Search Results (35)

The mechanical properties of materials are fundamentally determined by the behavior of atomic bonds under stress. Probing bond behavior during deformation, however, is highly challenging, particularly for materials with complex chemical compositions and/or atomic structures, such as metallic glasses (MGs). As a result, a significant gap exists in the current understanding of the mechanical properties of MGs in relation to the atomic bond behavior and how this relationship is influenced by metallurgical factors (e.g., alloy composition, processing conditions). Here, we present our study of the compositional effects on the tensile behavior of atomic bonds in Cu_93−xZr_xAl₇ (x = 40, 50, 60 at.%) MGs using large-scale molecular dynamics (MD) simulations and statistical analysis. Specifically, we examine the populations (fractions), mean bond lengths, mean bond z-lengths, and mean bond z-strains of the different bond types before and during tensile loading (in the z-direction), and we compare these quantities across the different alloy compositions. Among our key findings, we show that increasing the Zr content in the alloy composition leads to shortened Zr-Zr, Al-Cu, Al-Zr, and Cu-Zr bonds and elongated Cu-Cu bonds, as evidenced by their mean bond lengths. During deformation, the shorter Zr-Zr bonds and longer Cu-Cu bonds in the higher-Zr-content alloys, compared with those in the x = 40 alloy, appear stronger (more elastic stretching in the z-direction) and weaker (less z-stretching), respectively, consistent with general expectations. In contrast, the Al-Cu, Al-Zr, and Cu-Zr bonds in the higher-Zr-content alloys appear weaker in the elastic regime, despite their shortened mean bond lengths. This apparent paradox can be reconciled by considering the fractions of these bonds associated with icosahedral clusters, which are known to be more resistant to deformation than the rest of the glassy structure. We also discuss how the compositional effects on the bond behavior relate to variations in the overall stress–strain behavior of the different alloys. Full article

The whimsical Las Vegas/Monte Carlo cubic dice are generalized to construct the combinatorial problem of enumerating all n-dimensional hypercube dice and dice of other shapes that exhibit cubic, icosahedral, and higher symmetries. By utilizing powerful generating function techniques for various irreducible representations, we derive the combinatorial enumerations of all possible dice in n-dimensional space with hyperoctahedral symmetries. Likewise, a number of shapes that exhibit icosahedral symmetries such as a truncated dodecahedron and a truncated icosahedron are considered for the combinatorial problem of dice enumerations with the corresponding shapes. We consider several dice with cubic symmetries such as the truncated octahedron, dodecahedron, and Rubik’s cube shapes. It is shown that all enumerated dice are chiral, and we provide the counts of chiral pairs of dice in the n-dimensional space. During the combinatorial enumeration, it was discovered that two different shapes of dice exist with the same chiral pair count culminating to the novel concept of isochiral polyhedra. The combinatorial problem of dice enumeration is generalized to multi-coloring partitions. Applications to chirality in n-dimension, molecular clusters, zeolites, mesoporous materials, cryptography, and biology are also pointed out. Applications to the nonlinear n-dimensional hypercube and other dicey encryptions are exemplified with romantic, clandestine messages: “I love U” and “V Elope at 2”. Full article

This article examines the processes of structure formation occurring during joint plastic deformation by the explosion of copper and molybdenum. These components are dissimilar metals with very limited mutual solubility under normal conditions, and the circumstances allowing for their interaction, as well as the products of the mechanochemical reactions of such interactions, have not been sufficiently studied and require new approaches. A cluster approach was used to describe the processes of structure formation, which describes phase formation as the process transitioning of the polyhedron of the initial phase into the polyhedron of the final phase. This work shows that under the conditions under consideration, not only is the formation of solid solutions in the contact zone with smooth concentration transitions from one component to another possible, but also the formation of new structural states, which can be represented as localized icosahedral atomic configurations (amorphous metal clusters). Such a structure is capable of locally strengthening the composite, which is confirmed by microhardness studies. Full article

