Metalloid Atoms Research Articles

Prediction of the thermal-physical properties of amorphous nickel alloys Ni2B, Ni44Nb56, Ni62Nb38 according to component data

The replacement of traditional materials with amorphous alloys and the operation of products made from them are determined by the structural, temporal and temperature stability of disordered environments. In particular, the thermal stability of an amorphous alloy directly depends on its thermophysical characteristics. Therefore, the article demonstrates the applicability of the rule of mixing components and the use of their data on thermophysical properties in the crystalline state to evaluate similar characteristics of alloys from the metal – metalloid and transition metal – transition metal groups in the amorphous phase. It has been established that for the transition metal – transition metal group, the assessment of the heat capacity of amorphous nickel alloys gives a better approximation to the experimentally established values than for an alloy from the metal – metalloid group. The reasons for the discrepancy between the assessment and experimental data for an alloy from the metal – metalloid group are possibly the covalency of the atomic bonds in contrast to the metallic bond for alloys from the transition metal – transition metal group, the smaller size of the metalloid atoms, its greater mobility and the effect on the refinement of alloy grains. The possibility of an amorphous alloy inheriting some properties of one of the components is indicated, which requires experimental verification.

Metalloid-Organic Intermolecular Complexes with Charge State-Controlled Conformations.

Shape alterations of molecular systems, induced by their (electric) charging/discharging, could facilitate useful electronic and/or mechanical functions in molecular-scale devices and machines. The present study reports structures, stabilities, charge distributions, and IR spectra for a group of complexes of a main-group metalloid (boron) atom with hydrocarbon molecules. The considered systems include the smallest species demonstrating the basic principle of operation, as well as their size-extended analogues, generalizing it to larger counterparts based on such units. The system geometries vary considerably between neutral and ionic counterparts and exhibit two-three typical conformations related to twisting by up to about 90 degrees. The predicted structures correlate with specific infrared spectra, which can enable their experimental identification and transformation tracking. The above-mentioned characteristics suggest the potential utility of such systems for intermolecular switches, with the possible spectral monitoring of their functioning.

Tetrahexahedral binary transition metal compound sub-nanoclusters

We explore new transition metal (TM) compound sub-nanoclusters, TM8X6 (TM = Mn, Fe, Co and X = P, B, As), using density functional theory. Their optimized geometric structures show the same polyhedral structure (tetrahexahedron) independent of a kind of TM and metalloid (X), where eight TM atoms form a cubic structure capped with six metalloid (X) atoms. Incorporating an extra TM atom into the TM cubic results in an endohedral structure, TM9X6. Encapsulation of an additional TM atom merely changes the binding energy except for the Co boride cluster. The binding energy of Co8B6 increases by incorporating an additional Co atom, in which it is observed that the electron density is accumulated between B and all Co atoms (Co atoms both at the center and at the edges), but in other clusters, the electron excess is found mainly between TM atoms. The MnnP6 (n = 8 and 9) clusters have a high adiabatic electron affinity (>6 eV) due to the relatively large difference in electronegativity between Mn and P. The highest occupied molecular orbital and lowest unoccupied molecular orbital gaps of all clusters lie in the visible range. The interaction between nanoclusters and graphene with a single vacancy is studied as a function of the different cluster landing site on the graphene, where the geometric structure change of the clusters strongly depends on the adsorption site.

Nature of anomalous electrical resistance in Co73-xFe4CrxSi12B11 amorphous microwires

Influence of structural relaxation and composition of microwires of metallic amorphous alloys Co73-xFe4CrxSi12B11 (x = 0, 2, 4, 6, 8) on the character and mechanisms of temperature dependence of electrical resistance r(T) has been studied in a wide temperature range (from 4.2 K to crystallization temperature). It is shown that alloys with more than 2 at.% Cr have a number of specific properties, which are significantly differentiate them from Fe- and Ni-rich alloys, as well as many Co-rich amorphous alloys. The features of Cr-doped Co-rich alloys are explained by two reasons: firstly, very strong quantum interference effects of the electron-electron interaction and weak localization of electrons caused by scattering of electrons by the potential created by randomly distributed chromium atoms, and secondly, partially reversible compositional structural relaxation leading to clustering of the amorphous phase at T > 300 °C. It is assumed that the resulting Cr-rich clusters, in which chromium atoms are bonded to metalloid atoms, can enhance these interference effects. The contributions from various mechanisms of interaction and scattering of electrons to the change in electrical resistance with temperature and composition of the alloy are analyzed. The fitting parameters for them are determined and compared with the known data.

