Microstructure and Properties of PIN-PZN-PZ-PT Piezoelectric Ceramics Designed by MPB Linear Rules

doi:10.15541/jim20250098

Abstract

Abstract:

High-performance piezoelectric ceramics are indispensable in modern electromechanical systems, and multi-component materials like quaternary Pb(In_1/2Nb_1/2)O₃-Pb(Zn_1/3Nb_2/3)O₃-PbZrO₃-PbTiO₃ (PIN-PZN-PZ-PT) have attracted significant attention due to their unique properties at the morphotropic phase boundary (MPB). However, to achieve enhanced piezoelectric and thermal performance by design and optimization for MPB compositions through precisely adjusting the PbTiO₃ (PT) content is facing major challenges. Here, the ceramics were synthesized using a conventional solid-state reaction method, and the MPB compositions were initially predicted by employing a linear combination rule that accounts for the contributions of each component. The predicted phases were then confirmed by X-ray diffraction (XRD) analysis, followed by comprehensive electrical tests to measure the piezoelectric constant (d₃₃) and Curie temperature (T_C). Experimental results reveal that the MPB position is strongly influenced by PT content. As the PT fraction increases, the rhombohedral phase gradually decreases while the tetragonal phase becomes predominant, thus shifting the phase equilibrium. Specifically, the optimal composition (x) ranges are 0.245-0.265 for (1-x)(0.3PIN-0.6PZN-0.1PZ)-xPT, 0.290-0.330 for (1-x)(0.3PIN-0.5PZN-0.2PZ)-xPT, and 0.305-0.345 for (1-x)(0.3PIN-0.4PZN-0.3PZ)-xPT. Notably, the 0.735(0.3PIN-0.6PZN-0.1PZ)-0.265PT sample exhibits superior performance with a d₃₃ of 425 pC/N and a T_C of 253 ℃. These findings demonstrate that precise modulation of the PT content is crucial for controlling the phase balance at the MPB and thereby optimizing the piezoelectric properties. In conclusion, this study successfully identifies the optimal MPB compositions for PIN-PZN-PZ-PT ceramics, highlighting their promising potential for advanced piezoelectric applications and laying a solid foundation for future process improvements and long-term stability research.

Key words: morphotropic phase boundary, piezoelectric constant, Curie temperature, phase structure, perovskite

CLC Number:

TM282

XU Xiaoyu, ZHOU Liyang, FENG Xiaoying, WANG Hui, YAN Bin, XU Jie, GAO Feng. Microstructure and Properties of PIN-PZN-PZ-PT Piezoelectric Ceramics Designed by MPB Linear Rules[J]. Journal of Inorganic Materials, 2025, 40(11): 1285-1292.

Figures/Tables 17

Fig. 1 Schematic diagram of a MPB component for PIN-PZN- PZ-PT quaternary piezoelectric ceramics

Table 1 Composition design of PIN-PZN-PZ-PT piezoelectric ceramics

Sample	s₁	s₂	s₃	x	Sample’s label
A	0.3	0.6	0.1	0.205-0.285	A205-A285
B	0.3	0.5	0.2	0.290-0.370	B290-B370
C	0.3	0.4	0.3	0.285-0.365	C285-C365

Fig. 2 XRD patterns of PIZZT ceramics (a) A205-A285; (b) B290-B370; (c) C285-C365

Fig. 3 XRD peak fitting patterns of PIZZT ceramics at 2θ=43.5°-46.2° (a) A205-A285; (b) B290-B370; (c) C285-C365. Colorful figures are available on website

Fig. 4 Dielectric properties of PIZZT ceramics as a function of PT content (a) Dielectric constant; (b) Dielectric loss tangent

Fig. 5 Temperature dependent on dielectric properties and Curie temperature of PIZZT ceramics (a) A205-A285; (b) B290-B370; (c) C285-C365; (d) Curie temperatures of A, B and C. Colorful figures are available on website

Fig. 6 P-E loops of PIZZT ceramics (a) A205-A285; (b) B290-B370; (c) C285-C365. Colorful figures are available on website

Fig. 7 Ferroelectric performance of PIZZT ceramics as a function of PT content (a) Pr; (b) Ec

Fig. 8 Changes in d33* of PIZZT ceramics with PT content

Fig. 9 Piezoelectric properties of PIZZT ceramics as a function of PT content (a) d33; (b) kp and Qm

