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2005-08-24
Enhancing the Alloy Analyzer with Patterns of Analysis
Formal techniques have been shown to be useful in the development of correct software. But the level of expertise required of practitioners of these techniques prohibits their widespread adoption. Formal techniques need to be tailored to the commercial software developer. Alloy is a lightweight specification language supported by the Alloy Analyzer (AA), a tool based on off-the-shelf SAT technology. The tool allows a user to check interactively whether given properties are consistent or valid with respect to a high-level specification, providing an environment in which the correctness of such a specification may be established. However, Alloy is not particularly suited to expressing program specifications and the feedback provided by AA can be misleading where the specification under analysis or the property being checked contains inconsistencies. In this paper, we address these two shortcomings. Firstly, we present a lightweight language called "Loy", tailored to the specification of object-oriented programs. An encoding of Loy into Alloy is provided so that AA can be used for automated analysis of Loy program specifications. Secondly, we present some "patterns of analysis" that guide a developer through the analysis of a Loy specification in order to establish its correctness before implementation.
0508109v1
2008-02-21
First principles calculations of the electronic and geometric structure of $Ag_{27}Cu_{7}$ nanoalloy
\emph{Ab initio} calculations of the structure and electronic density of states (DOS) of the perfect core-shell $Ag_{27}Cu_{7}$ nanoalloy attest to its $D_{5h}$ symmetry and confirm that it has only 6 non-equivalent (2 $Cu$ and 4 $Ag$) atoms. Analysis of bond-length, average formation energy, heat of formation of $Ag_{27}Cu_{7}$ and $L1_2$ $Ag-Cu$ alloys provide an explanation for the relative stability of the former with respect to the other nanoalloys in the same family. The HOMO-LUMO gap is found to be 0.77 eV, in agreement with previous results. Analysis of the DOS of $Ag_{27}Cu_{7}$, $L1_2$ $Ag-Cu$ alloys and related systems provides insight into the effects of low coordination, contraction/expansion and the presence of foreign atoms on the DOS of $Cu$ and $Ag$. While some characteristics of the DOS are reminiscent of those of the phonon-stable $L1_2$ $Ag-Cu$ alloys, the $Cu$ and $Ag$ states hybridize significantly in $Ag_{27}Cu_{7}$, compensating the $d$-band narrowing that each atom undergoes and hindering the dip in the DOS found in the bulk alloys. Charge density plots of $Ag_{27}Cu_{7}$ provide further insights into the relative strengths of the various interatomic bonds. Our results for the electronic and geometric structure of this nanoalloy can be explained in terms of length and strength hierarchies of the bonds, which may have implications also for the stability of alloy in any phase or size.
0802.2987v1
2008-03-24
Effect of static and dynamic disorder on electronic transport of $RCo_2$ compounds: a study of $Ho(Al_xCo_{1-x})_2$ alloys
We present experimental results on thermoelectric power ({\em S}) and electrical resistivity ($\rho $) of pseudobinary alloys Ho(Al$_x$Co$_{1-x}$)$_2$ ($0 \leq x \leq 0.1 $), in the temperature range 4.2 K to 300 K. The work focuses on the effects of static (induced by alloying) and dynamic (induced by temperature) disorder on the magnetic state and electronic transport in a metallic system with itinerant metamagnetic instability. Spatial fluctuations of the local magnetic susceptibility in the alloys lead to a development of a partially ordered magnetic ground state of the itinerant 3d electron system. This results in a strong increase of the residual resistivity and a suppression of the temperature-dependent resistivity. Thermopower exhibits a complex temperature variation in both the magnetically ordered and in the paramagnetic state. This complex temperature variation is referred to the electronic density of states features in vicinity of Fermi energy and to the interplay of magnetic and impurity scattering. Our results indicate that the magnetic enhancement of the Co 3d-band in RCo$_{\rm 2}$--based alloys upon a substitution of Co by non-magnetic elements is mainly related to a progressive localization of the Co -- 3d electrons caused by disorder. We show that the magnitude of the resistivity jump at the Curie temperature for RCo$_{\rm 2}$ compounds exhibiting a first order phase transition is a non-monotonic function of the Curie temperature due to a saturation of the 3d--band spin fluctuation magnitude at high temperatures.
0803.3380v3
2010-03-18
Ab-initio description of heterostructural alloys: Thermodynamic and structural properties of Mg_x Zn_{1-x} O and Cd_x Zn_{1-x} O
Pseudobinary heterostructural alloys of ZnO with MgO or CdO are studied by composing the system locally of clusters with varying ratio of cations. We investigate fourfold (wurtzite structure) and sixfold (rocksalt structure) coordination of the atoms. By means of density functional theory we study a total number of 256 16-atom clusters divided into 22 classes for the wurtzite structure and 16 classes for the rocksalt structure for each of the alloy systems. The fraction with which each cluster contributes to the alloy is determined for a given temperature T and composition x within (i) the generalized quasi-chemical approximation, (ii) the model of a strict-regular solution, and (iii) the model of microscopic decomposition. From the cluster fractions we derive conclusions about the miscibility and the critical compositions at which the average crystal structure changes. Thermodynamic properties such as the mixing free energy and the mixing entropy are investigated for the three different statistics. We discuss the consequences of the two different local lattice structures for characteristic atomic distances, cohesive energies, and the alloys' elasticities. The differences in the properties of Mg_x Zn_{1-x} O and Cd_x Zn_{1-x} O are explained and discussed.
1003.3614v2
2010-09-16
First-principles calculations of phase transition, elasticity, and thermodynamic properties for TiZr alloy
tructural transformation, pressure dependent elasticity behaviors, phonon, and thermodynamic properties of the equiatomic TiZr alloy are investigated by using first-principles density-functional theory. Our calculated lattice parameters and equation of state for $\alpha$ and $\omega$ phases as well as the phase transition sequence of $\alpha$$\mathtt{\rightarrow}$$\omega$$\mathtt{\rightarrow}$$\beta$ are consistent well with experiments. Elastic constants of $\alpha$ and $\omega$ phases indicate that they are mechanically stable. For cubic $\beta$ phase, however, it is mechanically unstable at zero pressure and the critical pressure for its mechanical stability is predicted to equal to 2.19 GPa. We find that the moduli, elastic sound velocities, and Debye temperature all increase with pressure for three phases of TiZr alloy. The relatively large $B/G$ values illustrate that the TiZr alloy is rather ductile and its ductility is more predominant than that of element Zr, especially in $\beta$ phase. Elastic wave velocities and Debye temperature have abrupt increase behaviors upon the $\alpha$$\mathtt{\rightarrow}$$\omega$ transition at around 10 GPa and exhibit abrupt decrease feature upon the $\omega$$\mathtt{\rightarrow}$$\beta$ transition at higher pressure. Through Mulliken population analysis, we illustrate that the increase of the \emph{d}-band occupancy will stabilize the cubic $\beta$ phase. Phonon dispersions for three phases of TiZr alloy are firstly presented and the $\beta$ phase phonons clearly indicate its dynamically unstable nature under ambient condition. Thermodynamics of Gibbs free energy, entropy, and heat capacity are obtained by quasiharmonic approximation and Debye model.
1009.3073v3
2011-03-25
Anisotropic intrinsic anomalous Hall effect in ordered 3dPt alloys
By performing first principles calculations we investigate the intrinsic anomalous Hall conductivity (AHC) and its anisotropy in ordered L1o FePt, CoPt and NiPt ferromagnets, and their intermediate alloys. We demonstrate that the AHC in this family of compounds depends strongly on the direction of the magnetization in the crystal. We predict that such pronounced orientational dependence in combination with the general decreasing trend of the AHC when going from FePt to NiPt leads to a sign change of the AHC upon rotating the magnetization direction in the crystal of CoPt alloy. We also suggest that for a range of concentration x in Co(x)Ni(1-x)Pt alloy it is possible to achieve a complete quenching of the anomalous Hall current for a certain direction of the magnetization in the crystal. By analyzing the spin-resolved AHC in 3dPt alloys we endeavor to relate the overall trend of the AHC in these compounds to the changes in their densities of d-states around the Fermi energy upon varying the atomic number. Moreover, we show the generality of the phenomenon of anisotropic anomalous Hall effect by demonstrating its occurrence within the three-band tight-binding model.
1103.4941v2
2012-10-10
Determination of the crystal structures of In70-Ni30 and In70-Pd30 using perturbed angular correlation
According to phase diagrams based on x-ray measurements, In70-Pt30 has the cubic Sn7Ir3 crystal structure (D8f, cI40) but the alloys In70-Ni30 and In70-Pd30 have been variously reported to have either a cubic gamma-brass (D81-3, cI52) or the Sn7Ir3 structures. In this study, hyperfine interaction measurements are applied as an alternate method to identify phases. Perturbed angular correlation (PAC) measurements were made of characteristic nuclear quadrupole interactions of 111In/Cd probe atoms, and demonstrated a common, characteristic "signature" of the Sn7Ir3 structure in all three alloys. The Sn7Ir3 structure has two inequivalent Sn-sites with a 3:4 ratio of atoms and point symmetries indicate that the electric-field gradients at both sites should be axially symmetric. Measured perturbation functions for all three alloys exhibited two axially symmetric quadrupole interaction signals having the expected 3:4 ratio of amplitudes, as expected for the structure. Furthermore, ratios of the two quadrupole interaction frequencies in each alloy were characteristically large, with frequencies for probe atoms on In(3) sites roughly five times greater than on In(4) sites. Taken together, these observations confirm that all three phases have the Sn7Ir3 structure. Quadrupole interaction frequencies are also reported for isostructural alloys of gallium with Pt, Pd and Ni. Negligible inhomogeneous broadening was observed in measurements near room temperature in all six phases, indicating excellent atomic ordering at the stoichiometric 70:30 compositions.
1210.3076v1
2012-11-16
Localization for alloy-type models with non-monotone potentials
We consider a family of self-adjoint operators [H_\omega = - \Delta + \lambda V_\omega, \quad \omega \in \Omega = \bigtimes_{k \in \ZZ^d} \RR,] on the Hilbert space $\ell^2 (\ZZ^d)$ or $L^2 (\RR^d)$. Here $\Delta$ denotes the Laplace operator (discrete or continuous), $V_\omega$ is a multiplication operator given by the function $$V_\omega (x) = \sum_{k \in \ZZ^d} \omega_k u(x-k) on $\ZZ^d$, or \quad V_\omega (x) = \sum_{k \in \ZZ^d} \omega_k U(x-k) on $\RR^d$,$$ and $\lambda > 0$ is a real parameter modeling the strength of the disorder present in the model. The functions $u:\ZZ^d \to \RR$ and $U:\RR^d \to \RR$ are called single-site potential. Moreover, there is a probability measure $\PP$ on $\Omega$ modeling the distribution of the individual configurations $\omega \in \Omega$. The measure $\PP = \prod_{k \in \ZZ^d} \mu$ is a product measure where $\mu$ is some probability measure on $\RR$ satisfying certain regularity assumptions. The operator on $L^2 (\RR^d)$ is called alloy-type model, and its analogue on $\ell^2 (\ZZ^d)$ discrete alloy-type model. This thesis refines the methods of multiscale analysis and fractional moments in the case where the single-site potential is allowed to change its sign. In particular, we develop the fractional moment method and prove exponential localization for the discrete alloy-type model in the case where the support of $u$ is finite and $u$ has fixed sign at the boundary of its support. We also prove a Wegner estimate for the discrete alloy-type model in the case of exponentially decaying but not necessarily finitely supported single-site potentials. This Wegner estimate is applicable for a proof of localization via multiscale analysis.
1211.3891v1
2012-12-17
Alloying-related trends from first principles: An application to the Ti--Al--X--N system
Tailoring and improving material properties by alloying is a long-known and used concept. Recent research has demonstrated the potential of ab initio calculations in understanding the material properties at the nanoscale. Here we present a systematic overview of alloying trends when early-transition metals (Y, Zr, Nb, Hf, Ta) are added in the Ti$_{1-x}$Al$_x$N system, routinely used as a protective hard coating. The alloy lattice parameters tend to be larger than the corresponding linearised Vegard's estimation, with the largest deviation more than 2.5% obtained for Y$_{0.5}$Al$_{0.5}$N. The chemical strengthening is most pronounced for Ta and Nb, although also causing smallest elastic distortions of the lattice due to their atomic radii being comparable with Ti and Al. This is further supported by the analysis of the electronic density of states. Finally, mixing enthalpy as a measure of the driving force for decomposition into the stable constituents, is enhanced by adding Y, Zr and Nb, suggesting that the onset of spinodal decomposition will appear in these cases for lower thermal loads than for Hf and Ta alloyed Ti$_{1-x}$Al$_x$N.
1212.4052v2
2013-11-18
High-Temperature Activated AB2 Nanopowders for Metal Hydride Hydrogen Compression
A reliable process for compressing hydrogen and for removing all contaminants is that of the metal hydride thermal compression. The use of metal hydride technology in hydrogen compression applications though, requires thorough structural characterization of the alloys and investigation of their sorption properties. The samples have been synthesized by induction - levitation melting and characterized by Rietveld analysis of the X-Ray diffraction (XRD) patterns. Volumetric PCI (Pressure-Composition Isotherm) measurements have been conducted at 20, 60 and 90 oC, in order to investigate the maximum pressure that can be reached from the selected alloys using water of 90oC. Experimental evidence shows that the maximum hydrogen uptake is low since all the alloys are consisted of Laves phases, but it is of minor importance if they have fast kinetics, given a constant volumetric hydrogen flow. Hysteresis is almost absent while all the alloys release nearly all the absorbed hydrogen during desorption. Due to hardware restrictions, the maximum hydrogen pressure for the measurements was limited at 100 bars. Practically, the maximum pressure that can be reached from the last alloy is more than 150 bars.
1311.4465v1
2014-09-11
Microscopic, first-principles model of strain-induced interaction in concentrated size-mismatched alloys
The harmonic Kanzaki-Krivoglaz-Khachaturyan model of strain-induced interaction is generalized to concentrated size-mismatched alloys and adapted to first-principles calculations. The configuration dependence of both Kanzaki forces and force constants is represented by real-space cluster expansions that can be constructed based on the calculated forces. The model is implemented for the fcc lattice and applied to Cu$_{1-x}$Au$_x$ and Fe$_{1-x}$Pt$_x$ alloys for concentrations $x=0.25$, 0.5, and 0.75. The asymmetry between the $3d$ and $5d$ elements leads to large quadratic terms in the occupation-number expansion of the Kanzaki forces and thereby to strongly non-pairwise long-range interaction. The main advantage of the full configuration-dependent lattice deformation model is its ability to capture this singular many-body interaction. The roles of ordering striction and anharmonicity in Cu-Au and Fe-Pt alloys are assessed. Although the harmonic force constants defined with respect to the unrelaxed lattice are unsuitable for the calculation of the vibrational entropies, the phonon spectra for ordered and disordered alloys are found to be in good agreement with experimental data. The model is further adapted to concentration wave analysis and Monte Carlo simulations by means of an auxiliary multi-parametric real-space cluster expansion, which is used to find the ordering temperatures. Good agreement with experiment is found for all systems except CuAu$_3$ (due to the known failure of the generalized gradient approximation) and FePt$_3$, where the discrepancy is likely due to the neglect of magnetic disorder.
1409.3596v1
2015-02-18
Anomalous electrical conductivity in rapidly crystallized Cu${}_{50-x}$Zr${}_{x}$ (x = 50 - 66.6) alloys
Cu${}_{50-x}$Zr${}_{x}$ (x = 50, 54, 60 and 66.6) polycrystalline alloys were prepared by arc-melting. The crystal structure of the ingots has been examined by X-ray diffraction. Non-equilibrium martensitic phases with monoclinic structure were detected in all the alloys except Cu${}_{33.4}$Zr${}_{66.6}$. Temperature dependencies of electrical resistivity in the temperature range of T = 4 - 300 K have been measured as well as room temperature values of Hall coefficients and thermal conductivity. Electrical resistivity demonstrates anomalous behavior. At the temperatures lower than 20 K, their temperature dependencies are non-monotonous with pronounced minima. At elevated temperatures they have sufficiently non-linear character which cannot be described within framework of the standard Bloch--Gr\"{u}neisen model. We propose generalized Bloch--Gr\"{u}neisen model with variable Debye temperature which describes experimental resistivity dependencies with high accuracy. We found that both the electrical resistivity and the Hall coefficients reveal metallic-type conductivity in the Cu-Zr alloys. The estimated values of both the charge carrier mobility and the phonon contribution to thermal and electric conductivity indicate the strong lattice defects and structure disorder.