Effect of Si and B on the Electrochemical Behavior of FeCoNiCr-Based High-Entropy Amorphous Alloys

The ability to produce high-entropy alloys with an amorphous structure, so-called high-entropy metallic glasses (HEMGs), offers the possibility to produce new compositions with good mechanical properties and resistance to corrosion. In this study, corrosion behavior was studied in two HEMGs, FeCoNiCrB and FeCoNiCr(BSi). In both cases, the total amount of metalloid atoms was kept constant at 20 at.%. The electrochemical behavior of these alloys was studied by means of linear polarization resistance (LPR) measurements and electrochemical impedance spectroscopy in a 3 wt.% NaCl solution. The effect of corrosion was characterized by using X-ray photoelectron spectroscopy (XPS) and the surface morphology was checked using a scanning electron microscope (SEM). The results show that samples with B but without Si exhibit better corrosion resistance due to its chemical homogeneity and lack of structural heterogeneity.

Impact of F and S doping on (Mn,Fe)2(P,Si) giant magnetocaloric materials

The quarternary (Mn,Fe)2(P,Si)-based materials with a giant magnetocaloric effect (GMCE) at the ferromagnetic transition TC are promising bulk materials for solid-state magnetic refrigeration. In the present study we demonstrate that doping with the light elements fluorine and sulfur can be used to adjust TC near room temperature and tune the magnetocaloric properties. For F doping the first-order magnetic transition (FOMT) of Mn0.60Fe1.30P0.64Si0.36Fx (x = 0.00, 0.01, 0.02, 0.03) is enhanced, which is explained by an enhanced magnetoelastic coupling. The magnetic entropy change |ΔSm| at a field change (Δμ0H) of 2 T markedly improved by 30% from 14.2 Jkg−1K−1 (x = 0.00) at 335 K to 20.2 Jkg−1K−1 (x = 0.03) at 297 K. For the F doped material the value of |ΔSm| for Δμ0H = 1 T reaches 11.6 Jkg−1K−1 at 294 K, which is consistent with the calorimetric data (12.4 Jkg−1K−1). Neutron diffraction experiments reveal enhanced magnetic moments by F doping in agreement with the prediction of DFT calculation. For S doping in Mn0.60Fe1.25P0.66-ySi0.34Sy (y = 0.00, 0.01, 0.02, 0.03, 0.04) three impurity phases have been found from microstructural analysis, which reduce the stability of the FOMT in the main phase and decrease TC, e.g. the |ΔSm| reduces from 7.9(12.6) Jkg-1K-1 (332 K) for the undoped sample to 3.4(6.2) Jkg-1K-1 (313 K) for the maximum doped sample for Δμ0H = 1(2) T. Neutron diffraction experiments combined with first-principles theoretical calculation, distinguish the occupation of F/S dopants and the tuning mechanism for light element doping, corresponding to subtle structural changes and a strengthening of the covalent bonding between metal and metalloid atoms. It is found that the light elements F and S can effectively regulate the magnetocaloric properties and provide fundamental understanding of (Mn,Fe)2(P,Si)-based intermetallic compounds.

Chemical affinity can govern notch-tip brittle-to-ductile transition in metallic glasses

Chemical short-range order (CSRO) has emerged as an important index of material properties for multicomponent metallic alloys and glasses, but its role in transition between brittle and ductile fracture mechanisms is not understood. Here, using molecular dynamics simulations of fracture in notched samples of a nominally brittle metallic glass Fe80P20, we show that the fracture mode can be altered from crack propagation to shear banding by tuning​ CSRO. The underlying mechanism is identified as the agglomeration of metalloid (P) atoms as heterogeneous brittle zones with the formation of CSRO, leading to brittle fracture. By reducing the extent of CSRO, shear banding at the notch tip becomes the dominant failure mechanism.

Influence of tantalum concentrations on the magnetic properties of amorphous CoFeTaB thin-films

The structural and magnetic properties of amorphous CoFeTaB thin-films were studied as a function of tantalum concentration. The investigations of the structural properties of amorphous CoFeTaB thin-films were undertaken to confirm layer thickness, interface roughness, and their amorphous structure. Temperature dependent magnetic characterizations were performed in order to extract Curie temperatures and their saturation magnetizations of each structure. Curie temperatures and saturation magnetizations of amorphous CoFeTaB thin-films show similar behaviour, where both quantities decrease with increasing tantalum concentration in thin-film structures. These reductions can be attributed to a result of a transfer of electrons from the metalloid atoms to the unfilled d holes of the 3d transition metals, and diffusion of tantalum atoms towards the ferromagnetic layer during thin-film deposition. Investigation of tuning both Curie temperature and magnetization by the addition of a non-magnetic transition metal is crucial for the development of spintronic applications.

