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. 2022 Oct 9;15(19):6998.
doi: 10.3390/ma15196998.

Annealing-Dependent Morphotropic Phase Boundary in the BiMg0.5Ti0.5O3-BiZn0.5Ti0.5O3 Perovskite System

João Pedro V Cardoso  1 , Vladimir V Shvartsman  2 , Anatoli V Pushkarev  3 , Yuriy V Radyush  3 , Nikolai M Olekhnovich  3 , Dmitry D Khalyavin  4 , Erik Čižmár  5 , Alexander Feher  5 , Andrei N Salak  1
Affiliations

Annealing-Dependent Morphotropic Phase Boundary in the BiMg0.5Ti0.5O3-BiZn0.5Ti0.5O3 Perovskite System

João Pedro V Cardoso et al. Materials (Basel). .

Abstract

The annealing behavior of (1-x)BiMg0.5Ti0.5O3−xBiZn0.5Ti0.5O3 [(1-x)BMT−xBZT] perovskite solid solutions synthesized under high pressure was studied in situ via X-ray diffraction and piezoresponse force microscopy. The as prepared ceramics show a morphotropic phase boundary (MPB) between the non-polar orthorhombic and ferroelectric tetragonal states at 75 mol. % BZT. It is shown that annealing above 573 K results in irreversible changes in the phase diagram. Namely, for compositions with 0.2 < x < 0.6, the initial orthorhombic phase transforms into a ferroelectric rhombohedral phase. The new MPB between the rhombohedral and tetragonal phases lies at a lower BZT content of 60 mol. %. The phase diagram of the BMT−BZT annealed ceramics is formally analogous to that of the commercial piezoelectric material lead zirconate titanate. This makes the BMT−BZT system promising for the development of environmentally friendly piezoelectric ceramics.

Keywords: X-ray diffraction; conversion polymorphism; high-pressure synthesis; lead-free; piezoresponse force microscopy.

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Conflict of interest statement

The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to publish the results.

Figures

Figure 1
Figure 1
SEM images of the fractured surfaces of the (1-x)BMT–xBZT sample (x = 0.70) synthesized under high pressure: (a) as prepared, (b) annealed at 770 K and (c) annealed at 970 K.
Figure 2
Figure 2
The most representative ranges of the XRD patterns of the as-prepared (1-x)BMT–xBZT sample (x = 0.70) at the first thermal cycle: (a) upon heating to 773 K and (b) upon cooling to room temperature. The structural phases at room temperature before and after the annealing are the orthorhombic Pnnm and the tetragonal P4mm, respectively.
Figure 3
Figure 3
The most representative ranges of the XRD patterns of the as-prepared (1-x)BMT–xBZT sample (x = 0.40) at the first thermal cycle: (a) upon heating to 773 K and (b) upon cooling to room temperature. The structural phases at room temperature before and after the annealing are the orthorhombic Pnnm and the tetragonal R3c, respectively.
Figure 4
Figure 4
State diagram of the (1-x)BMT–xBZT perovskite phases upon heating to their temperature stability limit (a) and upon subsequent cooling (b). The area marked as “A” corresponds to the Pnnm + P4mm phase mixture.
Figure 5
Figure 5
The normalized unit-cell volume of the (1-x)BMT–xBZT perovskite phases before and after annealing as a function of the BZT content (x). The error bars are smaller than the symbols. The dashed lines indicate the compositions corresponding to the morphotropic phase boundary (MPB) before and after annealing. The solid straight line is a reference to the Vegard’s law.
Figure 6
Figure 6
The primitive perovskite cell parameters of the (1-x)BMT–xBZT perovskite phases as a function of the BZT content (x) before (a) and after (b) annealing with the borders of the different phase ranges indicated.
Figure 7
Figure 7
Topography (a,d), vertical PFM amplitude (b,e), and lateral PFM amplitude (c,f) images of the 0.45BMT–0.55BZT ceramics before (a–c) and after annealing (d–f).
Figure 8
Figure 8
Topography (a,d), vertical PFM amplitude (b,e), and lateral PFM amplitude (c,f) images of the 0.35BMT–0.65BZT ceramics before (a–c) and after annealing (d–f).
See this image and copyright information in PMC

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