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2023-01-12
Hydrogen storage in C14 type TiVZrMnCoFe high entropy alloy
In this present investigation, we discussed the synthesis, microstructure, and hydrogen storage behavior intermetallic Laves phase in a hexanal TiVZrMnCoFe high entropy alloy. In this HEA, three elements are hydride-forming elements and the other three are non-hydride-forming elements (Fe, Mn, Co). The thermodynamic parameter like enthalpy of mixing was calculated using Meidmas model.The possibility of developing high entropy Laves phase-based hydrogen storage materials was advocated.
2301.04942v1
2023-03-27
Thermoelectric Properties of Mg doped Mercury Selenide HgSe
Using the density functional theory (DFT) in combination with Boltzmann transport theory, the influence of Mg concentrations (x) doping on the thermoelectric properties of Hg1-xMgxSe ternary alloys was systematically investigated. The generalized gradient approximations of Perdew-Burke-Ernzerhof (GGA-PBE) have been used to illustrate the exchange correlation potential. Various thermoelectric transport parameters, such as the Seebeck coefficient (S), the thermal conductivity over relaxation time, the electrical conductivity over relaxation time, the power factor (PF) and the figure of merit (ZT) have been deduced and discussed. The obtained results of thermoelectric properties show that the studied materials can be useful for room temperature thermoelectric devices. It is also found that Mg compositions can increase the thermal efficiency of the HgSe alloy.
2303.15179v1
2023-06-12
Wide Range Thin-FIlm Ceramic Metal-Alloy Thermometers with Low Magnetoresistance
Many thermal measurements in high magnetic fields require thermometers that are sensitive over a wide temperature range, are low mass, have a rapid thermal response, and have a minimal, easily correctable magnetoresistance. Here we report the development of a new granular-metal oxide ceramic composite (cermet) for this purpose formed by co-sputtering of the metallic alloy nichrome Ni$_{0.8}$Cr$_{0.2}$ and the insulator silcon dioxide SiO$_2$. The resulting thin films are sensitive enough to be used from room temperature down to below 100 mK in magnetic fields up to at least 35 tesla.
2306.06950v2
2023-11-22
Nonrelaxational FMR peak broadening in spatially inhomogeneous films
The modification of magnetic properties in spatially inhomogeneous epitaxial films of magnetic shape memory alloys in martensitic state with the temperature variation has been studied. The proposed theoretical model is based on Landau theory of martensitic transformation and statistical model of martensitic state. It was shown that that spatial inhomogeneity of the material leads to the dispersion of local martensitic transformation temperatures resulting in the variation of local magnetic anisotropy values. This model allows describing the dramatic ferromagnetic resonance line broadening observed in the experiments in epitaxial films of magnetic shape memory alloys at low temperatures.
2311.13733v1
2024-03-06
Tellurization of Pd(111): absence of PdTe$_2$ but formation of a TePd$_2$ surface alloy
In a recent publication [2D Materials, 8, 045033 (2021), arXiv:2103.11403], it was reported that the growth of a monolayer PdTe$_2$ in ultra-high vacuum could be achieved by deposition of tellurium on a palladium (111) crystal surface and subsequent thermal annealing. By means of low-energy electron diffraction intensity (LEED-IV) structural analysis, we show that the obtained $\left(\sqrt{3}\times \sqrt{3} \right)\textrm{R30}^\circ$ superstructure is in fact a TePd$_2$ surface alloy. Attempts to produce a PdTe$_2$ layer in ultra-high vacuum by increasing the Te content on the surface were not successful.
2403.03564v1
1997-06-06
Exactly Solvable Model of Superconducting Magnetic Alloys
A model describing the Anderson impurity in the Bardeen-Cooper-Schriffer superconductor is proven to exhibit hidden integrability and is diagonalized exactly by the Bethe ansatz.
9706063v1
1998-05-05
Strain-dependent local empirical pseudopotentials for lattice mismatched III-V semiconductors, their alloys, heterostructures and nanostructures
For the latest EPM potentials, please see appendix A in Physical Review B, 59, 15270 (1999)
9805051v2
1998-09-09
Optimization of alloy-analogy-based approaches to the infinite-dimensional Hubbard model
An analytical expression for the self-energy of the infinite-dimensional Hubbard model is proposed that interpolates between different exactly solvable limits. We profit by the combination of two recent approaches that are based on the alloy-analogy (Hubbard-III) solution: The modified alloy-analogy (MAA) which focuses on the strong-coupling regime, and the Edwards-Hertz approach (EHA) which correctly recovers the weak-coupling regime. Investigating the high-energy expansion of the EHA self-energy, it turns out that the EHA reproduces the first three exactly known moments of the spectral density only. This may be insufficient for the investigation of spontaneous magnetism. The analysis of the high-energy behavior of the CPA self-consistency equation allows for a new interpretation of the MAA: The MAA is the only (two-component) alloy-analogy that correctly takes into account the first four moments of the spectral density. For small U, however, the MAA does not reproduce Fermi-liquid properties. The defects of the MAA as well as of the EHA are avoided in the new approach. We discuss the prospects of the theory and present numerical results in comparison with essentially exact quantum Monte Carlo data. The correct high-energy behavior of the self-energy is proved to be a decisive ingredient for a reliable description of spontaneous magnetism.
9809139v1
1998-10-27
Relationship between resistivity and specific heat in a canonical non-magnetic heavy fermion alloy system: UPt_5-xAu_x
UPt_(5-x)Au_x alloys form in a single crystal structure, cubic AuBe_5-type, over a wide range of concentrations from x = 0 to at least x = 2.5. All investigated alloys, with an exception for x = 2.5, were non-magnetic. Their electronic specific heat coefficient $\gamma$ varies from about 60 (x = 2) to about 700 mJ/mol K^2 (x = 1). The electrical resistivity for all alloys has a Fermi-liquid-like temperature variation, \rho = \rho_o + AT^2, in the limit of T -> 0 K. The coefficient A is strongly enhanced in the heavy-fermion regime in comparison with normal and transition metals. It changes from about 0.01 (x = 0) to over 2 micro-ohm cm/K^2 (x = 1). A/\gamma^2, which has been postulated to have a universal value for heavy-fermions, varies from about 10^-6 (x = 0, 0.5) to 10^-5 micro-ohm cm (mol K/mJ)^2 (x > 1.1), thus from a value typical of transition metals to that found for some other heavy-fermion metals. This ratio is unaffected, or only weakly affected, by chemical or crystallographic disorder. It correlates with the paramagnetic Curie-Weiss temperature of the high temperature magnetic susceptibility.
9810361v1
2001-01-04
Formation of hyperfine fields in alloys
This work deals with the analysis of experimental data on the average magnetization of $Fe_{1-x}Me_x$ (Me=Sn,Si) disordered alloys, the average and local hyperfine fields (HFF) at the Fe nuclei. The effect of the metalloid concentration on the HFF is studied with the help of the results of first- principles calculations of ordered alloys. The disorder is taken into account by means of model systems. The dependences obtained correspond to those experimentally observed. Experimental data on the ratio of the average HFF at Fe nuclei to the average magnetisation in alloys with sp-elements show that the ratio decreases proportionally with the metalloid concentration. This change in the ratio is bound up with three factors. First, the contribution of the valence electron polarization by the neighboring atoms, that is positive (unlike the polarization by the own magnetic moment), increases with the change of the disorder degree (increase of concentration). Second, the appearance of the impurities, i.e. metalloid atoms, in the nearest environment of Fe leads to the orbital moment increase. And, finally, the change of the disorder degree, as in the first case, results in an increase in the orbital magnetic moment and its positive contribution to the HFF. The value and the degree of the influence of these contributions to the HFF is discussed.
0101033v1
2001-06-24
The Effect of Lattice Vibrations on Substitutional Alloy Thermodynamics
A longstanding limitation of first-principles calculations of substitutional alloy phase diagrams is the difficulty to account for lattice vibrations. A survey of the theoretical and experimental literature seeking to quantify the impact of lattice vibrations on phase stability indicates that this effect can be substantial. Typical vibrational entropy differences between phases are of the order of 0.1 to 0.2 k_B/atom, which is comparable to the typical values of configurational entropy differences in binary alloys (at most 0.693 k_B/atom). This paper describes the basic formalism underlying ab initio phase diagram calculations, along with the generalization required to account for lattice vibrations. We overview the various techniques allowing the theoretical calculation and the experimental determination of phonon dispersion curves and related thermodynamic quantities, such as vibrational entropy or free energy. A clear picture of the origin of vibrational entropy differences between phases in an alloy system is presented that goes beyond the traditional bond counting and volume change arguments. Vibrational entropy change can be attributed to the changes in chemical bond stiffness associated with the changes in bond length that take place during a phase transformation. This so-called ``bond stiffness vs. bond length'' interpretation both summarizes the key phenomenon driving vibrational entropy changes and provides a practical tool to model them.
0106490v1
2002-03-22
Multiple defect model for non-monotonic structure relaxation in binary systems like Pd-Er alloys charged with hydrogen
In binary metallic systems like the Pd--Er alloys charged with hydrogen the observed structure evolution exhibits complex dynamics. It is characterized by non-monotonic time variations in an Er-rich fraction respect with an Er-poor fraction observed experimentally. The present paper proposes a qualitative model for this non-monotonic structure relaxation. We assume that the alloy have crystalline defects which trap (or emit) an additional amount of Er atoms. Hydrogen atoms into the alloy disturb the phase equilibrium as well as change the defects capacity with respect to Er atoms. Both of these factors lead to the spatial redistribution of Er atoms and cause the interface between the Er-rich and the Er-poor phase to move. The competition of diffusion fluxes in system is responsible for non-monotonic time variations, for example, in the relative volume of the enriched phase. We have found the conditions when the interface motion can change its direction several times during the system relaxation to a new equilibrium state. From our point of view this effect is the essence of the hydrogen induced non-monotonic relaxation observed in such systems. The numerical simulation confirms the basic assumptions.
0203456v2
2002-08-09
Intersubband absorption linewidth in GaAs quantum wells due to scattering by interface roughness, phonons, alloy disorder, and impurities
We calculate the intersubband absorption linewidth in quantum wells (QWs) due to scattering by interface roughness, LO phonons, LA phonons, alloy disorder, and ionized impurities, and compare it with the transport energy broadening that corresponds to the transport relaxation time related to electron mobility. Numerical calculations for GaAs QWs clarify the different contributions of each individual scattering mechanism to absorption linewidth and transport broadening. Interface roughness scattering contributes about an order of magnitude more to linewidth than to transport broadening, because the contribution from the intrasubband scattering in the first excited subband is much larger than that in the ground subband. On the other hand, LO phonon scattering (at room temperature) and ionized impurity scattering contribute much less to linewidth than to transport broadening. LA phonon scattering makes comparable contributions to linewidth and transport broadening, and so does alloy disorder scattering. The combination of these contributions with significantly different characteristics makes the absolute values of linewidth and transport broadening very different, and leads to the apparent lack of correlation between them when a parameter, such as temperature or alloy composition, is changed. Our numerical calculations can quantitatively explain the previously reported experimental results.
0208195v1
2004-07-14
An ab-initio theoretical investigation of the soft-magnetic properties of permalloys
We study Ni80Fe20-based permalloys with the relativistic spin-polarized Korringa-Kohn-Rostoker electronic structure method. Treating the compositional disorder with the coherent potential approximation, we investigate how the magnetocrystalline anisotropy, K, and magnetostriction, lambda, of Ni-rich Ni-Fe alloys vary with the addition of small amounts of non-magnetic transition metals, Cu and Mo. From our calculations we follow the trends in K and lambda and find the compositions of Ni-Fe-Cu and Ni-Fe-Mo where both are near zero. These high permeability compositions of Ni-Fe-Cu and Ni-Fe-Mo match well with those discovered experimentally. We monitor the connection of the magnetic anisotropy with the number of minority spin electrons, Nmin. By raising Nmin via artificially increasing the band-filling of Ni80Fe20, we are able to reproduce the key features that underpin the magnetic softening we find in the ternary alloys. The effect of band-filling on the dependence of magnetocrystalline anisotropy on atomic short-range order in Ni80Fe20 is also studied. Our calculations, based on a static concentration wave theory, indicate that the susceptibility of the high permeability of the Ni-Fe-Cu and Ni-Fe-Mo alloys to their annealing conditions is also strongly dependent on the alloys' compositions. An ideal soft magnet appears from these calculations.
0407355v1
2004-07-27
Phase-field simulations of solidification in binary and ternary systems using a finite element method
We present adaptive finite element simulations of dendritic and eutectic solidification in binary and ternary alloys. The computations are based on a recently formulated phase-field model that is especially appropriate for modelling non-isothermal solidification in multicomponent multiphase systems. In this approach, a set of governing equations for the phase-field variables, for the concentrations of the alloy components and for the temperature has to be solved numerically, ensuring local entropy production and the conservation of mass and inner energy. To efficiently perform numerical simulations, we developed a numerical scheme to solve the governing equations using a finite element method on an adaptive non-uniform mesh with highest resolution in the regions of the phase boundaries. Simulation results of the solidification in ternary Ni$_{60}$Cu$_{40-x}$Cr$_{x}$ alloys are presented investigating the influence of the alloy composition on the growth morphology and on the growth velocity. A morphology diagram is obtained that shows a transition from a dendritic to a globular structure with increasing Cr concentrations. Furthermore, we comment on 2D and 3D simulations of binary eutectic phase transformations. Regular oscillatory growth structures are observed combined with a topological change of the matrix phase in 3D. An outlook for the application of our methods to describe AlCu eutectics is given.
0407694v1
2005-07-12
Precipitation in Al-Zr-Sc alloys: a comparison between kinetic Monte Carlo, cluster dynamics and classical nucleation theory
Zr and Sc precipitate in aluminum alloys to form the Al\_3Zr\_xSc\_{1-x} compound which, for low supersaturations of the solid solution, exhibits the L1\_2 structure. The aim of the present study is to model at an atomic scale the kinetics of precipitation and to build mesoscopic models so as to extend the range of supersaturations and annealing times that can be simulated up to values of practical interest. In this purpose, we use some ab initio calculations and experimental data to fit an Ising type model describing thermodynamics of the Al-Zr-Sc system. Kinetics of precipitation are studied with a kinetic Monte Carlo algorithm based on an atom-vacancy exchange mechanism. Cluster dynamics is then used to model at a mesoscopic scale all the different stages of homogeneous precipitation in the two binary Al-Zr and Al-Sc alloys. This technique correctly manages to reproduce both the kinetics of precipitation simulated with kinetic Monte Carlo as well as experimental observations. Focusing on the nucleation stage, it is shown that classical theory well applies as long as the short range order tendency of the system is considered. This allows us to propose an extension of classical nucleation theory for the ternary Al-Zr-Sc alloy.
0507259v2
2006-03-12
Kinetic theory of nucleation and coarsening
Classical theory of nucleation based on Becker-Doering equations and coarsening for a binary alloy.
