Premartensite to martensite transition and its implications on the origin of modulation in Ni2MnGa ferromagnetic shape memory alloy

We present here results of temperature dependent high resolution synchrotron x-ray powder diffraction study of sequence of phase transitions in Ni2MnGa. Our results show that the incommensurate martensite phase results from the incommensurate premartensite phase, and not from the austenite phase assumed in the adaptive phase model. The premartensite phase transforms to the martensite phase through a first order phase transition with coexistence of the two phases in a broad temperature interval (~40K), discontinuous change in the unit cell volume as also in the modulation wave vector across the transition temperature and considerable thermal hysteresis in the characteristic transition temperatures. The temperature variation of the modulation wave vector q shows smooth analytic behaviour with no evidence for any devilish plateau corresponding to an intermediate or ground state commensurate lock-in phases. The existence of the incommensurate 7M like modulated structure down to 5K suggests that the incommensurate 7M like modulation is the ground state of Ni2MnGa and not the Bain distorted tetragonal L10 phase or any other lock-in phase with a commensurate modulation. These findings can be explained within the framework of the soft phonon model

The collapsed tetragonal phase as a strongly covalent and fully nonmagnetic state: persistent magnetism with interlayer As-As bond formation in Rh-doped Ca0.8_{0.8}Sr0.2_{0.2}Fe2_2As2_2

A well-known feature of CaFe$_{2}$As$_{2}$-based superconductors is the pressure-induced collapsed tetragonal phase that is commonly ascribed to the formation of an interlayer As-As bond. Using detailed X-ray scattering and spectroscopy, we find that Rh-doped Ca$_{0.8}$Sr$_{0.2}$Fe$_{2}$As$_{2}$ does not undergo a first-order phase transition and that local Fe moments persist despite the formation of interlayer As-As bonds. Our density functional theory calculations reveal that the Fe-As bond geometry is critical for stabilizing magnetism and that the pressure-induced drop in the $c$ lattice parameter observed in pure CaFe$_{2}$As$_{2}$ is mostly due to a constriction within the FeAs planes. These phenomena are best understood using an often overlooked explanation for the equilibrium Fe-As bond geometry, which is set by a competition between covalent bonding and exchange splitting between strongly hybridized Fe $3d$ and As $4p$ states. In this framework, the collapsed tetragonal phase emerges when covalent bonding completely wins out over exchange splitting. Thus the collapsed tetragonal phase is properly understood as a strong, covalent phase that is fully nonmagnetic with the As-As bond forming as a byproduct.Comment: 6 pages, 2 figures, and 1 table. Supplemental materials are available by reques

Phase formation of a biocompatible Ti-based alloy under kinetic constraints studied via in-situ high-energy X-ray diffraction

The biocompatible Ti40Cu34Pd14Zr10Sn2 bulk metallic glass was rapidly heated, also known as flash-annealed, at varying heating rates up to 1579 K/s. Thereby, the phase formation was characterized via advanced in-situ high-energy X-ray diffraction. It has been found that the evolving kinetic constraints can be used as a tool to deliberately alter the crystalline phase formation. This novel processing route permits to select phases to crystallize to a predefined fraction and, thus, to potentially design the microstructure of materials according to a specified property-profile. Consequently, flash-annealing poses a unique synthesis route to design materials with, for instance, good biomechanical compatibility

Ultra-stiff metallic glasses through bond energy density design

The elastic properties of crystalline metals scale with their valence electron density. Similar observations have been made for metallic glasses. However, for metallic glasses where covalent bonding predominates, such as metalloid metallic glasses, this relationship appears to break down. At present, the reasons for this are not understood. Using high energy x-ray diffraction analysis of melt spun and thin film metallic glasses combined with density functional theory based molecular dynamics simulations, we show that the physical origin of the ultrahigh stiffness in both metalloid and non-metalloid metallic glasses is best understood in terms of the bond energy density. Using the bond energy density as novel materials design criterion for ultra-stiff metallic glasses, we are able to predict a Co$_{33.0}$Ta$_{3.5}$B$_{63.5}$ short range ordered material by density functional theory based molecular dynamics simulations with a high bond energy density of 0.94 eV Å$^{-3}$ and a bulk modulus of 263 GPa, which is 17% greater than the stiffest Co-B based metallic glasses reported in literature.The authors acknowledge support by the German National Science Foundation (DFG) within the SPP-1594. Simulations were performed with computing resources granted by JARA-HPC from RWTH Aachen University under project JARA0131. Parts of this research were carried out at the light source PETRA III (beamline P02.1) at DESY, a member of the Helmholtz Association (HGF). WJC also acknowledges the support of the EPSRC/Rolls-Royce Strategic Partnership (EP/M005607/1)

Kinetic alteration of the 6Mg(NH2)2-9LiH-LiBH4 system by co-adding YCl3 and Li3N

The 6Mg(NH2)2-9LiH-LiBH4 composite system has a maximum reversible hydrogen content of 4.2 wt% and a predicted dehydrogenation temperature of about 64 °C at 1 bar of H2. However, the existence of severe kinetic barriers precludes the occurrence of de/re-hydrogenation processes at such a low temperature (H. Cao, G. Wu, Y. Zhang, Z. Xiong, J. Qiu and P. Chen, J. Mater. Chem. A, 2014, 2, 15816-15822). In this work, Li3N and YCl3 have been chosen as co-additives for this system. These additives increase the hydrogen storage capacity and hasten the de/re-hydrogenation kinetics: a hydrogen uptake of 4.2 wt% of H2 was achieved in only 8 min under isothermal conditions at 180 °C and 85 bar of H2 pressure. The re-hydrogenation temperature, necessary for a complete absorption process, can be lowered below 90 °C by increasing the H2 pressure above 185 bar. Moreover, the results indicate that the hydrogenation capacity and absorption kinetics can be maintained roughly constant over several cycles. Low operating temperatures, together with fast absorption kinetics and good reversibility, make this system a promising on-board hydrogen storage material. The reasons for the improved de/re-hydrogenation properties are thoroughly investigated and discussed

Microscopic structure and dynamics of glass forming Zr2Co melts and the impact of different late transition metals on the melt properties

We studied the short-range order and the atomic dynamics of stable and undercooled binary Zr2Co alloy melts as well as their density and viscosity. The containerless processing technique of electrostatic levitation was used to achieve deep undercooling and to avoid contaminations. Static structure factors are determined by combining this technique with neutron and high energy X-ray diffraction. Co self-diffusion coefficients are measured by quasielastic neutron scattering. Our results reveal that the short-range order of the Zr2Co melts closely resembles that previously observed for Zr64Ni36. We consider this as the origin of the very similar melt dynamics of these two alloys at same temperatures. On the other hand, the difference in the structure and dynamics when compared with those of Zr2Cu and Zr2Pd shows clearly that not only the atomic sizes, but also electronic properties or chemical bonding have an important influence on the melt properties of Zr-based glass forming melts