On the presence of covalently bound phosphorus in amorphous Ni–Co–P and Fe–Co–P electroplates

It is shown (based on XRD patterns) that coatings electrodeposited from solutions containing cations of iron metal group [Ni(II) + Co(II) or Fe(II) + Co(II)] and hypophosphite anions are characterized by amorphous (or nanocrystalline) structure. EDX data testify that the obtained metal coatings contain substantial amounts of phosphorus. To identify the chemical state of phosphorus in these coatings, valence-to-core (vtc) X-ray emission spectroscopy (XES) method is used that allows to separate a presence in the prepared samples of elemental metal atoms and metal atoms covalently bound with metalloid atoms (P atoms in our case). Joint quantitative analysis of vtc XES and EDX data allows us to conclude that all phosphorus in the electrodeposited Ni–Co–P and Fe–Co–P coatings is covalently bound with metal atoms (as phosphide) and no elemental (or “free”) phosphorus is present in these coatings.

Structural, electronic and optical properties of metalloid element (B, Si, Ge, As, Sb, and Te) doped g-ZnO monolayer: A DFT study

Stable geometries, electronic structure, and optical properties of ZnO monolayer doped with metalloid element (M = B, Si, Ge, As, Sb, and Te) atom have been studied using density functional theory. It is found that among these elements Ge, As, and Sb can be effectively doped at Zn site in the ZnO monolayer with the formation energies ranging from −1.02 to −0.96 eV. Except B element, all the metalloid atoms prefer to protrude out of the plane of the ZnO monolayer. The nonmagnetic nature of the ZnO monolayer is retained with the doping of B, Si, Ge, As, and Sb atom, while Te atom induces the magnetism in ZnO monolayer (2 μB). While doping of Si, As, Sb, and Te in ZnO monolayer resulted in a red shift in the absorption spectra of doped ZnO monolayer and the blue shift is observed for B and Ge doped ZnO. The static dielectric constant for ZnO monolayer is 1.49. With the doping of these metalloid elements in ZnO monolayer, the dielectric constant can be tuned from 1.36 to 2.84. These results are potentially useful for optoelectronic applications and the development of optical nanostructures.

DFT study on tailoring the structural, electronic and optical properties of bilayer graphene through metalloids intercalation

Current study investigates the opto-electronic trends of bilayer graphene (BLG), functionalized through metalloid atoms adopting first-principles DFT approach. Intercalation of single/double metalloid atoms in BLG having single/di vacancy of C atoms was carried out and their effects on opto-electronic behaviors were determined. Results indicate that, metalloids incorporation in BLG causes disruption in aromatic rings of graphene, thereby breaking the high symmetric K-point in its electronic structure. Intercalation of metalloids in BLG also creates secondary Dirac points in its electronic structure. In addition, few metalloids induce a finite band gap at the high symmetric K-point. Absorption and reflectivity parameters of metalloids intercalated BLG systems were also calculated. The absorption coefficient quantity was improved in the visible region after metalloids incorporation in BLG. The static reflectivity parameter of metalloids intercalated BLG gains higher values in comparison to its pristine counterpart.

Combined QTAIM and ETS-NOCV investigation of the interactions in ClnM[PhB(NtBu)2] complexes with M = Si & Ge (n = 0), As & Sb (n = 1), Te & Po (n = 2).

In this work, the nature of the chemical interactions between the metalloid atom (M=Si, Ge, As, Sb, Te, Po) and the nitrogen atoms in the bora-amidinate (bam) complexes (ClnM[PhB(NtBu)2]) are investigated, mainly via density-based indices. The descriptors used are derived using the quantum theory of atoms in molecules and natural orbitals for chemical valence approaches. It is shown that the strongest interaction is achieved with silicon. Indeed, it is generally the lightest metalloid in a particular group of the periodic table (i.e., Si, As, and Te for groups 14-16, respectively) that exhibits the strongest bond in the bam complex. This suggests that the atomic radius of the metalloid is a useful parameter for predicting the bonding strength. Extended transition state (ETS) decomposition results indicate that the interactions are more electrostatic than due to orbital interactions.

