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The physical phenomena and engineering applications of martensitic phase transformations are the focus of intense ongoing research. The martensitic phase transformation and functional properties such as the shape-memory effect and superelasticity are strongly affected by the crystal size at the nanoscale. The current state of research on the impact of crystal size on the phase stability of the martensite is reviewed summarizing experimental results of various nanostructured martensitic materials and discussing the corresponding theoretical approaches. The review outlines the effects of crystal size on the complex morphology of the martensite, leading to interface structures not encountered in coarse-grained bulk materials. The unique shape-memory properties of martensitic materials can persist even at the nanoscale. Nanocrystalline martensitic materials can be processed to obtain tailored functional properties in combination with enhanced strength. Structural changes of metallic nanowires are similar to those arising by martensitic phase transformations and also can lead to shape-memory effects, as predicted by atomistic simulations.

Results of a systematic study are presented to review various effects of crystal size on the martensitic phase transformations in nanocrystalline NiTi shape memory alloys. The transformation temperatures and the transformed volume fraction strongly decrease with decreasing grain size less than about 100 nm. Transformation to martensite is not observed in grains smaller than a critical grain size of about 50 nm. The nanograins significantly impact the morphology of B199 martensite composed of (001) compound twins that occur at an atomic scale and violate the well established theory of martensite formation. Self-accommodation occurs by a herringbone morphology of two twinned variants. Contrary to the martensite, grain size hardly impacts the transformation to the R-phase. The experimental results are explained by a size dependent transformation barrier that accounts for the suppression of the martensitic transformation, its thermal stability and unique morphology in the nanograins.