0603330v1
2006-07-12
Title Cluster-Variational Treatment of Disordered Mixed Spin Ising Model
A disordered alloy Ap B1-p where both A and B represent the magnetic atoms with respective spin SA =1/2 and SB =1 and whose magnetic interaction can be described through Ising Hamiltonian is treated using the cluster-variational method. In this method it is assumed that the system is built out of building block which is embedded in an effective field. Taking building block as 4-atom cluster the approximate free energy of the alloy is then obtained by treating the interactions between spins within the cluster of all possible configurations in exact manner and the rest of the interaction by an effective variational field . The magnetization M and transition temperature Tc are then calculated for different concentration and exchange parameters (JAA, JBB and JAB). The magnetization M exhibits different kinds of ferrimagnetic behaviour depending on concentration and relative strength of intra- and inter- sub-network exchange interactions. For antiferromagnetic JAB, the sub-network magnetization saturates and aligned antiferromagnetically at low temperature. The existence of compensation temperature Tcm, where total magnetization reverses its direction, depends sensitively on relative values of JAA/ JAB and JBB/ JAB and p. For B (A)-rich alloy with small JAB, the direction of net magnetization remains same upto Tc and a maximum of M appears at intermediate T < Tc when JBB>> JAA (JBB<< JAA).When magnitude of JAB > JAA, JBB, Tc exhibits a maximum with p. The transition temperature is much less than the mean-field value for all cases. The magnetic susceptibility for diverges and is Curie-Wiess like at T >>Tc. The meta-magnetic behaviour at high magnetic field has been found. Some of these results are in tune with experimental observation in amorphous rare-earth-transition metal alloys.
0607299v1
2006-12-27
Calculation of conduction-to-conduction and valence-to-valence transitions between bound states in (In,Ga)As/GaAs quantum dots
We have calculated the conduction-to-conduction and valence-to-valence absorption spectrum of bound states in (In,Ga)As/GaAs quantum dots charged with up to three electrons or holes. Several features emerge: (i) In pure (non-alloyed) InAs/GaAs dots, the 1S-1P_1 and 1S-1P_2 conduction intraband transitions are fully in-plane polarized along [1\bar 10] and [110], respectively, while valence transitions are weakly polarized because the hole P states do not show any in-plane preferential orientation. (ii) In alloyed In_{0.6}Ga_{0.4}As/GaAs dots the [110] and [1\bar 10] polarization of the corresponding 1S-1P conduction intraband transitions is weakened since the two 1P states are mixed by alloy fluctuations. The polarization of valence intraband transitions is insensitive to changes in alloy fluctuations. (iii) For light polarized along [001], we find a strong valence-to-valence transition that involves a weakly confined hole state with predominant light-hole character. (iv) When charging the dots with a few electrons, the conduction intraband transitions display spectroscopic shifts of ~1-2 meV. These shifts are a result of correlation effects (captured by configuration-interaction) and not well described within the Hartree-Fock approximation. (v) When charging the dots with holes, valence intraband spectra are more complex than the conduction intraband spectra as hole states are strongly affected by spin-orbit coupling, and configuration mixing is more pronounced. Spectroscopic shifts can no longer be identified unambiguously. These predictions could be tested in single-dot spectroscopy of n-doped and p-doped quantum dots.
0612648v1
2007-02-15
Real space screened-exchange method for semiconductors and their alloys
This paper has been withdrawn by the author(s), due a crucial error in Eqn. 30.
0702345v2
2007-06-04
Interplay between thermal percolation and jamming upon dimer adsorption on binary alloys
Using Monte Carlo simulations we study jamming and percolation processes upon the random sequential adsorption of dimers on binary alloys with different degrees of structural order. We obtain the equimolar mixtures used as substrates by applying the isomorphism between an alloy and the Ising model (conserved order parameter). The annealing temperature $T$ of the mixture then is a continuous parameter that characterizes the different sets of substrates, shaping the deposition process. As the alloy undergoes an order-disorder phase transition at the Onsager critical temperature ($T_{c}$), the jamming and percolating properties of the dimers deposited over the substrate are subjected to non-trivial changes. These are reflected in a density-temperature phase diagram with three well-defined regions. We find that for $T < T^* = 1.22 T_{c}$ the occurrence of jamming prevents the onset of percolating clusters, while percolation is possible for $T > T^{*}$. Particular attention is focused close to $T^{*}$, where the interplay between jamming and percolation restricts fluctuations, forcing exponents seemingly different from the standard percolation universality class. By analogy with a thermal transition, we study the onset of percolation by using the {\it temperature} (in this case, the substrate annealing temperature) as a control parameter. By proposing thermal scaling Ansatzes we analyze the behavior of the percolation threshold and its thermally induced fluctuations. Also, the fractal dimension of the percolating cluster is determined. Based on these measurements and the excellent data collapsing, we conclude that the universality class of standard percolation is preserved for all temperatures.
0706.0562v1
2008-07-31
Non-substitutional single-atom defects in the Ge_(1-x)Sn_x alloy
Ge_(1-x)Sn_x alloys have proved difficult to form at large x, contrary to what happens with other group IV semiconductor combinations. However, at low x they are typical examples of well-behaved substitutional compounds, which is desirable for harnessing the electronic properties of narrow band semiconductors. In this paper, we propose the appearance of another kind of single-site defect ($\beta-Sn$), consisting of a single Sn atom in the center of a Ge divacancy, that may account for these facts. Accordingly, we examine the electronic and structural properties of these alloys by performing extensive numerical ab-initio calculations around local defects. The results show that the environment of the $\beta$ defect relaxes towards a cubic octahedral configuration, facilitating the nucleation of metallic white tin and its segregation, as found in amorphous samples. Using the information stemming from these local defect calculations, we built a simple statistical model to investigate at which concentration these $\beta$ defects can be formed in thermal equilibrium. These results agree remarkably well with experimental findings, concerning the critical concentration above which the homogeneous alloys cannot be formed at room temperature. Our model also predicts the observed fact that at lower temperature the critical concentration increases. We also performed single site effective-field calculations of the electronic structure, which further support our hypothesis.
0807.5025v1
2009-07-06
A theoretical study of the cluster glass-Kondo-magnetic disordered alloys
The physics of disordered alloys, such as typically the well known case of CeNi1-xCux alloys, showing an interplay among the Kondo effect, the spin glass state and a magnetic order, has been studied firstly within an average description like in the Sherrington-Kirkpatrick model. Recently, a theoretical model (PRB 74, 014427 (2006)) involving a more local description of the intersite interaction has been proposed to describe the phase diagram of CeNi1-xCux. This alloy is an example of the complex interplay between Kondo effect and frustration in which there is in particular the onset of a cluster-glass state. Although the model given in Ref. PRB 74, 014427 (2006) has reproduced the different phases relatively well, it is not able to describe the cluster-glass state. We study here the competition between the Kondo effect and a cluster glass phase within a Kondo Lattice model with an inter-cluster random Gaussian interaction. The inter-cluster term is treated within the cluster mean-field theory for spin glasses, while, inside the cluster, an exact diagonalisation is performed including inter-site ferromagnetic and intra-site Kondo interactions. The cluster glass order parameters and the Kondo correlation function are obtained for different values of the cluster size, the intra-cluster ferromagnetic coupling and the Kondo intra-site coupling. We obtain, for instance, that the increase of the Kondo coupling tends to destroy the cluster glass phase.
0907.0981v1
2010-03-26
Contact superconductivity in In-PbTe junctions
The authors report on electron transport studies on superconductor-semiconductor hybrid structures of indium and n-type lead telluride, either in the form of quantum wells or bulk crystals. In-PbTe contacts form by spontaneous alloying, which occurs already at room temperature. The alloyed phase penetrates deeply into PbTe and forms metallic contacts even in the presence of depletion layers at the semiconductor surface. Although the detailed structure of this phase is unknown, we observe that it exhibits a superconducting transition at temperatures below 10 K. This causes such substantial reduction of the contact resistances that they even become comparable to those predicted for ideal superconductor-normal conductor contacts. Most importantly, this result indicates that the interface phase in the superconducting state becomes nearly homogeneous - in contrast to the structure expected for alloyed contacts. We suggest that the unusual interface superconductivity is linked to the unique properties of PbTe, namely, its huge static dielectric constant. Apparently the alloyed interface phase contains superconducting precipitates randomly distributed within the depletion layers, and their Coulomb charging energies are extremely small. According to the existing models of the granular superconductivity, even very weak Josephson coupling between the neighboring precipitates gives rise to the formation of a global superconducting phase which explains our observations.
1003.5140v1
2010-06-24
Kinetics of natural aging in Al-Mg-Si alloys studied by positron annihilation lifetime spectroscopy
The process of natural aging in pure ternary Al-Mg-Si alloys was studied by positron annihilation lifetime spectroscopy in real time in order to clarify the sequence and kinetics of clustering and precipitation. It was found that natural aging takes place in at least five stages in these alloys, four of which were directly observed. This is interpreted as the result of complex interactions between vacancies and solute atoms or clusters. One of the early stages of positron lifetime evolution coincides with a clustering process observed by differential scanning calorimetry (DSC) and involves the formation of a positron trap with \sim 0.200 ns lifetime. In later stages, a positron trap with a higher lifetime develops in coincidence with the DSC signal of a second clustering reaction. Mg governs both the kinetics and the lifetime change in this stage. Within the first 10 min after quenching, a period of nearly constant positron lifetime was found for those Mg-rich alloys that later show an insufficient hardness response to artificial aging, the so-called "negative effect." The various processes observed could be described by two effective activation energies that were found by varying the aging temperature from 10 to 37\degree C.
1006.4778v4
2011-10-28
Self-consistent supercell approach to alloys with local environment effects
We present an efficient and accurate method for calculating electronic structure and related properties of random alloys with a proper treatment of local environment effects. The method is a generalization of the locally self-consistent Green's function (LSGF) technique for the exact muffin-tin orbital (EMTO) method. An alloy system in the calculations is represented by a supercell with a certain set of atomic distribution correlation functions. The Green's function for each atom in the supercell is obtained by embedding the cluster of neighboring atoms lying within a local interaction zone (LIZ) into an effective medium and solving the cluster Dyson equation exactly. The key ingredients of the method are locality, which makes it linearly scaling with the number of atoms in the supercell, and coherent-potential self-consistency of the effective medium, which results in a fast convergence of the electronic structure with respect to the LIZ size. To test the performance and accuracy of the method, we apply it to two systems: Fe-rich bcc-FeCr random alloy with and without a short-range order, and a Cr-impurity on the Fe surface. Both cases demonstrate the importance of taking into account the local environment effects for correct description of magnetic and bulk properties.
1110.6354v3
2011-11-18
Tight-binding analysis of the electronic structure of dilute bismide alloys of GaP and GaAs
We develop an atomistic, nearest-neighbor sp3s* tight-binding Hamiltonian to investigate the electronic structure of dilute bismide alloys of GaP and GaAs. Using this model we calculate that the incorporation of dilute concentrations of Bi in GaP introduces Bi-related defect states in the band gap, which interact with the host matrix valence band edge via a Bi composition dependent band anti-crossing (BAC) interaction. By extending this analysis to GaBiAs we demonstrate that the observed strong variation of the band gap Eg and spin-orbit-splitting (SO) energy with Bi composition can be well explained in terms of a BAC interaction between the extended states of the GaAs valence band edge and highly localized Bi-related defect states lying in the valence band, with the change in Eg also having a significant contribution from a conventional alloy reduction in the conduction band edge energy. Our calculated values of Eg and SO are in good agreement with experiment throughout the investigated composition range x less than 13%. In particular, our calculations reproduce the experimentally observed crossover to an Eg < SO regime at approximately 10.5% Bi composition in bulk GaBiAs. Recent x-ray spectroscopy measurements have indicated the presence of Bi pairs and clusters even for Bi compositions as low as 2%. We include a systematic study of different Bi nearest-neighbor environments in the alloy to achieve a quantitative understanding of the effect of Bi pairing and clustering on the GaBiAs electronic structure.
1111.4394v1
2012-04-10
Crystal structure of Cu-Sn-In alloys around the η phase field studied by neutron diffraction
The study of the Cu-Sn-In ternary system has become of great importance in recent years, due to new environmental regulations forcing to eliminate the use of Pb in bonding technologies for electronic devices. A key relevant issue concerns the intermetallic phases which grow in the bonding zone and are determining in their quality and performance. In this work, we focus in the {\eta}-phase (Cu2In or Cu6Sn5) that exists in both end binaries and as a ternary phase. We present a neutron diffraction study of the constitution and crystallography of a series of alloys around the 60 at.% Cu composition, and with In contents ranging from 0 to 25 at.%, quenched from 300\degreeC. The alloys were characterized by scanning electron microscopy, probe microanalysis and high-resolution neutron diffraction. The Rietveld refinement of neutron diffraction data allowed to improve the currently available model for site occupancies in the hexagonal {\eta}-phase in the binary Cu-Sn as well as in ternary alloys. For the first time, structural data is reported in the ternary Cu-Sn-In {\eta}-phase as a function of composition, information that is of fundamental technological importance as well as valuable input data for ongoing modelisations of the ternary phase diagram.
1204.2154v1
2012-06-20
The influence of magnetic sublattice dilution on magnetic order in CeNiGe3 and UNiSi2
Polycrystalline samples of the Y-diluted antiferromagnet CeNiGe3 (T_N = 5.5 K) and Th-diluted ferromagnet UNiSi2 (T_C = 95 K) were studied by means of x-ray powder diffraction, magnetization and specific heat measurements performed in a wide temperature range. The lattice parameters of the Ce1-xYxNiGe3 alloys decrease linearly with increasing the Y content, while the unit cell volume of U1-xThxNiSi2 increases linearly with rising the Th content. The ordering temperatures of the systems decrease monotonically with increasing x down to about 1.2 K in Ce0.4Y0.6NiGe3 and 26 K in U0.3Th0.7NiSi2, forming a dome of a long-range magnetic order on their magnetic phase diagrams. The suppression of the magnetic order is associated with distinct broadening of the anomalies at T_N,C due to crystallographic disorder being a consequence of the alloying. Below the magnetic percolation threshold xc of about 0.68 and 0.75 in the Ce- and U-based alloys, respectively, the long-range magnetic order smoothly evolves into a short-range one, forming a tail on the magnetic phase diagrams. The observed behaviour Ce1-xYxNiGe3 and U1-xThxNiSi2 is characteristic of diluted magnetic alloys. (c) 2012 IOP Publishing Ltd.
