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Shear bands originating from in situ tensile tests of Al$_{88}$Y$_{7}$Fe$_{5}$ melt-spun ribbons conducted in a transmission electron microscope are compared with ones which had formed ex situ during cold rolling. During in situ straining, the observations of a spearhead-like shear front, a meniscus-like foil thickness reduction and no apparent shear steps to accommodate strain suggest shear band initiation by a rejuvenating shear front followed by shearing along the already softened paths. This leads to necking and subsequent failure under the reduced constraint of a 2D geometry in the thin foil and thus explains the observed lack of ductility under tension. In contrast, shear bands formed during cold rolling display distinct alternating density changes and shear off-sets. An explanation for this difference may be that in situ shear bands rip before such features could develop. Moreover, both in and ex situ experiments suggest that initiation, propagation and arrest of shear bands occur during different stages., Comment: submitted to Scripta Materialia

Strongly confined NaVO$^+$ segregation and its thermo-responsive functionality at the interface between simple sputter-deposited amorphous vanadium oxide thin films and soda-lime glass was substantiated in the present study by in-situ temperature-controlled Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The obtained ToF-SIMS depth profiles provided unambiguous evidence for a reversible transformation that caused systematic switching of the NaVO$^+$/ Na$^+$ and Na$^+$/ VO$^+$ intensities upon cycling the temperature between 25 $^\circ$C and 340 $^\circ$C. Subsequently, NaVO complexes were found to be reversibly formed (at 300 $^\circ$C) in vanadium oxide diffused glass, leading to thermo-responsive electrical behaviour of the thin film glass system. This new segregation -- and diffusion-dependent multifunctionality of NaVO$^+$ -- points towards applications as an advanced material for thermo-optical switches, in smart windows or in thermal sensors.

Shear bands resulting from plastic deformation in cold-rolled Al$_{88}$Y$_{7}$Fe$_{5}$ metallic glass were observed to display alternating density changes along their propagation direction. Electron-energy loss spectroscopy (EELS) was used to investigate the volume plasmon energy losses in and around shear bands. Energy shifts of the peak centre and changes in the peak width (FWHM) reflecting the damping were precisely determined within an accuracy of a few meV using an open source python module (Hyperspy) to fit the shapes of the plasmon and zero-loss peaks with Lorentzian functions. The maximum bulk plasmon energy shifts were calculated for the bright and dark shear band segments relative to the matrix to be about 38 and 14 meV, respectively. The damping was observed to be larger for the denser regions. The analysis presented here suggests that the changes in the plasmons are caused by two contributions: (i) Variable damping in the shear band segments due to changes in the medium-range order (MRO). This affects the static structure factor S(k), which, in turn, leads to either reduced or increased damping according to the Ziman-Baym formula. (ii) The ionic density and the effective electron mass appearing in the zero-momentum plasmon frequency formula $E_p(q=0)$ are coupled and give rise to small variations in the plasmon energy. The model predicts plasmon energy shifts in the order of meV.

The impact of severe plastic deformation by high-pressure torsion on the relaxation of the glassy and supercooled liquid states of Pd$_{40}$Ni$_{40}$P$_{20}$ was investigated using a combination of differential scanning calorimetry, low-temperature heat capacity and fluctuation electron microscopy. The changes in the calorimetric signals due to deformation and subsequent heat treatments were analyzed and a correlation between deformation (rejuvenation) and annealing (relaxation) was found in relation to medium-range order (MRO). Moreover, a coupling between the occurrence of an exothermic peak in the supercooled liquid state and specific changes in the MRO types were identified. These findings are comprehended in a potential energy landscape scheme offering a new approach for MRO engineering of glasses.

Micro- or minor alloying of metallic glasses is of technological interest. An originally ductile Pd-based monolithic bulk metallic glass (Pd$_{40}$Ni$_{40}$P$_{20}$) was selectively manipulated by additions of Fe or Co. The alloying effects were extreme, showing either exceptional ductility upon Co addition or immediate catastrophic failure upon Fe addition when tested under uniaxial compression or 3-point bending. The amorphous structure was characterized prior to deformation with respect to its medium-range order (MRO) using variable resolution fluctuation electron microscopy (VR-FEM). We observe striking differences in the MRO between the ductile and brittle metallic glasses, with the ductile glasses exhibiting a rich structural diversity and MRO correlation lengths up to 6 nm. The MRO heterogeneity seems to enable easier shear banding and hence enhance the deformability.

