The impact of ultrahigh (dis)charge rates on the phase transition mechanism in LiFePO4 Li-ion electrodes is revealed by in situ synchrotron diffraction. At high rates the solubility limits in both phases increase dramatically, causing a fraction of the electrode to bypass the first-order phase transition. The small transforming fraction demonstrates that nucleation rates are consequently not limiting the transformation rate. In combination with the small fraction of the electrode that transforms at high rates, this indicates that higher performances may be achieved by further optimizing the ionic/electronic transport in LiFePO4 electrodes.
Phase transitions in Li-ion electrode materials during (dis)charge are decisive for battery performance, limiting high-rate capabilities and playing a crucial role in the cycle life of Li-ion batteries. However, the difficulty to probe the phase nucleation and growth in individual grains is hindering fundamental understanding and progress. Here we use synchrotron microbeam diffraction to disclose the cycling rate-dependent phase transition mechanism within individual particles of LiFePO4, a key Li-ion electrode material. At low (dis)charge rates well-defined nanometer thin plate-shaped domains co-exist and transform much slower and concurrent as compared with the commonly assumed mosaic transformation mechanism. As the (dis)charge rate increases phase boundaries become diffuse speeding up the transformation rates of individual grains. Direct observation of the transformation of individual grains reveals that local current densities significantly differ from what has previously been assumed, giving new insights in the working of Li-ion battery electrodes and their potential improvements.
In situ three-dimensional (3-D) X-ray diffraction experiments have been performed at a synchrotron source on low-alloyed multiphase TRIP steels containing 0.25 wt.% Si and 0.44 wt.% Al and produced with different bainitic holding times, in order to assess the influence of the bainitic transformation on the thermal stability of individual austenite grains with respect to their martensitic transformation. A detailed characterization of the austenite grain volume distribution at room temperature was performed as a function of the prior bainitic holding time. In addition, the martensitic transformation behaviour of individual metastable grains was studied in situ during cooling to a temperature of 100 K. Both the carbon content and the grain volume play a key role in the stability of the austenite grains below 15 lm 3 , while the carbon content exerts the dominant effect in the stability of the bigger grains. Measurements also suggest that the tetragonality of the thermally formed martensite is suppressed.
Using high-resolution neutron diffraction measurements for Mn-rich hexagonal Mn-Fe-P-Si compounds, we show that the substitution of Mn for Fe on the 3f sites results in a linear decrease of the Fe/Mn(3f ) magnetic moments, while the Mn(3g) magnetic moments remain constant. With increasing temperature, the Mn(3g) magnetic moments show almost no change, while the Fe/Mn(3f ) moments decrease quickly when the transition temperature is approached. The reduction of the magnetic moments at the transition temperature and in the high-temperature range is discussed based on changes in interatomic distances and lattice parameters and high-temperature magnetic-susceptibility measurement.
The stability of the retained austenite has been studied in situ in low-alloyed transformation-induced-plasticity (TRIP) steels using high-energy X-ray diffraction during tensile tests at variable temperatures down to 153 K. A detailed powder diffraction analysis has been performed to probe the austenite-to-martensite transformation by characterizing the evolution of the phase fraction, load partitioning and texture of the constituent phases simultaneously. Our results show that at lower temperatures the mechanically induced austenite transformation is significantly enhanced and extends over a wider deformation range, resulting in a higher elongation at fracture. Low carbon content grains transform first, leading to an initial increase in average carbon concentration of the remaining austenite. Later the carbon content saturates while the austenite still continues to transform. In the elastic regime the probed {h k l} planes develop different strains reflecting the elastic anisotropy of the constituent phases. The observed texture evolution indicates that the austenite grains oriented with the {2 0 0} plane along the loading direction are transformed preferentially as they show the highest resolved shear stress. For increasing degrees of plastic deformation the combined preferential transformation and grain rotation results in the standard deformation texture for austenite with the {1 1 1} component along the loading direction. The mechanical stability of retained austenite in TRIP steel is found to be a complex interplay between carbon concentration in the austenite, grain orientation, load partitioning and temperature.
We have performed specific-heat measurements on the heavy-fermion superconductor URu 2 Si 2 in magnetic fields up to 17.5 T. A sharp peak in the specific heat signals the antiferromagnetic transition at T N ϭ17.5 K, which shifts to lower temperatures in applied magnetic fields. In order to describe the specific heat below T N , we have used the characteristic features of the excitation spectrum measured by neutron scattering. The relative field dependence of the antiferromagnetic transition temperature T N and the energy gap ⌬ in the magnetic excitation spectrum can be described by a single scaling relation of the form ͓1Ϫ(B/B 0 ) 2 ͔. The scaling field of 48.5 T is close to the metamagnetic transition field B*ϭ40 T, where the heavy-fermion state is suppressed.
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