Although the existence of 13-atom icosahedral clusters in one-component close-packed undercooled liquids was predicted more than half a century ago by Frank, the existence of such icosahedral clusters is less clear in liquid alloys. We study the lowest-energy structures of 13-atom AxB13-x Lennard-Jones binary clusters using the modified space-fixed genetic algorithm and the artificial Lennard-Jones potential designed by Kob and Andersen. Curiously, the lowest-energy structures are non-icosahedral for almost all compositions. The role played by the icosahedral cluster in a binary glass is questionable.
Aluminium alloy AA7075 (Al-Zn-Mg-Cu) specimens were prepared using selective laser melting, also known as powder bed fusion additive manufacturing. In the as-manufactured state, which represents a locally rapidly solidified condition, the prevalence of a previously unreported icosahedral quasicrystal with 5-fold symmetry was observed. The icosahedral quasicrystal, which has been termed nu-phase, was comprised of Zn, Cu and Mg.
The structural properties of the simulated $\rm Cu_αZr_{1-α}$ glassy alloys are studied in the wide range of the copper concentration $α$ to clarify the impact of the composition on the number density of the icosahedral clusters. Both bond orientational order parameters and Voronoi tessellation methods are used to identify these clusters. Our analysis shows that abundance of the icosahedral clusters and the chemical composition of these clusters are essentially non monotonic versus $α$ and demonstrate local extrema. That qualitatively explains the existence of pinpoint compositions of high gla…
In a narrow composition range centered at Zn74.5Au10.5Yb15.0, Tsai-type icosahedral quasicrystal is formed in alloys quenched from 880 C. This quasicrystal belongs to the primitive type with the 6-dimensional lattice parameter a6D=7.378 A. The quasicrystal was not formed in the slowly cooled specimen, and was considered a metastable phase. The stable phase is a 2/1 approximant of the lattice parameter a2/1=23.271 A. This approximant forms exclusively in Zn76.0Au9.0Yb15.0 alloy annealed at 530 C. In addition, Zn70.5Au15.5Tb14.0 alloy annealed at 505 C forms a Tsai-type 1/1 approximant (a1/1=14.…
Selective laser melting (SLM) is rapidly evolving to become a mainstream technology. However, the fundamental mechanisms of solidification and microstructure development inherent to the non-equilibrium conditions of this additive manufacturing method, which differ largely from those typical of conventional processing techniques, remain widely unknown. In this work, an in-depth characterization of the microstructure of Al7075 SLM processed samples, built from powder mixtures containing ZrH2 microparticles, demonstrates the occurrence of icosahedral quasicrystal-enhanced nucleation during laser …
Icosahedral quasicrystals spontaneously form from the melt in simulations of Al--Cu--Fe alloys. We model the interatomic interactions using oscillating pair potentials tuned to the specific alloy system based on a database of density functional theory (DFT)-derived energies and forces. Favored interatomic separations align with the geometry of icosahedral motifs that overlap to create face-centered icosahedral order on a hierarchy of length scales. Molecular dynamics simulations, supplemented with Monte Carlo steps to swap chemical species, efficiently sample the configuration space of our mod…
Binary Cu-Zr system is a representative bulk glassformer demonstrating high glass forming ability due to pronounced icosahedral local ordering. From the first glance, Ni-Zr system is the most natural object to expect the same behavior because nickel and copper are neighbours in the periodic table and have similar physicochemical properties. However, doing molecular dynamics simulations of $\rm Ni_αZr_{1-α}$ alloys described by embedded atom model potential, we observe different behaviour. We conclude that the Ni-Zr system has the same glass-forming ability as an additive binary Lennard-Jones m…
To understand the formation of the Bergman cluster in the F-type icosahedral quasicrystal, crystallographic relations between the quasicrystal and the intermetallic-compound H and Zn$_{23}$Y$_6$ phases in the Zn-Mg-Y alloy system were investigated mainly by transmission electron microscopy. It was found that, although sample rotations of about 1° were required to obtain simple crystallographic relations, the orientation relationship was established among the cubic-$Fm\overline{3}m$ Zn$_{23}$Y$_6$ structure, the hexagonal-$P6_3/mmc$ H structure, and the F-type icosahedral quasicrystal (IQ); tha…
