Strain-stabilized Al-containing high-entropy sublattice nitrides

The dislocation width for shuffle 60° dislocation in semiconductors Si and Ge have been calculated by the improved P-N theory in which the discrete effect has been taken into account. Peierls barrier and stress have been evaluated with considering the contribution of strain energy. The discrete effect make dislocation width wider, and Peierls barrier and stress lower. The dislocation width of 60° dislocation in Si and Ge is respectively about 3.84 A and 4.00 A (∼1b, b is the Burgers vector). In the case of 60° dislocation, after considering the contribution of strain energy, Peierls barrier and stress are increased. The Peierls barrier for 60° dislocation in Si and Ge is respectively about 15 meV/A and 12–14 meV/A, Peierls stress is about 3.8 meV/A3 (0.6 GPa) and 2.7–3.3 meV/A3 (0.4–0.5 GPa). The Peierls stress for Si agrees well with the numerical results and the critical stress at 0 K extrapolated from experimental data. Ge behaves similarly to Si.

The effects of couple stresses on dislocation strain energy

This work examines the free vibration and stability of a spinning, elastic disk-spindle system. The extended operator formulation is exploited to discretize the system using Galerkin’s method (Parker, 1999). The coupled vibration modes of the system consist of disk modes, in which the disk dominates the system deformation, and spindle modes, in which the spindle dominates the system deformation. Both the natural frequencies and vibration modes are strongly affected by disk flexibility. If the membrane stresses associated with disk rotation are neglected then the system exhibits flutter instabilities, but these instabilities are not present when membrane stresses are modeled. Natural frequency veering between disk and spindle frequencies is prominent at low speeds and substantially affects the spectrum and stability. No veering is observed at high speeds where rotational stress stiffening diminishes disk-spindle coupling and causes the natural frequencies to converge to those of a rotating spindle carrying a rigid disk. Changes to the vibration modes are examined in terms of a strain energy ratio measuring the contribution of the disk strain energy to the total modal strain energy.

First principles investigation into the phase stability and enhanced hardness of TiN-ScN and TiN-YN alloys

In microstructures such as whiskers, their surface free energy is supposed to determine the criterion on whether the whisker growth can take place ; then a critical dimension for the whisker growth should exist, depending on the degree of the excessive energy that drives the whisker growth. In this respect, the excessive energy included in matt Sn deposits plated on Cu substrates has been estimated to be approximately 1×10 -22 J atom ' in terms of chemical potential. Furthermore the contribution of grain-boundary free energy and strain energy to the excessive energy has been estimated. It has been shown that the grain-boundary free energy seems not to contribute to the excessive energy. On the other hand, it has been found that the strain energy sufficient for the whisker growth requires far more stress (ca. +400 or -400MPa) than we usually observe (ca. -lOMPa). From these, it has been suggested that such a high stress can be attributed to the extremely large distortion of crystal lattice in an atomic level instead of macro-strains. The source of the distortion is supposed to be produced by the excessive Sn atoms generated by imbalanced diffusion between Sn and Cu.

