Measuring stress-induced martensite microstructures using far-field high-energy diffraction microscopy.

Modern X-ray diffraction techniques are now allowing researchers to collect long-desired experimental verification data sets that are in situ, three-dimensional, on the same length scales as critical microstructures, and using bulk samples. These techniques need to be adapted for advanced material systems that undergo combinations of phase transformation, twinning and plasticity. One particular challenge addressed in this article is direct analysis of martensite phases in far-field high-energy diffraction microscopy experiments. Specifically, an algorithmic forward model approach is presented to analyze phase transformation and twinning data sets of shape memory alloys. In the present implementation of the algorithm, the crystallographic theory of martensite (CTM) is used to predict possible martensite microstructures (i.e. martensite orientations, twin mode, habit plane, twin plane and twin phase fractions) that could form from the parent austenite structure. This approach is successfully demonstrated on three single- and near-single-crystal NiTi samples where the fundamental assumptions of the CTM are not upheld. That is, the samples have elastically strained lattices, inclusions, precipitates, subgrains, R-phase transformation and/or are not an infinite plate. The results indicate that the CTM still provides structural solutions that match the experiments. However, the widely accepted maximum work criterion for predicting which solution of the CTM should be preferred by the material does not work in these cases. Hence, a more accurate model that can simulate these additional structural complexities can be used within the algorithm in the future to improve its performance for non-ideal materials.

Cationic Ordering Coupled to Reconstruction of Basic Building Units during Synthesis of High-Ni Layered Oxides.

Metal (M) oxides are one of the most interesting and widely used solids, and many of their properties can be directly correlated to the local structural ordering within basic building units (BBUs). One particular example is the high-Ni transition metal layered oxides, potential cathode materials for Li-ion batteries whose electrochemical activity is largely determined by the cationic ordering in octahedra (e.g., the BBUs in such systems). Yet to be firmly established is how the BBUs are inherited from precursors and subsequently evolve into the desired ordering during synthesis. Herein, a multimodal in situ X-ray characterization approach is employed to investigate the synthesis process in preparing LiNi0.77Mn0.13Co0.10O2 from its hydroxide counterpart, at scales varying from the long-range to local individual octahedral units. Real-time observation corroborated by first-principles calculations reveals a topotactic transformation throughout the entire process, during which the layered framework is retained; however, due to preferential oxidation of Co and Mn over Ni, significant changes happen locally within NiO6 octahedra. Specifically, oxygen loss and the associated symmetry breaking occur in NiO6; as a consequence, Ni2+ ions become highly mobile and tend to mix with Li, causing high cationic disordering upon formation of the layered oxides. Only through high-temperature heat treatment, Ni is further oxidized, thereby inducing symmetry reconstruction and, concomitantly, cationic ordering within NiO6 octahedra. Findings from this study shed light on designing high-Ni layered oxide cathodes and, more broadly, various functional materials through synthetic control of the constituent BBUs.