Enhanced reversibility and unusual microstructure of a phase-transforming material

Materials undergoing reversible solid-to-solid martensitic phase transformations are desirable for applications in medical sensors and actuators, eco-friendly refrigerators and energy conversion devices. The ability to pass back and forth through the phase transformation many times without degradation of properties (termed ‘reversibility’) is critical for these applications. Materials tuned to satisfy a certain geometric compatibility condition have been shown to exhibit high reversibility, measured by low hysteresis and small migration of transformation temperature under cycling. Recently, stronger compatibility conditions called the ‘cofactor conditions’ have been proposed theoretically to achieve even better reversibility. Here we report the enhanced reversibility and unusual microstructure of the first martensitic material, Zn45Au30Cu25, that closely satisfies the cofactor conditions. We observe four striking properties of this material. (1) Despite a transformation strain of 8%, the transformation temperature shifts less than 0.5 °C after more than 16,000 thermal cycles. For comparison, the transformation temperature of the ubiquitous NiTi alloy shifts up to 20 °C in the first 20 cycles. (2) The hysteresis remains approximately 2 °C during this cycling. For comparison, the hysteresis of the NiTi alloy is up to 70 °C (refs 9, 12). (3) The alloy exhibits an unusual riverine microstructure of martensite not seen in other martensites. (4) Unlike that of typical polycrystal martensites, its microstructure changes drastically in consecutive transformation cycles, whereas macroscopic properties such as transformation temperature and latent heat are nearly reproducible. These results promise a concrete strategy for seeking ultra-reliable martensitic materials.

[1]  H. Gerstein,et al.  An initial investigation of the bending and torsional properties of Nitinol root canal files. , 1988, Journal of endodontics.

[2]  Shore,et al.  Hysteresis and hierarchies: Dynamics of disorder-driven first-order phase transformations. , 1992, Physical review letters.

[3]  Yoshiyuki Nakata,et al.  Thermal Cycling Effects in an Aged Ni-rich Ti–Ni Shape Memory Alloy , 1987 .

[4]  Robert V. Kohn,et al.  Symmetry, texture and the recoverable strain of shape-memory polycrystals , 1996 .

[5]  Masatoshi Imada,et al.  Metal-insulator transitions , 1998 .

[6]  J. Ball,et al.  Fine phase mixtures as minimizers of energy , 1987 .

[7]  V. Torra,et al.  Systematic study of the martensitic transformation in a Cu-Zn-Al alloy. reversibility versus irreversibility via acoustic emission , 1987 .

[8]  R. James,et al.  Hysteresis and unusual magnetic properties in the singular Heusler alloy Ni45Co5Mn40Sn10 , 2010 .

[9]  Eckhard Quandt,et al.  High cyclic stability of the elastocaloric effect in sputtered TiNiCu shape memory films , 2012 .

[10]  Richard D. James,et al.  A Way to Search for Multiferroic Materials with “Unlikely” Combinations of Physical Properties , 2005 .

[11]  S. Haile,et al.  Phase transformation and hysteresis behavior in Cs1 - xRbxH2PO4 , 2010 .

[12]  Richard D. James,et al.  Study of the cofactor conditions: Conditions of supercompatibility between phases , 2013, 1307.5930.

[13]  A. Saxena,et al.  Magnetism and Structure in Functional Materials , 2008 .

[14]  Nevill Mott,et al.  Metal-insulator transitions , 1973 .

[15]  J. Mackenzie,et al.  The crystallography of martensite transformations II , 1954 .

[16]  P. Anderson,et al.  Transformation-induced plasticity during pseudoelastic deformation in Ni–Ti microcrystals , 2009 .

[17]  M. Wuttig,et al.  Combinatorial search of thermoelastic shape-memory alloys with extremely small hysteresis width , 2006, Nature materials.

[18]  Hsiao-Ying Shadow Huang,et al.  Strain Accommodation during Phase Transformations in Olivine‐Based Cathodes as a Materials Selection Criterion for High‐Power Rechargeable Batteries , 2007 .

[19]  A. Heckmann,et al.  Structural and functional fatigue of NiTi shape memory alloys , 2004 .

[20]  Yong S. Chu,et al.  Identification of Quaternary Shape Memory Alloys with Near‐Zero Thermal Hysteresis and Unprecedented Functional Stability , 2010 .

[21]  J. Sethna,et al.  Crackling noise , 2001, Nature.

[22]  Oliver Gutfleisch,et al.  Giant magnetocaloric effect driven by structural transitions. , 2012, Nature materials.

[23]  X. Moya,et al.  Giant Electrocaloric Strength in Single‐Crystal BaTiO3 , 2013, Advanced materials.

[24]  T. Tadaki,et al.  ATOMIC CONFIGURATION DETERMINED BY ALCHEMI AND X-RAY DIFFRACTION OF THE L21 TYPE PARENT PHASE IN A CU-AU-ZN SHAPE MEMORY ALLOY , 1990 .

[25]  Nevill Mott,et al.  Metal-insulator transitions , 1974 .

[26]  T. Tadaki,et al.  Atomic configuration studied by ALCHEMI and X-ray diffraction of a stabilized M18R martensite in a β phase Cu-Au-Zn alloy , 1990 .

[27]  J. Humbeeck,et al.  Transmission electron microscopy study of phase compatibility in low hysteresis shape memory alloys , 2010 .

[28]  M. Pitteri,et al.  Continuum Models for Phase Transitions and Twinning in Crystals , 2002 .

[29]  Stefan Müller,et al.  Energy barriers and hysteresis in martensitic phase transformations , 2009 .

[30]  J. Sethna,et al.  Crackling noise : Complex systems , 2001 .

[31]  K. Bhattacharya Microstructure of martensite : why it forms and how it gives rise to the shape-memory effect , 2003 .

[32]  M. Wechsler O the Theory of the Formation of Martensite. , 1953 .

[33]  The Direct Conversion of Heat to Electricity Using Multiferroic Alloys , 2011 .