1502.05297v1
2015-05-28
High-throughput in-situ characterization and modelling of precipitation kinetics in compositionally graded alloys
The development of new engineering alloy chemistries is a time consuming and iterative process. A necessary step is characterization of the nano/microstructure to provide a link between the processing and properties of each alloy chemistry considered. One approach to accelerate the identification of optimal chemistries is to use samples containing a gradient in composition, ie. combinatorial samples, and to investigate many different chemistries at the same time. However, for engineering alloys, the final properties depend not only on chemistry but also on the path of microstructure development which necessitates characterization of microstructure evolution for each chemistry. In this contribution we demonstrate an approach that allows for the in-situ, nanoscale characterization of the precipitate structures in alloys, as a function of aging time, in combinatorial samples containing a composition gradient. The approach uses small angle x-ray scattering (SAXS) at a synchrotron beamline. The Cu-Co system is used for the proof-of-concept and the combinatorial samples prepared contain a gradient in Co from 0% to 2%. These samples are aged at temperatures between 450{\textdegree}C and 550{\textdegree}C and the precipitate structures (precipitate size, volume fraction and number density) all along the composition gradient are simultaneously monitored as a function of time. This large dataset is used to test the applicability and robustness of a conventional class model for precipitation that considers concurrent nucleation, growth and coarsening and the ability of the model to describe such a large dataset.
1505.07658v2
2015-06-23
Atomic-scale investigation of creep behavior in nanocrystalline Mg and Mg-Y alloys
Magnesium (Mg) and its alloys offer great potential for reducing vehicular mass and energy consumption due to their inherently low densities. Historically, widespread applicability has been limited by low strength properties compared to other structural Al-, Ti- and Fe-based alloys. However, recent studies have demonstrated high-specific-strength in a number of nanocrystalline Mg-alloys. Even so, applications of these alloys would be restricted to low-temperature automotive components due to microstructural instability under high temperature creep loading. Hence, this work aims to gain a better understanding of creep and associated deformation behavior of columnar nanocrystalline Mg and Mg-yttrium (Y) (up to 3at.%Y(10wt.%Y)) with a grain size of 5 nm and 10 nm. Using molecular dynamics (MD) simulations, nanocrystalline magnesium with and without local concentrations of yttrium is subjected to constant-stress loading ranging from 0 to 500 MPa at different initial temperatures ranging from 473 to 723 K. In pure Mg, the analyses of the diffusion coefficient and energy barrier reveal that at lower temperatures (i.e., T < ~423K) the contribution of grain boundary diffusion to the overall creep deformation is stronger that the contribution of lattice diffusion. However, at higher temperatures (T > ~423K) lattice diffusion dominates the overall creep behavior. Interestingly, for the first time, we have shown that the(101-1),(101-2),(101-3) and (101-6) boundary sliding energy is reduced with the addition of yttrium. This softening effect in the presence of yttrium suggests that the experimentally observed high temperature beneficial effects of yttrium addition is likely to be attributed to some combination of other reported creep strengthening mechanisms or phenomena such as formation of stable yttrium oxides at grain boundaries or increased forest dislocation-based hardening.
1506.07149v1
2015-08-12
Localization of Fe d-states in Ni-Fe-Cu alloys and implications for ultrafast demagnetization
Ni$_{80}$Fe$_{20}$ (Py) and Py-Cu exhibit intriguing ultrafast demagnetization behavior, where the Ni magnetic moment shows a delayed response relative to the Fe [S. Mathias et al., PNAS {\bf 109}, 4792 (2012)]. To unravel the mechanism responsible for this behavior, we have studied Py-Cu alloys for a wide range of Cu concentrations using X-ray magnetic circular dichroism (XMCD). The magnetic moments of Fe and Ni are found to respond very differently to Cu alloying: Fe becomes a strong ferromagnet in Py, with the magnetic moment largely unaffected by Cu alloying. In contrast, the Ni magnetic moment decreases continuously with increasing Cu concentration. Our results are corroborated by ab-initio calculations of the electronic structure, which we discuss in the framework of virtual bound states (VBSs). For high Cu concentrations, Ni exhibits VBSs below the Fermi level, which are likely responsible for an increased orbital/spin magnetic ratio at high Cu concentrations. Fe exhibits VBSs in the minority band, approximately 1 eV above the Fermi level in pure Py, that move closer to the Fermi level upon Cu alloying. A strong interaction between the VBSs and excited electrons above the Fermi level enhances the formation of localized magnons at Fe sites, which explains the different behavior between Fe and Ni during ultrafast demagnetization.
1508.03015v1
2015-12-17
The statistical physics of multi-component alloys using KKR-CPA
We apply variational principles from statistical physics and the Landau theory of phase transitions to multicomponent alloys using the multiple-scattering theory of Korringa-Kohn-Rostoker (KKR) and the coherent potential approximation (CPA). This theory is a multicomponent generalization of the $S^{(2)}$ theory of binary alloys developed by G. M. Stocks, J. B. Staunton, D. D. Johnson and others. It is highly relevant to the chemical phase stability of high-entropy alloys as it predicts the kind and size of finite-temperature chemical fluctuations. In doing so it includes effects of rearranging charge and other electronics due to changing site occupancies. When chemical fluctuations grow without bound an absolute instability occurs and a second-order order-disorder phase transition may be inferred. The S$^{(2)}$ theory is predicated on the fluctuation-dissipation theorem; thus we derive the linear response of the CPA medium to perturbations in site-dependent chemical potentials in great detail. The theory lends itself to a natural interpretation in terms of competing effects: entropy driving disorder and favorable pair interactions driving atomic ordering. To further clarify interpretation we present results for representative ternary alloys CuAgAu, NiPdPt, RhPdAg, and CoNiCu within a frozen charge (or band-only) approximation. These results include the so-called Onsager mean field correction that extends the temperature range for which the theory is valid.
1512.05797v1
2016-02-12
Suppressing diborane production during the hydrogen release of metal borohydrides: The example of alloyed Al(BH$_4$)$_3$
Aluminum borohydride (Al(BH$_4$)$_3$) is an example of a promising hydrogen storage material with exceptional hydrogen densities by weight and volume and a low hydrogen desorption temperature. But, unfortunately, its production of diborane (B$_2$H$_6$) gases upon heating to release the hydrogen restricts its practical use. To elucidate this issue, we investigate the properties of a number of metal borohydrides with the same problem and find that the electronegativity of the metal cation is not the best descriptor of diborane production. We show that, instead, the closely related formation enthalpy is a better descriptor and we find that diborane production is an exponential function thereof. We conclude that diborane production is sufficiently suppressed for formation enthalpies of $-$80 kJ/mol BH$_4$ or lower, providing specific design guidelines to tune existing metal borohydrides or synthesize new ones. We then use first-principles methods to study the effects of Sc alloying in Al(BH$_4$)$_3$. Our results for the thermodynamic properties of the Al$_{1-x}$Sc$_x$(BH$_4$)$_3$ alloy clearly show the stabilizing effect of Sc alloying and thus the suppression of diborane production. We conclude that stabilizing Al(BH$_4$)$_3$ and similar borohydrides via alloying or other means is a promising route to suppress diborane production and thus develop viable hydrogen storage materials.
1602.04185v1
2016-11-02
Nature of low dimensional structural modulations and relative phase stability in MoS2/WS2-ReS2 transition metal dichalcogenide alloys
We report on the various types of Peierls like two dimensional structural modulations and relative phase stability of 2H and 1T poly-types in MoS2-ReS2 and WS2-ReS2 alloy system. Theoretical calculation predicts a polytype phase transition cross over at ~50 at.% of Mo and W in ReS2 in both monolayer and bulk form, respectively. Experimentally, two different types of structural modulations at 50% and a modulation corresponding to trimerization at 75% alloy composition is observed for MoS2-ReS2 and only one type of modulation is observed at 50% WS2-ReS2 alloy system. The 50% alloy system is found to be a suitable monolithic candidate for metal semiconductor transition with minute external perturbation. ReS2 is known to be in 2D Peierls distorted 1Td structure and forms a chain like superstructure. Incorporation of Mo and W atoms in the ReS2 lattice modifies the metal-metal hybridization between the cations and influences the structural modulation and electronic property of the system. The results offer yet another effective way to tune the electronic structure and poly-type phases of this class of materials other than intercalation, strain, and vertical stacking arrangement.
1611.00478v1
2017-01-25
Composition dependent band offsets of ZnO and its ternary alloys
We report the calculated fundamental band gaps of \emph{wurtzite} ternary alloys Zn$_{1-x}$M$_x$O (M=Mg, Cd) and the band offsets of the ZnO/Zn$_{1-x}$M$_x$O heterojunctions, these II-VI materials are important for electronics and optoelectronics. Our calculation is based on density functional theory within the linear muffin-tin orbital (LMTO) approach where the modified Becke-Johnson (MBJ) semi-local exchange is used to accurately produce the band gaps, and the coherent potential approximation (CPA) is applied to deal with configurational average for the ternary alloys. The combined LMTO-MBJ-CPA approach allows one to simultaneously determine both the conduction band and valence band offsets of the heterojunctions. The calculated band gap data of the ZnO alloys scale as $E_g=3.35+2.33x$ and $E_g=3.36-2.33x+1.77x^2$ for Zn$_{1-x}$Mg$_x$O and Zn$_{1-x}$Cd$_x$O, respectively, where $x$ being the impurity concentration. These scaling as well as the composition dependent band offsets are quantitatively compared to the available experimental data. The capability of predicting the band parameters and band alignments of ZnO and its ternary alloys with the LMTO-CPA-MBJ approach indicate the promising application of this method in the design of emerging electronics and optoelectronics.
1701.07147v1
2017-03-07
Thermodynamic Stabilization of Precipitates through Interface Segregation: Chemical Effects
Precipitation hardening, which relies on a high density of intermetallic precipitates, is a commonly utilized technique for strengthening structural alloys. Structural alloys are commonly strengthened through a high density of small size intermetallic precipitates. At high temperatures, however, the precipitates coarsen to reduce the excess energy of the interface, resulting in a significant reduction in the strengthening provided by the precipitates. In certain ternary alloys, the secondary solute segregates to the interface and results in the formation of a high density of nanosize precipitates that provide enhanced strength and are resistant to coarsening. To understand the chemical effects involved, and to identify such systems, we develop a thermodynamic model using the framework of the regular nanocrystalline solution model. For various global compositions, temperatures and thermodynamic parameters, equilibrium configuration of Mg-Sn-Zn alloy is evaluated by minimizing the Gibbs free energy function with respect to the region-specific (bulk solid-solution, interface and precipitate) concentrations and sizes. The results show that Mg$_2$Sn precipitates can be stabilized to nanoscale sizes through Zn segregation to Mg/Mg$_2$Sn interface, and the precipitates can be stabilized against coarsening at high-temperatures by providing a larger Zn concentration in the system. Together with the inclusion of elastic strain energy effects and the input of computationally informed interface thermodynamic parameters in the future, the model is expected to provide a more realistic prediction of segregation and precipitate stabilization in ternary alloys of structural importance.
1703.02621v2
2017-07-13
Anomalous random correlations of force constants on the lattice dynamical properties of disordered Au-Fe alloys
Au-Fe alloys are of immense interest due to their biocompatibility, anomalous hall conductivity, and applications in various medical treatment. However, irrespective of the method of preparation, they often exhibit a high-level of disorder, with properties sensitive to the thermal or magnetic annealing temperatures. We calculate lattice dynamical properties of Au$_{1-x}$Fe$_x$ alloys using density functional theory methods, where, being a multisite property, reliable interatomic force constant (IFC) calculations in disordered alloys remain a challenge. We follow a two fold approach: (1) an accurate IFC calculation in an environment with nominally zero chemical pair correlations to mimic the homogeneously disordered alloy; and (2) a configurational averaging for the desired phonon properties (e.g., dispersion, density of states, and entropy). We find an anomalous change in the IFC's and phonon dispersion (split bands) near $x$=0.19, which is attributed to the local stiffening of the Au-Au bonds when Au is in the vicinity of Fe. Other results based on mechanical and thermo-physical properties reflect a similar anomaly: Phonon entropy, e.g., becomes negative below $x$=0.19, suggesting a tendency for chemical unmixing, reflecting the onset of miscibility gap in the phase diagram. Our results match fairly well with reported data, wherever available.
1707.04060v1
2017-07-13
Microstructural and magnetic property evolution with different heat-treatment conditions in an alnico alloy
Further property enhancement of alnico, an attractive near-term, non-rare-earth permanent magnet alloy system, primarily composed of Al, Ni, Co, and Fe, relies on improved morphology control and size refinement of its complex spinodally decomposed nanostructure that forms during heat-treatment. Using a combination of transmission electron microscopy and atom probe tomography techniques, this study evaluates the magnetic properties and microstructures of an isotropic 32.4Fe-38.1Co-12.9Ni-7.3Al-6.4Ti-3.0Cu (wt.$\%$) alloy in terms of processing parameters such as annealing temperature, annealing time, application of an external magnetic field, as well as low-temperature "draw" annealing. Optimal spinodal morphology and spacing is formed within a narrow temperature and time range ($\sim 840 \unicode{x2103}$ and 10 min during thermal-magnetic annealing (MA). The ideal morphology is a mosaic structure consisting of periodically arrayed $\sim 40$ nm diameter (Fe-Co)-rich rods ($\alpha_1$ phase) embedded in an (Al-Ni)-rich ($\alpha_2$ phase) matrix. A Cu-enriched phase with a size of $\sim$ 3-5 nm is located at the corners of two adjacent $\{110\}$ facets of the $\alpha_1$ phase. The MA process significantly increased remanence ($B_\text{r}$) ($\sim$ 40-70 $\%$) of the alloy due to biased elongation of the $\alpha_1$ phase along the $\langle100\rangle$ crystallographic direction, which is closest in orientation to the applied magnetic field. The optimum magnetic properties of the alloy with an intrinsic coercivity ($H_\text{cj}$) of 1845 Oe and a maximum energy product ($BH_\text{max}$) of 5.9 MGOe were attributed to the uniformity of the mosaic structure.
1707.04165v1
2017-08-09
Materials selection rules for amorphous complexion formation in binary metallic alloys
Complexions are phase-like interfacial features that can influence a wide variety of properties, but the ability to predict which material systems can sustain these features remains limited. Amorphous complexions are of particular interest due to their ability to enhance diffusion and damage tolerance mechanisms, as a result of the excess free volume present in these structures. In this paper, we propose a set of materials selection rules aimed at predicting the formation of amorphous complexions, with an emphasis on (1) encouraging the segregation of dopants to the interfaces and (2) lowering the formation energy for a glassy structure. To validate these predictions, binary Cu-rich metallic alloys encompassing a range of thermodynamic parameter values were created using sputter deposition and subsequently heat treated to allow for segregation and transformation of the boundary structure. All of the alloys studied here experienced dopant segregation to the grain boundary, but exhibited different interfacial structures. Cu-Zr and Cu-Hf formed nanoscale amorphous intergranular complexions while Cu-Nb and Cu-Mo retained crystalline order at their grain boundaries, which can mainly be attributed to differences in the enthalpy of mixing. Finally, using our newly formed materials selection rules, we extend our scope to a Ni-based alloy to further validate our hypothesis, as well as make predictions for a wide variety of transition metal alloys.
1708.02971v2
2017-11-29
Mechanical consequences of dynamically loaded NiTi wires under typical actuator conditions in rehabilitation and neuroscience
In the field of rehabilitation and neuroscience shape memory alloys play a crucial role as lightweight actuators. Devices are exploiting the shape memory effect by transforming heat into mechanical work. In rehabilitation applications, dynamic loading of the respective device occurs, which in turn influences the mechanical consequences of the phase transforming alloy. Hence in this work, dynamic thermomechanical material behavior of temperature triggered phase transforming NiTi shape memory alloy wires with different chemical compositions and geometries is experimentally investigated. Storage modulus and mechanical loss factor of NiTi alloys at different temperatures and loading frequencies are analyzed under force controlled conditions. Counterintuitive storage modulus and loss factor dependent trends regarding the loading frequency dependency of the mechanical properties on the materials composition and geometry are hence obtained. It could be revealed that loss factors show a pronounced loading frequency dependency, whereas the storage modulus was not affected. It is shown that force controlled conditions lead to a lower storage modulus than expected. Further it turned out that a simple empirical relation can capture the characteristic temperature dependency of the storage modulus, which is an important input relation for modeling the rehabilitation device behavior under different dynamic and temperature loading conditions, taking directly into account the material behavior of the shape memory alloy.
