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X-ray and neutron diffraction are particularly useful for characterizing ferroelectric materials in situ, e.g., during application of temperature, pressure, electric field, and stress. In this review, we introduce many experimental approaches for such measurements and highlight important discoveries in ferroelectrics that utilized diffraction. We focus our examples on polycrystalline ferroelectrics, though many of the approaches and analysis methods can also be applied to thin films and single crystals. Methods discussed for characterization of structure include, phase identification, line profile analysis, whole pattern fitting, pair distribution functions, and the x-ray diffraction based three-dimensional microscopy. Further advancement of these and other techniques offers potential for continued important contributions to the fundamental understanding of ferroelectric materials.

Structure and phase transitions of (1 − y)((1 − x)Bi1/2Na1/2TiO3–xBi1/2K1/2TiO3)–yK0.5Na0.5NbO3 (x; y) piezoceramics (0.1 ≤ x ≤ 0.4; 0 ≤ y ≤ 0.05) were investigated by transmission electron microscopy, neutron diffraction, temperature-dependent x-ray diffraction, and Raman spectroscopy. The local crystallographic structure at room temperature (RT) does not change by adding K0.5Na0.5NbO3 to Bi1/2Na1/2TiO3–xBi1/2K1/2TiO3 for x = 0.2 and 0.4. The average crystal structure and microstructure on the other hand develop from mainly long-range polar order with ferroelectric domains to short-range order with polar nanoregions displaying a more pronounced relaxor character. The (0.1; 0) and (0.1; 0.02) compositions exhibit monoclinic Cc space group symmetry, which transform into Cc + P4bm at 185 and 130 °C, respectively. This high temperature phase is stable at RT for the morphotropic phase boundary compositions of (0.1; 0.05) and all compositions with x = 0.2. For the compositions of (0.1; 0) and (0.1; 0.02), local structural changes on heating are evidenced by Raman; for all other compositions, changes in the long-range average crystal structure were observed.

The macroscopic electromechanical coupling properties of ferroelectric polycrystals are composed of linear and nonlinear contributions. The nonlinear contribution is typically associated with the extrinsic effects related to the creation and motion of domain walls. To quantitatively compare the macroscopic nonlinear properties of a lead zirconate titanate ceramic and the degree of domain orientation, in-situ neutron and high-energy x-ray diffraction experiments are performed and they provide the domain orientation density as a function of the external electric field and mechanical compression. Furthermore, the macroscopic strain under the application of external electrical and mechanical loads is measured and the nonlinear strain is calculated by means of the linear intrinsic piezoelectric effect and the linear intrinsic elasticity. The domain orientation density and the nonlinear strain show the same dependence on the external load. The scaling factor that relates to the two values is constant and is the same for both electrical and mechanical loadings.

Preferred orientation in textured ceramics is often assessed by comparing the relative intensities of x-ray diffraction reflections to those of a randomly oriented ceramic using the Lotgering degree of orientation (f). However, this paper provides evidence that indiscriminate assessments of f can be misleading. Using measured intensities of a modestly textured tape cast bismuth titanate (Na0.5Bi4.5Ti4O15) ceramic, calculated f values vary from 7.4 to 73.2% depending on the reflections included in the calculation. The texture is also quantified by calculating the orientation distribution function (ODF) using measured pole figures. A model is then presented that demonstrates f is nonlinear with the multiple of preferred (00l)-orientations, the standard unit of the 00l pole figure.