The widespread implementation of the hydrogen economy demands access to materials with a high weight percentage of hydrogen. Mg-based hydrogen storage alloys have become a research hot-spot in recent years owing to their high hydrogen storage capacity, good reversibility of hydrogen absorption/desorption, low cost, and abundant resources. However, high decomposition temperature of Mg-based hydrideslimits their practical usage. Hydrogen is lightest of all elements, typically it need large volumes or high pressures to store appreciable amount of hydrogen.To overcome these challenges research activities are currently going on metal hydrides and complex hydrides based on transition metal. The main challenges come when endothermic decomposition enthalpy is considered. It becomes difficult to release the hydrogen at ambient thermodynamic conditions. On the other hand, the meta-stable hydrides are characterized by a low reaction enthalpy and a decomposition reaction that is thermodynamically favourable under the ambient conditions. The good kinetics along with evolution of hydrogen around the room temperature possessed by these materials offer much promise for underground storage and it can be used as a grid energy.The present research specifically focus on transition metal based complex hydrides such as NaMgMnH6 and NaMgFeH6 for hydrogen storage and especially predicted the crystal structure of the same using VASP simulation package. ABCX6 and AB2X6 were taken as reference composition A,B,C and X were substituted with Na, Mg, transition metals(Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu) and H, respectively.From the ICSD database search the corresponding structural variants were considered as trial structure to predict the ground state structure of these newly designed compounds. using the predicted ground state structure for these compounds, important properties like formation energy, hydrogen site energy, partial density of states(pDOS), electron density(ED), Mulliken effective charge(MEC), Bader electron charge(BEC), Born effective charge, ELF and COHP were calculated. the calculated properties of these compounds were compared with the well known reference compounds. We found that both NaMgMnH6 and NaMgFeH6 are stable with negative formation energy and als othey are semiconductors with the band gap value of 0.51eV and 1.01 eV, respectively. from the calculated electronic structure we found that both these materials are having indirect band behaviour. Analysing the electronic density of states, charge density and various charges mentioned above the chemical bonding behaviour was established as iono-covalent in nature. from the force as well as stress minimisation considering 53 structural variants as input the ground state structure, its space group, equilibrium lattice parameters and atom positions are listed. Also from the energy vs. volume curve for the ground state structure, the equilibrium volume, bulk modulus and pressure derivatives were found out. Among NaMgMnH6 and NaMgFeH6 our spin polarised calculation show that NaMgMnH6 is possesing spontaneous magnetic polarisation with substantial magnetic moment at the Mn site. Among the considered paramagnetic, ferromagnetic, as well as A-, C-,and G- antiferromagnetic configurations the G type antiferromagnetic configuration is found to be the ground state for NaMgMnH6.

Growth and alloy formation of Fe on flat and stepped Pt substrates

The spatial accuracy of deformable image registration (DIR) is important in the implementation of image guided adaptive radiotherapy techniques for cancer in the pelvic region. Validation of algorithms is best performed on phantoms with fiducial markers undergoing controlled large deformations. Excised porcine bladders, exhibiting similar filling and voiding behavior as human bladders, provide such an environment. The aim of this study was to determine the spatial accuracy of different DIR algorithms on CT images of ex vivo porcine bladders with radiopaque fiducial markers applied to the outer surface, for a range of bladder volumes, using various accuracy metrics. Five excised porcine bladders with a grid of 30-40 radiopaque fiducial markers attached to the outer wall were suspended inside a water-filled phantom. The bladder was filled with a controlled amount of water with added contrast medium for a range of filling volumes (100-400 ml in steps of 50 ml) using a luer lock syringe, and CT scans were acquired at each filling volume. DIR was performed for each data set, with the 100 ml bladder as the reference image. Six intensity-based algorithms (optical flow or demons-based) implemented in theMATLAB platform DIRART, a b-spline algorithm implemented in the commercial software package VelocityAI, and a structure-based algorithm (Symmetric Thin Plate Spline Robust Point Matching) were validated, using adequate parameter settings according to values previously published. The resulting deformation vector field from each registration was applied to the contoured bladder structures and to the marker coordinates for spatial error calculation. The quality of the algorithms was assessed by comparing the different error metrics across the different algorithms, and by comparing the effect of deformation magnitude (bladder volume difference) per algorithm, using the Independent Samples Kruskal-Wallis test. The authors found good structure accuracy without dependency on bladder volume difference for all but one algorithm, and with the best result for the structure-based algorithm. Spatial accuracy as assessed from marker errors was disappointing for all algorithms, especially for large volume differences, implying that the deformations described by the registration did not represent anatomically correct deformations. The structure-based algorithm performed the best in terms of marker error for the large volume difference (100-400 ml). In general, for the small volume difference (100-150 ml) the algorithms performed relatively similarly. The structure-based algorithm exhibited the best balance in performance between small and large volume differences, and among the intensity-based algorithms, the algorithm implemented in VelocityAI exhibited the best balance. Validation of multiple DIR algorithms on a novel physiological bladder phantom revealed that the structure accuracy was good for most algorithms, but that the spatial accuracy as assessed from markers was low for all algorithms, especially for large deformations. Hence, many of the available algorithms exhibit sufficient accuracy for contour propagation purposes, but possibly not for accurate dose accumulation.