Recent discovery of various magnetism in Tsai-type quasicrystalline approximants, in whose alloys rare-earth ions located on icosahedral apices are coupled with each other via the Ruderman--Kittel--Kasuya--Yosida interaction, opens an avenue to find novel magnetism originating from the icosahedral symmetry. Here we investigate classical and quantum magnetic states on an icosahedral cluster within the Heisenberg interactions of all bonds. Simulated annealing and numerical diagonalization are performed to obtain the classical and quantum ground states. We obtain qualitative correspondence of cla…
Structure-Dependent Chemical Order Modification in Strained Alloy Nanoparticles
Guangdong Technion – Israel Institute of Technology（广东以色列理工学院）；Universidad de Castilla-La Mancha（卡斯蒂利亚-拉曼恰大学）；Aristotle University of Thessaloniki（塞萨洛尼基亚里士多德大学）
This paper reports formation enthalpies of phases in the Al-Mn-Pd ternary alloy system as calculated from first principles using electronic density functional theory. We consider all crystal structures as reported in the assessed phase diagrams of the ternary and its binary alloy subsystems (Al-Mn, Al-Pd, and Mn-Pd), as well as additional reported or hypothetical structures. Icosahedral and decagonal quasicrystalline approximants are among the structures that we predict to be stable, or nearly so. Our results suggest the need for careful experimental reexamination of phase stability in each of…
Almost three quarters of a century ago, Charles Frank proposed that the deep supercooling observed in metallic liquids is due to icosahedral short-range order (ISRO), which is incompatible with the long-range order of crystal phases. Some evidence in support of this hypothesis has been published previously. However, those studies were based on a small population of maximum supercooling measurements before the onset of crystallization. Here, the results of a systematic statistical study of several hundred maximum supercooling measurements on Ti39.5Zr39.5Ni21 and Zr80Pt20 liquids are presented. …
During the solidification of Al-Sm metallic glasses the evolution of the supercooled liquid atomic structure has been identified with an increasing population of icosahedral-like clusters with increasing Sm concentration. These clusters exhibit slower kinetics compared to the remaining clusters in the liquid leading to enhanced amorphous phase stability and glass forming ability (GFA). Maximum icosahedral-ordering and atomic packing density have been found for the Al90Sm10 and Al85Sm15 alloys, respectively, whereas minimum cohesive energy has been found for the Al93Sm7 which is consistent with…
Understanding the mechanisms which relate properties of liquid and solid phases is crucial for fabricating new advanced solid materials, such as glasses, quasicrystals and high-entropy alloys. Here we address this issue for quasicrystal-forming Al-Cu-Fe alloys which can serve as a model for studying microscopic mechanisms of quasicrystal formation. We study experimentally two structural-sensitive properties of the liquid -- viscosity and undercoolability -- and compare results with \textit{ab initio} investigations of short-range order (SRO). We observe that SRO in Al-Cu-Fe melts is polytetrah…
Using molecular simulations, we shed light on the mechanism underlying crystal nucleation in metal alloys and unravel the interplay between crystal nucleation and glass transition, as the conditions of crystallization lie close to this transition. While decreasing the temperature of crystallization usually results in a lower free energy barrier, we find an unexpected reversal of behavior for glass-forming alloys as the temperature of crystallization approaches the glass transition. For this purpose, we simulate the crystallization process in two glass-forming Copper alloys, $Ag_6Cu_4$, which h…
The bowing of the energy of the three lowest band-to-band transitions in $β$-(Al$_{x}$Ga$_{1-x}$)$_2$O$_3$ alloys was resolved using a combined density functional theory (DFT) and generalized spectroscopic ellipsometry (GSE) approach. The DFT calculations of the electronic band structure of both, $β$-Ga$_2$O$_3$ and $θ$-Al$_2$O$_3$, allow extracting of the linear portion of the energy shift in the alloys, and provide a method for quantifying the role of coherent strain present in the $β$-(Al$_{x}$Ga$_{1-x}$)$_2$O$_3$ thin films on (010) $β$-Ga$_2$O$_3$ substrates. The energies of band-to-band …
Prediction of the glass forming ability (GFA) of alloys remains a major challenge. We are not able to predict the composition dependence of the GFA of even binary alloys. To investigate the effect of each element's propensity to form particular crystal structures on glass formation, we focus on binary alloys composed of elements with the same size, but different atomic symmetries using the patchy-particle model. For mixtures with atomic symmetries that promote different crystal structures, the minimum critical cooling rate $R_c$ is only a factor of $5$ lower than that for the pure substances. …
