Density and Young׳s Modulus of ternary glasses close to the eutectic composition in the CaO–Al2O3–SiO2-system

The elastic properties and the density of ternary glass forming systems within the CaO–SiO₂–Al₂O₃-system (CAS) were evaluated. Different glass compositions near the lowest eutectic (1170 °C) composition within the CaO–Al₂O₃–SiO₂-system have been melted from pure raw materials. Their target compositions differed not more than 4 wt% for each component. Exact chemical compositions were measured by x-ray fluorescence. The density, and acoustic properties were determined and the Young׳s Moduli were derived herefrom. It was of special interest to obtain information on these properties and their dependencies upon small variations in the composition. The density values were between 2.600 and 2.667 g cm⁻³ and the packing density factors V_p of the oxides glasses using the ionic radii of Pauling were in the range from 0.559 to 0.571. The determined data were compared to different model calculations. Density model calculations show relative deviations between 2 and 6%. The values calculated from the model for Young׳s Modulus by Makishima and Mackenzie (1973) [1] were somewhat smaller than the measured ones. The correction by Rocherulle et al. (1989) [3] of the Makishima model showed better agreement with the measured values.     

Hydrogen storage in TiO2 functionalized (10, 10) single walled carbon nanotube (SWCNT) – First principles study

Hydrogen storage in titanium dioxide (TiO₂) functionalized (10, 10) armchair single walled carbon nanotube (SWCNT) is investigated through first principle calculations using density functional theory (DFT). This first principles study uses Vienna Ab-initio Simulation Package (VASP) with ultrasoft pseudopotentials and local density approximation (LDA). The necessary benchmark and other systematic calculations were carried out to project the hydrogen storage capability of the designed system. Interestingly, the TiO₂ molecules functionalized on the outer surface of SWCNT do not undergo any dimerization/clustering thus giving excellent stability and usable gravimetric hydrogen storage capacity of 5.7 wt.% and the value nearly fulfills the US DOE target (i.e. 6 wt.%). The band structure and density of states (DOS) plots suggest that the functionalization can lead a way to transform the nature (metallic → semiconducting) of the pristine SWCNT. The nominal values of H₂ storage capacity and binding energies give much hope for using CNT functionalized with TiO₂ as a practical and reversible hydrogen storage medium (HSM).     

A Puzzle of Quantum Phase Transition on Gd-IMC by Tuning of Conduction Electron Concentration

Based on the critical unstable of both crystal and magnetic structure of Gd-intermetallic compound near the competition of two strongly independent subsystem （＂local 4f7＂ and ＂conduction electron concentration＂）, a new QPT （quantum point transition） is predicted by calculation of： （1） The band structure and density of state by density functional theory where a strong narrowing fluidity of fermions around EF with shifted to negative value ＂-0.8 eV ＂is observable in the Gd-intermetalliccompound system while in the Y-case, it is not dominated. An antiferromagnetic state on the fluidity of conduction band can be investigated; （2） The internal magnetic field due to short range exchange interaction Jij between the nearest neighbor of local magnetic moment of stable s-state of Gd （L = 0） through the mean field approximation and of Eigenvalue-Eigenfunction ~.（k） are calculated. While a strong negative value of Jy is predicted, the eigenvalue L（k） of the system shows a strong antiferromagnetic phase in the reciprocal lattice direction 〈010〉, 〈001〉 in the correlation length 3.38 ~A. Although the antiferromagnetic state at Rc 〈_ 3.38 °A is a puzzle but it is completely dominated at Rc = 9 °A after passing through the competition between ）.λmin（O） and λmin（π） in the ranger of 3.2 °A 〈 Rc 〈 9 °A. Since both of the antiferromagnetic subsystems are sensitive to the predicted KF, the effect of decreasing of conduction electron is proposed to investigate, the change of the antiferromagnetic ordering state to the competition of ferromagnetic state （in direction 〈010〉） and antiferromagnetic state （in direction 〈001 〉 and 〈 100〉） resulted to paramagnetic state in the long range Rc = 9 °A.     

Study of the solubility of Pb,Bi and Sn in aluminum by mixed CALPHAD/DFT methods: Applicability to aluminum machining alloys

The aim of this work is a formulation of a thermodynamic model for the development of new aluminum machining alloys. The three additives Bi, Pb and Sn have proven to help machining. Hence, a review of the literature showed that the liquid phase equilibria and thermodynamic data for the three binary systems Al-Bi, Al-Pb and Al-Sn is very thorough but the limited information for the FCC solution required the use of Density Functional Theory (DFT) to predict thermodynamic data. The partial heat of mixing of these three machining additives in Al(FCC) are obtained and the results helped to improve the thermodynamic model using the CALPHAD method. It was shown that for all three binary systems, the thermodynamic data obtained at three fixed compositions and that obtained for a very dilute solution gave different enthalpy curves. The thermodynamic model was used to compute the ternary systems Al-Bi-Pb, Al-Bi-Sn and Al-Pb-Sn and small adjustable parameters were added to reproduce the literature data.     