Role of Mn and Cr on structural parameters and strain energy during FCC-HCP martensitic transformation in Fe-Mn-Cr shape memory alloys

Carnitine acyltransferases have crucial functions in fatty acid metabolism. Members of this enzyme family show distinctive substrate preferences for short-, medium- or long-chain fatty acids. The molecular mechanism for this substrate selectivity is not clear as so far only the structure of carnitine acetyltransferase has been determined. To further our understanding of these important enzymes, we report here the crystal structures at up to 2.0-A resolution of mouse carnitine octanoyltransferase alone and in complex with the substrate octanoylcarnitine. The structures reveal significant differences in the acyl group binding pocket between carnitine octanoyltransferase and carnitine acetyltransferase. Amino acid substitutions and structural changes produce a larger hydrophobic pocket that binds the octanoyl group in an extended conformation. Mutation of a single residue (Gly-553) in this pocket can change the substrate preference between short- and medium-chain acyl groups. The side chains of Cys-323 and Met-335 at the bottom of this pocket assume dual conformations in the substrate complex, and mutagenesis studies suggest that the Met-335 residue is important for catalysis.

The high reactivity of both positive and negative interfacial regions in metal-oxygen (M-O2) batteries leads to a variety of parasitic degradation reactions that reduce reversibility on charge/discharge and can lead to rapid cell failure. To reversibly access the high theoretical specific energies these chemistries promise (3456 and 1602 Wh·kg-1 for Li-O2 and Na-O2, respectively), reducing charging overpotentials and the design of new electrode and electrolyte materials with improved stabilities are key targets. Considering the M|electrolyte interface, where decomposition reactions and dendrite formation generates severe safety concerns as well as reduced cycling stabilities, surface protection of the alkali metal anode by pre-treatment techniques or additive formulation has been among the more successful methodologies.1 In this work, we present a formulation strategy targeting enhanced cycling stabilities of the metal anode in M-O2 cells. Initially demonstrated in the Li-O2 chemistry, we report on an in-depth investigation into the electrochemical performance and the spectroscopic and diffusional properties of ternary ionic liquid (IL)-molecular solvent blend electrolytes.2 By introduction of the IL and exploring a wide formulation range (Figure 1a), we attain significant enhancements in the stability of practically-relevant electrolyte materials that otherwise fail rapidly at alkali metal anodes (Figure 1b), achieving the highest Coulombic efficiencies for Li plating/stripping in this solvent. The optimized formulations consequently displayed enhanced performances in Li-O2 full cells and ex situ characterization of Li surfaces also revealed the suppression of dendrite formation and important changes in the solid electrolyte interphase as a result of modulating solvent reactivity. Using Raman spectroscopy and diffusional analyses, we relate this closely to the local solvation environments involving the reactive solvent component in optimized formulations and, therefore, elucidate critical solvent/Li-salt ratios for improved stability.By understanding key shifts in Raman spectra relating to solvation effects in concentrated Li formulations, and how this modulates cycling performances, we further demonstrate the applicability of this relationship and formulation strategy to the Na-O2 battery chemistry. Therein, the Na metal interface is comparably more reactive and, therefore, presents greater stability challenges, with decomposition reactions in non-optimized formulations more rapidly causing plating and stripping at the anode to fail. However, we demonstrate the plating/stripping of Na (Figure 1c) and cycle lifetime in Na-O2 cells can be hugely improved by applying the above strategy and understandings of critical solvation interactions to equivalent formulations based on Na-salts. Y. Yu, G. Huang, J.-Z. Wang, K. Li, J.-L. Ma, and X.-B. Zhang, Adv. Mater. (Weinheim, Ger.), 32 (38), 2004157 (2020). A. R. Neale, R. Sharpe, S. R. Yeandel, C.-H. Yen, K. V. Luzyanin, P. Goddard, E. A. Petrucco, and L. J. Hardwick, Adv. Funct. Mater., 31 (27), 2010627 (2021). Figure 1. (a) Ternary plot highlighting the changes in stability of Li/Na metal anode cycling as a function of the studied formulation ranges and example voltage profiles of symmetric (b) Li|Li cells and (c) Na|Na cells with non-optimized (navy/purple) and optimized (orange) electrolyte formulations. Figure 1

