS-II: the genesis of a modern open-source all purpose crystallography software package," Journal of Applied Crystallography, vol. 46(2), pp. 544-549, 2013.

P. Wang, Y. Li, and Y. Lu, "Enhanced piezoelectric properties of (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 lead-free ceramics by optimizing calcination and sintering temperature," Journal of the European Ceramic Society, vol. 31(11), pp. 2005-2012, 2011.

W. Ji, B. Fang, X. Lu, S. Zhang, N. Yuan, and J. Ding, "Tailoring structure and performance of BCZT ceramics prepared via hydrothermal method," Physica B: Condensed Matter, vol. 567, pp. 65-78, 2019.

G. Herrera-Pérez, I. Castillo-Sandoval, O. Solís-Canto, G. Tapia- Padilla, A. Reyes-Rojas, and L. E. Fuentes-Cobas, "Local piezo-response for lead-free Ba0.9Ca0.1Ti0.9Zr0.1O3 electro-ceramic by switching spectroscopy," Materials Research, vol. 21(2), 2018.

M. Gao, W. Ge, X. Li, H. Yuan, C. Liu, H. Zhao, Y. Ma, and Y. Chang, "Enhanced dielectric and energy storage properties in Fe‐Doped BCZT ferroelectric ceramics," physica status solidi (a), vol. 217(16), pp. 2000253, 2020.

W. Li, Z. Xu, R. Chu, P. Fu, and G. Zang, "Structural and dielectric properties in the (Ba1−xCax)(Ti0.95Zr0.05)O3 ceramics," Current Applied Physics, vol. 12(3), pp. 748-751, 2012.

R. Hayati, M. A. Bahrevar, T. Ebadzadeh, V. Rojas, N. Novak, and J. Koruza, "Effects of Bi2O3 additive on sintering process and dielectric, ferroelectric, and piezoelectric properties of (Ba0.85Ca0.15)(Zr0.1Ti0.9)O3 lead-free piezoceramics," Journal of the European Ceramic Society, vol. 36(14), pp. 3391-3400, 2016.

M.C. Chang, and S. -C. Yu, "Raman study for (Ba1−xCax)TiO3 and Ba(Ti1−yCay)O3 crystalline ceramics," Journal of Materials Science Letters, vol. 19(15), pp. 1323-1325, 2000.

H.M. Rietveld, "A Profile Refinement Method for Nuclear and Magnetic Structures," Journal of Applied Crystallography, vol. 2, pp. 65-71, 1969.

B.H. Toby, "R factors in Rietveld analysis: How good is good enough?," Powder diffraction, vol. 21(1), pp. 67-70, 2006.

S. Grazulis, D. Chateigner, R.T. Downs, A.F.T. Yokochi, M. Quiros, L. Lutterotti, E. Manakova, J. Butkus, P. Moeck, and A. Le Bail, "Crystallography Open Database - an open-access collection of crystal structures," Journal Applied Crystallography, vol. 42(Pt 4), pp. 726-729, 2009.

N. Buatip, N. Promsawat, N. Pisitpipathsin, O. Namsar, P. Pawasri, K. Ounsung, K. Phabsimma, S.T. Rattananchan, P. Janphuang, and S. Projprapai, "Investigation on electrical properties of BCZT ferroelectric ceramics prepared at various sintering conditions," Integrated Ferroelectrics, vol. 187(1), pp. 45-52, 2018.

K.H. Hardtl, "Electrical and Mechanical Losses in Ferroelectric Ceramics," Ceramics International, vol. 8, pp. 121-127, 1982.

Z. Raddaoui, S. El Kossi, J. Dhahri, N. Abdelmoula, and K. Taibi, "Study of diffuse phase transition and relaxor ferroelectric behavior of Ba0.97Bi0.02Ti0.9Zr0.05Nb0.04O3 ceramic," RSC Advances, vol. 9(5), pp. 2412-2425, 2019.

P.M. Dragan Damjanovic, and Nava Setter, "Ferroelectric Sensors," IEEE SENSORS JOURNAL, vol. 1, pp. 191-206, 2001.

X. Chao, Z. Wang, Y. Tian, Y. Zhou, and Z. Yang, "Ba(Cu0.5W0.5) O3-induced sinterability, electrical and mechanical properties of (Ba0.85Ca0.15Ti0.90Zr0.10)O3 ceramics sintered at low temperature," Materials Research Bulletin, vol. 66, pp. 16-25, 2015.




How to Cite

J. Tangsritrakul, T. Sonkami, C. Wichittanakom, C. Dokkhan, and P. Wiroonpochit, “Investigations on phase coexistence and functional properties of BCZT lead-free piezoceramic ”, J Met Mater Miner, vol. 31, no. 3, pp. 20–26, Sep. 2021.



Original Research Articles