Investigating the relationship between the glass-forming ability (GFA), mechanical properties, and structure of metallic glasses is crucial to understanding the nature of the metallic glass state. In this study, the correlation among the atomic structure, electronic valence band, and properties have been studied using Zr₅₀Cu_44.5−xAl_5.5Ag_x (x = 0, 1.5, 3 at.%) bulk metallic glasses (BMGs). The results reveal that through the micro-addition of Ag, the GFA of Zr₅₀Cu_44.5Al_5.5 BMG can be enhanced; meanwhile, the critical diameter of Zr₅₀Cu_44.5Al_5.5 glass rods increases from approximately 2.5 mm to 5.0 mm with the addition of 3% Ag. Through the addition of Ag, the thermal stability of Zr₅₀Cu_44.5Al_5.5 BMG is improved, and the proportion of icosahedral-like clusters increases. The plasticity of the Zr₅₀Cu_44.5−xAl_5.5Ag_x (x = 0, 1.5, 3 at.%) BMGs decreased from 4.6% to 0.8% with the addition of Ag. The valence band spectrum of the Zr₅₀Cu_44.5−xAl_5.5Ag_x (x = 0, 1.5, 3 at.%) BMGs indicates that with the addition of Ag, the p-d hybridization near the Fermi level is enhanced, and the binding energy will move to a lower value. Full article

Salt mines are a special type of hypersaline environment. Current research mainly focuses on prokaryotes, and the understanding of viruses in salt mines remains limited. Understanding viruses in hypersaline environments is of great significance for revealing the formation and maintenance of microbial communities, energy flow and element cycling, and host ecological functions. A phage infecting Halomonas titanicae was isolated from Yipinglang Salt Mine in China, designated Halomonas titanicae phage vB_HtiS_YPHTV-1 (YPHTV-1). Transmission electron microscopy revealed that YPHTV-1 had an icosahedral head with a diameter of 49.12 ± 0.15 nm (n = 5) and a long noncontractile tail with a length of 141.7 ± 0.58 nm (n = 5), indicating that it was a siphovirus. The one-step growth curve showed that the burst size of YPHTV-1 was 69 plaque forming units (PFUs) cell⁻¹. The genome of YPHTV-1 was 37,980 bp with a GC content of 36.2%. The phylogenetic analysis of the six conserved proteins indicated that YPHTV-1 formed a cluster with Bacillus phages and was separated from phages infecting Halomonas. The average nucleotide identity (ANI), phylogenetic, and network analyses indicated that the phage YPHTV-1 represented a new genus under Caudoviricetes. In total, 57 open reading frames (ORFs) were predicted in the YPHTV-1 genome, 30 of which could be annotated in the database. Notably, several auxiliary metabolic genes were encoded by YPHTV-1, such as ImmA/IrrE family metalloendopeptidase, mannose-binding lectin (MBL) folding metallohydrolase, M15 family of metal peptidases, MazG-like family protein, O antigen ligase, and acyltransferase. These genes potentially enabled the host bacterium to resist ionizing radiation, ultraviolet light (UV), mitomycin C, β-lactam antibiotic, high osmotic pressure, and nutritional deficiencies. These findings highlight the role of haloviruses in the life cycle of halobacteria. Full article

Traditionally, drugs were obtained by extraction from medicinal plants, but more recently also by organic synthesis. Today, medicinal chemistry continues to focus on organic compounds and the majority of commercially available drugs are organic molecules, which can incorporate nitrogen, oxygen, and halogens, as well as carbon and hydrogen. Aromatic organic compounds that play important roles in biochemistry find numerous applications ranging from drug delivery to nanotechnology or biomarkers. We achieved a major accomplishment by demonstrating experimentally/theoretically that boranes, carboranes, as well as metallabis(dicarbollides), exhibit global 3D aromaticity. Based on the stability–aromaticity relationship, as well as on the progress made in the synthesis of derivatized clusters, we have opened up new applications of boron icosahedral clusters as key components in the field of novel healthcare materials. In this brief review, we present the results obtained at the Laboratory of Inorganic Materials and Catalysis (LMI) of the Institut de Ciència de Materials de Barcelona (ICMAB-CSIC) with icosahedral boron clusters. These 3D geometric shape clusters, the semi-metallic nature of boron and the presence of exo-cluster hydrogen atoms that can interact with biomolecules through non-covalent hydrogen and dihydrogen bonds, play a key role in endowing these compounds with unique properties in largely unexplored (bio)materials. Full article