The work presented in this thesis was dedicated to the development of novel systems based on pyridinium salts for the heterolytic dihydrogen activation and evaluation of their suitability as catalysts for catalytic hydrogenation. These systems contain a pyridinium salt as hydride acceptor and a basic nitrogen or oxygen function as proton acceptor. Initially, an intramolecular system was envisioned, in which the pyridinium salt is linked with a basic amine and the hydrogen cleavage should occur through a concerted transition state. Due to the low stability of the starting materials, mainly decomposition products were observed after test reactions at high temperatures and hydrogen pressures ranging from 50-100 bar. As a next step, a bimolecular system based on pyridinium salts and sterically hindered alcoxides was evaluated. For this purpose, electrophilic N-acyl ammonium salts and phenolates derived from commercially available BHT derivatives were prepared. However, in the presence of hydrogen gas no reaction was observed and starting materials were recovered. ITAMI and co-workers demonstrated the formation of pyridylidenes from pyridinium salts in the presence of a strong base. These highly reactive intermediates could then undergo formal addition of H2. Known pyridinium salt/dihydropyridine systems are Hantzsch esters and nicotinamide derivatives. Both classes of pyridinium salts were tested for H2 activation reactions. Although the formation of the corresponding dihydropyridines was observed, deuteration experiments proved that the reaction did not proceed via dihydrogen splitting. Furthermore, the ability of these N protected pyridinium salts to reduce selected substrates was rather poor. Finally, the activation of dihydrogen was achieved by reaction of a pyridinium salt as described by ITAMI in the presence of base. First, a 1,3,5 triarylpyridinium salt was synthesized, which could be transformed into the corresponding pyridylidene in the presence of LiHMDS. This intermediate was trapped by quenching with S8. Reaction with H2 led to its activation and the corresponding 1,2 dihydropyridine was formed. Dihydrogen activation was confirmed by reaction with deuterium gas, as the 2H NMR spectra showed the signal of the corresponding CD2 group. Studies towards catalytic applications of that system showed that imine 255 was reduced to the corresponding amine in the presence of stoichiometric amounts of base and 20 mol% of catalyst loading.

Dislocations are thought to be the principal mechanism of high ductility of the novel B2 structure intermetallic compounds YAg and YCu. In this paper, the edge dislocation core structures of two primary slip systems 〈100〉{010} and 〈100〉{011̄1} for YAg and YCu are presented theoretically within the lattice theory of dislocation. The governing dislocation equation is a nonlinear integro-differential equation and the variational method is applied to solve the equation. Peierls stresses for 〈100〉{010} and 〈100〉{011̄1} slip systems are calculated taking into consideration the contribution of the elastic strain energy. The core width and Peierls stress of a typical transition-metal aluminide NiAl is also reported for the purpose of verification and comparison. The Peierls stress of NiAl obtained here is in agreement with numerical results, which verifies the correctness of the results obtained for YAg and YCu. Peierls stresses of the 〈100〉{011̄1} slip system are smaller than those of 〈100〉{010} for the same intermetallic compounds originating from the smaller unstable stacking fault energy. The obvious high unstable stacking fault energy of NiAl results in a larger Peierls stress than those of YAg and YCu although they have the same B2 structure. The results show that the core structure and Peierls stress depend monotonically on the unstable stacking fault energy.

Formation, stability, and solubility of metal oxide nanoparticles: Surface entropy, enthalpy, and free energy of ferrihydrite

Role of misfit strain and proximity in epigrowth modes I. Strong epilayer-substrate interaction