1711.11079v1
2018-01-16
Magnetic irreversibility and pinning force density in the Mo$_{100-x}$Re$_x$ alloy superconductors
We have measured the isothermal field dependence of magnetization of the Mo$_{100-x}$Re$_x$ (15 $\leq$ x $\leq$ 48) alloys, and have estimated the critical current and pinning force density from these measurements. We have performed structural characterization of the above alloys using standard techniques, and analyzed the field dependence of critical current and pinning force density using existing theories. Our results indicate that dislocation networks and point defects like voids and interstitial imperfections are the main flux line pinning centres in the Mo$_{100-x}$Re$_x$ alloys in the intermediate fields, i.e., in the small bundle flux line pinning regime. In this regime, the critical current density is also quite robust against increasing magnetic field. In still higher fields, the critical current density is affected by flux creep. In the low field regime, on the other hand, the pinning of the flux lines seems to be influenced by the presence of two superconducting energy gaps in the Mo$_{100-x}$Re$_x$ alloys. This modifies the field dependence of critical current density, and also seems to contribute to the asymmetry in the magnetic irreversibility exhibited by the isothermal field dependence of magnetization
1801.05093v1
2018-03-12
Understanding the mechanical properties of reduced activation steels
Reduced activation ferritic/martensitic (RAFM) steels are structural materials with potential application in Generation-IV fission and fusion reactors. We use density-functional theory to scrutinize the micro-mechanical properties of the main alloy phases of three RAFM steels based on the body-centered cubic FeCrWVMn solid solution. We assess the lattice parameters and elastic properties of ferromagnetic $\alpha$-Fe and Fe$_{91}$Cr$_{9}$, which are the main building blocks of the RAFM steels, and present a detailed analysis of the calculated alloying effects of V, Cr, Mn, and W on the mechanical properties of Fe$_{91}$Cr$_{9}$. The composition dependence of the elastic parameters is decomposed into electronic and volumetric contributions and studied for alloying levels that cover the typical intervals in RAFM steels. A linear superposition of the individual solute effects on the properties of Fe$_{91}$Cr$_{9}$ is shown to provide an excellent approximation for the \emph{ab initio} values obtained for the RAFM steels. The intrinsic ductility is evaluated through Rice's phenomenological theory using the surface and unstable stacking fault energies, and the predictions are contrasted with those obtained by empirical criteria. Alloying with V or W is found to enhance the ductility, whereas additional Cr or Mn turns the RAFM base alloys more brittle.
1803.04178v1
2018-05-10
First-principles investigation on diffusion mechanism of alloying elements in dilute Zr alloys
Impurity diffusion in Zr is potentially important for many applications of Zr alloys, and in particular for their use of nuclear reactor cladding. However, significant uncertainty presently exists about which elements are vacancy vs. interstitial diffusers, which can inhibit understanding and prediction of their behavior under different temperature, irradiation, and alloying conditions. Therefore, first-principles calculations based on density functional theory (DFT) have been employed to predict the temperature-dependent dilute impurity diffusion coefficients for 14 substitutional alloying elements in hexagonal closed packed (HCP) Zr. Vacancy-mediated diffusion was modeled with the eight-frequency model. Interstitial contributions to diffusion are estimated from interstitial formation and select migration energies. Formation energies for each impurity in nine high-symmetry interstitial sites were determined, including significant effects of thermal expansion. The dominant diffusion mechanism of each solute in HCP Zr was identified in terms of the calculated vacancy-mediated activation energy, lower and upper bounds of interstitial activation energy, and the formation entropy, suggesting a rough relation with the metallic radii of solutes. It is predicted that Cr, Cu, V, Zn, Mo, W, Au, Ag, Al, Nb, Ta and Ti all diffuse predominantly by an interstitial mechanism, while Hf, Zr, and Sn are likely to be predominantly vacancy-mediated diffusers at low temperature and interstitial diffusers at high temperature, although the identification of mechanisms for these elements at high-temperature is quite uncertain.
1805.04128v1
2018-11-29
Magnetocrystalline Anisotropy of Fe-based $L1_0$ Alloys: Validity of Approximate Methods to Treat the Spin-Orbit Interaction
First-principles calculations are used to gauge different levels of approximation to calculate the magnetocrystalline anisotropy energies (MAE) of five $L1_0$ FeMe alloys (Me=Co, Cu, Pd, Pt, Au). We find that a second-order perturbation (2PT) treatment of the spin-orbit interaction (SOI) breaks down for the alloys containing heavier ions, while it provides a very accurate description of the MAE behaviour of FeCo, FeCu, and FePd. Moreover, the robustness of the 2PT approximation is such that in these cases it accounts for the MAE of highly-non-neutral alloys and, thus, it can be used to predict their performance when dopants are present or when they are subject to applied gate bias, which are typical conditions in working magnetoelectric devices. We also observe that switching of the easy axis direction can be induced in some of these alloys by addition or removal of, at least, one electron per cell. In all cases, the details of the bandstructure are responsible for the finally observed MAE value and, therefore, suggest a limited predicting power of models based on the expected orbital moment values and bandwidths. Finally, we have confirmed the importance of various calculation parameters to obtain converged MAE values, in particular, those related to the accuracy of the Fermi level determination.
1811.12100v1
2019-11-12
Semiconducting SiGeSn High-Entropy Alloy: A Density Functional Theory Study
High-entropy alloys (HEAs), which have been intensely studied due to their excellent mechanical properties, generally refer to alloys with multiple equimolar or nearly equimolar elements. According to this definition, Si-Ge-Sn alloys with equal or comparable concentrations of the three Group IV elements belong to the category of HEAs. As a result, the equimolar elements of Si-Ge-Sn alloys likely cause their atomic structures to exhibit the same core effects of metallic HEAs such as lattice distortion. Here we apply density functional theory (DFT) calculations to show that the SiGeSn HEA indeed exhibits a large local distortion effect. Unlike metallic HEAs, our Monte Carlo and DFT calculations show that the SiGeSn HEA exhibits no chemical short-range order due to the similar electronegativity of the constituent elements, thereby increasing the configurational entropy of the SiGeSn HEA. Hybrid density functional calculations show that the SiGeSn HEA remains semiconducting with a band gap of 0.38 eV, promising for economical and compatible mid-infrared optoelectronics applications. We then study the energetics of neutral single Si, Ge, and Sn vacancies and (expectedly) find wide distributions of vacancy formation energies, similar to those found in metallic HEAs. However, we also find anomalously small lower bounds (e.g., 0.04 eV for a Si vacancy) in the energy distributions, which arise from the bond reformation near the vacancy. Such small vacancy formation energies and their associated bond reformations retain the semiconducting behavior of the SiGeSn HEA, which may be a signature feature of a semiconducting HEA that differentiates from metallic HEAs.
1911.04677v1
2020-01-09
Tuning of structural phase, magnetic spin order and electrical conductivity in mechanical alloyed material of alpha-Fe2O3 and alpha-Cr2O3 oxides
Alpha-Fe2O3 and alpha-Cr2O3 has been mechanical alloyed to prepare Fe1-xCrxO3 oxides for x = 0.2-0.8. Synchrotron X-ray diffraction and Raman spectra have shown inhomogeneous structure of {\alpha}-Fe2O3 and {\alpha}-Cr2O3 phases in as-alloyed samples. The as-alloyed samples have shown soft ferromagnetic properties with signature of two Morin transitions. The heat treatment of as-alloyed samples has homogenized structure and successfully incorporated the Cr atoms into the lattice sites of Fe atoms in {\alpha}-Fe2O3. The magnetic and electrical properties have been modified in the heat treated samples. For example, canted antiferromagnetic order has been appeared as an effect of heat treatment, irrespective of the Cr content in Fe1-xCrxO3. The magnetic field induced spin flop transition has been observed at a critical magnetic field that depends on Cr content in the system. The M\"ossbauer spectrum at room temperature has been fitted with two sextets. The variation of M\"ossbauer parameters suggest a distribution of magnetic spin order between Fe and Cr ions in the rhombohedral structure of Fe1-xCrxO3. The electrical conductivity, derived from current-voltage characteristics of the heat treated samples, has been enhanced by increasing Cr content in alpha-Fe2O3 structure. The experimental results have been explained based on the theoretical models available in literature.
2001.02831v1
2021-07-12
Machine-learning potentials enable predictive $\textit{and}$ tractable high-throughput screening of random alloys
We present an automated procedure for computing stacking fault energies in random alloys from large-scale simulations using moment tensor potentials (MTPs) with the accuracy of density functional theory (DFT). To that end, we develop an algorithm for training MTPs on random alloys. In the first step, our algorithm constructs a set of ~10000 or more training candidate configurations with 50-100 atoms that are representative for the atomic neighborhoods occurring in the large-scale simulation. In the second step, we use active learning to reduce this set to ~100 most distinct configurations - for which DFT energies and forces are computed and on which the potential is ultimately trained. We validate our algorithm for the MoNbTa medium-entropy alloy by showing that the MTP reproduces the DFT $\frac{1}{4}[111]$ unstable stacking fault energy over the entire compositional space up to a few percent. Contrary to state-of-the-art methods, e.g., the coherent potential approximation (CPA) or special quasi-random structures (SQSs), our algorithm naturally accounts for relaxation, is not limited by DFT cell sizes, and opens opportunities to efficiently investigate follow-up problems, such as chemical ordering. In a broader sense, our algorithm can be easily modified to compute related properties of random alloys, for instance, misfit volumes, or grain boundary energies. Moreover, it forms the basis for an efficient construction of MTPs to be used in large-scale simulations of multicomponent systems.
2107.05620v2
2019-01-07
Strain and Band-Gap Engineering in Ge-Sn Alloys via P Doping
Ge with a quasi-direct band gap can be realized by strain engineering, alloying with Sn, or ultrahigh n-type doping. In this work, we use all three approaches together to fabricate direct-band-gap Ge-Sn alloys. The heavily doped n-type Ge-Sn is realized with CMOS-compatible nonequilibrium material processing. P is used to form highly doped n-type Ge-Sn layers and to modify the lattice parameter of P-doped Ge-Sn alloys. The strain engineering in heavily-P-doped Ge-Sn films is confirmed by x-ray diffraction and micro Raman spectroscopy. The change of the band gap in P-doped Ge-Sn alloy as a function of P concentration is theoretically predicted by density functional theory and experimentally verified by near-infrared spectroscopic ellipsometry. According to the shift of the absorption edge, it is shown that for an electron concentration greater than 1x10^20 cm-3 the band-gap renormalization is partially compensated by the Burstein-Moss effect. These results indicate that Ge-based materials have high potential for use in near-infrared optoelectronic devices, fully compatible with CMOS technology.
1901.01721v1
2019-10-12
A phase-field approach for modeling equilibrium solute segregation at the interphase boundary in binary alloys
A number of experimental and theoretical findings in age hardening alloys suggest that specific solute elements preferentially segregate to and reduce the energy of the interphase boundary (IB). This segregation mechanism can stabilize the precipitation microstructure against coarsening, allowing higher operating temperatures in structural applications. Herein, we present a phase field model of solute segregation to IBs that separate matrix and precipitate phases in binary alloys. The proposed modeling framework is capable of capturing bulk thermodynamics and interfacial free energies, while also accounting for various mass transport mechanisms. Analytical equilibrium solutions of one-dimensional systems are presented, and excess IB quantities are evaluated independent of the Gibbs dividing surface convention. With the aid of the parallel tangent construction, IB segregation isotherms are established in terms of the alloy composition and the model parameters describing the free energy functions. Under the regular solution approximation, computational studies elucidating the dependence of the IB energy and segregation levels on temperature and free energy model parameters are presented. We show that the model is consistent with the Gibbs adsorption equation; therefore, it is possible to compare the adsorption behavior predicted by the model parameters with experiments and atomistic simulations. Future work on extending the model to ternary alloys, and incorporating the effect of elastic interactions on IB segregation is expected.
1910.05606v2
2018-12-26
Accurate high-resolution depth profiling of magnetron sputtered transition metal alloy films containing light species: A multi-method approach
We present an assessment of a multi-method approach based on ion beam analysis to obtain high-resolution depth profiles of the total chemical composition of complex alloy systems. As a model system we employ an alloy based on several transition metals and containing light species. Samples have been investigated by a number of different ion-beam based techniques, i.e., Rutherford Backscattering Spectrometry, Particle-Induced X-ray Emission, Elastic Backscattering Spectrometry and Time-of-Flight/Energy Elastic Recoil Detection Analysis. Sets of spectra obtained from these different techniques were analyzed both independently and following an iterative and self-consistent approach yielding a more accurate depth profile of the sample, including both metallic heavy constituents (Cr, Fe and Ni) as well as the rather reactive light species (C, O) in the alloy. A quantitative comparison in terms of achievable precision and accuracy is made and the limitations of the single method approach are discussed for the different techniques. The multi-method approach is shown to yield significantly improved and accurate information on stoichiometry, depth distribution, and thickness of the alloy with the improvements being decisive for a detailed correlation of composition to the material properties such as corrosion strength. The study also shows the increased relative importance of experimental statistics for the achievable accuracy in the multi-method approach.
1812.10340v2
2019-02-07
BInGaN alloys nearly lattice-matched to GaN for high-power high-efficiency visible LEDs
InGaN-based visible LEDs find commercial applications for solid-state lighting and displays, but lattice mismatch limits the thickness of InGaN quantum wells that can be grown on GaN with high crystalline quality. Since narrower wells operate at a higher carrier density for a given current density, they increase the fraction of carriers lost to Auger recombination and lower the efficiency. The incorporation of boron, a smaller group-III element, into InGaN alloys is a promising method to eliminate the lattice mismatch and realize high-power, high-efficiency visible LEDs with thick active regions. In this work we apply predictive calculations based on hybrid density functional theory to investigate the thermodynamic, structural, and electronic properties of BInGaN alloys. Our results show that BInGaN alloys with a B:In ratio of 2:3 are better lattice matched to GaN compared to InGaN and, for indium fractions less than 0.2, nearly lattice matched. Deviations from Vegard's law appear as bowing of the in-plane lattice constant with respect to composition. Our thermodynamics calculations demonstrate that the solubility of boron is higher in InGaN than in pure GaN. Varying the Ga mole fraction while keeping the B:In ratio constant enables the adjustment of the (direct) gap in the 1.75-3.39 eV range, which covers the entire visible spectrum. Holes are strongly localized in non-bonded N 2p states caused by local bond planarization near boron atoms. Our results indicate that BInGaN alloys are promising for fabricating nitride heterostructures with thick active regions for high-power, high-efficiency LEDs.
1902.02692v1
2020-04-09
Magnetic Damping in Epitaxial Fe Alloyed with Vanadium and Aluminum
To develop low-moment, low-damping metallic ferromagnets for power-efficient spintronic devices, it is crucial to understand how magnetic relaxation is impacted by the addition of nonmagnetic elements. Here, we compare magnetic relaxation in epitaxial Fe films alloyed with light nonmagnetic elements of V and Al. FeV alloys exhibit lower intrinsic damping compared to pure Fe, reduced by nearly a factor of 2, whereas damping in FeAl alloys increases with Al content. Our experimental and computational results indicate that reducing the density of states at the Fermi level, rather than the average atomic number, has a more significant impact in lowering damping in Fe alloyed with light elements. Moreover, FeV is confirmed to exhibit an intrinsic Gilbert damping parameter of $\simeq$0.001, among the lowest ever reported for ferromagnetic metals.
2004.04840v3
2020-05-18
Band Alignments of Emerging Wurtzite BAlN and BGaN Semiconductors
The wurtzite III-Nitrides family of semiconductors, which include the compounds GaN, InN, and AlN, along with their derivative ternary alloys, is highly priced for its wide range of bandgaps, lattice constant tunability, high breakdown voltages, and thermal and chemical stability. The incorporation of wurtzite BxAl1-xN and BxGa1-xN ternary alloys into this family introduces an even larger range of bandgaps, lattice constants, and refractive indices, which indicates their potential in the fields of optoelectronics and power devices. An important parameter in the design of cutting edge devices is the band alignment between the different alloys. In our work, the natural band offset values between wz-BxAl1-xN and wz-BxGa1-xN alloys were investigated using ab initio simulations. The Vienna Ab initio Simulation Package was used to perform density functional theory calculations in order to obtain lattice parameters, band gap energies, and relative electrostatic potential lineups. Through these calculations, we were able to quantify the natural band offset values for the materials of interest, and as such were able to identify some general qualitative features associated with the different alloys we studied. As the growth and fabrication of wz-BAlN and wz-BGaN crystals matures, we hope that our results can provide a theoretical basis for design and analysis of cutting-edge devices.