The identification of glassy defects in amorphous materials is a long-standing but imperative problem which hinders our deep understanding of the structural origin of mechanical behavior in metallic glasses (MGs). Here, a combination of experiments and numerical simulations were used to reconstruct the atomic packing of MGs. Using the integration of synchrotron X-ray diffraction (XRD) datasets, ab initio molecular dynamics simulations, as well as reverse Monte Carlo simulation, we determined the three-dimensional atomic positions of a series of binary MGs CuxZr100-x (x = 50, 56, 60, 64). Then we uncovered the connection of short-range clusters as well as the nature of the medium range order (MRO). It turns out that full icosahedral tend to connect to each other forming the back bones, with dimensions positively correlated with the Cu content. By quantifying the discontinuity of full icosahedral networks, we identified the MRO defects which were found to be highly influenced by the macroscopic chemical contents. Here, the density of MRO defects is growing with the decrease of Cu contents. These results suggest the reason for the stable kinetic properties and good glass forming ability of the Cu64Zr36 system, which is rich in full icosahedral clusters <0,0,12,0> but a lack of MRO defects. Full article

Electrochemical CO₂ reduction reactions can lead to high value-added chemical and materials production while helping decrease anthropogenic CO₂ emissions. Copper metal clusters can reduce CO₂ to more than thirty different hydrocarbons and oxygenates yet they lack the required selectivity. We present a computational characterization of the role of nano-structuring and alloying in Cu-based catalysts on the activity and selectivity of CO₂ reduction to generate the following one-carbon products: carbon monoxide (CO), formic acid (HCOOH), formaldehyde (H₂C=O), methanol (CH₃OH) and methane (CH₄). The structures and energetics were determined for the adsorption, activation, and conversion of CO₂ on monometallic and bimetallic (decorated and core@shell) 55-atom Cu-based clusters. The dopant metals considered were Ag, Cd, Pd, Pt, and Zn, located at different coordination sites. The relative binding strength of the intermediates were used to identify the optimal catalyst for the selective CO₂ conversion to one-carbon products. It was discovered that single atom Cd or Zn doping is optimal for the conversion of CO₂ to CO. The core@shell models with Ag, Pd and Pt provided higher selectivity for formic acid and formaldehyde. The Cu-Pt and Cu-Pd showed lowest overpotential for methane formation. Full article

Pre-plastic deformation (PPD) treatments on bulk metallic glasses (BMGs) have previously been shown to be helpful in producing multiple shear bands. In this work, the applicability of the PPD approach on BMGs with different Poisson’s ratios was validated based on experimental and simulation observations. It was found that for BMGs with high Poisson’s ratios (HBMGs, e.g., Zr₅₆Co₂₈Al₁₆ and Zr₄₆Cu₄₆Al₈), the PPD treatment can easily trigger a pair of large plastic deformation zones consisting of multiple shear bands. These PPD-treated HBMGs clearly display improved strength and compressive plasticity. On the other hand, the mechanical properties of BMGs with low Poisson’s ratios (LBMG, e.g., Fe₄₈Cr₁₅Mo₁₄Y₂C₁₅B₆) become worse due to a few shear bands and micro-cracks in extremely small plastic deformation zones. Additionally, for the PPD-treated HBMGs with similar high Poisson’s ratios, the Zr₅₆Co₂₈Al₁₆ BMG exhibits much larger plasticity than the Zr₄₆Cu₄₆Al₈ BMG. This phenomenon is mainly due to more defective icosahedral clusters in the Zr₅₆Co₂₈Al₁₆ BMG, which can serve as nucleation sites for shear transformation zones (STZs) during subsequent deformation. The present study may provide a basis for understanding the plastic deformation mechanism of BMGs. Full article

The atomic structure of medium-range order in metallic glasses is investigated by using molecular dynamics (MD) simulations. Glass formation processes were simulated by rapid cooling from liquid phases of a model binary alloy system of different-sized elements. Two types of short-range order of atomic clusters with the five-fold symmetry are found in glassy phases: icosahedral clusters (I-clusters) formed around the smaller-sized atoms and Frank–Kasper clusters (i.e., Z14, Z15, and Z16 clusters (Z-clusters)) formed around the bigger-sized atoms. Both types of clusters (I-and Z-clusters) are observed even in liquid phases and the population of them goes up as the temperature goes down. A considerable atomic size difference between alloying elements would enhance the formation of both the I- and Z-clusters. In glassy phases, the I- and Z-clusters are mutually connected to form a complicated network, and the network structure becomes denser as the structural relaxation goes on. In the network, the medium-range order is mainly constructed by the volume sharing type connection between I- and Z-clusters. Following Nelson’s disclination theory, the network structure can be understood as a random network of Z-clusters, which is complimentarily surrounded by another type of network formed by I-clusters. Full article