Grain boundary self-diffusion of $^{57}$Co, $^{51}$Cr, $^{59}$Fe and $^{54}$Mn in a coarse-grained, single-phase fcc CoCrFeMnNi high entropy alloy is measured in a wide temperature range of 643 to 1273~K in both C- and B-type kinetic regimes after Harrison's classification. The results suggest that the product of the pertinent segregation factors, $s$, and the grain boundary width, $\delta$, is about 0.5~nm for all elements at temperatures $T>800$~K. Whereas one short-circuit contribution is observed at higher temperatures above 800~K, the penetration profiles in the C-type kinetic regime (643 -- 703~K) reveal two distinct contributions that hint towards a phase decomposition at a fraction of high-angle grain boundaries at these temperatures. A correlative microscopy combining transmission Kikuchi diffraction and atom probe tomography manifests formation of neighbouring Ni-Mn-rich and Cr-rich precipitates at a segment of high angle grain boundaries. Transmission electron microscopy revealed an increased dislocation density in the vicinity of such interfaces which is suggested to be a reason of the enhanced diffusion rates at low temperatures for such short circuits., Comment: 17 pages, 11 figures

Tracer diffusion of all constituting elements is studied at various temperatures in a series of (CoCrFeMn)$_{100-x}$Ni$_x$ alloys with compositions ranging from pure Ni to the equiatomic CoCrFeMnNi high-entropy alloy. At a given homologous temperature, the measured tracer diffusion coefficients change non-monotonically along the transition from pure Ni to the concentrated alloys and finally to the equiatomic CoCrFeMnNi alloy. This is explained by atomistic Monte-Carlo simulations based on a modified embedded-atom potentials, which reveal that local heterogeneities of the atomic configurations around a vacancy cause correlation effects and induce significant deviations from predictions of the random alloy model., Comment: 16 pages; 10 figures

Notched bars of bulk metallic glasses, Pd$_{40}$Ni$_{40}$P$_{20}$ and Zr$_{52.5}$Cu$_{17.9}$Ni$_{14.6}$Al$_{10}$Ti$_{5}$, were deformed under 3-point bending conditions, resulting in the formation of shear bands before failure. The immediate environment of shear bands was investigated in detail using fluctuation electron microscopy to extract information on the strain-induced modifications of the medium-range order (MRO) and its lateral extension. Characteristic material-independent gradients were observed for the tensile and compressive sides of the samples indicating the impact of the local stress state on the MRO. Our results reveal an upper limit of a few microns for the lateral extension of the shear-affected environments of shear bands.

Understanding ductility or brittleness of monolithic bulk metallic glasses (BMGs) requires detailed knowledge of the amorphous structure. The medium range order (MRO) of ductile Pd$_{40}$Ni$_{40}$P$_{20}$ and brittle Zr$_{52.5}$Cu$_{17.9}$Ni$_{14.6}$Al$_{10}$Ti$_5$ (Vit105) was characterized prior to and after notched 3-point bending tests using variable-resolution fuctuation electron microscopy. Here we show the presence of a second larger MRO correlation length in the ductile material which is not present in the brittle material. A comparison with literature suggests that the larger correlation length accounts for larger shear transformation zones (STZs) which increase the heterogeneity. This enables an easier shear band formation and thus explains the difference in deformability.

Grain boundary tracer diffusion of Ni, Fe and Cr was studied in a Ni-base 602CA coarse-grained alloy. A co-existence of several short-circuit contributions was distinguished at higher temperatures in Harrison's B-type regime (773-873 K), which were related to different families of high-angle grain boundaries with distinct coverages by precipitates and segregation levels as revealed by HAADF-STEM combined with EDX measurements. Annealing at 873 K for 18 hours resulted in Cr23C6-type carbides coexisting with an \alpha-Cr-Mn-enriched phase in addition to sequential segregation layers of Al, Fe and Ni around them. Curved and hackly grain boundaries showed a high density of plate-like carbides, whereas straight grain boundaries were composed of globular carbides with similar chemical composition variations and additionally with alternating layers of Cr and Ni in between the carbides, similar to microstructures after a spinodal decomposition. At lower temperatures, discontinuous interfaces with Cr and Cr-carbide enrichment dominated and the alloy annealed at 403 K for 72 hours contained plate-like Cr23C6-type carbides surrounded by a Ni-rich layer around them. The Ni grain boundary diffusion rates at these relatively low temperatures (formally belonging to C-type kinetics) showed an anomalous character being almost temperature independent. This specific diffusion behaviour was explained by a concomitant relaxation of transformation-induced elastic strains occurring on a longer time scale with respect to grain boundary diffusion. Thermodynamic insights into the probable mechanism of decomposition at grain boundaries are provided., Comment: 21 pages, 14 figures