2005.08407v1
2020-05-22
Photo-degradation Protection in 2D In-Plane Heterostructures Revealed by Hyperspectral Nanoimaging: the Role of Nano-Interface 2D Alloys
Single-layer heterostructures exhibit striking quasiparticle properties and many-body interaction effects that hold promise for a range of applications. However, their properties can be altered by intrinsic and extrinsic defects, thus diminishing their applicability. Therefore, it is of paramount importance to identify defects and understand 2D materials' degradation over time using advanced multimodal imaging techniques as well as stabilize degradation via built-in interface protection. Here we implemented a liquid-phase precursor approach to synthesize 2D in-plane MoS2-WS2 heterostructures exhibiting nanoscale alloyed interfaces and map exotic interface effects during photo-degradation using a novel combination of hyperspectral tip-enhanced photoluminescence, Raman and near-field nanoscopy. Surprisingly, 2D alloyed regions exhibit remarkable thermal and photo-degradation stability providing protection against oxidation. Coupled with surface and interface strain, 2D alloy regions create localized potential wells that concentrate excitonic species via a charge carrier funneling effect. These results provide a clear understanding of the importance of 2D alloys as systems able to withstand degradation effects over time, and could be now used to stabilize optoelectronic devices based on 2D materials.
2005.11361v1
2020-05-28
A Comparative Analysis of Inconel 718 Made by Additive Manufacturing and Suction Casting: Microstructure Evolution in Homogenization
Homogenization is one of the critical stages in the post-heat treatment of additive manufacturing (AM) component to achieve uniform microstructure. During homogenization, grain coarsening could be an issue to reserve strength, which requires careful design of both time and temperature. Therefore, a proper design of homogenization becomes particularly important for AM design, for which work hardening is usually no longer an option. In this work, we discovered an intriguing phenomenon during homogenization of suction-cast and AM Inconel 718 superalloys. Through both short and long-term isothermal heat treatments at 1180{\deg}C, we observed an abnormal grain growth in the suction-cast alloy but continuous recrystallization in the alloy made by laser powder bed fusion (LPBF). The grain size of AM samples keeps as small as 130 {\mu}m and is even slightly reduced after homogenization for 12 hours. The homogeneity of Nb in the AM alloys is identified as the critical factor for NbC formation, which further influences the recrystallization kinetics at 1180{\deg}C. Multi-type dislocation behaviors are studied to elucidate the grain refinement observed in homogenized alloys after LPBF. This work provides a new pathway on microstructure engineering of AM alloys for improved mechanical performance superior to traditionally manufactured ones.
2005.14089v2
2020-08-01
Trends in elastic properties of Ti-Ta alloys from first-principles calculations
The martensitic start temperature ($M_{\text{s}}$) is a technologically fundamental characteristic of high-temperature shape memory alloys. We have recently shown [Phys. Rev. B 94, 224104 (2016)] that the two key features in describing the composition dependence of $M_\text{s}$ are the $T=0$ K phase stability and the difference in vibrational entropy which, within the Debye model, is directly linked to the elastic properties. Here, we use density functional theory together with special quasi-random structures to study the elastic properties of disordered martensite and austenite Ti-Ta alloys as a function of composition. We observe a softening in the tetragonal shear elastic constant of the austenite phase at low Ta content and a \emph{non-linear} behavior in the shear elastic constant of the martensite. A minimum of 12.5$\%$ Ta is required to stabilize the austenite phase at $T = 0$ K. Further, the shear elastic constants and Young's modulus of martensite exhibit a maximum for Ta concentrations close to 30$\%$. Phenomenological, elastic-constant-based criteria suggest that the addition of Ta enhances the strength, but reduces the ductile character of the alloys. In addition, the directional elastic stiffness, calculated for both martensite and austenite, becomes more isotropic with increasing Ta content. The reported trends in elastic properties as a function of composition may serve as a guide in the design of alloys with optimized properties in this interesting class of materials.
2008.00165v1
2021-02-28
Accommodation mechanisms in strain-transformable titanium alloys
A new $\beta$-metastable Ti-alloy is designed with the aim to obtain a TWIP alloy but positioned at the limit between the TRIP/TWIP and the TWIP dominated regime. The designed alloy exhibits a large ductility combined with an elevated and stable work-hardening rate. Deformation occurring by formation and multiplication of {332}<113> twins is evidenced and followed by in-situ electron microscopy, and no primary stress induced martensite is observed. Since microstructural investigations of the deformation mechanisms show a highly heterogeneous deformation, the reason of the large ductility is then investigated. The spatial strain distribution is characterized by micro-scale digital image correlation, and the regions highly deformed are found to stand at the crossover between twins, or at the intersection between deformation twins and grain boundaries. Detailed electron back-scattered imaging in such regions of interest finally allowed to evidence the formation of thin needles of stress induced martensite. The latter is thus interpreted as an accommodation mechanism, relaxing the local high strain fields, which ensures a large and stable plastic deformation of this newly designed Ti-alloy.
2103.00440v2
2021-03-26
Dissecting functional degradation in NiTi shape-memory-alloys containing amorphous regions via atomistic simulations
Molecular dynamics simulations are performed to provide a detailed understanding of the functional degradation of shape memory alloys at small scale. The origin of the experimentally reported accumulation of plastic deformation and the anomalous sudden increase of the residual strain under cyclic mechanical loading are explained by detailed insights into the relevant atomic scale processes. Our work reveals that the mechanical response of shape-memory-alloy pillars under cyclic compression is significantly influenced by the presence of an amorphous-like surface region as experimentally induced by focused ion beam milling. The main factor responsible for the observed degradation of superelasticity under cyclic loading is the accumulated plastic deformation and the resultant retained martensite originating from a synergetic contribution of the amorphous and crystalline shape-memory-alloy regions. We show that the reported sudden diminishment of the stress plateaus and hysteresis under cyclic loading is caused by the increased stability of the martensite phase due to the presence of the amorphous phase. Based on the identified mechanism responsible for the degradation, we validate reported methods of recovering the superelasticity and propose a new method to prohibit the synergetic contribution of the amorphous and crystalline regions, such as to achieve a sustainable operation of shape memory alloys at small scale.
2103.14319v2
2022-02-25
Role of Zirconium Conversion Coating in Corrosion Performance of Aluminum Alloys: An Integrated First-Principles and Multiphysics Modeling Approach
A variety of chromate-free conversion coatings are being actively investigated to improve the corrosion performance of light-weight alloys for aerospace and defense applications. Advancing conversion coating, however, requires an in-depth understanding of the underlying corrosion mechanisms in order to rationally design sustainable coatings. Here, we present a multiscale modeling approach to predict corrosion performance of metallic materials, with a focus on localized corrosion of Cu-containing aluminum alloys coated with ZrO2 layer. First-principles and transition-state theory are used to implement the kinetics model, which includes electrolyte-metal interfacial reactions. The modeling framework systematically characterizes and couples multiple electrochemical and physical (e.g., transport) phenomena to explore interrelationships between pit morphology, surface chemistry, and local environment. This multiscale model can quantitatively link the corrosion rate of ZrO2-coated aluminum alloys with the evolution of interfacial reactions during immersion, which is very difficult to establish using in situ experiments. We have evaluated the presented multiscale model using available experimental data. The rate of corrosion and pit stability were quantitatively assessed for various environmental parameters and applied potentials. Results show that Zr-based conversion coating strongly enhances the corrosion performance of aluminum alloys due to zirconium involvement in interfacial kinetics.
2202.12990v3
2022-03-16
Determination of Al occupancy and local structure for \b{eta}-(AlxGa1-x)2O3 alloys across nearly full composition range from Rietveld analysis
Al occupancy and local structure (bond length and bond angles) for monoclinic \b{eta}-(AlxGa1-x)2O3 alloys, with Al compositions (x) up to 90%, have been determined from Rietveld refinement of x-ray diffraction data. Al atom preferentially occupies octahedron (Oh) atomic site in comparison to tetrahedron (Td) atomic site. However, sizable number of Td atomic sites i.e. 20% for Al composition of 5% remain occupied by Al atoms, which is found to increase sharply with Al composition. The Oh atomic sites are not fully occupied by Al atoms even for Al composition of 90%. The lattice parameters (band gap) of \b{eta}-(AlxGa1-x)2O3 alloy decrease (increases) linearly with Al composition, but a change in slope of variation of both lattice parameters and band gap is observed at around Al composition of 50%. The lattice is found to be distorted for Al compositions more than 50% as indicated by large change in the bond angles. The lattice distortion is determined to be the origin for the observed change in slope for the variation of both lattice parameters and band gap for monoclinic \b{eta}-(AlxGa1-x)2O3 alloy system. Our results provide an insight in to the local structure of \b{eta}-(AlxGa1-x)2O3 alloys, which are required to have better understanding of their physical properties.
2203.08494v1
2016-03-07
Structural Phase Transition and Carrier Density Tuning in SnSexTe1-x Nanoplates for Topological Crystalline Insulators
For topological insulators and topological crystalline insulators (TCIs), their exotic surface states are promising for fundamental condensed matter physics research as well as future electronics such as low-dissipation electronics and spintronics. However, the high bulk carrier density that often dominates the transport property is the major materials challenge, critically hindering our ability to study and manipulate the surface states. In this manuscript, we demonstrate an alloying strategy, SnSexTe1-x, to effectively reduce the bulk carrier density. As long as SnSexTe1-x remains in the cubic crystal structure, it is predicted to be a TCI. We show systematic decrease of the bulk carrier density with the increasing Se concentration, demonstrating that the alloying principle works. In addition, we map out the phase diagram of the cubic to the orthorhombic structural transition as a function of the Se concentration. This was made possible by studying alloy nanoplates which remain single-crystalline and is either in the cubic or the orthorhombic phase, in contrast to bulk alloys that would exhibit polycrystalline grains. Lastly, we investigate systematically the ferroelectric transition associated with the structural transition from the cubic to the rhombohedral phase for SnSexTe1-x. This is the first ferroelectric transition study of the alloy system SnSexTe1-x.
1603.02241v1
2016-03-11
Quantum Critical Behavior in a Concentrated Ternary Solid Solution
Quantum critical behavior has been associated with some of the most exotic emergent states of matter including high-temperature superconductivity. Much of the research into quantum critical point (QCP) physics has been hampered by the lack of model systems simple enough to be analyzed by theory. Here, we show that the concentrated solid solution fcc alloys, including the so-called high-entropy alloys, are ideal model systems to study the effects of chemical disorder on emergent properties near a quantum critical region. The face centered cubic (fcc) alloy NiCoCrx with x near 1 is found to be close to the Cr concentration where the ferromagnetic transition temperature, Tc, goes to 0. Near this composition these alloys exhibit a resistivity linear in temperature to 2 K, a linear magnetoresistance, an excess -TlnT contribution to the low temperature heat capacity and excess low temperature entropy. All of the low temperature electrical, magnetic and thermodynamic properties of the alloys with compositions near x near 1 are not typical of a Fermi liquid and suggest strong magnetic fluctuations associated with a quantum critical region. The limit of extreme chemical disorder in these simple fcc materials thus provides a novel and unique platform to study quantum critical behavior in a highly tunable system.
1603.03781v1
2016-12-19
Anomalous Hardening in Magnesium Driven by a Size-Dependent Transition in Deformation Modes
Magnesium (Mg) and its alloys hold great potential as an energy-saving structural material for automative, aerospace applications. However, the use of Mg alloys has been limited due to poor ductility and formability. Poor mechanical properties of Mg alloys origin from the insufficient number of slip systems, and deformation twinning plays an important role to accommodate plastic deformation. Here, we report a comprehensive experimental and modeling study to understand crystal size effect on the transformation in deformation modes in twin oriented Mg single crystals. The experiments reveal two regimes of size effects: (1) single twin propagation, where a typical "smaller the stronger" behavior was dominant in pillars {\le} 18 {\mu}m in diameter, and (2) twin-twin interaction, which results in anomalous strain hardening in pillars > 18 {\mu}m. Molecular dynamics simulations further indicate a transition from twinning to dislocation mediated plasticity for crystal sizes below a few hundred nanometers. Our results provide new understanding of the fundamental deformation modes of twin oriented Mg from nano-scale to bulk, and insights to design Mg alloys with superior mechanical properties through dimensional refinement. This subsequently can materialize into more utilization of Mg alloys as a structural material in technologically relevant applications.
1612.06275v1
2018-04-11
Clustering kinetics during natural ageing of Al-Cu based alloys with (Mg, Li) additions
Room temperature solute clustering in aluminium alloys, or natural ageing, despite its industrial relevance, is still subject to debate, mostly due to its experimentally challenging nature. To better understand the complex multi-constituents' interactions at play, we have studied ternary and quaternary subsystems based on the Al-Cu alloys, namely Al-Cu-Mg, Al-Cu-Li and Al-Cu-Li-Mg. We used a recently introduced correlative technique using small-angle neutrons and X-ray scattering (SANS and SAXS) to extract the chemically resolved kinetics of room temperature clustering in these alloys, which we completed with differential scanning calorimetry (DSC) and micro-hardness measurements. The comparison of the clustering behaviours of each subsystem allowed us to highlight the paramount role of Mg as a trigger for diffusion and clustering. Indeed, while a strong natural ageing was observed in the Al-Cu-Mg alloy, virtually none was shown for Al-Cu-Li. A very slight addition of Mg (0.4%) to this system, however, drastically changed the situation to a rapid formation of essentially Cu-rich hardening clusters, Mg only joining them later in the reaction. This diffusion enabling effect of Mg is discussed in terms of diffusion mechanism and complex interactions with the quenched-in vacancies.
1804.03899v2
2018-04-12
Unusual composition dependence of transformation temperatures in Ti-Ta-X shape memory alloys
Ti-Ta-X (X = Al, Sn, Zr) compounds are emerging candidates as high-temperature shape memory alloys (HTSMAs). The stability of the one-way shape memory effect (1WE), the exploitable pseudoelastic (PE) strain intervals as well as the transformation temperature in these alloys depend strongly on composition, resulting in a trade-off between a stable shape memory effect and a high transformation temperature. In this work, experimental measurements and first-principles calculations are combined to rationalize the effect of alloying a third component to Ti-Ta based HTSMAs. Most notably, an $\textit{increase}$ in the transformation temperature with increasing Al content is detected experimentally in Ti-Ta-Al for low Ta concentrations, in contrast to the generally observed dependence of the transformation temperature on composition in Ti-Ta-X. This inversion of trend is confirmed by the $\textit{ab-initio}$ calculations. Furthermore, a simple analytical model based on the $\textit{ab-initio}$ data is derived. The model can not only explain the unusual composition dependence of the transformation temperature in Ti-Ta-Al, but also provide a fast and elegant tool for a qualitative evaluation of other ternary systems. This is exemplified by predicting the trend of the transformation temperature of Ti-Ta-Sn and Ti-Ta-Zr alloys, yielding a remarkable agreement with available experimental data.
1804.04546v1
2019-12-22
Ab initio modeling of the energy landscape for screw dislocations in body-centered cubic high-entropy alloys
In traditional body-centered cubic (bcc) metals, the core properties of screw dislocations play a critical role in plastic deformation at low temperatures. Recently, much attention has been focused on refractory high-entropy alloys (RHEAs), which also possess bcc crystal structures. However, unlike face-centered cubic high-entropy alloys (HEAs), there have been far fewer investigations on bcc HEAs, specifically on the possible effects of chemical short-range order (SRO) in these multiple principal element alloys on dislocation mobility. Here, using density functional theory, we investigate the distribution of dislocation core properties in MoNbTaW RHEAs alloys, and how they are influenced by SRO. The average values of the core energies in the RHEA are found to be larger than those in the corresponding pure constituent bcc metals, and are relatively insensitive to the degree of SRO. However, the presence of SRO is shown to have a large effect on narrowing the distribution of dislocation core energies and decreasing the spatial heterogeneity of dislocation core energies in the RHEA. It is argued that the consequences for the mechanical behavior of HEAs is a change in the energy landscape of the dislocations which would likely heterogeneously inhibit their motion.
1912.10506v3
2020-02-04
The Crystallography of Aluminum and its Alloys
This chapter begins with pure aluminium and a discussion of the form of the crystal structure and different unit cells that can be used to describe the crystal structure. Measurements of the face-centred cubic lattice parameter and thermal expansion coefficient in pure aluminium are reviewed and parametrisations given that allow the reader to evaluate them across the full range of temperatures where aluminium is a solid. A new concept called the vacancy triangle is introduced and demonstrated as an effective means for determining vacancy concentrations near the melting point of aluminium. The Debye-Waller factor, quantifying the thermal vibration of aluminium atoms in pure aluminium, is reviewed and parametrised over the full range of temperatures where aluminium is a solid. The nature of interatomic bonding and the history of its characterisation in pure aluminium is reviewed with the unequivocal conclusion that it is purely tetrahedral in nature. The crystallography of aluminium alloys is then discussed in terms of all of the concepts covered for pure aluminium, using prominent alloy examples. The electron density domain theory of solid-state nucleation and precipitate growth is introduced and discussed as a new means of rationalising phase transformations in alloys from a crystallographic point of view.