Table 2 Piezoelectric properties of PIZZT ceramics

Sample	ε_r	T_C/ ℃	P_r/ (μC·cm^-2)	E_c/ (kV·cm^-1)	d₃₃/ (pC·N^-1)	k_p
A205	1346	227	34.7	9.1	168	0.33
A225	1588	232	35.1	9.7	303	0.36
A245	2686	241	36.2	10.4	360	0.44
A265	3146	253	34.1	12.2	425	0.50
A285	2337	268	27.1	14.7	367	0.42
B290	2118	273	33.1	11.7	360	0.46
B310	2365	284	29.5	15.2	334	0.39
B330	2311	279	28.4	16.4	295	0.33
B350	1903	304	25.2	18.2	260	0.34
B370	1400	308	19.4	19.1	243	0.29
C285	1198	284	37.11	10.0	255	0.34
C305	1758	299	37.14	10.1	270	0.38
C325	1312	302	31.8	17.4	260	0.36
C345	1281	303	26.59	19.9	255	0.33
C365	1179	317	21.36	15.14	230	0.29

Table 3 Comparison of lead-based piezoelectric ceramic properties

Designation	T_C/℃	d₃₃/(pC·N^-1)	k_p	ε_r	Ref.
PMN-PT	159	663	-	5260	[4]
PMN-PIN-PT	245	450	0.49	2970	[6]
PNN-PZ-PT	115	986	0.693	9015	[13]
PNN-PH-PT	110	970	0.65	6000	[15]
Sr-PMN-PT	210	630	0.52	4000	[3]
Sm-PMN-PT	89	1510	-	13000	[11]
PIN-PMN-PT	245	450	0.49	2970	[5]
PZW-PMN-PZT	150	450	-	3811	[17]
PZT-5A	360	390	0.5	1750	[18]
PZT-5H	193	590	0.64	3300	[18]
PMN-PZ-PT	230	661	0.63	2441	[19]
PIN-PMN-PT	219	505	0.62	2120	[20]
PIN-PSN-PT	280	360	-	-	[21]
PIZZT	253	425	0.50	3146	This work

Table S1 Rhombohedral and tetragonal phase content of A, B and C

Sample classification	Sample	T/%	R/%	Sample classification	Sample	T/%	R/%
A	A205	0	100	C	C285	32	68
	A225	33	67		C305	42	58
	A245	48	52		C325	53	47
	A265	67	33		C345	57	43
	A285	81	19		C365	86	14
B	B290	53	47
	B310	54	46
	B330	56	44
	B350	66	34
	B370	83	17

Fig. S1 SEM images of PIZZT ceramics (a) A205-A285; (b) B290-B370; (c) C285-C365

Fig. S2 Grain size distribution of PIZZT ceramics (a) A205-A285; (b) B290-B370; (c) C285-C365

Fig. S3 Densities of PIZZT ceramic as a function of PT content

Fig. S4 Electrostriction of PIZZT ceramics (a) A205-A285; (b) B290-B370; (c) C285-C365