1206.4392v1
2012-11-02
Elasticity behavior, phonon spectra, and the pressure-temperature phase diagram of HfTi alloy: A density-functional theory study
The pressure-induced phase transition, elasticity behavior, thermodynamic properties, and $P\mathtt{-}T$ phase diagram of $\alpha$, $\omega$, and $\beta$ equiatomic HfTi alloy are investigated using first-principles density-functional theory (DFT). The simulated pressure-induced phase transition of the alloy follows the sequence of $\alpha\mathtt{\rightarrow}\omega\mathtt{\rightarrow}\beta$, in agreement with the experimental results of Hf and Ti metals. Our calculated elastic constants show that the $\alpha$ and $\omega$ phases are mechanically stable at ambient pressure, while the $\beta$ phase is unstable, where a critical pressure of 18.5 GPa is predicted for its mechanical stability. All the elastic constants, bulk modulus, and shear modulus increase upon compression for the three phases of HfTi. The ductility of the alloy is shown to be well improved with respect to pure Hf and Ti metals. The Mulliken charge population analysis illustrates that the increase of the d-band occupancy will stabilize the $\beta$ phase under pressure. The phonon spectra and phonon density of states are studied using the supercell approach for the three phases, and the stable nature of $\alpha$ and $\omega$ phases at ambient pressure are observed, while the $\beta$ phase is only stable along the [110] direction. With the Gibbs free energy calculated from DFT-parametrized Debye model as a function of temperature and pressure, the phase transformation boundaries of the $\alpha$, $\omega$, and $\beta$ phases of HfTi are identified.
1211.0375v1
2013-04-16
Modeling the amorphous structure of a mechanically alloyed Ti50Ni25Cu25 alloy using anomalous wide-angle x-ray scattering and reverse Monte Carlo simulations
An amorphous Ti50Ni25Cu25 alloy was produced by 19 h of mechanical alloying. Anomalous wide angle x-ray scattering data were collected at six energies and six total scattering factors were obtained. By considering the data collected at two energies close to the Ni and Cu K edges, two differential anomalous scattering factors around the Ni and Cu atoms were obtained, showing the chemical environments around these atoms are different. The eight factors were used as input data to the reverse Monte Carlo method used to compute the partial structure factors STi-Ti(K), STi-Cu(K), STi-Ni(K), SCu-Cu(K), SCu-Ni(K) and SNi-Ni(K). From their Fourier transformation, the partial pair distribution functions GTi-Ti(r), GTi-Cu(r), GTi-Ni(r), GCu-Cu(r), GCu-Ni(r) and GNi-Ni(r) were obtained, and the coordination numbers and interatomic atomic distances for the first neighbors were determined.
1304.4604v1
2013-09-12
12-band $\textbf{k}\cdot\textbf{p}$ model for dilute bismide alloys of (In)GaAs derived from supercell calculations
Incorporation of bismuth (Bi) in dilute quantities in (In)GaAs has been shown to lead to unique electronic properties that can in principle be exploited for the design of high efficiency telecomm lasers. This motivates the development of simple models of the electronic structure of these dilute bismide alloys, which can be used to evaluate their potential as a candidate material system for optical applications. Here, we begin by using detailed calculations based on an $sp^{3}s^{*}$ tight-binding model of (In)GaBi$_{x}$As$_{1-x}$ to verify the presence of a valence band-anticrossing interaction in these alloys. Based on the tight-binding model the derivation of a 12-band $\textbf{k}\cdot\textbf{p}$ Hamiltonian for dilute bismide alloys is outlined. We show that the band structure obtained from the 12-band model is in excellent agreement with full tight-binding supercell calculations. Finally, we apply the 12-band model to In$_{0.53}$Ga$_{0.47}$Bi$_{x}$As$_{1-x}$ and compare the calculated variation of the band gap and spin-orbit-splitting to a variety of spectroscopic measurements performed on a series of MBE-grown In$_{0.53}$Ga$_{0.47}$Bi$_{x}$As$_{1-x}$/InP layers.
1309.3305v1
2014-01-23
Magnetization, magnetostriction, and their relationship in Invar Fe$_{1-x}A_{x}$ ($A={\rm Pt},{\rm Ni}$)
A method is proposed for investigating the spontaneous magnetization, the spontaneous volume magnetostriction, and their relationship in disordered face-centered-cubic Fe$_{0.72}$Pt$_{0.28}$ and Fe$_{0.65}$Ni$_{0.35}$ in the temperature interval $0 \leq T/T_{\rm C} < 1$. It relies on the disordered local moment formalism and the observation that the reduced magnetization in each of the investigated materials is accurately described by an equation of the form $M(T)/M(0) = [ 1 -s (T/T_{\rm C})^{3/2}- (1-s)(T/T_{\rm C})^{p} ]^{q}$. The present approach yields interesting results. The alloys at zero Kelvin share several physical properties: the volume in a partially disordered local moment state shrinks as the fraction of Fe moments which point down increases in the interval $0 < x^{{\rm Fe}\downarrow} < 1/2$, following closely $V(0) - 4 [V(0)-V(1/2)] x^{{\rm Fe}\downarrow} (1-x^{{\rm Fe}\downarrow})$, while the magnetization collapses, following closely $M(0) - 2 M(0) x^{{\rm Fe}\downarrow}$; the volume in the homogeneous ferromagnetic state greatly exceeds that in the disordered local moment state; $x^{{\rm Fe}\downarrow}(0)$ is close to zero. These common properties can account for a variety of intriguing phenomena displayed by both alloys, including the anomaly in the magnetostriction at zero Kelvin and, more surprisingly perhaps, the scaling between the reduced magnetostriction and the reduced magnetization squared below the Curie temperature. However, the thermal evolution of the fraction of Fe moments which point down depends strongly on the alloy under consideration. This, in turn, can explain the observed marked difference in the temperature dependence of the reduced magnetization between the two alloys.
1401.6089v2
2014-08-19
Exploring quantum phase transition in Pd_{1-x}Ni_x nanoalloys
Pd$_{1-x}$Ni$_x$ alloy system is an established ideal transition metal system possessing a composition induced paramagnetic to ferromagnetic quantum phase transition (QPT) at the critical concentration $x_c \sim$ 0.026 in bulk. A low-temperature non-Fermi liquid (NFL) behaviour around $x_c$ usually indicates the presence of quantum criticality (QC) in this system. In this work, we explore the existence of such a QPT in nanoparticles of this alloy system. We synthesized single-phase, polydispersed and 40-50 nm mean diameter crystalline nanoparticles of Pd$_{1-x}$Ni$_x$ alloys, with $x$ near $x_c$ and beyond, by a chemical reflux method. In addition to the determination of the size, composition, phase and crystallinity of the alloys by microscopic and spectroscopic techniques, the existence of a possible QPT was explored by resistivity and DC magnetization measurements. A dip in the value of the exponent $n$ near $x_c$, and a concomitant peak in the constant $A$, of the $AT^n$ dependence of the low temperature ($T$) resistivity indicate the presence of a quantum-like phase transition in the system. The minimum value of $n$, however, remains within the Fermi liquid regime ($n >$ 2). The DC magnetization results suggest an anticipatory presence of a superparamagnetic to ferromagnetic QPT in the mean-sized nanoparticles. The observation of a possible quantum critical NFL behaviour ($n <$ 2) through resistivity is argued to be inhibited by the electron-magnon scatterings present in the smaller nanoparticles.
1408.4316v1
2015-01-27
From solid solution to cluster formation of Fe and Cr in $α$-Zr
To understand the mechanisms by which Fe and Cr additions increase the corrosion rate of irradiated Zr alloys, a combination of experimental (atom probe tomography, x-ray diffraction and thermoelectric power measurements) and modelling (density functional theory) techniques are employed to investigate the non-equilibrium solubility and clustering of Fe and Cr in binary Zr alloys. Cr occupies both interstitial and substitutional sites in the {\alpha}-Zr lattice, Fe favours interstitial sites, and a low-symmetry site that was not previously modelled is found to be the most favourable for Fe. Lattice expansion as a function of alloying concentration (in the dilute regime) is strongly anisotropic for Fe additions, expanding the $c$-axis while contracting the $a$-axis. Defect clusters are observed at higher solution concentrations, which induce a smaller amount of lattice strain compared to the dilute defects. In the presence of a Zr vacancy, all two-atom clusters are more soluble than individual point defects and as many as four Fe or three Cr atoms could be accommodated in a single Zr vacancy. The Zr vacancy is critical for the increased solubility of defect clusters, the implications for irradiation induced microstructure changes in Zr alloys are discussed.
1501.06732v3
2015-03-13
Broken Time Reversal Symmetry in Superconducting Pr1-xCexPt4Ge12
We report results of zero-field muon spin relaxation experiments on the filled-skutterudite superconductors~Pr$_{1-x}$Ce$_{x}$Pt$_4$Ge$_{12}$, $x = 0$, 0.07, 0.1, and 0.2, to investigate the effect of Ce doping on broken time-reversal symmetry (TRS) in the superconducting state. In these alloys broken TRS is signaled by the onset of a spontaneous static local magnetic field~$B_s$ below the superconducting transition temperature. We find that $B_s$ decreases linearly with $x$ and $\to 0$ at $x \approx 0.4$, close to the concentration above which superconductivity is no longer observed. The (Pr,Ce)Pt$_4$Ge$_{12}$ and isostructural (Pr,La)Os$_4$Sb$_{12}$ alloy series both exhibit superconductivity with broken TRS, and in both the decrease of $B_s$ is proportional to the decrease of Pr concentration. This suggests that Pr-Pr intersite interactions are responsible for the broken TRS\@. The two alloy series differ in that the La-doped alloys are superconducting for all La concentrations, suggesting that in (Pr,Ce)Pt$_4$Ge$_{12}$ pair-breaking by Ce doping suppresses superconductivity. For all $x$ the dynamic muon spin relaxation rate decreases somewhat in the superconducting state. This may be due to Korringa relaxation by conduction electrons, which is reduced by the opening of the superconducting energy gap.
1503.03967v1
2015-04-20
Engineering the electronic bandgaps and band edge positions in carbon-substituted 2D boron nitride: a first-principles investigation
Modification of graphene to open a robust gap in its electronic spectrum is essential for its use in field effect transistors and photochemistry applications. Inspired by recent experimental success in the preparation of homogeneous alloys of graphene and boron nitride (BN), we consider here engineering the electronic structure and bandgap of C$_{2x}$B$_{1-x}$N$_{1-x}$ alloys via both compositional and configurational modification. We start from the BN end-member, which already has a large bandgap, and then show that (a) the bandgap can in principle be reduced to about 2 eV with moderate substitution of C $(x<0.25)$; and (b) the electronic structure of C$_{2x}$B$_{1-x}$N$_{1-x}$ can be further tuned not only with composition $x$, but also with the configuration adopted by C substituents in the BN matrix. Our analysis, based on accurate screened hybrid functional calculations, provides a clear understanding of the correlation found between the bandgap and the level of aggregation of C atoms: the bandgap decreases most when the C atoms are maximally isolated, and increases with aggregation of C atoms due to the formation of bonding and anti-bonding bands associated with hybridization of occupied and empty defect states. We determine the location of valence and conduction band edges relative to vacuum and discuss the implications on the potential use of 2D C$_{2x}$B$_{1-x}$N$_{1-x}$ alloys in photocatalytic applications. Finally, we assess the thermodynamic limitations on the formation of these alloys using a cluster expansion model derived from first-principles.
1504.05062v1
2015-05-20
Ab initio prediction of the mechanical properties of alloys: The case of Ni/Mn-doped ferromagnetic Fe
First-principles alloy theory, formulated within the exact muffin-tin orbitals method in combination with the coherent-potential approximation, is used to study the mechanical properties of ferromagnetic body-centered cubic (bcc) Fe$_{1-x}$M$_x$ alloys (M=Mn or Ni, $0\le x \le 0.1$). We consider several physical parameters accessible from \emph{ab initio} calculations and their combinations in various phenomenological models to compare the effect of Mn and Ni on the properties of Fe. Alloying is found to slightly alter the lattice parameters and produce noticeable influence on elastic moduli. Both Mn and Ni decrease the surface energy and the unstable stacking fault energy associated with the $\{110\}$ surface facet and the $\{110\}\langle111\rangle$ slip system, respectively. Nickel is found to produce larger effect on the planar fault energies than Mn. The semi-empirical ductility criteria by Rice and Pugh consistently predict that Ni enhances the ductility of Fe but give contradictory results in the case of Mn doping. The origin of the discrepancy between the two criteria is discussed and an alternative measure of the ductile-brittle behavior based on the theoretical cleavage strength and single-crystal shear modulus $G\{110\}\langle111\rangle$ is proposed.
1505.05443v1
2015-05-31
Residual stress induced stabilization of martensite phase and its effect on the magneto-structural transition in Mn rich Ni-Mn-In/Ga magnetic shape memory alloys
The irreversibility of the martensite transition in magnetic shape memory alloys (MSMAs) with respect to external magnetic field is one of the biggest challenges that limits their application as giant caloric materials. This transition is a magneto-structural transition that is accompanied with a steep drop in magnetization (i.e., 'delta M') around the martensite start temperature (Ms) due to the lower magnetization of the martensite phase. In this communication, we show that 'delta M' around Ms in Mn rich Ni-Mn based MSMAs gets suppressed by two orders of magnitude in crushed powders due to the stabilization of the martensite phase at temperatures well above the Ms and the austenite finish (Af) temperatures due to residual stresses. Analysis of the intensities and the FWHM of the x-ray powder diffraction patterns reveals stabilized martensite phase fractions as 97, 75 and 90% with corresponding residual microstrains as 5.4, 5.6 and 3% in crushed powders of the three different Mn rich Ni-Mn alloys, namely, Mn1.8Ni1.8In0.4, Mn1.75Ni1.25Ga and Mn1.9Ni1.1Ga, respectively. Even after annealing at 773 K, the residual stress stabilised martensite phase does not fully revert to the equilibrium cubic austenite phase as the magneto-structural transition is only partially restored with reduced value of 'delta M'. Our results have very significant bearing on application of such alloys as inverse magnetocaloric and barocaloric materials.
1506.00266v1
2015-06-17
Two-dimensional connective nanostructures of electrodeposited Zn on Au(111) induced by spinodal decomposition
Phase-formation of surface alloying by spinodal decomposition has been studied for the first time at an electrified interface. For this aim Zn was electrodeposited on Au(111) from the ionic liquid AlCl3-MBIC (58:42) containing 1 mM Zn(II) at different potentials in the underpotential range corresponding to submonolayer up to monolayer coverage. Structure evolution was observed by in situ electrochemical scanning tunneling microscopy (STM) at different times after starting the deposition via potential jumps and at temperatures of 298 K and 323 K. Spinodal or labyrinth two-dimensional structures predominate at middle coverage, both in deposition and dissolution experiments. They are characterized by a length scale of typically 5 nm which has been determined from the power spectral density of the STM images. Structure formation and surface alloying is governed by slow kinetics with a rate constant k with activation energy of 120 meV and preexponential factor of 0.17 Hz. The evolution of the structural features is described by a continuum model and is found to be in good agreement with the STM observations. From the experimental and model calculation results we conclude that the two-dimensional phase-formation in the Zn on Au(111) system is dominated by surface alloying. The phase separation of a Zn-rich and a Zn-Au alloy phase is governed by 2D spinodal decomposition.