2002.01562v1
2020-02-11
Modification of the charge and magnetic order of a low dimensional ferromagnet by molecule-surface bonding
The ability to design and control the spin and charge order of low dimensional materials on the molecular scale offers an intriguing pathway towards the miniaturization of spintronic technology towards the nanometer scale. In this work, we focus on the adsorption induced modifications of the magnetic and electronic properties of a low dimensional ferromagnetic surface alloy after the adsorption of the prototypical organic molecule perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA). For this metal-organic interface, we observe the formation of a localized $\sigma$-like bond between the functional molecular groups and the surface alloy atoms. This strong chemical bonding coincides with a lifting of the characteristic surface alloy band structure and a reduction of the magnitude of the local magnetic moments of the Dy atoms by 18%. We attribute both findings to a mixing of spin-degenerate molecular states with spin-split states of the Dy-Ag surface alloy via the sigma-like bonds between PTCDA and the Dy surface alloy atoms. Our findings clearly demonstrate the potential of tailored molecule-surface sigma-bonds to control not only the electronic but also the magnetic order of low dimensional materials.
2002.04296v2
2020-02-11
A Multiscale Constitutive Model for Metal Forming of Dual Phase Titanium Alloys by Incorporating Inherent Deformation and Failure Mechanisms
Ductile metals undergo a considerable amount of plastic deformation before failure. Void nucleation, growth and coalescence is the mechanism of failure in such metals. {\alpha}/{\beta} titanium alloys are ductile in nature and are widely used for their unique set of properties like specific strength, fracture toughness, corrosion resistance and resistance to fatigue failures. Voids in these alloys were reported to nucleate on the phase boundaries between {\alpha} and {\beta} phase. Based on the findings of crystal plasticity finite element method (CPFEM) based investigation of the void growth at the interface of {\alpha} and {\beta} phases [1], [2], a void nucleation, growth, and coalescence model has been formulated. An existing single-phase crystal plasticity theory is extended to incorporate underlying physical mechanisms of deformation and failure in dual phase titanium alloys. Effects of various factors (stress triaxiality, Lode parameter, deformation state (equivalent strain), and phase boundary inclination) on void nucleation, growth and coalescence are used to formulate the constitutive model while their interaction with a conventional crystal plasticity theory is established. An extensive parametric assessment of the model is carried out to quantify and understand the effects of the material parameters on the overall material response. Performance of the proposed model is then assessed and verified by comparing the results of the proposed model with the RVE study results. Application of the constitutive model for utilisation in the design and optimisation of the forming process of {\alpha}/{\beta} titanium alloy components is also demonstrated using experimental data.
2002.04459v1
2020-02-18
Magnetic and all-optical switching properties of amorphous Tb$_x$Co$_{100-x}$ alloys
Amorphous Tb$_{x}$Co$_{100-x}$ magnetic alloys exhibit a list of intriguing properties, such as perpendicular magnetic anisotropy, high magneto-optical activity and magnetization switching using ultrashort optical pulses. Varying the Tb:Co ratio in these alloys allows for tuning properties such as the saturation magnetic moment, coercive field and the performance of the light-induced magnetization switching. In this work, we investigate the magnetic, optical and magneto-optical properties of various Tb$_{x}$Co$_{100-x}$ thin film alloy compositions. We report on the effect the choice of different seeding layers has on the structural and magnetic properties of Tb$_{x}$Co$_{100-x}$ layers. We also demonstrate that for a range of alloys, deposited on fused silica substrates, with Tb content of 24-30 at.$\%$, helicity dependent all-optical switching of magnetization can be achieved, albeit in a multi-shot framework. We explain this property to arise from the helicity-dependent laser induced magnetization on the Co sublattice due to the inverse Faraday effect. Our study provides an insight into material aspects for future potential hybrid magneto-plasmonic TbCo-based architectures.
2002.07544v3
2020-07-01
Bandgap Lowering in Mixed Alloys of Cs2Ag(SbxBi1-x)Br6 Double Perovskite Thin Films
Halide double perovskites have gained significant attention, owing to their composition of low-toxicity elements, stability in air and long charge-carrier lifetimes. However, most double perovskites, including Cs2AgBiBr6, have wide bandgaps, which limit photo conversion efficiencies. The bandgap can be reduced through hallowing with Sb3+, but Sb-rich alloys are difficult to synthesise due to the high formation energy of Cs2AgSbBr6, which itself has a wide bandgap. We develop a solution-based route to synthesis phase-pure Cs2Ag(SbxBi1-x)Br6 thin films, with the mixing parameter x continuous varying over the entire composition range. We reveal that the mixed alloys (x between 0.5 and 0.9) demonstrate smaller bandgaps (as low as 2.08 eV) than the pure Sb- (2.18 eV) and Bi-based (2.25 eV) compounds, with strong deviation from Vegard's law. Through in-depth computations, we propose that bandgap lowering arises from the Type II band alignment between Cs2AgBiBr6 and Cs2AgSbBr6. The energy mismatch between the Bi and Sb s and p atomic orbitals, coupled with their non-linear mixing, results in the alloys adopting a smaller bandgap than the pure compounds. Our work demonstrates an approach to achieve bandgap reduction and highlights that bandgap bowing may be found in other double perovskite alloys by pairing together materials forming a Type II band alignment.
2007.00388v1
2020-07-02
Interfacial giant tunnel magnetoresistance and bulk-induced large perpendicular magnetic anisotropy in (111)-oriented junctions with fcc ferromagnetic alloys: A first-principles study
We study the tunnel magnetoresistance (TMR) effect and magnetocrystalline anisotropy in a series of magnetic tunnel junctions (MTJs) with $L1_1$-ordered fcc ferromagnetic alloys and MgO barrier along the [111] direction. Considering the (111)-oriented MTJs with different $L1_1$ alloys, we calculate their TMR ratios and magnetocrystalline anisotropies on the basis of the first-principles calculations. The analysis shows that the MTJs with Co-based alloys (CoNi, CoPt, and CoPd) have high TMR ratios over 2000$\%$. These MTJs have energetically favored Co-O interfaces where interfacial antibonding between Co $d$ and O $p$ states is formed around the Fermi level. We find that the resonant tunneling of the antibonding states, called the interface resonant tunneling, is the origin of the obtained high TMR ratios. Our calculation of the magnetocrystalline anisotropy shows that many $L1_1$ alloys have large perpendicular magnetic anisotropy (PMA). In particular, CoPt has the largest value of anisotropy energy $K_{\rm u} \approx 10\,{\rm MJ/m^3}$. We further conduct a perturbation analysis of the PMA with respect to the spin-orbit interaction and reveal that the large PMA in CoPt and CoNi mainly originates from spin-conserving perturbation processes around the Fermi level.
2007.01068v2
2020-09-10
Atomic and electronic structure of two-dimensional Mo(1-x)WxS2 alloys
Alloying enables engineering of the electronic structure of semiconductors for optoelectronic applications. Due to their similar lattice parameters, the two-dimensional semiconducting transition metal dichalcogenides of the MoWSeS group (MX2 where M= Mo or W and X=S or Se) can be grown as high-quality materials with low defect concentrations. Here we investigate the atomic and electronic structure of Mo(1-x)WxS2 alloys using a combination of high-resolution experimental techniques and simulations. Analysis of the Mo and W atomic positions in these alloys, grown by chemical vapour transport, shows that they are randomly distributed, consistent with Monte Carlo simulations that use interaction energies determined from first-principles calculations. Electronic structure parameters are directly determined from angle resolved photoemission spectroscopy measurements. These show that the spin-orbit splitting at the valence band edge increases linearly with W content from MoS2 to WS2, in agreement with linear-scaling density functional theory (LS-DFT) predictions. The spin-orbit splitting at the conduction band edge is predicted to reduce to zero at intermediate compositions. Despite this, polarisation-resolved photoluminescence spectra on monolayer Mo0.5W0.5S2 show significant circular dichroism, indicating that spin-valley locking is retained. These results demonstrate that alloying is an important tool for controlling the electronic structure of MX2 for spintronic and valleytronic applications.
2009.04807v1
2020-10-27
Surface segregation in multicomponent high entropy alloys: Atomistic simulations versus a multilayer analytical model
This paper compares two approaches for investigating the near-surface composition profile that results from surface segregation in the so-called Cantor alloy, an equi-molar alloy of CoCrFeMnNi. One approach consists of atomistic computer simulations by a combination of Monte Carlo, molecular dynamics and molecular statics techniques, and the other is a nearest neighbor analytical calculation performed in the regular solution approximation with a multilayer model, developed here for the first time for a N-component system and tested for the 5-component Cantor alloy. This type of comparison is useful because a typical computer simulation requires the use of ~100 parallel processors for 2 to 3 hours, whereas a similar calculation by means of the analytical model can be performed in a few seconds on a laptop machine. The results obtained show qualitatively good agreement between the two approaches. Thus, while the results of the computer simulations are presumably more reliable, and provide an atomic scale picture, if massive computations are required, for example, in order to optimize the composition of a multicomponent alloy, then an initial screening of the composition space by the analytical model could provide a highly useful means of narrowing the regions of interest, in the same way that the CALPHAD method allows rapid investigation of phase diagrams in complex multinary systems.
2010.14141v1
2020-11-05
Preparation of the AlTiNiCuCox system high-entropy alloys and structural analysis
This study aimed to explore and develop a new material with high cost-effectiveness, excellent strength, light weight, high hardness, great wear resistance, corrosion resistance, and favorable oxidation resistance. Structural analysis suggested that, with the change in Co addition amount, the surface morphology and structure of the alloy system changed. XRD analysis indicated that, the alloy system was the FCC+BCC mixed structure. In addition, metallographical demonstrated that, with the increase in Co content, the dendritic crystal transformed from big block to dendritic structure, then to snowflake, gradually to petal-like, and finally to petal shape. SEM-EDS analysis revealed that, Cu element was enriched in interdendritic site, while Ti, Ni, Al and Co elements were enriched in dendrite. Besides, TEM and TEM-EDS analysis indicated that, there was nano-size precipitate of small particles in the Cu-enriched block region, along with dislocation; further, there was twin structure inside the dendrite, as well as the second phase with different morphology, and the second phase showed coherency with the matrix. The above analysis suggested that, the intercrystalline structure was the Cu-enriched phase of FCC structure; the internal matrix of grain was the NiTi and TiCo phases of BCC structure; and the second phases inside the grain were the AlCu2Ti,AlNi2Ti,AlCo2Ti and CuNi phases of FCC structure. Taken together, the AlTiNiCuCox system novel alloys have changed phase structures and phase types of the alloy system.
2011.02799v1
2020-12-16
A tool to predict coercivity in magnetic materials
Magnetic coercivity is often viewed to be lower in alloys with negligible (or zero) values of the anisotropy constant. However, this explains little about the dramatic drop in coercivity in FeNi alloys at a non-zero anisotropy value. Here, we develop a theoretical and computational tool to investigate the fundamental interplay between material constants that govern coercivity in bulk magnetic alloys. The two distinguishing features of our coercivity tool are that: (a) we introduce a large localized disturbance, such as a spike-like magnetic domain, that provides a nucleation barrier for magnetization reversal; and (b) we account for magneto-elastic energy -- however small -- in addition to the anisotropy and magnetostatic energy terms. We apply this coercivity tool to show that the interactions between local instabilities and material constants, such as anisotropy and magnetostriction constants, are key factors that govern magnetic coercivity in bulk alloys. Using our model, we show that coercivity is minimum at the permalloy composition (Fe-21.5Ni-78.5) at which the alloy's anisotropy constant is not zero. We systematically vary the values of the anisotropy and magnetostriction constants, around the permalloy composition, and identify new combinations of material constants at which coercivity is small. More broadly, our coercivity tool provides a theoretical framework to potentially discover novel magnetic materials with low coercivity.
2012.09320v1
2021-08-03
On the martensitic transformation in Fe$_{x}$Mn$_{80-x}$Co$_{10}$Cr$_{10}$ high-entropy alloy
High-entropy alloys (HEAs), and even medium-entropy alloys (MEAs), are an intriguing class of materials in that structure and property relations can be controlled via alloying and chemical disorder over wide ranges in the composition space. Employing density-functional theory combined with the coherent-potential approximation to average over all chemical configurations, we tune free energies between face-centered-cubic (fcc) and hexagonal-close-packed (hcp) phases in Fe$_{x}$Mn$_{80-x}$Co$_{10}$Cr$_{10}$ systems.~Within Fe-Mn-based alloys, we show that the martensitic transformation and chemical short-range order directly correlate with the fcc-hcp energy difference and stacking-fault energies, which are in quantitative agreement with recent experiments on a $x$=40~at.\% polycrystalline HEA/MEA. Our predictions are further confirmed by single-crystal measurements on a$x$=40at.\% using transmission-electron microscopy, selective-area diffraction, and electron-backscattered-diffraction mapping. The results herein offer an understanding of transformation-induced/twinning-induced plasticity (TRIP/TWIP) in this class of HEAs and a design guide for controlling the physics behind the TRIP effect at the electronic level.
2108.01636v1
2021-08-15
Characterization of Fe_3 O_4/Au-Ag@MoS_2 nanoparticles for brain cancer treatment using magneto plasmonic approach
This study investigates the treatment of brain cancer by the magnetic hyperthermia approach and nanoparticles including Fe_3 O_4 core with gold, silver alloy shell, and MoS_2 coating. Optical properties of these nanoparticles within the tumor, including the extinction coefficient and surface plasmon peak (SPR) as a function of size, structure, different compositions, and thickness are also investigated using the effective medium theory. Moreover, the impact of temperature distribution was assessed through the analytical modeling of alternating current (AC) magnetic field. The results of this study indicated that nanoparticles with a compound of Fe_3 O_4 - Au_0.25 Ag_0.75@MoS_2 and a thickness of 3 nm of gold-silver alloy and 3 layers of MoS_2 have the best coefficient of extinction and SPR in the biological window. The gold-silver alloy improved the extinction coefficient and, at the same time, prevented the accumulation of magnetic nanoparticles. Since the gold-silver alloy alone cannot function within the range of biological windows, MoS_2 was used, which increased the extinction efficiency at higher wavelengths. Examination of the temperature distribution in the tumor for the proposed alloy compound indicated that after a short time from the start of irradiation, the tumor temperature reaches 45 C degree. Also, the temperature distribution within the tumor tissue reached its maximum value at the center of the tumor and decreased dramatically as getting away from the center. The use of magnetic hyperthermia enabled localized delivery of therapeutic dose to malignant brain tumors; hence, exhibiting superior performance/efficiency over the photothermal method.
2108.06715v2
2021-08-24
Identifying the Dirac point composition in Bi1-xSbx alloys using the temperature dependence of quantum oscillations
The thermal chiral anomaly is a new mechanism for thermal transport that occurs in Weyl semimetals (WSM). It is attributed to the generation and annihilation of energy at Weyl points of opposite chirality. The effect was observed in the Bi1-xSbx alloy system, at x=11% and 15%, which are topological insulators at zero field and driven into an ideal WSM phase by an external field. Given that the experimental uncertainty on x is of the order of 1%, any systematic study of the effect over a wider range of x requires precise knowledge of the transition composition xc at which the electronic bands at the L-point in these alloys have Dirac-like dispersions. At x>xc, the L-point bands are inverted and become topologically non-trivial. In the presence of a magnetic field along the trigonal direction, these alloys become WSMs. This paper describes how the temperature dependence of the frequency of the Shubnikov-de Haas oscillations F(x,T) at temperatures of the order of the cyclotron energy can be used to find xc and characterize the topology of the electronic Fermi surface. Alloys with topologically trivial bands have dF(x,T)/dT>0, those with Dirac/Weyl fermions display dF(x,T)/dT<0.
2108.10917v1
2021-09-09
Investigation of the phase occurrence and H sorption properties in the Y33.33Ni66.67-xAlx (0 <= x <= 33.33) system
The Y33.33Ni66.67-xAlx system has been investigated in the region 0 <= x <= 33.3. The alloys were synthesized by induction melting. Phase occurrence and structural properties were studied by X-Ray powder Diffraction (XRD). The Al solubility in each phase has been investigated by XRD and Electron Probe Micro-Analysis (EPMA). The hydrogenation properties were characterized by pressure-composition isotherm measurements and kinetic curves at 473 K. For x = 0, the binary Y33.33Ni66.67 alloy crystallizes in the cubic superstructure with F4-3m space group and ordered Y vacancies. For 1.67 <= x <= 8.33, the alloys contain mainly Y(Ni, Al)2 and Y(Ni, Al)3 pseudobinary phases; while for 16.67 <= x <= 33.33 they are mainly formed by ternary line compounds Y3Ni6Al2, Y2Ni2Al and YNiAl. Contrary to the binary Y33.33Ni66.67, Y(Ni, Al)2 pseudo-binary compounds crystalize in C15 phase (space group Fd-3m ) with disordered Y vacancies. The solubility limit of Al in the C15 YNi2-yAly phase is y = 0.11 (i.e., x = 3.67). The Y(Ni, Al)3 phase changes from rhombohedral (PuNi3-type, R-3m) to hexagonal (CeNi3-type, P63/mmc) structure for x increasing from 5.00 to 6.67. Upon hydrogenation, the disproportion of C15 Y(Ni, Al)2 and losses of crystallinity of YNi and Y2Ni2Al are the main reasons causing capacity decay of Y33.33Ni66.67-xAlx (0 <= x <= 33.33) alloys upon cycling.