In this paper, experiments were carried out on (Zr_0.5Cu_0.4Al_0.1)_100-xNb_x (x = 0, 3, 6 at.%) amorphous alloys, and the corresponding ab initio molecular dynamics simulation was performed. The results showed that stable structures of Nb-centered and Al-centered icosahedral (-like) atomic clusters were formed after a small amount of (3 at.%) Nb was added. Stable and close-packed backbone structures were formed by the means of interconnection and matching of the two kinds of stable clusters in the alloys, which also enhanced the overall heterogeneity of the structures, thereby improving the strength and macroscopic plasticity. In addition, when more (6 at.%) Nb was added, the stable Al-centered clusters were replaced by some stable Nb-centered clusters in the alloys, and the stability and heterogeneity of the structures were partly reduced, which reduced the strength and macroscopic plasticity. Full article

Molecular dynamics simulations are performed to investigate the changes of packing structures, and thermodynamic quantities including internal energy, entropy, and free energy are used to determine temperature regime and transition time of atomic packing structures. The simulation results show different packing structures as the component composition changes, and there are different packing patterns during cooling. For these Cu-Ag alloy clusters containing only a small number of atoms of Cu, they present FCC packing structures in different parts at high temperatures, and then there are transformations to icosahedral structures. With the increase in content of Cu atoms, there is a transition mechanism from molten state to icosahedron. When the content of Cu atoms is appropriate, core-shell structures can be formed at room temperature. Full article

Complex metallic alloys (CMAs) are materials composed of structurally complex intermetallic phases (SCIPs). The SCIPs consist of large unit cells containing hundreds or even thousands of atoms. Well-defined atomic clusters are found in their structure, typically of icosahedral point group symmetry. In SCIPs, a long-range order is observed. Aluminum-based CMAs contain approximately 70 at.% Al. In this paper, the corrosion behavior of bulk Al-based CMAs is reviewed. The Al–TM alloys (TM = transition metal) have been sorted according to their chemical composition. The alloys tend to passivate because of high Al concentration. The Al–Cr alloys, for example, can form protective passive layers of considerable thickness in different electrolytes. In halide-containing solutions, however, the alloys are prone to pitting corrosion. The electrochemical activity of aluminum-transition metal SCIPs is primarily determined by electrode potential of the alloying element(s). Galvanic microcells form between different SCIPs which may further accelerate the localized corrosion attack. The electrochemical nobility of individual SCIPs increases with increasing concentration of noble elements. The SCIPs with electrochemically active elements tend to dissolve in contact with nobler particles. The SCIPs with noble metals are prone to selective de-alloying (de–aluminification) and their electrochemical activity may change over time as a result of de-alloying. The metal composition of the SCIPs has a primary influence on their corrosion properties. The structural complexity is secondary and becomes important when phases with similar chemical composition, but different crystal structure, come into close physical contact. Full article

In this work, using the first-principle density functional theory (DFT) method, we study the properties of a new material based on pillared graphene and the icosahedral clusters of boron B₁₂ as a supercapacitor electrode material. The new composite material demonstrates a high specific quantum capacitance, specific charge density, and a negative value of heat of formation, which indicates its efficiency. It is shown that the density of electronic states increases during the addition of clusters, which predictably leads to an increase in the electrode conductivity. We predict that the use of a composite based on pillared graphene and boron will increase the efficiency of existing supercapacitors. Full article

We explore the quantum capacitance, stability, and electronic properties of single-walled carbon nanotubes decorated with B12 icosahedral boron clusters by first-principle calculation methods implemented in the SIESTA code. After the optimization of the built supercells, the B12 clusters formed bonds with the walls of the carbon nanotubes and demonstrated metallic properties in all cases. The network of carbon nanotubes with its large area and branched surface is able to increase the capacity of the electric double-layer capacity, but the low quantum capacity of each nanotube in this network limits its application in supercapacitors. We found that the addition of boron clusters to both the outer and inner walls increased the quantum capacitance of carbon nanotubes. The calculation of the transmission function near the Fermi energy showed an increase in the conductivity of supercells. It was also found that an increase in the concentration of boron clusters in the structure led to a decrease in the heat of formation that positively affects the stability of supercells. The calculation of the specific charge density showed that with an increase in the boron concentration, the considered material demonstrated the properties of an asymmetric electrode. Full article