Alloy Stabilized Wurtzite Ground State Structures of Zinc-Blende Semiconducting Compounds
用价力场模型和密度泛函理论计算了A $_x$ B $_{1-x}$ C纤锌矿（WZ）合金的基态结构，其中$x=$分别为0.25，0.5和0.75.结果表明，基态WZ合金的应变能和形成焓总是比相应的锌基合金低。因此，我们建议通过合金化可以稳定WZ相。这一新的想法得到以下事实的支持：WZ AlP $_{0.5}$ Sb $_{0.5}$、AlP $_{0.75}$ Sb $_{0.25}$、ZnS $_{0.5}$ Te $_{0.5}$和ZnS $_{0.75}$ Te $_{0.25}$合金在最低能量结构中比相应的ZB合金更稳定。据我们所知，这是合金采用与两个母相不同的结构的第一个例子。
Predicting the ground state of alloy systems is challenging due to the large number of possible configurations. We identify an easily computed descriptor for the stability of binary surface alloys, the effective coordination number $\mathscr{E}$. We show that $\mathscr{E}(M)$ correlates well with the enthalpy of mixing, from density functional theory (DFT) calculations on $M_x$Au$_{1-x}$/Ru [$M$ = Mn or Fe]. At each $x$, the most favored structure has the highest [lowest] value of $\mathscr{E}(M)$ if the system is non-magnetic [ferromagnetic]. Importantly, little accuracy is lost upon replacin…
As approaching the glass transition, particle motion in liquids becomes highly heterogeneous and regions with virtually no mobility coexist with liquid-like domains. This complex dynamics is believed to be responsible for different phenomena including non-exponential relaxation and the breakdown of Stokes-Einstein relation. Understanding the relationships between dynamical heterogeneities and local structure in metallic liquids and glasses is a major scientific challenge. Here we use classical molecular dynamics simulations to study the atomic dynamics and microscopic structure of $\mbox{Cu}_{…
We report a systematic investigation on the magnetization relaxation properties of iron-based half-metallic Heusler alloy Fe$_{2}$Cr$_{1-x}$Co_${x}$Si (FCCS) thin films using broadband angular-resolved ferromagnetic resonance. Band structure engineering through Co doping (x) demonstrated by first-principles calculations is shown to tune the intrinsic magnetic damping over an order of magnitude, namely 0.01-0.0008. Notably, the intrinsic damping constants for samples with high Co concentration are among the lowest reported for Heusler alloys and even comparable to magnetic insulator yttrium iro…
Many mixed ionic/electronic conductors (MIECs) applied in fuel cell electrodes can be considered as alloys between perovskite oxides and ordered oxygen vacancy compounds. For example, in the model MIEC (STF), low oxygen diffusion barrier exist in SrTiO3 lattice, when it has been mixed with SrFeO2.5 with intrinsic oxygen deficiency, the ionic conductivity can be greatly improved. Meanwhile, the electronic conductivity can be optimized by controlling the defect chemistry of the alloy. However, the configurational space is too large in such alloys so that it is difficult for direct atomic modelin…
In the warm dense regime, where the electron temperature is increased to the same order of the Fermi temperature, the dynamical stability of elemental metals depends on its electronic band structure as well as its crystal structure. It has been known that phonon hardening occurs due to an enhanced internal pressure caused by electron excitations as in close-packed simple metals, whereas phonon softening occurs at a specific point in the Brillouin zone as in body-centered cubic metals. Here, we investigate the dynamical stability of binary ordered alloys (Au and Cu) in the L1$_0$ and L1$_2$ str…
Structural prediction for the discovery of novel materials is a long sought after goal of computational physics and materials sciences. The success is rather limited for methods such as the simulated annealing method (SA) that require expensive density functional theory (DFT) calculations and follow unintelligent search paths. Here a machine-learning based crystal combinatorial optimization program (CCOP) with a fitting-search style is proposed to drastically improve the efficiency of structural search in SA. CCOP uses a graph neural network energy prediction model to reduce the DFT cost and a…
The ab initio electronic structure calculations of the Ni$_{2}$MnGa The alloy indicate that the orthorhombic 4O structure exhibits the lowest energy compared to all known martensitic structures. The 4O structure is formed by nanotwin double layers, i.e., oppositely oriented nanotwins consisting of two (101) lattice planes of nonmodulated martensitic structure. It exhibits the lowest occupation of density of states at the Fermi level. The total energy 1.98 meV/atom below the energy of nonmodulated martensite is achieved within structural relaxation by shifting Mn and Ga atoms at the nanotwin bo…