1506.05206v2
2015-06-22
Structure of the glass-forming metallic liquids by ab-initio and classical molecular dynamics, a case study: quenching the Cu60Ti20Zr20 alloy
We consider the question of the amorphization of metallic alloys by melt quenching, as predicted by molecular dynamics simulations with semi-empirical potentials. The parametrization of the potentials is discussed on the example of the ternary Cu-Ti-Zr transition metals alloy, using as reference the ab-initio simulation. The pair structure in the amorphous state is computed from a potential of the Stillinger Weber form. The transferability of the parameters during the quench is investigated using two parametrizations: from solid state data, as usual, and from a new parametrization on the liquid structure. When the adjustment is made on the pair structure of the liquid, a satisfactory transferability is found between the pure components and their alloys. The liquid structure predicted in this way agrees well with experiment, in contrast with the one obtained using the adjustment on the solid. The final structure, after quenches down to the amorphous state, determined with the new set of parameters is shown to be very close to the ab-initio one, the latter being in excellent agreement with recent X-rays diffraction experiments. The corresponding critical temperature of the glass transition is estimated from the behavior of the heat capacity. Discussion of the consistency between the structures predicted using semi-empirical potentials and ab-initio simulation, and comparison of different experimental data underlines the question of the dependence of the final structure on the thermodynamic path followed to reach the amorphous state.
1506.06530v3
2015-08-04
Effect of Atomic Size and Valence Electron Concentration on the Formation of fcc or bcc Solid Solid Solutions in High Entropy Alloys
The possibility of solid solution formation in high entropy alloys (HEAs) has been calculated for alloys with four to seven elements, using a rule previously reported. Thirty elements were included: transition elements of the fourth, fifth and sixth periods of the periodic table, and aluminum. A total of 2,799,486 systems were analyzed. The percentage of solid solutions that would be formed in HEAs decreases from 35.9% to 26.4%, as the number of elements increases from four to seven. The structure of the solid solutions, fcc, bcc or a mixture of fcc and bcc, that would be formed, has been predicted using a previously reported observation. The percentage of systems with fcc or bcc structure decreases as the number of elements increases from four to seven. The percentages of solid solutions with fcc, bcc or a mixture of fcc and bcc were calculated, for alloys with four to seven elements, but maintaining one constant element. Systems in which the constant element has valence electron concentration, VEC, from three to four, would have bcc structure in around 50% of the systems. Systems in which the constant element has VEC from ten to twelve, around 75% of systems would present fcc structure.
1508.00935v2
2016-01-13
An Optimal Block Diagonal Preconditioner for Heterogeneous Saddle Point Problems in Phase Separation
The phase separation processes are typically modeled by Cahn-Hilliard equations. This equation was originally introduced to model phase separation in binary alloys, where phase stands for concentration of different components in alloy. When the binary alloy under preparation is subjected to a rapid reduction in temperature below a critical temperature, it has been experimentally observed that the concentration changes from a mixed state to a visibly distinct spatially separated two phase for binary alloy. This rapid reduction in the temperature, the so-called "deep quench limit", is modeled effectively by obstacle potential. The discretization of Cahn-Hilliard equation with obstacle potential leads to a block $2 \times 2$ {\em non-linear} system, where the $(1,1)$ block has a non-linear and non-smooth term. Recently a globally convergent Newton Schur method was proposed for the non-linear Schur complement corresponding to this non-linear system. The proposed method is similar to an inexact active set method in the sense that the active sets are first approximately identified by solving a quadratic obstacle problem corresponding to the $(1,1)$ block of the block $2 \times 2$ system, and later solving a reduced linear system by annihilating the rows and columns corresponding to identified active sets. For solving the quadratic obstacle problem, various optimal multigrid like methods have been proposed. In this paper, we study a non-standard norm that is equivalent to applying a block diagonal preconditioner to the reduced linear systems. Numerical experiments confirm the optimality of the solver and convergence independent of problem parameters on sufficiently fine mesh.
1601.03230v1
2016-04-13
A 3D Printed Superconducting Aluminium Microwave Cavity
3D printing of plastics, ceramics, and metals has existed for several decades and has revolutionized many areas of manufacturing and science. Printing of metals in particular has found a number of applications in fields as diverse as customized medical implants, jet engine bearings, and rapid prototyping in the automotive industry. Whilst many techniques can be used for 3D printing metals, they commonly rely on computer controlled melting or sintering of a metal alloy powder using a laser or electron beam. The mechanical properties of parts produced in such a way have been well studied, but little attention has been paid to their electrical properties. Here we show that a microwave cavity (resonant frequencies 9.9 and 11.2 GHz) 3D printed using an Al-12Si alloy exhibits superconductivity when cooled below the critical temperature of aluminium (1.2 K), with a performance comparable to the common 6061 alloy of aluminium. Superconducting cavities find application in numerous areas of physics, from particle accelerators to cavity quantum electrodynamics experiments. The result is achieved even with a very large concentration of non-superconducting silicon in the alloy of 12.18%, compared to Al-6061, which has between 0.4 to 0.8%. Our results may pave the way for the possibility of 3D printing superconducting cavity configurations that are otherwise impossible to machine.
1604.04301v2
2016-04-21
A review of the effects of chemical and phase segregation on the mechanical behaviour of multi-phase steels
In the drive towards higher strength alloys, a diverse range of alloying elements is employed to enhance their strength and ductility. Limited solid solubility of these elements in steel leads to segregation during casting which affects the entire down-stream processing and eventually the mechanical properties of the finished product. Although it is thought that the presence of continuous bands lead to premature failure, it has not been possible to verify this link. This poses as increasingly greater risk for higher alloyed, higher strength steels which are prone to centre-line segregation: it is thus vital to be able to predict the mechanical behaviour of multi-phase (MP) steels under loading. This review covers the microstructure and properties of galvanised advanced high strength steels with particular emphasis to their use in automotive applications. In order to understand the origins of banding, the origins of segregation of alloying elements during casting and partitioning in the solid state will be discussed along with the effects on the mechanical behaviour and damage evolution under (tensile) loading. Attention will also be paid to the application of microstructural models in tailoring the production process to enable suppression of the effects of segregation upon banding. Finally, the theory and application of the experimental techniques used in this work to elucidate the structure and properties will be examined.
1604.06485v1
2016-05-28
Clock statistics for 1d Schrödinger operators
We study the 1d Schr\"odinger operators with alloy type random supercritical decaying potential and prove the clock convergence for the local statistics of eigenvalues. We also consider, besides the standard i.i.d. case, more general ones with exponentially decaying correlations.
1605.08825v1
2016-06-11
Random alloy fluctuations and structural inhomogeneities in $c$-plane In$_{x}$Ga$_{1-x}$N quantum wells: theory of ground and excited electron and hole states
We present a detailed theoretical analysis of the electronic structure of $c$-plane InGaN/GaN quantum wells with indium contents varying between 10\% and 25\%. The electronic structure of the quantum wells is treated by means of an atomistic tight-binding model, accounting for variations in strain and built-in field due to random alloy fluctuations. Our analysis reveals strong localisation effects in the hole states. These effects are found not only in the ground states, but also the excited states. We conclude that localisation effects persist to of order 100~meV into the valence band, for as little as 10\% indium in the quantum well, giving rise to a significant density of localised states. We find, from an examination of the modulus overlap of the wave functions, that the hole states can be divided into three regimes of localisation. Our results also show that localisation effects due to random alloy fluctuations are far less pronounced for electron states. However, the combination of electrostatic built-in field, alloy fluctuations and structural inhomogeneities, such as well-width fluctuations, can nevertheless lead to significant localisation effects in the electron states, especially at higher indium contents. Overall, our results are indicative of individually localised electron and hole states, consistent with the experimentally proposed explanation of time-dependent photoluminescence results in $c$-plane InGaN/GaN QWs.
1606.03616v1
2016-06-13
Theoretical analysis of influence of random alloy fluctuations on the opto-electronic properties of site-controlled (111)-oriented InGaAs/GaAs quantum dots
We use an $sp^3d^5s^* $ tight-binding model to investigate the electronic and optical properties of realistic site-controlled (111)-oriented InGaAs/GaAs quantum dots. Special attention is paid to the impact of random alloy fluctuations on key factors that determine the fine-structure splitting in these systems. Using a pure InAs/GaAs quantum dot as a reference system, we show that the combination of spin-orbit coupling and biaxial strain effects can lead to sizeable spin-splitting effects in these systems. Then, a realistic alloyed InGaAs/GaAs quantum dot with 25\% InAs content is studied. Our analysis reveals that the impact of random alloy fluctuations on the electronic and optical properties of (111)-oriented InGaAs/GaAs quantum dots reduces strongly as the lateral size of the dot increases and approaches realistic sizes. For instance the optical matrix element shows an almost vanishing anisotropy in the (111)-growth plane. Furthermore, conduction and valence band mixing effects in the system under consideration are strongly reduced compared to standard (100)-oriented InGaAs/GaAs systems. All these factors strongly indicate a reduced fine structure splitting in site-controlled (111)-oriented InGaAs/GaAs quantum dots. Thus, we conclude that quantum dots with realistic (50-80~nm) base length represent promising candidates for polarization entangled photon generation, consistent with recent experimental data.
1606.03980v1
2016-06-13
Crystallographic features and state stability of the decagonal quasicrystal in the Al-Co-Cu alloy system
In the Al-Co-Cu alloy system, both the decagonal quasicrystal with the space group of $P\overline{10}m2$ and its approximant Al$_{13}$Co$_4$ phase with monoclinic $Cm$ symmetry are present around 20 at.% Co-10 at.% Cu. In this study, we examined the crystallographic features of prepared Al-(30-x) at.% Co-x at.% Cu samples mainly by transmission electron microscopy in order to make clear the crystallographic relation between the decagonal quasicrystal and the monoclinic Al$_{13}$Co$_4$ structure. The results revealed a coexistence state consisting of decagonal quasicrystal and approximant Al$_{13}$Co$_4$ regions in Al-20 at.% Co-10 at.% Cu alloy samples. With the help of the coexistence state, the orientation relationship was established between the monoclinic Al$_{13}$Co$_4$ structure and the decagonal quasicrystal. In the determined relationship, the crystallographic axis in the quasicrystal was found to be parallel to the normal direction of the (010)$_{\rm m}$ plane in the Al$_{13}$Co$_4$ structure, where the subscript m denotes the monoclinic system. Based on data obtained experimentally, the state stability of the decagonal quasicrystal was also examined in terms of the Hume-Rothery (HR) mechanism on the basis of the nearly-free-electron approximation. It was found that a model based on the HR mechanism could explain the crystallographic features such as electron diffraction patterns and atomic arrangements found in the decagonal quasicrystal. In other words, the HR mechanism is most likely appropriate for the stability of the decagonal quasicrystal in the Al-Co-Cu alloy system.
1606.04043v2
2016-11-09
First-principles Study on Formation of LPSO Structures for Ternary Alloys Revisited from Short-range Order
We investigate the formation of long-period stacking ordered (LPSO) structure for Mg-Y-Zn ternary alloys based on the short-range order (SRO) tendency of energetically competitive disordered phases. We find that unisotropic SRO tendencies for structures with stacking faults cannot be simply interpreted by arithmetic average of SRO for constituent fcc and hcp stackings, indicating that the SRO should be significantly affected by periodically-introduced stacking faults. We also find that SRO for neighboring Y-Zn pair, which should have positive sign to form specific L12 type cluster found in LPSO, is strongly affected by the distance between stacking faults: e.g., five atomic layer distance does not prefer in-plane Y-Zn pair, while seven atomic layer distance prefer both in- and inter-plane Y-Zn pair. These facts strongly indicate that ordering tendency for the Mg-Y-Zn alloy is significantly dominated by the stacking faults as well as their periodicity. We also systematically investigate correlation between SRO for other Mg-RE-Zn (RE = La, Tb, Dy, Ho, Er) alloys and the physical property of RE elements. We find that while SRO for RE-Zn pair does not show effective correlation with atomic radius, it has strong quadratic correlation with atomic radius considering unisotoropy along in- and inter-plane directions.
1611.02866v1
2017-03-08
Chromium-vacancy clusters in dilute bcc Fe-Cr alloys: an ab initio study
Using an ab initio approach, we explore the stability of small vacancy and vacancy-chromium clusters in dilute body-centred cubic Fe-Cr alloys. To explain experimental observations described in C.D. Hardie et al., J. Nucl. Mater. 439, 33 (2013) and showing the occurrence of Cr segregation in low-Cr alloys, we investigate if chromium can form stable bound configurations with vacancies in alloys with chromium concentration below the low-temperature chromium solubility limit of 10-11 at. %. We find that a single vacancy can attract up to four Cr atoms in the most energetically favourable cluster configuration. The binding energy of a cluster containing a single vacancy and from one to eight Cr atoms can be well described by a linear function of the number of chromium atoms in the second, third and fifth nearest neighbour coordination. The magnetic origin of the binding energy trend is confirmed by a correlation between the average value of the magnetic moment of a Cr atom and the binding energy. Similar trends are also found for di-vacancy-Cr clusters, confirming that they likely also characterise larger systems not yet accessible to ab initio calculations. The ratio of the binding energy to the number of Cr atoms increased more than twice in the di-vacancy case in comparison with a single vacancy case.
1703.02767v1
2017-11-14
Cluster dynamics modeling of Mn-Ni-Si precipitates in ferritic-martensitic steel under irradiation
Mn-Ni-Si precipitates (MNSPs) are known to be responsible for irradiation-induced hardening and embrittlement in structural alloys used in nuclear reactors. Studies have shown that precipitation of the MNSPs in 9-Cr ferritic-martensitic (F-M) alloys, such as T91, is strongly associated with heterogeneous nucleation on dislocations, coupled with radiation-induced solute segregation to these sinks. Therefore it is important to develop advanced predictive models for Mn-Ni-Si precipitation in F-M alloys under irradiation based on an understanding of the underlying mechanisms. Here we use a cluster dynamics model, which includes multiple effects of dislocations, to study the evolution of MNSPs in a commercial F-M alloy T91. The model predictions are calibrated by data from proton irradiation experiments at 400 {\deg}C. Radiation induced solute segregation at dislocations is evaluated by a continuum model that is integrated into the cluster dynamics simulations, including the effects of dislocations as heterogeneous nucleation sites. The result shows that MNSPs in T91 are primarily irradiation-induced and, in particular, both heterogeneous nucleation and radiation-induced segregation at dislocations are necessary to rationalize the experimental observations.
1711.05008v1
2017-12-18
Large-scale atomistic simulations demonstrate dominant alloy disorder effects in GaBi$_x$As$_{1-x}$/GaAs multiple quantum wells
Bismide semiconductor materials and heterostructures are considered a promising candidate for the design and implementation of photonic, thermoelectric, photovoltaic, and spintronic devices. This work presents a detailed theoretical study of the electronic and optical properties of strongly-coupled GaBi$_x$As$_{1-x}$/GaAs multiple quantum well (MQW) structures. Based on a systematic set of large-scale atomistic tight-binding calculations, our results reveal that the impact of atomic-scale fluctuations in alloy composition is stronger than the inter-well coupling effect, and plays an important role in the electronic and optical properties of MQW structures. Independent of QW geometry parameters, alloy disorder leads to a strong confinement of charge carriers, a large broadening of the hole energies, and a red shift in the ground-state transition wavelength. Polarisation-resolved optical transition strengths exhibit a striking effect of disorder, where the inhomogeneous broadening could exceed an order of magnitude for MQWs, in comparison to a factor of about three for single quantum wells. The strong influence of alloy disorder effects persists when small variations in the size and composition of MQWs typically expected in a realistic experimental environment are considered. The presented results highlight the limited scope of continuum methods and emphasise on the need for large-scale atomistic approaches to design devices with tailored functionalities based on the novel properties of bismide materials.