2109.04182v1
2021-09-14
Creep properties and deformation mechanisms of single-crystalline $γ^\prime$-strengthened superalloys in dependence of the Co/Ni ratio
Co-base superalloys are considered as promising high temperature materials besides the well-established Ni-base superalloys. However, Ni appears to be an indispensable alloying element also in Co-base superalloys. To address the influence of the base elements on the deformation behavior, high-temperature compressive creep experiments were performed on a single crystal alloy series that was designed to exhibit a varying Co/Ni ratio and a constant Al, W and Cr content. Creep tests were performed at 900 {\deg}C and 250 MPa and the resulting microstructures and defect configurations were characterized via electron microscopy. The minimum creep rates differ by more than one order of magnitude with changing Co/Ni ratio. An intermediate CoNi-base alloy exhibits the overall highest creep strength. Several strengthening contributions like solid solution strengthening of the $\gamma$ phase, effective diffusion coefficients or stacking fault energies were quantified. Precipitate shearing mechanisms differ significantly when the base element content is varied. While the Ni-rich superalloys exhibit SISF and SESF shearing, the Co-rich alloys develop extended APBs when the $\gamma^\prime$ phase is cut. This is mainly attributed to a difference in planar fault energies, caused by a changing segregation behavior. As result, it is assumed that the shearing resistivity and the occurring deformation mechanisms in the $\gamma^\prime$ phase are crucial for the creep properties of the investigated alloy series.
2109.06767v1
2021-11-02
Multiscale simulations of uni-polar hole transport in (In,Ga)N quantum well systems
Understanding the impact of the alloy micro-structure on carrier transport becomes important when designing III-nitride-based LED structures. In this work, we study the impact of alloy fluctuations on the hole carrier transport in (In,Ga)N single and multi-quantum well systems. To disentangle hole transport from electron transport and carrier recombination processes, we focus our attention on uni-polar (p-i-p) systems. The calculations employ our recently established multi-scale simulation framework that connects atomistic tight-binding theory with a macroscale drift-diffusion model. In addition to alloy fluctuations, we pay special attention to the impact of quantum corrections on hole transport. Our calculations indicate that results from a virtual crystal approximation present an upper limit for the hole transport in a p-i-p structure in terms of the current-voltage characteristics. Thus we find that alloy fluctuations can have a detrimental effect on hole transport in (In,Ga)N quantum well systems, in contrast to uni-polar electron transport. However, our studies also reveal that the magnitude by which the random alloy results deviate from virtual crystal approximation data depends on several factors, e.g. how quantum corrections are treated in the transport calculations.
2111.01644v1
2022-04-06
First principles and Monte Carlo studies of adsorption and desorption properties from Pd$\rm_{1-x}$Ag$\rm_{x}$ surface alloy
The FCC structure of Pd$\rm_{1-x}$Ag$\rm_{x}$ ($\rm{x}=$ 0.25, 0.50, 0.75) alloys is considered as a fuel cell component in this study. We have looked into its qualities as a component of a fuel cell to see whether it could be potentially used as an alternative replacement of the Pt catalyst. We used Density Functional Theory (DFT) to study H and CO interaction with the surface, and Kinetic Monte Carlo~(KMC) to study H and CO desorption from the surface. The bulk modulus and equilibrium crystal structures of Pd$\rm_{1-x}$Ag$\rm_{x}$ alloys were computed using the GPAW code within plane wave basis set $\&$ a PBE exchange correlation functional treatment. The best values of a lattice constant for the system are obtained by total energy calculations versus lattice cell volumes as fitted to the stabilized jellium model. Surface energies, cohesive energies, and\ binding energy of Pd$\rm_{1-x}$Ag$\rm_{x}$ alloys were computed to analyze the stability properties of structures. Band structure calculations reveal the electronic and optical properties of these alloys. The density of states~(DOS) and projected density of states~(PDOS) show the availability of the eigenstates for occupation. The desorption process is studied within the Arrhenius type desorption rate $\&$ a temperature programming. The effects of lateral interactions between adsorbed molecules on first order desorption (molecular adsorption) $\&$ second order desorption were taken into account. Adsorption energies of H and CO on Pd$\rm_3$Ag~(111) as calculated using DFT is used in the process. The outcomes show good qualitative agreement with literature.
2204.02812v1
2022-06-21
Laser induced ultrafast Gd 4f spin dynamics in Co100-xGdx alloys by means of time-resolved XMCD
We have studied the laser induced ultrafast quenching of Gd 4f magnetic order in ferrimagnetic Co100-xGdx alloys to highlight the role of the inter-atomic exchange coupling. We have taken advantage of the ultrashort soft X-ray pulses deliver by the femtoslicing beamline at the BESSY II synchrotron radiation source at the Helmholtz-Zentrum Berlin to perform element- and time-resolved X-ray Magnetic Circular Dichroism spectroscopy.Our results show that the laser induced quenching of Gd 4f magnetic order occurs on very different time-scales for the Co72Gd28, the Co77Gd23 and the Co79Gd21 alloys. Most of the magnetic moment losses occur within the first picosecond (ps) while the electron distribution is strongly out of equilibrium. After the equilibration of the electrons and lattice temperatures (t > 1 ps), the magnetic losses occur on slower rates that depend on the alloy composition: increasing the Co composition speeds up the demagnetization of Gd 4f sublattice. The strength of the inter-atomic exchange coupling which depends on composition, determines the efficiency of the angular momentum flow from the Gd 4f spin towards the lattice. Our results are in qualitative agreements with the predictions of the microscopic three temperatures model for ferrimagnetic alloys.
2206.10422v1
2022-07-14
A Phase-Field Study on the Effects of Nanoparticles on Solidification and Grain Growth
Nanoparticle reinforced alloys offer the potential of high strength, high temperature alloys. While promising, during rapid solidification processes, alloys suffer from nanoparticle clustering, which can discount any strength benefit. An open-source phase-field model is developed using PRISMS-PF to explore the impact of nanoparticles and clustering on alloy solidification. Heterogenous nucleation and grain boundary pinning are explicitly included, and a wide range of nanoparticle area fractions and nucleation rates are modeled. At low area fractions less than 0.05, particle clustering increases grain size between 15-45% compared to a random distribution. Our quantitative analyses inform a modified Zener grain size relationship that not only depends on nanoparticle size and area fraction, but also on the nucleation rate. Grain size first drastically decreases before plateauing at higher nucleation rates. Our simulations reveal a strong preference of nanoparticles pinning grain boundaries. Pinning fraction increases rapidly with nucleation rate before saturating between 0.85-0.90. Across the range of area fractions and nucleation rates considered, the random and clustered grain sizes each collapse to a simple analytical expression that depends only on nanoparticle radius and pinning fraction. Comparisons against experimental data reveal the expressions deduced from our analyses fit reported grain sizes better than classic Zener analysis. A simple model of strength and cost tradeoffs indicates nanoparticles can be a cost-effective way to improve alloy strength.
2207.07153v1
2022-07-28
Inner relaxations in equiatomic single-phase high-entropy cantor alloy
The superior properties of high-entropy multi-functional materials are strongly connected with their atomic heterogeneity through many different local atomic interactions. The detailed element-specific studies on a local scale can provide insight into the primary arrangements of atoms in multicomponent systems and benefit to unravel the role of individual components in certain macroscopic properties of complex compounds. Herein, multi-edge X-ray absorption spectroscopy combined with reverse Monte Carlo simulations was used to explore a homogeneity of the local crystallographic ordering and specific structure relaxations of each constituent in the equiatomic single-phase face-centered cubic CrMnFeCoNi high-entropy alloy at room temperature. Within the considered fitting approach, all five elements of the alloy were found to be distributed at the nodes of the fcc lattice without any signatures of the additional phases at the atomic scale and exhibit very close statistically averaged interatomic distances (2.54-2.55 \r{A}) with their nearest-neighbors. Enlarged structural displacements were found solely for Cr atoms. The macroscopic magnetic properties probed by conventional magnetometry demonstrate no opening of the hysteresis loops at 5 K and illustrate a complex character of the long-range magnetic order after field-assisted cooling in $\pm$5 T. The observed magnetic behavior is assigned to effects related to structural relaxations of Cr. Besides, the advantages and limitations of the reverse Monte Carlo approach to studies of multicomponent systems like high-entropy alloys are highlighted.
2207.14063v1
2022-09-17
Superfunctional high-entropy alloys and ceramics by severe plastic deformation
High-entropy alloys and ceramics containing at least five principal elements have recently received high attention for various mechanical and functional applications. The application of severe plastic deformation (SPD), particularly the high-pressure torsion (HPT) method, combined with the CALPHAD and first-principles calculations resulted in the development of numerous superfunctional high-entropy materials with superior properties compared to the normal functions of engineering materials. This article reviews the recent advances in the application of SPD to developing superfunctional high-entropy materials. These superfunctional properties include (i) ultrahigh hardness levels comparable to the hardness of ceramics in high-entropy alloys, (ii) high yield strength and good hydrogen embrittlement resistance in high-entropy alloys; (iii) high strength, low elastic modulus, and high biocompatibility in high-entropy alloys, (iv) fast and reversible hydrogen storage in high-entropy hydrides, (v) photovoltaic performance and photocurrent generation on high-entropy semiconductors, (vi) photocatalytic oxygen and hydrogen production from water splitting on high-entropy oxides and oxynitrides, and (vii) CO2 photoreduction on high-entropy ceramics. These findings introduce SPD as not only a processing tool to improve the properties of existing high-entropy materials but also as a synthesis tool to produce novel high-entropy materials with superior properties compared with conventional engineering materials.
2209.08291v3
2022-10-02
Data-mining of In-Situ TEM Experiments: on the Dynamics of Dislocations in CoCrFeMnNi Alloys
High entropy alloys are a class of materials with many significant improvements in terms of mechanical properties as compared to ``classical'' alloys. The corresponding structure-property relations are not yet entirely clear, but it is commonly believed that the good mechanical performance is strongly related to dislocation interactions with the complex energy landscape formed due to alloying. Although in-situ Transmission Electron Microscopy (TEM) allows high-resolution studies of the structure and dynamics of moving dislocations and makes the local obstacle/energy ``landscape'' directly visible in the geometry of dislocations; such observation, however, are merely qualitative, and detailed three-dimensional analyses of the interaction between dislocations and the energy landscape is still missing. In this work, we utilized dislocations as ``probes'' for the local energy maxima which play the role of pinning points for the dislocation movement. To this end, we developed a unique data-mining approach that can perform coarse-grained spatio-temporal analysis, making ensemble averaging of a considerable number of snapshots possible. We investigate the effect of pinning points on the dislocation gliding behavior of CoCrFeMnNi alloy during in-situ TEM straining and find that (i) the pinning point strength changes when dislocations glide through and (ii) the pinning point moves along the direction close to the Burgers vector direction. Our data-mining method can be applied to dislocation motion in general, making it a useful tool for dislocation research.
2210.00478v1
2022-11-05
Accurate prediction of chemical short-range order and its effect on thermodynamic, structural, and electronic properties of disordered alloys: exemplified in Cu$_{3}$Au
Electronic-structure methods based on density-functional theory (DFT) were used to directly quantify the effect of chemical short-range order (SRO) on thermodynamic, structural, and electronic properties of archetypal face-centered-cubic (fcc) Cu$_{3}$Au alloy. We show that SRO can be tuned to alter bonding and lattice dynamics (i.e., phonons) and detail how these properties are changed with SRO. Thermodynamically favorable SRO improves phase stability of Cu$_{3}$Au from -0.0343 eV-atom$^{-1}$ to -0.0682 eV-atom$^{-1}$. We use DFT-based linear-response theory to predict SRO and its electronic origin, and accurately estimate the transition temperature, ordering instability (L1$_2$), and Warren-Cowley SRO parameters, observed in experiments. The accurate prediction of real-space SRO gives an edge over computationally and resource intensive approaches such as Monte-Carlo methods or experiments, which will enable large-scale molecular dynamic simulations by providing supercells with optimized SRO. We also analyze phonon dispersion and estimate the vibrational entropy changes in Cu$_{3}$Au (from 9k$_{B}$ at 300 K to 6$k_{B}$ at 100 K). We establish from SRO analysis that exclusion of chemical interactions may lead to a skewed view of true properties in chemically complex alloys. The first-principles methods described here are applicable to any arbitrary complex solid-solution alloys, including multi-principal-element alloys, so hold promise for designing technologically useful materials.
2211.02985v3
2022-11-17
Perspectives on Novel Refractory Amorphous High-Entropy Alloys in Extreme Environments
Two new refractory amorphous high-entropy alloys (RAHEAs) within the W--Ta--Cr--V and W--Ta--Cr--V--Hf systems were herein synthesized using magnetron-sputtering and tested under high-temperature annealing and displacing irradiation using \textit{in situ} Transmission Electron Microscopy. While the WTaCrV RAHEA was found to be unstable under such tests, additions of Hf in this system composing a new quinary WTaCrVHf RAHEA was found to be a route to achieve stability both under annealing and irradiation. A new effect of nanoprecipitate reassembling observed to take place within the WTaCrVHf RAHEA under irradiation indicates that a duplex microstructure composed of an amorphous matrix with crystalline nanometer-sized precipitates enhances the radiation response of the system. It is demonstrated that tunable chemical complexity arises as a new alloy design strategy to foster the use of novel RAHEAs within extreme environments. New perspectives for the alloy design and application of chemically-complex amorphous metallic alloys in extreme environments are presented with focus on their thermodynamic phase stability when subjected to high-temperature annealing and displacing irradiation.
2211.09853v1
2022-11-28
A ductility metric for refractory-based multi-principal-element alloys
We propose a quantum-mechanical dimensionless metric, the local$-$lattice distortion (LLD), as a reliable predictor of ductility in refractory multi-principal-element alloys (RMPEAs). The LLD metric is based on electronegativity differences in localized chemical environments and combines atomic$-$scale displacements due to local lattice distortions with a weighted average of valence$-$electron count. To evaluate the effectiveness of this metric, we examined body$-$centered cubic (bcc) refractory alloys that exhibit ductile$-$to$-$brittle behavior. Our findings demonstrate that local$-$charge behavior can be tuned via composition to enhance ductility in RMPEAs. With finite$-$sized cell effects eliminated, the LLD metric accurately predicted the ductility of arbitrary alloys based on tensile$-$elongation experiments. To validate further, we qualitatively evaluated the ductility of two refractory RMPEAs, i.e., NbTaMoW and Mo$_{72}$W$_{13}Ta$_{10}Ti$_{2.5}Zr$_{2.5}, through the observation of crack formation under indentation, again showing excellent agreement with LLD predictions. A comparative study of three refractory alloys provides further insights into the electronic-structure origin of ductility in refractory RMPEAs. This proposed metric enables rapid and accurate assessment of ductility behavior in the vast RMPEA composition space.
2211.15797v2
2023-01-07
Impact of Severe Plastic Deformation on Kinetics and Thermodynamics of Hydrogen Storage in Magnesium and Its Alloys
Magnesium and its alloys are the most investigated materials for solid-state hydrogen storage in the form of metal hydrides, but there are still unresolved problems with the kinetics and thermodynamics of hydrogenation and dehydrogenation of this group of materials. Severe plastic deformation (SPD) methods, such as equal-channel angular pressing (ECAP), high-pressure torsion (HPT), intensive rolling and fast forging, have been widely used to enhance the activation, air resistance, and hydrogenation/dehydrogenation kinetics of Mg-based hydrogen storage materials by introducing ultrafine/nanoscale grains and crystal lattice defects. These severely deformed materials, particularly in the presence of alloying additives or second-phase nanoparticles, can show not only fast hydrogen absorption/desorption kinetics but also good cycling stability. It was shown that some materials that are apparently inert to hydrogen can absorb hydrogen after SPD processing. Moreover, the SPD methods were effectively used for hydrogen binding-energy engineering and synthesizing new magnesium alloys with low thermodynamic stability for reversible low/room-temperature hydrogen storage, such as nanoglasses, high-entropy alloys, and metastable phases including the high-pressure {\gamma}-MgH2 polymorph. This article reviews recent advances in the development of Mg-based hydrogen storage materials by SPD processing and discusses their potential in future applications.