First-principle study of interfacial properties between γ-TiAl and TiC, VN

ABSTRACTThe adhesion, wettability, atomic bonding and electronic structure of γ-TiAl(110)/TiC(100) and γ-TiAl(110)/VN(100) interfaces were performed and investigated using first-principle calculations. Surface energy of γ-TiAl, TiC and VN with low crystal indices was calculated and compared, respectively. The three Al-terminated γ-TiAl(110)/ceramic(100) interface models were investigated to illustrate the interfacial bonding nature. The structure of Al atom placed on the top of the metalloid C and N atoms at the interface is the preferred interfacial structure with the larger work of adhesion. The electronic structure results show that the structure with metalloid site exists with the stronger polar covalent bonding between the interfacial Al and metalloid atom. The interfacial structure with metal site exhibits a mixture of the metallic features with some degree of covalent features. The simulation results are in agreement with the experimental results, in which the γ-TiAl/TiC interface exhibits the better wettability and stronger bonding than the γ-TiAl/VN interface.

The adhesion, stability, and electronic structure of γ-TiAl/VN interface: a first-principle study

The adhesion, stability, atomic bonding and electronic structure of γ-TiAl (110)/VN (100) interface were studied by first-principle calculation. Five interface structures with different atom stacking sequences (top- and bridge-) were considered to examine the bonding nature. Results indicated that the preferred interfacial structure is that Al atom locates above the ceramic’s metalloid atom, which has the largest ideal work of adhesion and the smallest interfacial energy. The top-site interface, where Al atom locates above the ceramic’s metalloid atom, is characterized by a strong Al–N polar covalent bond, whereas the other top-side interface with Al atom above the metal atom exhibits an Al–V and V–Ti metal bond characteristics. The hybridization between Al-sp and N-sp orbitals is the main interaction that strengthens the interfacial adhesion.

Structural, magnetic, and electronic properties of Fe82Si4B10P4 metallic glass

The structural, magnetic, and electronic properties of Fe82Si4B10P4 metallic glass were systemically investigated by theoretical simulations. Strong atomic interaction between Fe and metalloid atoms can be observed, while the direct metalloid-metalloid atomic bonds are rare due to the solute-solute avoidance effect. The calculated value of saturation magnetic flux density (BS) is ~1.65 T, approaching to experimental result, which is contributed by not only the electron exchange between Fe and metalloid atoms, but also the p-d orbital hybridization of Fe atoms. Moreover, Fe atoms with neighboring P atom behaving larger magnetic moments reveals the important role of P element for promoting the BS value. The potential correlation between magnetic behaviors and the local atomic packing in this study sheds some light on the structural origin of the soft magnetic properties and, thereby the theoretical guidance for the development of new soft-magnetic metallic glasses.

Atomic structures and electronic properties of interfaces between aluminum and carbides/nitrides: A first-principles study

We perform a first-principles investigation of the atomic structures and electronic properties of interfaces between aluminum and four kinds of ceramics, TiC, TiN, VC and VN, under three orientations (001), (110) and (111). We find that the stable interfaces are those with bonding between Al atom and metalloid C (or N) atom, which is attributed to the overlap of p states of Al and d states of metalloid atoms at Femi level forming covalent components. Among the interfaces with the three orientations, the (111) interfaces are found to possess the largest adhesion energy in that the stacking of atoms follows intrinsic atomic distribution and this interfacial bonding is relatively strong. It is also found that the interfaces between Al and metal carbides (TiC and VC) are more stable than those between Al and metal nitrides (TiN and VN).

First principles study of mechanical properties of FeMnP1-xTx (T=Si, Ga, Ge) compounds