1712.06720v2
2018-01-16
On the asymmetry of the forward and reverse martensitic transformations in shape memory alloys
Differential Scanning Calorimetric, DSC, runs taken during martensitic phase transformations in shape memory alloys, often look differently during cooling and heating. Similar asymmetry is observed e.g. for the numbers of hits or the critical exponents of energy and amplitude distributions (\epsilon and \alpha, respectively) in acoustic emission measurements. It is illustrated that, in accordance with empirical correlations, the above asymmetry of acoustic noises can be classified into two groups: the relative changes of the exponents during cooling and heating (\gamma \epsilon=(\epsilon h-\epsilon c)/\epsilon c as well as \gamma \alpha=(\alpha h-\alpha c)/\alpha c)) are either positive or negative. For positive \gamma values the number of hits and the total energy of acoustic emission are larger for cooling, and the situation is just the reverse for negative asymmetry. Our interpretation is based on the different ways of relaxation of the elastic strain energy during cooling as well as heating. It is illustrated that if the relaxed fraction of the total elastic strain energy (which would be stored without relaxations) during cooling is larger than the corresponding relaxed fraction during heating, then the asymmetry is positive. Magnetic emission noises, accompanied with martensitic phase transformations in ferromagnetic alloys, show similar asymmetry than those observed for thermal (DSC) and acoustic noises and depends on the constant external magnetic field too.
1801.05229v1
2018-06-03
Tunable stacking fault energies by tailoring local chemical order in CrCoNi medium-entropy alloys
High-entropy alloys (HEAs) are an intriguing new class of metallic materials due to their unique mechanical behavior. Achieving a detailed understanding of structure-property relationships in these materials has been challenged by the compositional disorder that underlies their unique mechanical behavior. Accordingly, in this work, we employ first-principles calculations to investigate the nature of local chemical order and establish its relationship to the intrinsic and extrinsic stacking fault energy (SFE) in CrCoNi medium-entropy solid-solution alloys, whose combination of strength, ductility and toughness properties approach the best on record. We find that the average intrinsic and extrinsic SFE are both highly tunable, with values ranging from -43 mJ.m-2 to 30 mJ.m-2 and from -28 mJ.m-2 to 66 mJ.m-2, respectively, as the degree of local chemical order increases. The state of local ordering also strongly correlates with the energy difference between the face-centered cubic (fcc) and hexagonal-close packed (hcp) phases, which affects the occurrence of transformation-induced plasticity. This theoretical study demonstrates that chemical short-range order is thermodynamically favored in HEAs and can be tuned to affect the mechanical behavior of these alloys. It thus addresses the pressing need to establish robust processing-structure-property relationships to guide the science-based design of new HEAs with targeted mechanical behavior.
1806.00718v1
2018-11-05
Outstanding Radiation Resistance of Tungsten-based High Entropy Alloys
A novel W-based refractory high entropy alloy with outstanding radiation resistance has been developed. The alloy was grown as thin films showing a bimodal grain size distribution in the nanocrystalline and ultrafine regimes and a unique 4 nm lamella-like structure revealed by atom probe tomography (APT). Transmission electron microscopy (TEM) and X-ray diffraction show an underlying body-centered cubic crystalline structure with certain black spots appearing after thermal annealing at elevated temperatures. Thorough analysis based on TEM and APT correlated the black spots with second phase particles rich in Cr and V. After both in situ and ex situ irradiation, these precipitates evolve to quasi-spherical particles with no sign of irradiation-created dislocation loops even after 8 dpa at either room temperature or 1073 K. Furthermore, nanomechanical testing shows a large hardness of 14 GPa in the as-deposited samples, with a slight increase after thermal annealing and almost negligible irradiation hardening. Theoretical modeling based on ab initio methodologies combined with Monte Carlo techniques predicts the formation of Cr and V rich second phase particles and points at equal mobilities of point defects as the origin of the exceptional radiation tolerance. The fact that these alloys are suitable for bulk production coupled with the exceptional radiation and mechanical properties makes them ideal structural materials for applications requiring extreme conditions.
1811.01915v1
2018-11-22
Nonlinearity in Canonical Ensemble for Multicomponent Alloys Revisited from Structural Degree of Freedoms
For classical discrete system under constant composition typically referred to substitutional alloys, we examine local nonlinearity in canonical average phi . We have respectively investigated the local and global behavior of nonlinearity through previously-introduced vector field A and through tropical limit of the vector field. While these studies indicated the importance of constraints to structural degree of freedoms (SDFs) for global nonlinearity, it has been still unclear how the constraints to SDF affects local nonlinearity. Based on statistical manifold, we make intuitive bridge between the SDF-based information and local nonlinearity, decomposing the local nonlinearity into two (for binary alloys with pair correlations) or three (for otherwise) contributions in terms of the Kullback-Leibler divergence, where this decomposition is independent of temperature and many-body interaction, and is defined on individual configuration. We also find that we can provide A-dependent as well as A-independent decomposition of the local nonlinearity, where non-separability in SDFs and its nonadditive character is independent of A, which indicates that information about evolution of the vector field should be required to address the non-separability and nonadditivity. The present work enables to quantify how configuration-dependent constraints to SDF affect local nonlinearity in canonical average for multicomponent alloys.
1811.09612v5
2018-11-23
3D Deep Learning with voxelized atomic configurations for modeling atomistic potentials in complex solid-solution alloys
The need for advanced materials has led to the development of complex, multi-component alloys or solid-solution alloys. These materials have shown exceptional properties like strength, toughness, ductility, electrical and electronic properties. Current development of such material systems are hindered by expensive experiments and computationally demanding first-principles simulations. Atomistic simulations can provide reasonable insights on properties in such material systems. However, the issue of designing robust potentials still exists. In this paper, we explore a deep convolutional neural-network based approach to develop the atomistic potential for such complex alloys to investigate materials for insights into controlling properties. In the present work, we propose a voxel representation of the atomic configuration of a cell and design a 3D convolutional neural network to learn the interaction of the atoms. Our results highlight the performance of the 3D convolutional neural network and its efficacy in machine-learning the atomistic potential. We also explore the role of voxel resolution and provide insights into the two bounding box methodologies implemented for voxelization.
1811.09724v1
2019-11-02
Direct Bandgap Emission from Hexagonal Ge and SiGe Alloys
Silicon crystallized in the usual cubic (diamond) lattice structure has dominated the electronics industry for more than half a century. However, cubic silicon (Si), germanium (Ge) and SiGe-alloys are all indirect bandgap semiconductors that cannot emit light efficiently. Accordingly, achieving efficient light emission from group-IV materials has been a holy grail in silicon technology for decades and, despite tremendous efforts, it has remained elusive. Here, we demonstrate efficient light emission from direct bandgap hexagonal Ge and SiGe alloys. We measure a subnanosecond, temperature-insensitive radiative recombination lifetime and observe a similar emission yield to direct bandgap III-V semiconductors. Moreover, we demonstrate how by controlling the composition of the hexagonal SiGe alloy, the emission wavelength can be continuously tuned in a broad range, while preserving a direct bandgap. Our experimental findings are shown to be in excellent quantitative agreement with the ab initio theory. Hexagonal SiGe embodies an ideal material system to fully unite electronic and optoelectronic functionalities on a single chip, opening the way towards novel device concepts and information processing technologies.
1911.00726v1
2020-01-17
Methods of electron transport in ab initio theory of spin stiffness
We present an ab initio theory of the spin-wave stiffness tensor for ordered and disordered itinerant ferromagnets with pair exchange interactions derived from a method of infinitesimal spin rotations. The resulting formula bears an explicit form of a linear-response coefficient which involves one-particle Green's functions and effective velocity operators encountered in a recent theory of electron transport. Application of this approach to ideal metal crystals yields more reliable values of the spin stiffness than traditional ill-convergent real-space lattice summations. The formalism can also be combined with the coherent potential approximation for an effective-medium treatment of random alloys, which leads naturally to an inclusion of disorder-induced vertex corrections to the spin stiffness. The calculated concentration dependence of the spin-wave stiffness of random fcc Ni-Fe alloys can be ascribed to a variation of the reciprocal value of alloy magnetization. Calculations for random iron-rich bcc Fe-Al alloys reveal that their spin-wave stiffness is strongly reduced owing to the atomic ordering; this effect takes place due to weakly coupled local magnetic moments of Fe atoms surrounded by a reduced number of Fe nearest neighbors.
2001.06279v2
2020-01-30
Lattice dynamics of $\textit{Pnma}$ Sn(S$_{1-x}$Se$_{x}$) solid solutions: energetics, phonon spectra and thermal transport
Alloying is widely used as a means to fine-tune the properties of thermoelectric materials by reducing the lattice thermal conductivity. However, the effects of compositional variation on the lattice dynamics of alloy systems are not well understood, due in part to the difficulty of building realistic first-principles models of structurally-complex solid solutions. This work builds on our previous study of Sn$_{n}$(S$_{1-x}$Se$_{x}$)$_{m}$ solid solutions [Gunn $\textit{et al.}$, $\textit{Chem. Mater.}$ $\textbf{31}$, $\textit{10}$, 3672, $\textbf{2019}$] to explore the lattice dynamics of the $\textit{Pnma}$ Sn(S$_{1-x}$Se$_{x}$) system, which has been widely studied for potential thermoelectric applications. We find that the vibrational internal energy and entropy have a large quantitative impact on the mixing free energy and are likely to be particularly important in alloy systems with competing phases. The thermodynamically-averaged phonon dispersions and density of states curves show that alloying preserves the structure of the low-frequency bands of modes associated with the Sn sublattice but broadens the high-frequency chalcogen bands into a near-continuous spectrum at the 50/50 mixed composition. This results in a general reduction in the phonon mode group velocities and an increase in the number of energy-conserving scattering channels for heat-carrying low-frequency modes, which is consistent with the decrease in thermal conductivity observed in experimental measurements. Finally, we discuss some of the limitations of our first-principles modelling approach and propose methods to address these in future studies.
2001.11311v1
2021-07-20
Controlled synthesis of MoxW1-xTe2 atomic layers with emergent quantum states
Recently, new states of matter like superconducting or topological quantum states were found in transition metal dichalcogenides (TMDs) and manifested themselves in a series of exotic physical behaviors. Such phenomena have been demonstrated to exist in a series of transition metal tellurides including MoTe2, WTe2 and alloyed MoxW1-xTe2. However, the behaviors in the alloy system have been rarely addressed due to their difficulty in obtaining atomic layers with controlled composition, albeit the alloy offers a great platform to tune the quantum states. Here, we report a facile CVD method to synthesize the MoxW1-xTe2 with controllable thickness and chemical composition ratios. The atomic structure of monolayer MoxW1-xTe2 alloy was experimentally confirmed by scanning transmission electron microscopy (STEM). Importantly, two different transport behaviors including superconducting and Weyl semimetal (WSM) states were observed in Mo-rich Mo0.8W0.2Te2 and W-rich Mo0.2W0.8Te2 samples respectively. Our results show that the electrical properties of MoxW1-xTe2 can be tuned by controlling the chemical composition, demonstrating our controllable CVD growth method is an efficient strategy to manipulate the physical properties of TMDCs. Meanwhile, it provides a perspective on further comprehension and shed light on the design of device with topological multicomponent TMDCs materials.
2107.09482v1
2018-07-18
Multi-Objective Bayesian Materials Discovery: Application on the Discovery of Precipitation Strengthened NiTi Shape Memory Alloys through Micromechanical Modeling
In this study, a framework for the multi-objective materials discovery based on Bayesian approaches is developed. The capabilities of the framework are demonstrated on an example case related to the discovery of precipitation strengthened NiTi shape memory alloys with up to three desired properties. In the presented case the framework is used to carry out an efficient search of the shape memory alloys with desired properties while minimizing the required number of computational experiments. The developed scheme features a Bayesian optimal experimental design process that operates in a closed loop. A Gaussian process regression model is utilized in the framework to emulate the response and uncertainty of the physical/computational data while the sequential exploration of the materials design space is carried out by using an optimal policy based on the expected hyper-volume improvement acquisition function. This scalar metric provides a measure of the utility of querying the materials design space at different locations, irrespective of the number of objectives in the performed task. The framework is deployed for the determination of the composition and microstructure of precipitation-strengthened NiTi shape memory alloys with desired properties, while the materials response as a function of microstructure is determined through a thermodynamically-consistent micromechanical model.
1807.06868v1
2019-01-21
Solid-State Thermal Energy Storage Using Reversible Martensitic Transformations
The identification and use of reversible Martensitic transformations, typically described as shape memory transformations, as a new class of solid-solid phase change material is experimentally demonstrated here for the first time. To prove this claim, time-domain thermoreflectance, frequency-domain thermoreflectance, and differential scanning calorimetry studies were conducted on commercial NiTi alloys to quantify thermal conductivity and latent heat. Additional Joule-heating experiments demonstrate successful temperature leveling during transient heating and cooling in a simulated environment. Compared to standard solid-solid materials and solid-liquid paraffin, these experimental results show that shape memory alloys provide up to a two order of magnitude higher Figure of Merit. Beyond these novel experimental results, a comprehensive review of >75 binary NiTi and NiTi-based ternary and quaternary alloys in the literature shows that shape memory alloys can be tuned in a wide range of transformation temperatures (from -50 to 330{deg}C), latent heats (from 9.1 to 35.1 J/g), and thermal conductivities (from 15.6 to 28 W/mK). This can be accomplished by changing the Ni and Ti balance, introducing trace elements, and/or by thermomechanical processing. Combining excellent corrosion resistance, formability, high strength and ductility, high thermal performance, and tunability, SMAs represent an exceptional phase change material that circumvents many of the scientific and engineering challenges hindering progress in this field.
1901.06990v1
2019-04-16
A phase-field study of elastic stress effects on phase separation in ternary alloys
Most of the commercially important alloys are multicomponent, producing multiphase microstructures as a result of processing. When the coexisting phases are elastically coherent, the elastic interactions between these phases play a major role in the development of microstructures. To elucidate the key effects of elastic stress on microstructural evolution when more than two misfitting phases are present in the microstructure, we have developed a microelastic phase-field model in two dimensions to study phase separation in ternary alloy system. Numerical solutions of a set of coupled Cahn-Hilliard equations for the composition fields govern the spatiotemporal evolution of the three-phase microstructure. The model incorporates coherency strain interactions between the phases using Khachaturyan's microelasticity theory. We systematically vary the misfit strains (magnitude and sign) between the phases along with the bulk alloy composition to study their effects on the morphological development of the phases and the resulting phase separation kinetics. We also vary the ratio of interfacial energies between the phases to understand the interplay between elastic and interfacial energies on morphological evolution. The sign and degree of misfit affect strain partitioning between the phases during spinodal decomposition, thereby affecting their compositional history and morphology. Moreover, strain partitioning affects solute partitioning and alters the kinetics of coarsening of the phases. The phases associated with higher misfit strain appear coarser and exhibit wider size distribution compared to those having lower misfit. When the interfacial energies satisfy complete wetting condition, phase separation leads to development of stable core-shell morphology depending on the misfit between the core (wetted) and the shell (wetting) phases.