Using first principles calculations based on density functional theory, we study the geometric, electronic, and magnetic properties of Pt, Ni and Co-based half Heusler alloys, namely, Pt$BC$, Ni$BC$ and Co$BC$ ($B$ = Cr, Mn and Fe; $C$ = Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb and Te). We calculate the formation energy of these alloys in various crystal symmetries, which include, the (face-centered) cubic $C1_{b}$ ($F\bar{4}$3m), orthorhombic ($Pnma$), as well as hexagonal ($P\bar{6}2m$ and $P6_{3}/mmc$) structures. It has been observed that out of all the 108 structures, studied here, energe…
Using the hybrid exchange-correlation functional within the density-functional theory, we have systematically investigated the structural and electronic properties of MO (M = Be, Mg, Ca, Sr, Ba, Zn, Cd) in binary rocksalt (B1), zincblende (B3) and wurtzite (B4) phases, including the structural parameters, bulk moduli, band gaps and deformation potentials. Our results agree well with the experimental data and other theoretical results, and give a better understanding of the relationship between the geometric and electronic structure. After calculating the band alignment, we find that in both th…
In this work, polycrystalline NiCrGa half Heusler alloy, which is predicted to be half-metallic ferromagnet from first principles calculations, has been synthesized by arc meting technique and its structural, magnetic as well as the electronic properties have been studied. The measured x-ray diffraction (XRD) pattern shows the signature of a disordered structure. From the magnetization measurements, there is no evidence of ferromagnetic ordering observed in this system down to the lowest temperature studied. Instead, the system shows the signature of an antiferromagnetic ordering at very low t…
Development of reliable interatomic potentials is crucial for theoretical studies of relationship between chemical composition, structure and observable properties in glass-forming metallic alloys. Due to ambiguity of potential parametrization procedure, some crucial properties of the system, such as crystallization stability or symmetry of the ground state crystal phase, may not be correctly reproduced in computer simulations. Here we address this issue for ${\rm Cu_{64.5}Zr_{35.5}}$ alloy described by two modifications of embedded atom model potential as well as by \textit{ab initio} molecul…
Alloy engineering of Magnetic phases in two-dimensional Chromium Trihalides
Institute of Physics, University of São Paulo（圣保罗大学物理研究所）；Department of Theoretical and Computational Chemistry, National University of Córdoba（科尔多瓦国立大学理论与计算化学系）；Department of Materials Engineering, University of São Paulo（圣保罗大学材料工程系）
Properties of the $ω$ structure are investigated for 27 transition elements from the viewpoints of thermodynamical and mechanical stability based on first-principles calculations. The thermodynamical stability of the $ω$ structure is compared with those for the body-centered cubic (BCC), face-centered cubic (FCC), and hexagonal close-packed (HCP) structures. Similarly to the case of those popular crystal structures, the occupation number for $d$ orbitals is found to roughly determine relative energy and volume of the nonmagnetic (NM) $ω$ structure. For the group 4 elements (Ti, Zr, and Hf), th…
Several approaches have been used to investigate the impact of Nitrogen (N) on the electronic structure of GaAs$_{1-x}$N$_{x}$ alloys, however, there is no agreement between theory and experiments about the importance of the different N interstitial defects in these alloys, and their nature is still unknown. Here we analyze the impact of five different N defects on the electronic structure of GaAs$_{1-x}$N$_{x}$ alloys, using density-functional methods: we calculate electronic states, formation energies and charge transition levels. The studied defects include N$_{As}$, As$_{Ga}$, As$_{Ga}$-N$…
Phase field crystal dynamics for binary systems: Derivation from dynamical density functional theory, amplitude equation formalism, and applications to alloy heterostructures
Using molecular dynamics simulations with embedded atom model potential, we study structural evolution of ${\rm Cu_{64.5}Zr_{35.5}}$ alloy during the cooling in a wide range of cooling rates $γ\in(1.5\cdot 10^{9},10^{13})$ K/s. Investigating short- and medium-range order, we show that structure of ${\rm Cu_{64.5}Zr_{35.5}}$ metallic glass essentially depends on cooling rate. In particular, a decrease of the cooling rate leads to a increase of abundances of both the icosahedral-like clusters and Frank-Kasper Z16 polyhedra. The amounts of these clusters in the glassy state drastically increase a…