References 21

[1]	EITEL R E, RANDALL C A, SHROUT T R, et al. New high temperature morphotropic phase boundary piezoelectrics based on Bi(Me)O₃-PbTiO₃ ceramics. Journal of Applied Physics, 2001, 40(10): 5999.
[2]	ZHANG S J, LEE S M, KIM D H, et al. Electromechanical properties of PMN-PZT piezoelectric single crystals near morphotropic phase boundary compositions. Journal of the American Ceramic Society, 2007, 90(12): 3859. DOI URL
[3]	LI F, ZHANG S J, YANG T N. The origin of ultrahigh piezoelectricity in relaxor-ferroelectric solid solution crystals. Nature Communications, 2016, 7: 13807. DOI PMID
[4]	YAMAMOTO N, YAMASHITA Y, HOSONO Y, et al. Electrical and physical properties of repoled PMN-PT single crystal sliver transducer. Sensors and Actuators A: Physical, 2013, 200(1): 16. DOI URL
[5]	WANG D, CAO M, ZHANG S J, et al. Phase diagram and properties of Pb(In_1/2Nb_1/2)O₃-Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ polycrystalline ceramics. Journal of the European Ceramic Society, 2012, 32(2): 433. DOI URL
[6]	WU J, CHANG Y F, YANG B, et al. Densification behavior and electrical properties of CuO-doped Pb(In_1/2Nb_1/2)O₃-Pb(Mg_1/3Nb_2/3)O₃- PbTiO₃ ternary ceramics. Ceramics International, 2016, 42(6): 7223. DOI URL
[7]	ZHAO L Y, HOU Y D, CHANG L M, et al. Microstructure and electrical properties of 0.5PZN-0.5PZT relaxor ferroelectrics close to the morphotropic phase boundary. Journal of Materials Research, 2011, 24(6): 2029. DOI URL
[8]	RAMESSH G, RAMACHANDRA M S, SIVASUBRAMANIAN V, et al. Electrocaloric effect in (1-x)PIN-xPT relaxor ferroelectrics. Journal of Alloys Compounds, 2016, 663: 444. DOI URL
[9]	QI X D, SUN E W, WANG J J, et al. Electromechanical properties of Mn-doped Pb(In_1/2Nb_1/2)O₃-Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ piezoelectric ceramics. Ceramics International, 2016, 42(14): 15332. DOI URL
[10]	LUO N, ZHANG S J, QIANG L, et al. New Pb(Mg_1/3Nb_2/3)O₃- Pb(In_1/2Nb_1/2)O₃-PbZrO₃-PbTiO₃ quaternary ceramics: morphotropic phase boundary design and electrical properties. ACS Applied Materials & Interfaces, 2016, 8(24): 15506.
[11]	LI C C, XU B, LIN D B. Atomic-scale origin of ultrahigh piezoelectricity in samarium-doped PMN-PT ceramics. Physical Review B, 2020, 101(14): 140102. DOI URL
[12]	FENG X Y, LIU J T, GAO F, et al. Effect of sintering atmosphere on the microstructure and electrical properties of Pb(Zr_1/2Ti_1/2)O₃- Pb(Zn_1/3Nb_2/3)O₃-Pb(Ni_1/3Nb_2/3)O₃ ceramics. Journal of Materials Science: Materials in Electronics, 2022, 33: 11613. DOI
[13]	FENG X Y, LI L L, XU X Y, et al. Microstructure evolution and properties of textured, Pb(Zr_1/2Ti_1/2)O₃-Pb(Zn_1/3Nb_2/3)O₃-Pb(Ni_1/3Nb_2/3)O₃ ceramics with plate-like BaZr_0.1Ti_0.9O₃ template. Journal of Alloys and Compounds, 2024, 1002: 175439. DOI URL
[14]	LI F, ZHANG S J, XU Z. Piezoelectricity-an important property for ferroelectrics during last 100 years. Acta Physica Sinica, 2020, 69(21): 217703. DOI URL
[15]	XU X Y, FENG X Y, GAO F, et al. Phase structure and electrical properties of 0.28PIN-0.32PZN-(0.4-x)PT-xPZ piezoelectric ceramics. Crystals, 2023, 13(9): 1362. DOI URL
[16]	LIM J B, ZHANG S J, SHROUT T R. Modified Pb(Yb,Nb)O₃- PbZrO₃-PbTiO₃ ternary system for high temperature applications. Ceramics International, 2012, 38(1): 277. DOI URL
[17]	YOO J Y, LEE S H, LEE K S. Piezoelectric and dielectric properties of low temperature sintering Pb(Zn_1/2W_1/2)O₃- Pb(Mn_1/3Nb_2/3)O₃-Pb(Zr,Ti)O₃ ceramics. Transactions on Electrical and Electronic Materials, 2008, 9(3): 91. DOI URL
[18]	GUO Q H, LI F, XIA F Q, et al. Piezoelectric ceramics with high piezoelectricity and broad temperature usage range. Journal of Materiomics, 2021, 7: 683. DOI URL
[19]	WANG P B, GUO Q H, LI F, et al. Pb(In_1/2Nb_1/2)O₃-PbZrO₃-PbTiO₃ternary ceramics with temperature-insensitive and superior piezoelectric property. Journal of European Ceramic Society, 2022, 42: 3848. DOI URL
[20]	WEI D D, HUANG H. Low-temperature sintering and enhanced piezoelectric properties of random and textured PIN-PMN-PT ceramics with Li₂CO₃. Journal of the American Ceramic Society, 2017, 100(3): 1073. DOI URL
[21]	LIN D, ZHANG S J, GORZKOWSKI E, et al. Investigation of morphotropic phase boundaries in PIN-PSN-PT relaxor ferroelectric ternary systems with high T_r-t and T_c phase transition temperatures. Journal of the European Ceramic Society, 2017, 37(8): 2813. DOI URL