1904.07401v1
2019-07-27
Elastic stiffness tensors of Zr-$x$Nb alloy in presence of defects: A molecular dynamics study
In a nuclear reactor, the Zr-$x$Nb alloy, which is used as a structural material in the core region, is irradiated by energetic particles that cause the atoms to be displaced from their lattice sites and giving rise to crystal defects. The local changes in the atomic arrangements lead to local deformations of the solid and thereby changes of its local mechanical properties. Understanding the mechanisms behind this evolution in the core region of a reactor, and its monitoring or controlling is a critical task in nuclear industry. In this work, using extensive molecular dynamics simulations, we have studied the effects of radiation damage on the local mechanical properties of Zr-$x$Nb alloy. In the first step, the effect of Nb-concentration on the mechanical stability of homogeneous Zr-$x$Nb alloy is investigated. In the second step, we have studied the local changes of the elastic constants due to local changes of the microstructure. These local changes include presence and accumulation of vacancies in the form of dislocation loops or voids, accumulation of Nb atoms in the form of clusters of different morphologies. This study covers both cases of $T=0^\circ$K and finite temperatures up to $T=600^\circ$K.
1907.11977v2
2019-10-29
Inward-growth plating of lithium driven by solid-solution based alloy phase for highly reversible lithium metal anode
Lithium metal batteries (LMB) are vital devices for high-energy-density energy storage, but Li metal anode is highly reactive with electrolyte and forms uncontrolled dendrite that can cause undesirable parasitic reactions thus poor cycling stability and raise safety concerns. Despite remarkable progress made to partly solve these issues, the Li metal still plate at the electrode/electrolyte interface where the parasitic reactions and dendrite formation invariably occur. Here we demonstrate the inward-growth plating of Li into a metal foil while avoiding surface deposition, which is driven by the reversible solid-solution based alloy phase change. Lithiation of the solid solution alloy phase facilitates the freshly generated Li atoms at the surface to sink into the foil, while the reversible alloy phase change is companied by the dealloying reaction during delithiation, which extracts Li atoms from inside of the foil. The yielded dendrite free Li anode produces an enhanced Coulombic efficiency of 99.5 plus or minus 0.2% with a reversible capacity of 1660 mA h $g^{-1}$ (3.3 mA h cm$^{-2}$).
1910.13159v1
2012-09-25
Sb concentration dependent structural and resistive properties of polycrystalline Bi-Sb alloys
Polycrystalline Bi-Sb alloys have been synthesized over a wide range of antimony concentration (8 at% to 20 at%) by solid state reaction method. In depth structural analysis using X-Ray diffraction (XRD) and temperature dependent resistivity measurement of synthesized samples have been performed. XRD data confirmed single phase nature of polycrystalline samples and revealed that complete solid solution is formed between bismuth and antimony. Rietveld refinement technique, utilizing MAUD software, has been used to perform detail structural analysis of the samples and lattice parameters of synthesized Bi-Sb alloys have been estimated. Lattice parameter and unit cell volume decreases monotonically with increasing antimony content. The variation of lattice parameters with antimony concentration depicts a distinct slope change beyond 12 at% Sb content sample. Band gap has been estimated from the thermal variation of resistivity data, with the 12% Sb content sample showing maximum value. It has been observed that, with increasing antimony concentration the transition from direct to indirect gap semiconductor is intimately related to the variation of the estimated lattice parameters. Band diagram for the polycrystalline Bi-Sb alloy system has also been proposed.
1209.5506v1
2014-06-01
Statistical Thermodynamics and Ordering Kinetics of D019-Type Phase: Application of the Models for H.C.P.-Ti-Al Alloy
Using the self-consistent field approximation, the static concentration waves approach and the Onsager-type kinetics equations, the descriptions of both the statistical thermodynamics and the kinetics of an atomic ordering of D019 phase are developed and applied for h.c.p.-Ti-Al alloy. The model of order-disorder phase transformation describes the phase transformation of h.c.p. solid solution into the D019 phase. Interatomic-interaction parameters are estimated for both approximations: one supposes temperature-independent interatomic-interaction parameters, while the other one includes the temperature dependence of interchange energies for Ti-Al alloy. The partial Ti-Al phase diagrams (equilibrium compositions of the coexistent ordered and disordered phases) are evaluated for both cases. The equation for the time dependence of D019- type long-range order (LRO) parameter is analyzed. The curves (showing the LRO parameter evolution) are obtained numerically for both temperature-independent interaction energies and temperature-dependent ones. Temperature dependence of the interatomic-interaction energies accelerates the LRO relaxation and diminishes a spread of the values of instantaneous and equilibrium LRO parameters versus the temperature. Both statistical-thermodynamics and kinetics results show that equilibrium LRO parameter for a non-stoichiometry (where an atomic fraction of alloying component is more than 0.25) can be higher than for a stoichiometry at high temperatures. The experimental phase diagram confirms the predicted (ordered or disordered) states for h.c.p.-Ti-Al.
1406.0162v1
2014-06-28
Superdiffusive heat conduction in semiconductor alloys -- I. Theoretical foundations
Semiconductor alloys exhibit a strong dependence of effective thermal conductivity on measurement frequency. So far this quasi-ballistic behaviour has only been interpreted phenomenologically, providing limited insight into the underlying thermal transport dynamics. Here, we show that quasi-ballistic heat conduction in semiconductor alloys is governed by L\'evy superdiffusion. By solving the Boltzmann transport equation (BTE) with ab initio phonon dispersions and scattering rates, we reveal a transport regime with fractal space dimension $1 < \alpha < 2$ and superlinear time evolution of mean square energy displacement $\sigma^2(t) \sim t^{\beta} (1 < \beta < 2)$. The characteristic exponents are directly interconnected with the order $n$ of the dominant phonon scattering mechanism $\tau \sim \omega^{-n} (n>3)$ and cumulative conductivity spectra $\kappa_{\Sigma}(\tau;\Lambda)\sim (\tau;\Lambda)^{\gamma}$ resolved for relaxation times or mean free paths through simple relations $\alpha = 3-\beta = 1 + 3/n = 2 - \gamma$. The quasi-ballistic transport inside alloys is no longer governed by Brownian motion, but instead dominated by L\'evy dynamics. This has important implications for the interpretation of thermoreflectance (TR) measurements with modified Fourier theory. Experimental $\alpha$ values for InGaAs and SiGe, determined through TR analysis with a novel L\'evy heat formalism, match ab initio BTE predictions within a few percent. Our findings lead to a deeper and more accurate quantitative understanding of the physics of nanoscale heat flow experiments.
1406.7341v2
2018-02-27
Computational study on microstructure evolution and magnetic property of laser additively manufactured magnetic materials
Additive manufacturing (AM) offers an unprecedented opportunity for the quick production of complex shaped parts directly from a powder precursor. But its application to functional materials in general and magnetic materials in particular is still at the very beginning. Here we present the first attempt to computationally study the microstructure evolution and magnetic properties of magnetic materials (e.g. Fe-Ni alloys) processed by selective laser melting (SLM). SLM process induced thermal history and thus the residual stress distribution in Fe-Ni alloys are calculated by finite element analysis (FEA). The evolution and distribution of the $\gamma$-Fe-Ni and FeNi$_3$ phase fractions were predicted by using the temperature information from FEA and the output from CALculation of PHAse Diagrams (CALPHAD). Based on the relation between residual stress and magnetoelastic energy, magnetic properties of SLM processed Fe-Ni alloys (magnetic coercivity, remanent magnetization, and magnetic domain structure) are examined by micromagnetic simulations. The calculated coercivity is found to be in line with the experimentally measured values of SLM-processed Fe-Ni alloys. This computation study demonstrates a feasible approach for the simulation of additively manufactured magnetic materials by integrating FEA, CALPHAD, and micromagnetics.
1802.09821v2
2018-08-22
Record-High Superconductivity in Niobium-Titanium Alloy
Here we report the observation of extraordinary superconductivity in a pressurized commercial niobium-titanium alloy. We find that its zero-resistance superconductivity persists from ambient pressure to the pressure as high as 261.7 GPa, a record high pressure up to which a known superconducting state can continuously survives. Remarkably, at such an ultra-high pressure, although the ambient pressure volume is shrunk by 45% without structural phase transition, the superconducting transition temperature (TC) increases to ~19.1 K from ~9.6 K, and the critical magnetic field (HC2) at 1.8 K has been enhanced to 19 T from 15.4 T. These results set new records for both of the TC and the HC2 among all the known alloy superconductors composed of only transition metal elements. The remarkable high pressure superconducting properties observed in the NbTi alloy not only expand our knowledge on this important commercial superconductor but also are helpful for a better understanding on the superconducting mechanism.
1808.07215v3
2018-12-12
Kinetic Monte Carlo simulations of vacancy diffusion in non-dilute Ni-X (X=Re,W,Ta) alloys
The mobility of vacancies in alloys may limit dislocation climb. Using a combined density functional theory and kinetic Monte Carlo approach we investigate vacancy diffusion in Ni-Re, Ni-W, and Ni-Ta binary alloys up to 10 at.% solute concentration. We introduce an interaction model that takes into account the chemical environment close to the diffusing atom to capture the effect of solute-host and solute-solute interactions on the diffusion barriers. In contrast to an ideal solid solution it is not only the diffusion barrier of the solute atom that influences the vacancy mobility, but primarily the change in the host diffusion barriers due to the presence of solute atoms. This is evidenced by the fact that the observed vacancy slowdown as a function of solute concentration is larger in Ni-W than in Ni-Re, even though Re is a slower diffuser than W. To model diffusion in complex, non-dilute alloys an explicit treatment of interaction energies is thus unavoidable. In the context of Ni-based superalloys two conclusions can be drawn from our kinetic Monte Carlo simulations: the observed slowdown in vacancy mobility is not sufficient to be the sole cause for the so-called Re-effect; and assuming a direct correlation between vacancy mobility, dislocation climb, and creep strength the experimentally observed similar effect of W and Re in enhancing creep strength can be confirmed.
1812.04989v1
2018-12-12
Thermodynamic Stability and Structural Insights for CH$_3$NH$_3$Pb$_{1-x}$Si$_x$I$_3$, CH$_3$NH$_3$Pb$_{1-x}$Ge$_x$I$_3$, and CH$_3$NH$_3$Pb$_{1-x}$Sn$_x$I$_3$ Hybrid Perovskite Alloys: A Statistical Approach from First Principles Calculations
The recent reaching of 20% of conversion efficiency by solar cells based on metal hybrid perovskites (MHP), e.g., the methylammonium (MA) lead iodide, CH3NH3PbI3 (MAPbI3), has excited the scientific community devoted to the photovoltaics materials. However, the toxicity of Pb is a hindrance for large scale commercial of MHP and motivates the search of another congener eco-friendly metal. Here, we employed first-principles calculations via density functional theory combined with the generalized quasichemical approximation to investigate the structural, thermodynamic, and ordering properties of MAPb1-xSixI3, MAPb1-xGexI3, and MAPb1-xSnxI3 alloys as pseudo-cubic structures. The inclusion of a smaller second metal, as Si and Ge, strongly affects the structural properties, reducing the cavity volume occupied by the organic cation and limitating the free orientation under high temperature effects. Unstable and metaestable phases are observed at room temperature for MAPb1-xSixI3, whereas MAPb1-xGexI3 is energetically favored for Pb-rich in ordered phases even at very low temperatures. Conversely, the high miscibility of Pb and Sn into MAPb1-xSnxI3 yields an alloy energetically favored as a pseudo-cubic random alloy with tunable properties at room temperature.
1812.05150v1
2019-02-05
The Dynamics of Magnetism in Fe-Cr Alloys with Cr Clustering
The dynamics of magnetic moments in iron-chromium alloys with different levels of Cr clustering show unusual features resulting from the fact that even in a perfect body-centred cubic structure, magnetic moments experience geometric magnetic frustration resembling that of a spin glass. Due to the long range exchange coupling and configuration randomness, magnetic moments of Cr solutes remain non-collinear at all temperatures. To characterise magnetic properties of Fe-Cr alloys, we explore the temperature dependence of magnetisation, susceptibility, Curie temperature and spin-spin correlations with spatial resolution. The static and dynamic magnetic properties are correlated with the microstructure of Fe-Cr, where magnetisation and susceptibility are determined by the size of Cr precipitates at nominal Cr concentrations. The Curie temperature is always maximised when the solute concentration of Cr in the $\alpha$ phase is close to 5 to 6 at.\%, and the susceptibility of Fe atoms is always enhanced at the boundary between a precipitate and solid solution. Interaction between Cr and Fe stimulates magnetic disorder, lowering the effective Curie temperature. Dynamic simulation of evolution of magnetic correlations shows that the spin-spin relaxation time in Fe-Cr alloys is in the 20 to 40 ps range.
1902.01645v1
2019-06-18
Machine-learned Interatomic Potentials for Alloys and Alloy Phase Diagrams
We introduce machine-learned potentials for Ag-Pd to describe the energy of alloy configurations over a wide range of compositions. We compare two different approaches. Moment tensor potentials (MTP) are polynomial-like functions of interatomic distances and angles. The Gaussian Approximation Potential (GAP) framework uses kernel regression, and we use the Smooth Overlap of Atomic Positions (SOAP) representation of atomic neighbourhoods that consists of a complete set of rotational and permutational invariants provided by the power spectrum of the spherical Fourier transform of the neighbour density. Both types of potentials give excellent accuracy for a wide range of compositions and rival the accuracy of cluster expansion, a benchmark for this system. While both models are able to describe small deformations away from the lattice positions, SOAP-GAP excels at transferability as shown by sensible transformation paths between configurations, and MTP allows, due to its lower computational cost, the calculation of compositional phase diagrams. Given the fact that both methods perform as well as cluster expansion would but yield off-lattice models, we expect them to open new avenues in computational materials modeling for alloys.
1906.07816v2
2020-04-14
Templated Dewetting-Alloying of NiCu Bilayers on TiO$_2$ Nanotubes Enables Efficient Noble Metal-Free Photocatalytic $H_2$ Evolution
Photocatalytic $H_2$ evolution reactions on pristine TiO$_2$ is characterized by low efficiencies due to trapping and recombination of charge carriers, and due to a sluggish kinetics of electron transfer. Noble metal (mainly Pt, Pd, Au) nanoparticles are typically decorated as cocatalyst on the TiO$_2$ surface to reach reasonable photocatalytic yields. However, owing to the high cost of noble metals, alternative metal cocatalysts are being developed. Here we introduce an approach to fabricate an efficient noble metal free photocatalytic platform for $H_2$ evolution based on alloyed NiCu cocatalytic nanoparticles at the surface of anodic TiO$_2$ nanotube arrays. NiCu bilayers are deposited onto the TiO$_2$ nanotubes by plasma sputtering. A subsequent thermal treatment is carried out that leads to dewetting, that is, owing to surface diffusion the Ni and Cu sputtered layers simultaneously mix with each other and split into NiCu nanoparticles at the nanotube surface. The approach allows for a full control over key features of the alloyed nanoparticles such as their composition, work function and cocatalytic ability towards $H_2$ generation. Dewetted-alloyed cocatalytic nanoparticles composed of equal Ni and Cu amounts not only are significantly more reactive than pure Ni or Cu nanoparticles, but also lead to $H_2$ generation rates that can be comparable to those obtained by conventional noble metal (Pt) decoration of TiO$_2$ nanotube arrays.