Magnetic refrigeration technology is considered as a better alternative to traditional steam compression scheme, since it has many advantages such as environment friendly characteristic, more compact solid refrigerant, low cost, etc. The mechanical stability is of essential importance for serving as magnetic refrigerant materials which work under repeatedly thermal and magnetic cycles. Recent experiment reveals that the polycrystalline FeMnP1-xSix compounds are brittle, and even fracture of samples during post heat treatment is observed. Therefore, the improvement of the ductility of Fe2P-Type FeMn-based magnetocaloric materials becomes an important issue in practical application. So far, there are few studies of the mechanical properties of these compounds. Alloying is an effective method to improve the mechanical properties of single phase materials, and Ga or Ge could be a better choice to replace the Si element. In this paper, we study the mechanical properties of giant magnetocaloric FeMnP1-xTx (T=Si, Ga, Ge) compounds by the projector augmented wave method as implemented in VASP (Vienna ab initio simulation package) in the framework of density functional theory. It is found that the lattice parameter, total energy, magnetic moment, elastic constant and the electronic structure of FeMnP1-xGax compounds are similar to those of FeMnP1-xGex compounds, therefore, it is believed that the FeMnP1-xGax compounds are candidate refrigerant for room temperature magnetic refrigeration. The relatively large single crystalline elastic constants of FeMnP1-xTx (T=Si, Ga, Ge) compounds show that this family of compounds is mechanically stable. This ensures the long-term applicability of FeMnP1-xTx compounds in magnetic refrigeration facilities. For polycrystalline compounds, we calculate their shear moduli and bulk moduli by Hill averaging scheme. And according to Pugh criterion, the ductility or brittleness characteristics of FeMnP1-xTx (T=Si, Ga, Ge) compounds are discussed. All the FeMnP0.67T0.33 (T=Si, Ga, Ge) compounds are ductile, among them, FeMnP0.67Ga0.33 compound shows the best ductility, whereas the ductility of FeMnP0.67Si0.33 compound is the weakest. This result proves that substituting P with Ga could improve the ductility of this class of compound. The mechanical properties of polycrystalline FeMnP0.33T0.67 compounds are close to the ductile/brittle critical point. For FeMnP0.33T0.67 compounds, the T atoms just occupy the 2c sites of metalloid atom in Fe2P-type structure, therefore it is expected that the occupation disorders of P and T atoms at high T concentration could improve the ductility of the compounds according to the result of FeMnP0.67Ga0.33 compound. Finally, the self-consistent elastic constants of different compounds are understood from the calculated electronic density of states and force theorem.

Theoretical study of lithium ionic conductors by electronic stress tensor density and electronic kinetic energy density.

We analyze the electronic structure of lithium ionic conductors, Li3PO4 and Li3PS4, using the electronic stress tensor density and kinetic energy density with special focus on the ionic bonds among them. We find that, as long as we examine the pattern of the eigenvalues of the electronic stress tensor density, we cannot distinguish between the ionic bonds and bonds among metalloid atoms. We then show that they can be distinguished by looking at the morphology of the electronic interface, the zero surface of the electronic kinetic energy density. © 2016 Wiley Periodicals, Inc.

Spin-exchange interaction between transition metals and metalloids in soft-ferromagnetic metallic glasses

High-performance magnetic materials have immense industrial and scientific importance in wide-ranging electronic, electromechanical, and medical device technologies. Metallic glasses with a fully amorphous structure are particularly suited for advanced soft-magnetic applications. However, fundamental scientific understanding is lacking for the spin-exchange interaction between metal and metalloid atoms, which typically constitute a metallic glass. Using an integrated experimental and molecular dynamics approach, we demonstrate the mechanism of electron interaction between transition metals and metalloids. Spin-exchange interactions were investigated for a Fe–Co metallic glass system of composition [(Co1−xFex)0.75B0.2Si0.05]96Cr4. The saturation magnetization increased with higher Fe concentration, but the trend significantly deviated from simple rule of mixtures. Ab initio molecular dynamics simulation was used to identify the ferromagnetic/anti-ferromagnetic interaction between the transition metals and metalloids. The overlapping band-structure and density of states represent ‘Stoner type’ magnetization for the amorphous alloys in contrast to ‘Heisenberg type’ in crystalline iron. The enhancement of magnetization by increasing iron was attributed to the interaction between Fe 3d and B 2p bands, which was further validated by valence-band study.

Electronic and magnetic properties of phosphorus across the first-order ferromagnetic transition of(Mn,Fe)2(P,Si,B)giant magnetocaloric materials

To study the evolution of the electronic states and magnetism of the metallic and metalloid atoms across the first-order ferromagnetic transition of (Mn,${\mathrm{Fe})}_{2}$(P,Si,B) compounds, x-ray absorption (XAS) and magnetic circular dichroism (XMCD) spectra were recorded at the $K$ edges of P, Mn, and Fe. Surprisingly, while the Fe and Mn XAS spectra do not show pronounced changes, the $K$-edge XAS of P is strongly modified across the ferromagnetic transition and is a fingerprint of electronic structure changes at the phase transition. The evolution of the $3p$ electronic states of phosphorus is linked to changes in metal-metalloid bonding. The amplitude of this effect is correlated to the discontinuity in interatomic distances at the transition and progressively disappears with boron substitution. Moreover, it is found that the P atoms carry a finite magnetic moment in the ferromagnetic state in accordance with the results of band-structure calculations.