2301.05009v1
2023-02-01
Magnetochemical coupling effects on thermodynamics, point-defect formation and diffusion in Fe-Ni alloys: a theoretical study
This thesis is a theoretical study of thermodynamic, point-defect formation and diffusion properties in Fe-Ni alloys with a focus on the magnetochemical effects. The results are derived from density functional theory (DFT) calculations and Monte Carlo (MC) simulations using a DFT-parametrized effective interaction model (EIM) with explicit atomic and spin variables. The first part of this work is focused on thermodynamics. We compute via DFT energetic, magnetic and vibrational properties and the bcc-fcc phase diagram, revealing the relative importance between magnetic and vibrational entropies. Combining MC simulations with the EIM, we obtain an fcc phase diagram across the Curie points. We also discuss Mn and Cr effects on phase stability. The second part of the work is dedicated to point-defect properties. We develop MC schemes to compute vacancy formation free energy in alloys. We show that vacancy formation in fcc Fe and Ni exhibits features that are well distinct from those in bcc Fe. The results in fcc Fe-Ni alloys reveal that magnetic disorder tends to increase vacancy formation free energy, while chemical disorder shows an opposite effect. We also study magnetic effects on the properties of self-interstitials in fcc Fe and Ni. The final part of the work is devoted to vacancy-mediated diffusion. We evaluate diffusion properties over the whole concentration range, probe into the magnetochemical effects on diffusion. This work fully takes into account the impacts of transversal and longitudinal spin fluctuations and the magnetochemical interplay. It provides an accurate and consistent prediction of thermodynamic, defect formation and diffusion properties in the Fe-Ni system, and contributes to a better understanding of effects of magnetism in austenitic steels. The applied approach is also transferable to the investigation of other magnetic alloys.
2302.00186v1
2023-02-07
On the occurrence of buoyancy-induced oscillatory growth instability in directional solidification of alloys
Recent solidification experiments identified an oscillatory growth instability during directional solidification of Ni-based superalloy CMSX4 under a given range of cooling rates. From a modeling perspective, the quantitative simulation of dendritic growth under convective conditions remains challenging, due to the multiple length scales involved. Using the dendritic needle network (DNN) model, coupled with an efficient Navier-Stokes solver, we reproduced the buoyancy-induced growth oscillations observed in CMSX4 directional solidification. These previous results have shown that, for a given alloy and temperature gradient, oscillations occur in a narrow range of cooling rates (or pulling velocity, $V_p$) and that the selected primary dendrite arm spacing ($\Lambda$) plays a crucial role in the activation of the flow leading to oscillations. Here, we show that the oscillatory behavior may be generalized to other binary alloys within an appropriate range of $(V_p,\Lambda)$ by reproducing it for an Al-4at.%Cu alloy. We perform a mapping of oscillatory states as a function of $V_p$ and $\Lambda$, and identify the regions of occurrence of different behaviors (e.g., sustained or damped oscillations) and their effect on the oscillation characteristics. Our results suggest a minimum of $V_p$ for the occurrence of oscillations and confirm the correlation between the oscillation type (namely: damped, sustained, or noisy) with the ratio of average fluid velocity $\overline V$ over $V_p$. We describe the different observed growth regimes and highlight similarities and contrasts with our previous results for a CMSX4 alloy.
2302.03427v1
2023-03-01
Interplay between magnetism and short-range order in medium- and high-entropy alloys: CrCoNi, CrFeCoNi, and CrMnFeCoNi
The impact of magnetism on predicted atomic short-range order in three medium- and high-entropy alloys is studied using a first-principles, all-electron, Landau-type linear response theory, coupled with lattice-based atomistic modelling. We perform two sets of linear-response calculations: one in which the paramagnetic state is modelled within the disordered local moment picture, and one in which systems are modelled in a magnetically ordered state, which is ferrimagnetic for the alloys considered in this work. We show that the treatment of magnetism can have significant impact both on the predicted temperature of atomic ordering and also the nature of atomic order itself. In CrCoNi, we find that the nature of atomic order changes from being $\mathrm{L}1_2$-like when modelled in the paramagnetic state to MoPt$_2$-like when modelled assuming the system has magnetically ordered. In CrFeCoNi, atomic correlations between Fe and the other elements present are dramatically strengthened when we switch from treating the system as magnetically disordered to magnetically ordered. Our results show it is necessary to consider the magnetic state when modelling multicomponent alloys containing mid- to late-$3d$ elements. Further, we suggest that there may be high-entropy alloy compositions containing $3d$ transition metals that will exhibit specific atomic short-range order when thermally treated in an applied magnetic field. This has the potential to provide a route for tuning physical and mechanical properties in this class of materials.
2303.00641v2
2023-03-06
High thermoelectric performance in metallic NiAu alloys
Thermoelectric (TE) materials seamlessly convert thermal into electrical energy and vice versa, making them promising for applications such as power generation or cooling. Although historically the TE effect was first discovered in metals, state-of-the-art research mainly focuses on doped semiconductors with large figure of merit, $zT$, that determines the conversion efficiency of TE devices. While metallic alloys have superior functional properties, such as high ductility and mechanical strength, they have mostly been discarded from investigation in the past due to their small Seebeck effect. Here, we realize unprecedented TE performance in metals by tuning the energy-dependent electronic scattering. Based on our theoretical predictions, we identify binary NiAu alloys as promising candidate materials and experimentally discover colossal power factors up to 34 mWm$^{-1}$K$^{-2}$ (on average 30 mWm$^{-1}$K$^{-2}$ from 300 to 1100 K), which is more than twice larger than in any known bulk material above room temperature. This system reaches a $zT$ up to 0.5, setting a new world record value for metals. NiAu alloys are not only orders of magnitude more conductive than heavily doped semiconductors, but also have large Seebeck coefficients originating from an inherently different physical mechanism: within the Au s band conduction electrons are highly mobile while holes are scattered into more localized Ni d states, yielding a strongly energy-dependent carrier mobility. Our work challenges the common belief that good metals are bad thermoelectrics and presents an auspicious paradigm for achieving high TE performance in metallic alloys through engineering electron-hole selective s-d scattering.
2303.03062v1
2023-05-19
Multi-component low and high entropy metallic coatings synthesized by pulsed magnetron sputtering
This paper presents the findings of the synthesis of multicomponent (Al, W, Ni, Ti, Nb) alloy coatings from mosaic targets. For the study, a pulsed magnetron sputtering method was employed under different plasma generation conditions: modulation frequency (10 Hz and 1000 Hz), and power (600 W and 1000 W). The processes achieved two types of alloy coatings, high entropy and classical alloys. After the deposition processes, scanning electron microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy techniques were employed to find the morphology, thickness, and chemical and phase compositions of the coatings. Nanohardness and its related parameters, namely H3.Er2, H.E, and 1.Er2H ratios, were measured. An annealing treatment was performed to estimate the stability range for the selected coatings. The results indicated the formation of as-deposited coatings exhibiting an amorphous structure as a single-phase solid solution. The process parameters had an influence on the resulting morphology-a dense and homogenous as well as a columnar morphology, was obtained. The study compared the properties of high-entropy alloy (HEA) coatings and classical alloy coatings concerning their structure and chemical and phase composition. It was found that the change of frequency modulation and the post-annealing process contributed to the increase in the hardness of the material in the case of HEA coatings.
2305.11466v1
2023-05-24
Machine Learning Prediction of Critical Cooling Rate for Metallic Glasses From Expanded Datasets and Elemental Features
We use a random forest model to predict the critical cooling rate (RC) for glass formation of various alloys from features of their constituent elements. The random forest model was trained on a database that integrates multiple sources of direct and indirect RC data for metallic glasses to expand the directly measured RC database of less than 100 values to a training set of over 2,000 values. The model error on 5-fold cross validation is 0.66 orders of magnitude in K/s. The error on leave out one group cross validation on alloy system groups is 0.59 log units in K/s when the target alloy constituents appear more than 500 times in training data. Using this model, we make predictions for the set of compositions with melt-spun glasses in the database, and for the full set of quaternary alloys that have constituents which appear more than 500 times in training data. These predictions identify a number of potential new bulk metallic glass (BMG) systems for future study, but the model is most useful for identification of alloy systems likely to contain good glass formers, rather than detailed discovery of bulk glass composition regions within known glassy systems.
2305.15390v1
2023-07-04
Metallurgy, superconductivity, and hardness of a new high-entropy alloy superconductor Ti-Hf-Nb-Ta-Re
We explored quinary body-centered cubic (bcc) high-entropy alloy (HEA) superconductors with valence electron concentrations (VECs) ranging from 4.6 to 5.0, a domain that has received limited attention in prior research. Our search has led to the discovery of new bcc Ti-Hf-Nb-Ta-Re superconducting alloys, which exhibit an interesting phenomenon of phase segregation into two bcc phases with slightly different chemical compositions, as the VEC increases. The enthalpy of the formation of each binary compound explains the phase segregation. All the alloys investigated were categorized as type-II superconductors, with superconducting critical temperatures ($T_\mathrm{c}$) ranging from 3.25 K to 4.38 K. We measured the Vickers microhardness, which positively correlated with the Debye temperature, and compared it with the hardness values of other bcc HEA superconductors. Our results indicate that $T_\mathrm{c}$ systematically decreases with an increase in hardness beyond a threshold of approximately 350 HV. Additionally, we plotted $T_\mathrm{c}$ vs. VEC for representative quinary bcc HEAs. The plot revealed the asymmetric VEC dependence. The correlation between the hardness and $T_\mathrm{c}$, as well as the asymmetric dependence of $T_\mathrm{c}$ on VEC can be attributed to the simultaneous effects of the electronic density of states at the Fermi level and electron-phonon coupling under the uncertainty principle, especially in the higher VEC region.
2307.01958v1
2023-08-23
Plastic deformation mechanisms during nanoindentation of W, Mo, V body-centered cubic single crystals and their corresponding W-Mo, W-V equiatomic random solid solutions
Deformation plasticity mechanisms in alloys and compounds may unveil the material capacity towards optimal mechanical properties. We conduct a series of molecular dynamics (MD) simulations to investigate plasticity mechanisms due to nanoindentation in pure tungsten, molybdenum and vanadium body-centered cubic single crystals, as well as the also body-centered cubic, equiatomic, random solid solutions (RSS) of tungsten--molybdenum and tungsten--vanadium alloys. Our analysis focuses on a thorough, side-by-side comparison of dynamic deformation processes, defect nucleation, and evolution, along with corresponding stress--strain curves. We also check the surface morphology of indented samples through atomic shear strain mapping. As expected, the presence of Mo and V atoms in W matrices introduces lattice strain and distortion, increasing material resistance to deformation and slowing down dislocation mobility of dislocation loops with a Burgers vector of 1/2 $\langle 111 \rangle$. Our side-by-side comparison displays a remarkable suppression of the plastic zone size in equiatomic W--V RSS, but not in equiatomic W--Mo RSS alloys, displaying a clear prediction for optimal hardening response equiatomic W--V RSS alloys. If the small-depth nanoindentation plastic response is indicative of overall mechanical performance, it is possible to conceive a novel MD-based pathway towards material design for mechanical applications in complex, multi-component alloys.
2308.12206v1
2023-09-18
Incorporation of random alloy GaBi$_{x}$As$_{1-x}$ barriers in InAs quantum dot molecules: alloy strain and orbital effects towards enhanced tunneling
Self-assembled InAs quantum dots (QDs), which have long hole-spin coherence times and are amenable to optical control schemes, have long been explored as building blocks for qubit architectures. One such design consists of vertically stacking two QDs to create a quantum dot molecule (QDM). The two dots can be resonantly tuned to form "molecule-like" coupled hole states from the hybridization of hole states otherwise localized in each respective dot. Furthermore, spin-mixing of the hybridized states in dots offset along their stacking direction enables qubit rotation to be driven optically, allowing for an all-optical qubit control scheme. Increasing the magnitude of this spin mixing is important for optical quantum control protocols. To enhance the tunnel coupling and spin-mixing across the dots, we introduce Bi in the GaAs inter-dot barrier. Previously, we showed how to model InAs/GaBiAs in an atomistic tight-binding formalism, and how the dot energy levels are affected by the alloy. In this paper, we discuss the lowering of the tunnel barrier, which results in a three fold increase of hole tunnel coupling strength in the presence of a 7% alloy. Additionally, we show how an asymmetric strain between the two dots caused by the alloy shifts the resonance. Finally, we discuss device geometries for which the introduction of Bi is most advantageous.
2309.10115v4
2023-11-02
Quantifying chemical short-range order in metallic alloys
Metallic alloys often form phases - known as solid solutions - in which chemical elements are spread out on the same crystal lattice in an almost random manner. The tendency of certain chemical motifs to be more common than others is known as chemical short-range order (SRO) and it has received substantial consideration in alloys with multiple chemical elements present in large concentrations due to their extreme configurational complexity (e.g., high-entropy alloys). Short-range order renders solid solutions "slightly less random than completely random", which is a physically intuitive picture, but not easily quantifiable due to the sheer number of possible chemical motifs and their subtle spatial distribution on the lattice. Here we present a multiscale method to predict and quantify the SRO state of an alloy with atomic resolution, incorporating machine learning techniques to bridge the gap between electronic-structure calculations and the characteristic length scale of SRO. The result is an approach capable of predicting SRO length scale in agreement with experimental measurements while comprehensively correlating SRO with fundamental quantities such as local lattice distortions. This work advances the quantitative understanding of solid-solution phases, paving the way for SRO rigorous incorporation into predictive mechanical and thermodynamic models.
2311.01545v2
2023-10-07
A holistic review on fatigue properties of additively manufactured metals
Additive manufacturing (AM) technology is undergoing rapid development and emerging as an advanced technique that can fabricate complex near-net shaped and light-weight metallic parts with acceptable strength and fatigue performance. A number of studies have indicated that the strength or other mechanical properties of AM metals are comparable or even superior to that of conventionally manufactured metals, but the fatigue performance is still a thorny problem that may hinder the replacement of currently used metallic components by AM counterparts when the cyclic loading and thus fatigue failure dominates. This article reviews the state-of-art published data on the fatigue properties of AM metals, principally including $S$--$N$ data and fatigue crack growth data. The AM techniques utilized to generate samples in this review include powder bed fusion (e.g., EBM, SLM, DMLS) and directed energy deposition (e.g., LENS, WAAM). Further, the fatigue properties of AM metallic materials that involve titanium alloys, aluminum alloys, stainless steel, nickel-based alloys, magnesium alloys, and high entropy alloys, are systematically overviewed. In addition, summary figures or tables for the published data on fatigue properties are presented for the above metals, the AM techniques, and the influencing factors (manufacturing parameters, e.g., built orientation, processing parameter, and post-processing). The effects of build direction, particle, geometry, manufacturing parameters, post-processing, and heat-treatment on fatigue properties, when available, are provided and discussed. The fatigue performance and main factors affecting the fatigue behavior of AM metals are finally compared and critically analyzed, thus potentially providing valuable guidance for improving the fatigue performance of AM metals.
2311.07046v1
2024-01-05
Hard-sphere model of the B2 to B19' phase transformation, and its application to predict the B19' structure in NiTi alloys and the B19 structures in other binary alloys
The pseudoelastic and pseudoplastic properties of NiTi alloys result from the closeness of the structures between the B2 cubic austenite and the B19' monoclinic martensite, and the facility to transform one into each other. Until now, the paths followed by the atoms during the B2 to B19' transformation were imagined as independent shears and shuffles. Here, we propose a simplified hard-sphere atomistic model of phase transformation decomposed into three distinct types of atomic movements. The model's inputs are the Ti and Ni atomic or ionic diameters and the monoclinic angle beta. The outputs are the lattice parameters of the B19' phase and the atomic positions. The results are remarkably close to those reported in the literature from X-ray diffraction experiments or DFT simulations. The hard-sphere model explains the change of enthalpy by the formation of short Ti-Ti bonds in B19'. It is also shown that the value of the monoclinic angle beta close to 97.9 degrees corresponds to the highest molar volume among all the possible hard-sphere monoclinic B19' structures; which suggests that it could be a consequence of a maximization of the vibrational entropy. The hard-sphere model was applied in the special case of absence of monoclinicity to predict the B19 structure. The calculations do not agree well with the B19 structure reported in NiTi alloys; they are however in excellent agreement with the B19 structures reported in other binary alloys, such as in AuTi, PdTi, and AuCd.
2401.02871v1
2024-01-29
Competition between phase ordering and phase segregation in the Ti$_x$NbMoTaW and Ti$_x$VNbMoTaW refractory high-entropy alloys
Refractory high-entropy alloys are under consideration for applications where materials are subjected to high temperatures and levels of radiation, such as in the fusion power sector. However, at present, their scope is limited because they are highly brittle at room temperature. One suggested route to mitigate this issue is by alloying with Ti. In this theoretical study, using a computationally efficient linear-response theory based on density functional theory calculations of the electronic structure of the disordered alloys, we study the nature of atomic short-range order in these multi-component materials, as well as assessing their overall phase stability. Our analysis enables direct inference of phase transitions in addition to the extraction of an atomistic, pairwise model of the internal energy of an alloy suitable for study via, e.g. Monte Carlo simulations. Once Ti is added into either the NbMoTaW or VNbMoTaW system, we find that there is competition between chemical phase ordering and segregation. These results shed light on observed chemical inhomogeneity in experimental samples, as well as providing fundamental insight into the physics of these complex systems.