2004.06561v1
2020-04-27
Understanding Mechanical Properties and Failure Mechanism of Germanium-Silicon Alloy at Nanoscale
We used molecular dynamics (MD) simulations to investigate the mechanical properties of cubic zinc blende (ZB) Si0.5Ge0.5 alloy nanowire (NW). Tersoff potential is employed to elucidate the effect of nanowire size, crystal orientations, and temperature on the material properties. We found that the reduction in the cross-sectional area results in lower ultimate tensile strength and Youngs modulus of this alloy which can be attributed to the increased surface to volume ratio. The [111] oriented Si0.5Ge0.5 NW exhibits the highest fracture strength compared to other crystal orientations but [110] orientation possesses the highest fracture toughness. The effect of temperature depicts an inverse relationship with the ultimate tensile strength and Youngs modulus. The increased temperature facilitates the failure of the material, thus degrades the materials strength. Our study reveals that the vacancy defects introduced via removal of either Si or Ge atoms exhibit similar behavior, and with the increase in vacancy concentration, both ultimate tensile strength and Youngs modulus reduces linearly. We further illustrate the failure characteristics of Si0.5Ge0.5 NW at two extremely low and high temperatures. The intrinsic failure characteristics of Si0.5Ge0.5 alloy is found to be insensitive to the temperature. Interestingly, at both temperatures, with the increasing strain, the cross-section of Si0.5Ge0.5 eventually resembles a neck as typically observed in ductile materials, although the NW failure is brittle in nature. Overall, this work offers a new perspective on understanding material properties and failure characteristics of ZB Si0.5Ge0.5 NW that will be a guide for designing Si-Ge based nanodevices.
2004.13445v1
2020-05-17
Solving the issues of multicomponent diffusion in an equiatomic NiCoFeCr medium entropy alloy
Estimating the diffusion coefficients experimentally in a four-component inhomogeneous alloy following the conventional diffusion couple method by intersecting three couples at the same composition is difficult unless a small composition range of constant diffusivity is identified. Additionally, the intrinsic diffusion coefficients of the components cannot be estimated in a system with more than two components. To solve these issues, we have followed the pseudo-binary and pseudo-ternary diffusion couple methods for estimating the diffusion coefficients at the equiatomic composition of NiCoFeCr medium entropy alloy. Along with the pseudo-binary interdiffusion coefficients, we have estimated the intrinsic diffusion coefficients of all the components by designing the pseudo-binary couples such that Ni and Co develop the diffusion profiles keeping Fe and Cr constant in one couple and Fe and Cr develop the diffusion profiles keeping Ni and Co constant in another couple. Subsequently, we have proposed the relations for calculating the tracer diffusion coefficients utilizing the thermodynamic details. We have found a good match with the data estimated directly following the radiotracer method at the equiatomic composition. Following, we have produced three pseudo-ternary diffusion couples intersecting at the compositions close to the equiatomic composition. The main pseudo-ternary interdiffusion coefficients of Fe are found to be higher than Ni and Co. Therefore, we have estimated different types of diffusion coefficients highlighting the complex diffusion process in the four-component NiCoFeCr medium entropy alloy.
2005.08160v1
2020-08-01
Electrical and thermal transport properties of medium-entropy SiyGeySnx alloys
Electrical and thermal transport properties of disordered materials have long been of both theoretical interest and engineering importance. As a new class of materials with an intrinsic compositional disorder, high/medium-entropy alloys (HEAs/MEAs) are being immensely studied mainly for their excellent mechanical properties. By contrast, electrical and thermal transport properties of HEAs/MEAs are less well studied. Here we investigate these two properties of silicon (Si)-germanium (Ge)-tin (Sn) MEAs, where we keep the same content of Si and Ge while increasing the content of Sn from 0 to 1/3 to tune the configurational entropy and thus the degree of compositional disorder. We predict all SiyGeySnx MEAs to be semiconductors with a wide range of bandgaps from near-infrared (0.28 eV) to visible (1.11 eV) in the light spectrum. We find that the bandgaps and effective carrier masses decrease with increasing Sn content. As a result, increasing the compositional disorder in SiyGeySnx MEAs enhances their electrical conductivity. For the thermal transport properties of SiyGeySnx MEAs, our molecular dynamics simulations show an opposite trend in the thermal conductivity of these MEAs at room temperature, which decreases with increasing compositional disorder, owing to enhanced Anderson localization and strong phonon-phonon anharmonic interactions. The enhanced electrical conductivity and weakened thermal conductivity make SiyGeySnx MEAs with high Sn content promising functional materials for thermoelectric applications. Our work demonstrates that HEAs/MEAs not only represent a new class of structural alloys but also a novel category of functional alloys with unique electrical and thermal transport properties.
2008.00352v1
2020-08-12
Phase stability of Au-Li binary systems studied using neural network potential
The miscibility of Au and Li exhibits a potential application as an adhesion layer and electrode material in secondary batteries. Here, to explore alloying properties, we constructed a neural network potential (NNP) of Au-Li binary systems based on density functional theory (DFT) calculations. To accelerate construction of NNPs, we proposed an efficient and inexpensive method of structural dataset generation. The predictions by the constructed NNP on lattice parameters and phonon properties agree well with those obtained by DFT calculations. We also investigated the mixing energy of Au$_{1-x}$Li$_{x}$ with fine composition grids, showing excellent agreement with DFT verifications. We found the existence of various compositions with structures on and slightly above the convex hull, which can explain the lack of consensus on the Au-Li stable phases in previous studies. Moreover, we newly found Au$_{0.469}$Li$_{0.531}$ as a stable phase, which has never been reported elsewhere. Finally, we examined the alloying process starting from the phase separated structure to the complete mixing phase. We found that when multiple adjacent Au atoms dissolved into Li, the alloying of the entire Au/Li interface started from the dissolved region. This paper demonstrates the applicability of NNPs toward miscible phases and provides the understanding of the alloying mechanism.
2008.05094v1
2020-08-16
High-throughput computational characterization of two-dimensional compositionally complex transition-metal chalcogenide alloys
Two-dimensional (2D) binary transition-metal chalcogenides (TMCs) like molybdenum disulfide exhibits excellent properties as materials for light adsorption devices. Alloying binary TMCs can form 2D compositionally complex TMC alloys (CCTMCAs) that possess remarkable properties from the constituent TMCs. We adopt a high-throughput workflow performing density functional theory (DFT) calculations based on the virtual crystal approximation (VCA) model (VCA-DFT). We test the workflow by predicting properties including in-plane lattice constants, band gaps, effective masses, spin-orbit coupling (SOC), and band alignments of the Mo-W-S-Se, Mo-W-S-Te, and Mo-W-Se-Te 2D CCTMCAs. We validate the VCA-DFT results by computing the same properties using unit cells and supercells of selected compositions. The VCA-DFT results of the abovementioned five properties are comparable to that of DFT calculations, with some inaccuracies in several properties of MoSTe and WSTe. Moreover, 2D CCTMCAs can form type II heterostructures as used in photovoltaics. Finally, we use Mo0.5W0.5SSe, Mo0.5W0.5STe, and Mo0.5W0.5SeTe 2D CCTMCAs to demonstrate the room-temperature entropy-stabilized alloys. They also exhibit high electrical conductivities at 300K, promising for light adsorption devices. Our work shows that the high-throughput workflow using VCA-DFT calculations provides a tradeoff between efficiency and accuracy, opening up opportunities in the computational design of other 2D CCTMCAs for various applications.
2008.06838v1
2020-08-17
Enhancement of spin Hall conductivity in W-Ta alloy
Generating pure spin currents via the spin Hall effect in heavy metals has been an active topic of research in the last decade. In order to reduce the energy required to efficiently switch neighbouring ferromagnetic layers for applications, one should not only increase the charge- to-spin conversion efficiency but also decrease the longitudinal resistivity of the heavy metal. In this work, we investigate the spin Hall conductivity in W_{1-x}Ta_{x} / CoFeB / MgO (x = 0 - 0.2) using spin torque ferromagnetic resonance measurements. Alloying W with Ta leads to a factor of two change in both the damping-like effective spin Hall angle (from - 0.15 to - 0.3) and longitudinal resistivity (60 - 120 {\mu}W cm). At 11% Ta concentration, a remarkably high spin Hall angle value of - 0.3 is achieved with a low longitudinal resistivity 100 {\mu}W cm, which could lead to a very low power consumption for this W-based alloy. This work demonstrates sputter-deposited W-Ta alloys could be a promising material for power-efficient spin current generation.
2008.07572v1
2021-03-03
On the early stages of precipitation during direct ageing of Alloy 718
The Ni-based superalloy Alloy 718 is used in aircraft engines as high-pressure turbine discs and must endure challenging demands on high-temperature yield strength, creep-, and oxidation-resistance. Nanoscale $\gamma^{\prime}$- and $\gamma^{\prime \prime}$-precipitates commonly found in duplet and triplet co-precipitate morphologies provide high-temperature strength under these harsh operating conditions. Direct ageing of Alloy 718 is an attractive alternative manufacturing route known to increase the yield strength at 650 $^{\deg}$C by at least +10 $\%$, by both retaining high dislocation densities and changing the nanoscale co-precipitate morphology. However, the detailed nucleation and growth mechanisms of the duplet and triplet co-precipitate morphologies of $\gamma^{\prime}$ and $\gamma^{\prime \prime}$ during the direct ageing process remain unknown. We provide a correlative high-resolution microscopy approach using transmission electron microscopy, high-angle annular dark-field imaging, and atom probe microscopy to reveal the early stages of precipitation during direct ageing of Alloy 718. Quantitative stereological analyses of the $\gamma^{\prime}$- and $\gamma^{\prime \prime}$-precipitate dispersions as well as their chemical compositions have allowed us to propose a qualitative model of the microstructural evolution. It is shown that fine $\gamma^{\prime}$- and $\gamma^{\prime \prime}$-precipitates nucleate homogeneously and grow coherently. However, $\gamma^{\prime \prime}$-precipitates also nucleate heterogeneously on dislocations and experience accelerated growth due to Nb pipe diffusion. Moreover, the co-precipitation reactions are largely influenced by solute availability and the potential for enrichment of Nb and rejection of Al+Ti.
2103.02763v1
2021-03-18
In Operando magnetometry study on the charge storage mechanism of SnCo alloy lithium ion batteries
In view of the long-standing controversy over the reversibility of transition metals in Sn-based alloys as anode for Li-ion batteries, an in situ real-time magnetic monitoring method was used to investigate the evolution of Sn-Co intermetallic during the electrochemical cycling. Sn-Co alloy film anodes with different compositions were prepared via magnetron sputtering without using binders and conductive additives. The magnetic responses showed that the Co particles liberated by Li insertion recombine fully with Sn during the delithiation to reform Sn-Co intermetallic into stannum richer phases Sn7Co3. However, as the Co content increases, it can only recombine partially with Sn into cobalt richer phases Sn3Co7. The unconverted Co particles may form a dense barrier layer and prevent the full reaction of Li with all the Sn in the anode, leading to lower capacities. These critical results shed light on understanding the reaction mechanism of transition metals, and provide valuable insights toward the design of high-performance Sn alloy based anodes.
2103.10141v1
2022-02-08
Kinetic Monte Carlo Modelling of Nano-oxide Precipitation and its Associated Stability under Neutron Irradiation for the Fe-Ti-Y-O system
While developing nuclear materials, predicting their behavior under long-term irradiation regimes spanning decades poses a significant challenge. We developed a novel Kinetic Monte Carlo (KMC) model to explore the precipitation behavior of Y-Ti-O oxides along grain boundaries within nanostructured ferritic alloys (NFA). This model also assessed the response of the oxides to neutron irradiation, even up simulated radiation damage levels in the desired long dpa range for reactor components. Our simulations investigated how temperature and grain boundary sinks influenced the oxide characteristics of a 12YWT-like alloy during heat treatments at 1023 K, 1123 K, and 1223 K. The oxide characteristics observed in our simulations were in good agreement with existing literature. Furthermore, the impact of grain boundaries on precipitation was found to be minimal. The resulting oxide configurations and positions were used in subsequent simulations that exposed them to simulated neutron irradiation to a total accumulated dose of 8 dpa at three temperatures: 673 K, 773 K, and 873 K, and at dose rates of 10^(-3), 10^(-4), and 10^(-5) dpa/s. This demonstrated the expected inverse relationship between oxide size and dose rate. In a long-term irradiation simulation at 873 K and 10^(-3) dpa/s was taken out to 66 dpa and found the oxides in the vicinity of the grain boundary were more susceptible to dissolution. Additionally, we conducted irradiation simulations of a 14YWT-like alloy to reproduce findings from neutron irradiation experiments. The larger oxides in the 14YWT-like alloy did not dissolve and displayed stability similar to the experimental results.
2202.03641v3
2022-02-28
Influence of hydrogen vacancy interactions on natural and artificial ageing of an AlMgSi alloy
The influence of hydrogen on the structural evolutions of an Al-Mg-Si alloy during natural and artificial ageing was investigated experimentally. The aim of the study was a better understanding of interactions between hydrogen and crystalline defects and especially vacancies. Experimental data demonstrate that during natural ageing in hydrogen environment, the hardening response is delayed. This is attributed to a slower recovery of excess vacancies linked to a lower mobility. To confirm and quantify the influence of hydrogen on the vacancy migration energy, artificial ageing was carried out in conditions where the vacancy concentration is constant. Hence, long-time annealing treatments were carried out to investigate the influence of hydrogen on the coarsening of rod-shaped precipitates. Using transmission electron microscopy and atom probe tomography, it was demonstrated that the precipitate volume fraction and composition are unchanged under H2 atmosphere but the coarsening kinetic is significantly reduced. This leads to a delayed softening, in good agreement with theoretical estimates. Thus, even a low concentration of hydrogen in solid solution significantly affects the mobility of alloying elements in the aluminium matrix. This is the result of hydrogen-vacancy interactions that lead to an increase of the vacancy migration energy. Based on classical coarsening theories, it was possible to demonstrate that this increase is of about 5% for a concentration of hydrogen close to the vacancy concentration.