2401.16243v2
2024-02-27
Linking Order to Strength in Metals
The metallurgy and materials communities have long known and exploited fundamental links between chemical and structural ordering in metallic solids and their mechanical properties. The highest reported strength achievable through the combination of multiple metals (alloying) has rapidly climbed and given rise to new classifications of materials with extraordinary properties. Metallic glasses and high-entropy alloys are two limiting examples of how tailored order can be used to manipulate mechanical behavior. Here, we show that the complex electronic-structure mechanisms governing the peak strength of alloys and pure metals can be reduced to a few physically-meaningful parameters based on their atomic arrangements and used (with no fitting parameters) to predict the maximum strength of any metallic solid, regardless of degree of structural or chemical ordering. Predictions of maximum strength based on the activation energy for a stress-driven phase transition to an amorphous state is shown to accurately describe the breakdown in Hall-Petch behavior at the smallest crystallite sizes for pure metals, intermetallic compounds, metallic glasses, and high-entropy alloys. This activation energy is also shown to be directly proportional to interstitial (electronic) charge density, which is a good predictor of ductility, stiffness (moduli), and phase stability in high-entropy alloys, and in solid metals generally. The proposed framework suggests the possibility of coupling ordering and intrinsic strength to mechanisms like dislocation nucleation, hydrogen embrittlement, and transport properties. It additionally opens the prospect for greatly accelerated structural materials design and development to address materials challenges limiting more sustainable and efficient use of energy.
2402.17728v1
2024-04-11
Tuning Magnetic and Optical Properties in MnxZn1-xPS3 Single Crystals by the Alloying Composition
The exploration of two-dimensional (2D) antiferromagnetic (AFM) materials has shown great promise and interest in tuning the magnetic and electronic properties as well as studying magneto-optical effects. The current work investigates the control of magneto-optical interactions in alloyed MnxZn1-xPS3 lamellar semiconductor single crystals, with the Mn/Zn ratio regulating the coupling strength. Magnetic susceptibility results show a retention of AFM order followed by a decrease in N\'eel temperatures down to ~ 40% Mn concentration, below which a paramagnetic behavior is observed. Absorption measurements reveal an increase in bandgap energy with higher Zn(II) concentration, and the presence of Mn(II) d-d transition below the absorption edge. DFT+U approach qualitatively explained the origin and the position of the experimentally observed mid band-gap states in pure MnPS3, and corresponding peaks visible in the alloyed systems MnxZn1-xPS3. Accordingly, emission at 1.3 eV in all alloyed compounds results from recombination from a 4T1g Mn(II) excited state to a hybrid p-d state at the valence band. Most significant, temperature-dependent photoluminescence (PL) intensity trends demonstrate strong magneto-optical coupling in compositions with x > 0.65. This study underscores the potential of tailored alloy compositions as a means to control magnetic and optical properties in 2D materials, paving the way for advances in spin-based technologies.
2404.07643v1
2019-11-22
Radiation Damage Studies on Titanium Alloys as High Intensity Proton Accelerator Beam Window Materials
A high-strength dual alpha+beta phase titanium alloy Ti-6Al-4V is utilized as a material for beam windows in several accelerator target facilities. However, relatively little is known about how material properties of this alloy are affected by high-intensity proton beam irradiation. With plans to upgrade neutrino facilities at J-PARC and Fermilab to over 1 MW beam power, the radiation damage in the window material will reach a few displacements per atom (dpa) per year, significantly above the ~0.3 dpa level of existing data. The RaDIATE collaboration has conducted a high intensity proton beam irradiation of various target and window material specimens at BLIP facility, including a variety of titanium alloys. Post-Irradiation Examination of the specimens in the 1st capsule, irradiated at up to 0.25 dpa, is in progress. Tensile tests in a hot cell at PNNL exhibited a clear signature of radiation hardening and loss of ductility for Ti-6Al-4V, while Ti-3Al-2.5V, with less beta phase, exhibited less severe hardening. Microstructural investigations will follow to study the cause of the difference in tensile behavior between these alloys. High-cycle fatigue (HCF) performance is critical to the lifetime estimation of beam windows exposed to a periodic thermal stress from a pulsed proton beam. The 1st HCF data on irradiated titanium alloys are to be obtained by a conventional bend fatigue test at Fermilab and by an ultrasonic mesoscale fatigue test at Culham Laboratory. Specimens in the 2nd capsule, irradiated at up to ~1 dpa, cover typical titanium alloy grades, including possible radiation-resistant candidates. These systematic studies on the effects of radiation damage of titanium alloys are intended to enable us to predict realistic lifetimes of current beam windows made of Ti-6Al-4V and to extend the lifetime by choosing a more radiation and thermal shock tolerant alloy.
1911.10198v1
1998-03-04
Non-mean-field theories of short range order and diffuse scattering anomalies in disordered alloys
Local, or short-range, order in disordered alloys is an important and exciting phenomenon which is quantified in electron, X-ray and neutron scattering experiments. It is discussed in many excellent reviews and books, as well as in the multitude of original research papers. This relatively short review of the subject does not attempt to discuss all aspects of the problem of local correlations in alloys. In particular, we will not touch such issues as multiatom (cluster) interactions, static displacements and vibrations of alloy atoms, partially ordered, multicomponent or amorphous alloys. As a result, we will concentrate on the Hamiltonian traditional for the considered problem, that of the Ising model on a rigid ideal lattice with pair, but otherwise arbitrary (i.e., of any range) interatomic interactions. The central object of the paper is the pair correlation function of the corresponding dynamical variables of the model, the occupation numbers or spin variables, the Fourier transform of which is proportional to the intensity of diffuse scattering caused by atomic short-range order. The main aim is to show that the expression for this quantity has certain internal structure analogous, e.g., to that of the averaged Green's function used in the electronic theory of disordered alloys. This structure is independent of the approximation used for the quantitative description of correlations. As will be seen, this structure alone, without further specification of a particular theory of short-range order, allows us to see new possibilities in diffuse scattering, some of which have recently been observed experimentally.
9803052v1
2008-11-14
Electronic transport in ferromagnetic alloys and the Slater-Pauling Curve
Experimental measurements of the residual resistivity $\rho(x)$ of the binary alloy system Fe$_{1-x}$Cr$_x$ have shown an anomalous concentration dependence which deviates significantly from Nordheim's rule. In the low ($x < 10%$) Cr concentration regime the resistivity has been found to increase linearly with $x$ until $\approx$ 10% Cr where the resistivity reaches a plateau persisting to $\approx$ 20% Cr. In this paper we present $ab$-$initio$ calculations of $\rho(x)$ which explain this anomalous behavior and which are based on the Korringa-Kohn-Rostoker (KKR) method in conjunction with the Kubo-Greenwood formalism. Furthermore we are able to show that the effects of short-range ordering or clustering have little effect via our use of the nonlocal coherent-potential approximation (NL-CPA). For the interpretation of the results we study the alloys' electronic structure by calculating the Bloch spectral function particularly in the vicinity of the Fermi energy. From the analysis of our results we infer that a similar behavior of the resistivity should also be obtained for iron-rich Fe$_{1-x}$V$_x$ alloys - an inference confirmed by further explicit resistivity calculations. Both of these alloy systems belong to the same branch of the famous Slater-Pauling plot and we postulate that other alloy systems from this branch should show a similar behavior. Our calculations show that the appearance of the plateau in the resistivity can be attributed to the dominant contribution of minority spin electrons to the conductivity which is nearly unaffected by increase in Cr/V concentration $x$ and we remark that this minority spin electron feature is also responsible for the simple linear variation of the average moment in the Slater-Pauling plot for these materials.
0811.2303v1
2012-07-19
The effect of size and distribution of rod-shaped β' precipitates on the strength and ductility of a Mg-Zn alloy
We report on a quantitative investigation into the effect of size and distribution of rod-shaped \beta' precipitates on strength and ductility of a Mg-Zn alloy. Despite precipitation strengthening being crucial for the practical application of magnesium alloys this study represents the first systematic examination of the effect of controlled deformation on the precipitate size distribution and the resulting strength and ductility of a magnesium alloy. Pre-ageing deformation was used to obtain various distributions of rod-shaped \beta' precipitates through heterogeneous nucleation. Alloys were extruded to obtain a texture so as to avoid formation of twins and thus to ensure that dislocations were the primary nucleation site. Pre-ageing strain refined precipitate length and diameter, with average length reduced from 440 nm to 60 nm and diameter from 14 nm to 9 nm. Interparticle spacings were measured from micrographs and indicated some inhomogeneity in the precipitate distribution. The yield stress of the alloy increased from 273 MPa to 309 MPa. The yield stress increased linearly as a function of reciprocal interparticle spacing, but at a lower rate than predicted for Orowan strengthening. Pre-ageing deformation also resulted in a significant loss of ductility (from 17% to 6% elongation). Both true strain at failure and uniform elongation showed a linear relationship with particle spacing, in agreement with models for the accumulation of dislocations around non-deforming obstacles. Samples subjected to 3% pre-ageing deformation showed a substantially increased ageing response compared to non-deformed material; however, additional deformation (to 5% strain) resulted in only modest changes in precipitate distribution and mechanical properties.
1207.4544v1
2014-10-20
Modeling the Elastic Energy of Alloys: Potential Pitfalls of Continuum Treatments
Some issues that arise when modeling elastic energy for binary alloys are discussed within the context of a Keating model and density functional calculations. The Keating model is based on atomistic modeling of elastic interactions in binary alloy using harmonic springs with species dependent equilibrium lengths. It is demonstrated that the continuum limit for the strain field are the usual equations of linear elasticity for alloys and that they correctly capture the coarse-grained displacement field. In addition, it is established that Euler-Lagrange equation of the continuum limit of the elastic energy will yield the same strain field equation. However, a direct calculation of the elastic energy of the atomistic model reveals that the continuum expression for the elastic energy is both qualitatively and quantitatively incorrect. This is because it does not take atomistic scale compositional non-uniformity into account. Importantly, we also shows that finely mixed alloys tend to have more elastic energy than segregated systems, which is the opposite of predictions by some continuum theories. It is also shown that for strained thin films the traditionally used effective misfit for alloys systematically underestimate the strain energy. In some models, this drawback is handled by including an elastic contribution to the enthalpy of mixing which is characterized in terms of the continuum concentration. The direct calculation of the atomistic model reveals that this approach suffers serious difficulties. It is demonstrated that elastic contribution to the enthalpy of mixing is non-isotropic and scale dependent. It also shown that such effects are present in density-functional theory calculations for the Si/Ge and Ag/Pt systems. This work demonstrates that it is critical to include the microscopic arrangements in any elastic model to achieve even qualitatively correct behavior.
1410.5472v2
2019-01-04
Alloy theory with atomic resolution for Rashba or topological systems
Interest in substitutional disordered alloys has recently reemerged with focus on the symmetry-sensitive properties in the alloy such as topological insulation and Rashba effect. A substitutional random alloy manifests a distribution of local environments, creating a polymorphous network. While the macroscopic average (monomorphous) structure may have the original high symmetry of the constituent compounds, many observable physical properties are sensitive to local symmetry, and are hence $<P(S_i)>$ rather than $P(S_0)$=$P(<S_i>)$. The fundamental difference between polymorphous $<P(S_i)>$ and monomorphous $P(S_0)$ led to the often-diverging results and the missing the atomic-scale resolution needed to discern symmetry-related physics. A natural approach capturing the polymorphous aspect is supercell model, which however suffers the difficulty of band folding ('spaghetti bands'), rendering the E vs k dispersion needed in topology and Rashba physics and seen in experiments, practically inaccessible. A solution that retains the polymorphous nature but restores the E vs k relation is to unfold the supercell bands. This yields alloy Effective Band Structure (EBS), providing a 3D picture of spectral density consisting of E- and k-dependent spectral weight with coherent and incoherent features, all created naturally by the polymorphous distribution of many local environments. We illustrate this EBS approach for CdTe-HgTe, PbSe-SnSe and PbS-PbTe alloys. We found properties that are critical for e.g. topological phase transition and Rashba splitting but totally absent in conventional monomorphous approaches, including (1) co-existing, wavevector- and energy-dependent coherent band splitting and incoherent band broadening, (2) coherent-incoherent transition along different k space directions, and (3) Rashba-like band splitting having both coherent and incoherent features.
1901.01289v2
2019-02-06
Efficient method for calculating Raman spectra of solids with impurities and alloys and its application to two-dimensional transition metal dichalcogenides
Raman spectroscopy is a widely used, powerful, and nondestructive tool for studying the vibrational properties of bulk and low-dimensional materials. Raman spectra can be simulated using first-principles methods, but due to the high computational cost calculations are usually limited only to fairly small unit cells, which makes it difficult to carry out simulations for alloys and defects. Here, we develop an efficient method for simulating Raman spectra of alloys, benchmark it against full density-functional theory calculations, and apply it to several alloys of two-dimensional transition metal dichalcogenides. In this method, the Raman tensor for the supercell mode is constructed by summing up the Raman tensors of the pristine system weighted by the projections of the supercell vibrational modes to those of the pristine system. This approach is not limited to 2D materials and should be applicable to any crystalline solids with defects and impurities. To efficiently evaluate vibrational modes of very large supercells, we adopt mass approximation, although it is limited to chemically and structurally similar atomic substitutions. To benchmark our method, we first apply it to Mo$_x$W$_{(1-x)}$S$_2$ monolayer in the H-phase, where several experimental reports are available for comparison. Second, we consider Mo$_x$W$_{(1-x)}$Te$_2$ in the T'-phase, which has been proposed to be 2D topological insulator, but where experimental results for the monolayer alloy are still missing. We show that the projection scheme also provides a powerful tool for analyzing the origin of the alloy Raman-active modes in terms of the parent system eigenmodes. Finally, we examine the trends in characteristic Raman signatures for dilute concentrations of impurities in MoS$_2$.
1902.02143v1
2020-04-24
Tensile behavior of dual-phase titanium alloys under high-intensity proton beam exposure: radiation-induced omega phase transformation in Ti-6Al-4V
A high-intensity proton beam exposure with 181 MeV energy has been conducted at Brookhaven Linac Isotope Producer facility on various material specimens for accelerator targetry applications, including titanium alloys as a beam window material. The radiation damage level of the analyzed capsule was 0.25 dpa at beam center region with an irradiation temperature around 120 degree C. Tensile tests showed increased hardness and a large decrease in ductility for the dual alpha+beta-phase Ti-6Al-4V Grade-5 and Grade-23 extra low interstitial alloys, with the near alpha-phase Ti-3Al-2.5V Grade-9 alloy still exhibiting uniform elongation of a few % after irradiation. Transmission Electron Microscope analyses on Ti-6Al-4V indicated clear evidence of a high-density of defect clusters with size less than 2 nm in each alpha-phase grain. The beta-phase grains did not contain any visible defects such as loops or black dots, while the diffraction patterns clearly indicated omega-phase precipitation in an advanced formation stage. The radiation-induced omega-phase transformation in the beta-phase could lead to greater loss of ductility in Ti-6Al-4V alloys in comparison with Ti-3Al-2.5V alloy with less beta-phase.
2004.11562v2
2021-03-28
Radiation-tolerant high-entropy alloys via interstitial-solute-induced chemical heterogeneities
High-entropy alloys (HEAs) composed of multiple principal elements have been shown to offer improved radiation resistance over their elemental or dilute-solution counterparts. Using NiCoFeCrMn HEA as a model, here we introduce carbon and nitrogen interstitial alloying elements to impart chemical heterogeneities in the form of the local chemical order (LCO) and associated compositional variations. Density functional theory simulations predict chemical short-range order (CSRO) (nearest neighbors and the next couple of atomic shells) surrounding C and N, due to the chemical affinity of C with (Co, Fe) and N with (Cr, Mn). Atomic-resolution chemical mapping of the elemental distribution confirms marked compositional variations well beyond statistical fluctuations. Ni+ irradiation experiments at elevated temperatures demonstrate a remarkable reduction in void swelling by at least one order of magnitude compared to the base HEA without C and N alloying. The underlying mechanism is that the interstitial-solute-induced chemical heterogeneities roughen the lattice as well as the energy landscape, impeding the movements of, and constraining the path lanes for, the normally fast-moving self-interstitials and their clusters. The irradiation-produced interstitials and vacancies therefore recombine more readily, delaying void formation. Our findings thus open a promising avenue towards highly radiation-tolerant alloys.
2103.15134v1