2202.13745v1
2022-03-10
3D Nanoscale Mapping of Short-Range Order in GeSn Alloys
GeSn on Si has attracted much research interest due to its tunable direct bandgap for mid-infrared applications. Recently, short-range order (SRO) in GeSn alloys has been theoretically predicted, which profoundly impacts the band structure. However, characterizing SRO in GeSn is challenging. Guided by physics-informed Poisson statistical analyses of Kth-nearest neighbors (KNN) in atom probe tomography, a new approach is demonstrated here for 3D nanoscale SRO mapping and semi-quantitative strain mapping in GeSn. For GeSn with ~14 at.% Sn, the SRO parameters of Sn-Sn 1NN in 10x10x10 nm$^{3}$ nanocubes can deviate from that of the random alloys by $\pm$15%. The relatively large fluctuation of the SRO parameters contributes to band-edge softening observed optically. Sn-Sn 1NN also tends to be more favored towards the surface, less favored under strain relaxation or tensile strain, while almost independent of local Sn composition. An algorithm based on least square fit of atomic positions further verifies this Poisson-KNN statistical method. Compared to existing macroscopic spectroscopy or electron microscopy techniques, this new APT statistical analysis uniquely offers 3D SRO mapping at nanoscale resolution in a relatively large volume with millions of atoms. It can also be extended to investigate SRO in other alloy systems.
2203.05667v1
2022-03-14
Nontrivial doping evolution of electronic properties in Ising-superconducting alloys
Transition metal dichalcogenides offer unprecedented versatility to engineer 2D materials with tailored properties to explore novel structural and electronic phase transitions. In this work, we present the atomic-scale evolution of the electronic ground state of a monolayer of Nb$_{1-\delta}$Mo$_{\delta}$Se$_2$ across the entire alloy composition range (0 < ${\delta}$ < 1) using low-temperature (300 mK) scanning tunneling microscopy and spectroscopy (STM/STS). In particular, we investigate the atomic and electronic structure of this 2D alloy throughout the metal to semiconductor transition (monolayer NbSe$_2$ to MoSe$_2$). Our measurements let us extract the effective doping of Mo atoms, the bandgap evolution and the band shifts, which are monotonic with ${\delta}$. Furthermore, we demonstrate that collective electronic phases (charge density wave and superconductivity) are remarkably robust against disorder. We further show that the superconducting TC changes non-monotonically with doping. This contrasting behavior in the normal and superconducting state is explained using first-principles calculations. We show that Mo doping decreases the density of states at the Fermi level and the magnitude of pair-breaking spin fluctuations as a function of Mo content. Our results paint a detailed picture of the electronic structure evolution in 2D TMD alloys, which is of utmost relevance for future 2D materials design.
2203.07432v1
2022-03-17
In situ characterization of vacancy ordering in Ge-Sb-Te phase-change memory alloys
Tailoring the degree of structural disorder in Ge-Sb-Te alloys is important for the development of non-volatile phase-change memory and neuro-inspired computing. Upon crystallization from the amorphous phase, these alloys form a cubic rocksalt-like structure with a high content of intrinsic vacancies. Further thermal annealing results in a gradual structural transition towards a layered structure and an insulator-to-metal transition. In this work, we elucidate the atomic-level details of the structural transition in crystalline GeSb2Te4 by in situ high-resolution transmission electron microscopy (HRTEM) experiments and ab initio density functional theory (DFT) calculations, providing a comprehensive real-time and real-space view of the vacancy ordering process. We also discuss the impact of vacancy ordering on altering the electronic and optical properties of GeSb2Te4, which is relevant to multilevel storage applications. The phase evolution paths in Ge-Sb-Te alloys are illustrated using a summary diagram, which serves as a guide for designing phase-change memory devices.
2203.09310v2
2022-03-21
Sm-Co-based amorphous alloy films for zero-field operation of transverse thermoelectric generation
Transverse thermoelectric generation using magnetic materials is essential to develop active thermal engineering technologies, for which the improvements of not only the thermoelectric output but also applicability and versatility are required. In this study, using combinatorial material science and lock-in thermography technique, we have systematically investigated the transverse thermoelectric performance of Sm-Co-based alloy films. The high-throughput material investigation revealed the best Sm-Co-based alloys with the large anomalous Nernst effect (ANE) as well as the anomalous Ettingshausen effect (AEE). In addition to ANE/AEE, we discovered unique and superior material properties in these alloys: the amorphous structure, low thermal conductivity, and large in-plane coercivity and remanent magnetization. These properties make it advantageous over conventional materials to realize heat flux sensing applications based on ANE, as our Sm-Co-based films can generate thermoelectric output without an external magnetic field. Importantly, the amorphous nature enables the fabrication of these films on various substrates including flexible sheets, making the large-scale and low-cost manufacturing easier. Our demonstration will provide a pathway to develop flexible transverse thermoelectric devices for smart thermal management.
2203.10737v2
2022-03-22
Silver-Gold Bimetallic Alloy versus Core-Shell Nanoparticles: Implications for Plasmonic Enhancement and Photothermal Applications
Bimetallic plasmonic nanoparticles enable tuning of the optical response and chemical stability by variation of the composition. The present numerical simulation study compares Ag-Au alloy, Ag@Au core-shell, and Au@Ag core-shell bimetallic plasmonic nanoparticles of both spherical and anisotropic (nanotriangle and nanorods) shapes. By studying both spherical and anisotropic (with LSPR in the near-infrared region) shapes, cases with and without interband transitions of Au can be decoupled. Explicit comparisons are facilitated by numerical models supported by careful validation and examination of optical constants of Au-Ag alloys reported in literature. Although both Au-Ag core-shell and alloy nanoparticles exhibit an intermediary optical response between that of pure Ag and Au nanoparticles, there are noticeable differences in the spectral characteristics. Also, the effect of the bimetallic constitution in anisotropic nanoparticles is starkly different from that in spherical nanoparticles due to the absence of Au interband transitions in the former case. In general, the improved chemical stability of Ag nanoparticles by incorporation of Au comes with a cost of reduction in plasmonic enhancement, also applicable to anisotropic nanoparticles with a weaker effect. A photothermal heat transfer study confirms that increased absorption by the incorporation of Au in spherical Ag nanoparticles also results in an increased steady state temperature. On the other hand, anisotropic nanoparticles are inherently better absorbers, hence better photothermal sources and their photothermal properties are apparently not strongly affected by the incorporation of one metal in the other.
2203.11682v1
2022-03-28
The influence of alloying on slip intermittency and the implications for dwell fatigue in titanium
Dwell fatigue, the reduction in fatigue life experienced by titanium alloys due to holds at stresses as low as 60% of yield, has been implicated in several uncontained jet engine failures. Dislocation slip has long been observed to be an intermittent, scale-bridging phenomenon, similar to that seen in earthquakes but at the nanoscale, leading to the speculation that large stress bursts might promote the initial opening of a crack. Here we observe such stress bursts at the scale of individual grains in situ, using high energy X-ray diffraction microscopy in Ti-7Al-O alloys. This shows that the detrimental effect of precipitation of ordered Ti_3Al is to increase the magnitude of rare pri<a> and bas<a> slip bursts associated with slip localisation. In contrast, the addition of trace O interstitials is beneficial, reducing the magnitude of bas<a> slip bursts and increasing the homogeneity between basal and prismatic <a> slip. This is further evidence that the formation of long paths for easy basal plane slip localisation should be avoided when engineering titanium alloys against dwell fatigue.
2203.14615v3
2022-03-29
Realistic micromagnetic description of all-optical ultrafast switching processes in ferrimagnetic alloys
Both helicity-independent and helicity-dependent all-optical switching processes driven by single ultrashort laser pulse have been experimentally demonstrated in ferrimagnetic alloys as GdFeCo. Although the switching has been previously reproduced by atomistic simulations, the lack of a robust micromagnetic framework for ferrimagnets limits the predictions to small nano-systems, whereas the experiments are usually performed with lasers and samples of tens of micrometers. Here we develop a micromagnetic model based on the extended Landau-Lifshitz-Bloch equation, which is firstly validated by directly reproducing atomistic results for small samples and uniform laser heating. After that, the model is used to study ultrafast single shot all-optical switching in ferrimagnetic alloys under realistic conditions. We find that the helicity-independent switching under a linearly polarized laser pulse is a pure thermal phenomenon, in which the size of inverted area directly correlates with the maximum electron temperature in the sample. On the other hand, the analysis of the helicity-dependent processes under circular polarized pulses in ferrimagnetic alloys with different composition indicates qualitative differences between the results predicted by the magnetic circular dichroism and the ones from inverse Faraday effect. Based on these predictions, we propose experiments that would allow to resolve the controversy over the physical phenomenon that underlies these helicity-dependent all optical processes.
2203.15460v1
2016-03-15
The two gap transitions in Ge$_{1-x}$Sn$_x$: effect of non-substitutional complex defects
The existence of non-substitutional $\beta$-Sn defects in Ge$_{1-x}$Sn$_{x}$ was confirmed by emission channeling experiments [Decoster et al., Phys. Rev. B 81, 155204 (2010)], which established that although most Sn enters substitutionally ($\alpha$-Sn) in the Ge lattice, a second significant fraction corresponds to the Sn-vacancy defect complex in the split-vacancy configuration ( $\beta$-Sn ), in agreement with our previous theoretical study [Ventura et al., Phys. Rev. B 79, 155202 (2009)]. Here, we present our electronic structure calculation for Ge$_{1-x}$Sn$_{x}$, including substitutional $\alpha$-Sn as well as non-substitutional $\beta$-Sn defects. To include the presence of non-substitutional complex defects in the electronic structure calculation for this multi-orbital alloy problem, we extended the approach for the purely substitutional alloy by Jenkins and Dow [Jenkins and Dow, Phys. Rev. B 36, 7994 (1987)]. We employed an effective substitutional two-site cluster equivalent to the real non-substitutional $\beta$-Sn defect, which was determined by a Green's functions calculation. We then calculated the electronic structure of the effective alloy purely in terms of substitutional defects, embedding the effective substitutional clusters in the lattice. Our results describe the two transitions of the fundamental gap of Ge$_{1-x}$Sn$_{x}$ as a function of the total Sn-concentration: namely from an indirect to a direct gap, first, and the metallization transition at higher $x$. They also highlight the role of $\beta$-Sn in the reduction of the concentration range which corresponds to the direct-gap phase of this alloy, of interest for optoelectronics applications.
1603.04802v1
2017-02-19
Atomic-ordering-induced quantum phase transition between topological crystalline insulator and Z2 topological insulator
Topological phase transition in a single material usually refers to transitions between a trivial band insulator and a topological Dirac phase, but the transition may also occur between different classes of topological Dirac phases. However, it is a fundamental challenge to realize quantum transition between Z2 nontrivial topological insulator (TI) and topological crystalline insulator (TCI) in one material because Z2 TI and TCI are hardly both co-exist in a single material due to their contradictory requirement on the number of band inversions. The Z2 TIs must have an odd number of band inversions over all the time-reversal invariant momenta, whereas, the newly discovered TCIs, as a distinct class of the topological Dirac materials protected by the underlying crystalline symmetry, owns an even number of band inversions. Here, take PbSnTe2 alloy as an example, we show that at proper alloy composition the atomic-ordering is an effective way to tune the symmetry of the alloy so that we can electrically switch between TCI phase and Z2 TI phase when the alloy is ordered from a random phase into a stable CuPt phase. Our results suggest that atomic-ordering provides a new platform to switch between different topological phases.
1702.05697v1
2019-03-22
Structure and mechanical behavior of ultrafine-grained aluminum-iron alloy stabilized by nanoscaled intermetallic particles
Ultrafine-grained aluminum alloys offer interesting multifunctional properties with a combination of high strength, low electrical resistivity, and low density. However, due to thermally induced grain coarsening, they typically suffer from an intrinsic poor thermal stability. To overcome this drawback, an Al-2%Fe alloy has been selected because of the low solubility of Fe in Al and their highly positive enthalpy of mixing leading to the formation of stable intermetallic particles. The two-phase alloy has been processed by severe plastic deformation to achieve simultaneously submicrometer Al grains and a uniform distribution of nanoscaled intermetallic particles. The influence of the level of deformation on the microstructure has been investigated thanks to transmission electron microscopy and atom probe tomography and it is shown that for the highest strain a partial dissolution of the metastable Al6Fe particle occurred leading to the formation of a Fe super saturated solid solution. The thermal stability, and especially the precipitation of particles from the ultrafine-grained solid solution and the way they pin grain boundaries has been investigated both from static annealing and in-situ transmission electron microscopy experiments. The correlation between microstructural features and microhardness has been established to identify the various strengthening contributions. Finally, it is 2 shown that ultrafine grained high purity Al with less than 0.01 at. % Fe in solid solution could preserve a grain size only 300nm after 1h at 250$^\circ$C.
1903.09391v1
2019-03-27
Predicting magnetization of ferromagnetic binary Fe alloys from chemical short range order
Among the ferromagnetic binary alloys, body centered cubic (bcc) Fe-Co is the one showing the highest magnetization. It is known experimentally that ordered Fe-Co structures show a larger magnetization than the random solid solutions with the same Co content. In this work, based on density functional theory (DFT) studies, we aim at a quantitative prediction of this feature, and point out the role of the orbital magnetic moments. Then, we introduce a DFT-based analytical model correlating local magnetic moments and chemical compositions for Co concentrations ranging from 0 to 70 at.%. It is also extended to predict the global magnetization of both ordered and disordered structures at given concentration and chemical short range orders. The latter model is particularly useful for interpreting experimental data. Based on these models, we note that the local magnetic moment of a Fe atom is mainly dictated by the Co concentration in its first two neighbor shells. The detailed local arrangement of the Co atoms has a minor effect. These simple models can fully reproduce the difference in magnetization between the ordered and disordered Fe-Co alloys between 30% and 70% Co, in good agreement with experimental data. Finally, we show that a similar model can be established for another bcc binary Fe alloy, the Fe-Ni, also presenting ferromagnetic interactions between atoms.
1903.11468v1
2019-03-27
Design, Fabrication and Characterization of FeAl-based Metallic-Intermetallic Laminate (MIL) Composites
FeAl-based MIL composites of various iron alloys were fabricated with an innovative 'multiple-thin-foil' configuration and 'two-stage reaction' strategy.
1903.11724v1
2019-03-29
Fe alloy slurry and a compacting cumulate pile across Earth's inner-core boundary
Seismic observations show a reduced compressional-wave gradient at the base of the outer core relative to the preliminary reference Earth model and seismic wave asymmetry between the east-west hemispheres at the top of the inner core. Here, we propose a model for the inner core boundary (ICB), where a slurry layer forms through fractional crystallization of an Fe alloy at the base of the outer core (F layer) above a compacting cumulate pile at the top of the inner core (F' layer). Using recent mineral physics data, we show that fractional crystallization of an Fe alloy (e.g., Fe-Si-O) with light element partitioning can explain the observed reduced velocity gradient in the F layer, in cases with a solid fraction of ~15(5)% in liquid with a compositional gradient due to preferential light element partitioning into liquid. The compacting cumulate pile in the F' layer may exhibit lateral variations in thickness between the east-west hemispheres due to lateral variations of large-scale heat flow in the outer core, which may explain the east-west asymmetry observed in the seismic velocity. Our interpretations suggest that the inner core with solid Fe alloy has a high shear viscosity of ~10^23 Pa s.
1903.12574v2