Excess properties and spectroscopic studies for binary system polyethylene glycol 600 + dimethyl sulfoxide at T =(298.15, 303.15,308.15, 313.15, and 318.15) K

The work presents density (ρ) and viscosity (η) data of binary system polyethylene glycol 600 (PEG) + dimethyl sulfoxide (DMSO) over the entire concentration range at T =(298.15,303.15,308.15,313.15 and 318.15) K and atmospheric pressure.On the basis of density and viscosity values,the excess properties of PEG (1) + DMSO (2) mixtures,including excess molar volume (VEm),viscosity deviation (△η),excess free energies of activation (△G*E),and isobaric thermal expansion coefficient (αp),were calculated.At the same time,in order to conjecture the density viscosity under different conditions,the density and viscosity data were fitted with the corresponding formula.The calculated results of VEm,△η,and △G*E were fitted with the Redlich-Kister equation to derive coefficients and estimate the standard deviations (σ) between the experimental and calculated values.Moreover,the intermolecular interaction of PEG with DMSO was discussed on the basis of FTIR and UV-Vis spectral results of PEG (1) + DMSO (2) mixtures.The results indicated that there were the hydrogen bonding and interactions of hvdroxvl hydrogen atoms in PEG with oxygen atoms in DMSO.     

CO oxidation catalyzed by silicon carbide (SiC) monolayer: A theoretical study

Developing metal−free catalysts for CO oxidation has been a key scientific issue in solving the growing environmental problems caused by CO emission. In this work, the potential of the silicon carbide (SiC) monolayer as a metal−free catalyst for CO oxidation was systematically explored by means of density functional theory (DFT) computations. Our results revealed that CO oxidation reaction can easily proceed on SiC nanosheet, and a three-step mechanism was proposed: (1) the coadsorption of CO and O₂ molecules, followed by (2) the formation of the first CO₂ molecule, and (3) the recovery of catalyst by a second CO molecule. The last step is the rate−determining one of the whole catalytic reaction with the highest barrier of 0.65 eV. Remarkably, larger curvature is found to have a negative effect on the catalytic performance of SiC nanosheet for CO oxidation. Therefore, our results suggested that flat SiC monolayer is a promising metal-free catalyst for CO oxidation.     

Hydrogen evolution reaction on in-plane platinum and palladium dichalcogenides via single-atom doping

Searching for the catalysts with excellent catalytic activity and high chemical stability is the key to achieve large-scale production of hydrogen (H₂) through hydrogen evolution reaction (HER). Two-dimensional (2D) platinum and palladium dichalcogenides with extraordinary electrical properties have emerged as the potential candidate for HER catalysts. Here, chemical stability, HER electrocatalytic activity, and the origin of improved HER performance of Pt/Pd-based dichalcogenides with single-atom doping (B, C, N, P, Au, Ag, Cu, Co, Fe, Ni, Zn) and vacancies are explored by first-principles calculations. The calculated defect formation energy reveals that most defective structures are thermodynamically stable. Hydrogen evolution performance on basal plane is obviously improved by single-atoms doping and vacancies. Particularly, Zn-doped and Te vacancy PtTe₂ have a ΔG_H value close to zero. Moreover, defect engineering displays a different performance on HER catalytic activity in sulfur group elements, in order of S < Te < Se in Pd-based chalcogenides, and S < Se < Te in Pt-based chalcogenides. The origin of improved hydrogen evolution performance is revealed by electronic structure and charge transfer. Our findings of the highly activating defective systems provide a theoretical basis for HER applications of platinum and palladium dichalcogenides.     

Molar volume of eutectic solvents as a function of molar composition and temperature☆

The conventional Rackett model for predicting liquid molar volume has been modified to cater for the effect of molar composition of the Deep Eutectic Solvents (DES). The experimental molar volume data for a group of commonly used DES has been used for optimizing the improved model. The data involved different molar compositions of each DES. The validation of the new model was performed on another set of DESs. The average relative deviation of the model on the training and validation datasets was approximately 0.1%while the Rackett model gave a relative deviation of more than 1.6%. The modified model deals with variations in DES molar com-position and temperature in a more consistent way than the original Rackett model which exhibits monotonic performance degradation as temperature moves away from reference conditions. Having the composition of the DES as a model variable enhances the practical utilization of the predicting model in diverse design and process simulation applications.     

DFT study of the oxygen reduction reaction on iron,cobalt and manganese macrocycle active sites

The best performing non-precious metal based catalysts for polymer electrolyte membrane fuel cells are manufactured by incorporation of nitrogen into a carbon structure in the presence of iron and cobalt. Herein, density functional theory (DFT) calculations have been performed to investigate the oxygen reduction reaction on catalyst active sites modelled as transition metal macrocycles with iron, cobalt or manganese central atoms. The effects of the transition metal and macrocycle structure have been investigated. The structure of the most promising active sites has been proposed, and the detailed potential energy profiles of the oxygen reduction reaction have been obtained over the active sites, including all intermediate steps with corresponding activation barriers. The efficiency of the active sites depends primarily on the transition metal nature, and the central iron atom accounts for the higher catalytic activity than cobalt and manganese. The central manganese atom can favour the two-electron oxygen reduction pathway and thus yielding hydrogen peroxide.     

Partitioning road networks using density peak graphs: Efficiency vs. accuracy

Road traffic networks are rapidly growing in size with increasing complexities. To simplify their analysis in order to maintain smooth traffic, a large urban road network can be considered as a set of small sub-networks, which exhibit distinctive traffic flow patterns. In this paper, we propose a robust framework for spatial partitioning of large urban road networks based on traffic measures. For a given urban road network, we aim to identify the different sub-networks or partitions that exhibit homogeneous traffic patterns internally, but heterogeneous patterns to others externally. To this end, we develop a two-stage algorithm (referred as FaDSPa) within our framework. It first transforms the large road graph into a well-structured and condensed density peak graph (DPG) via density based clustering and link aggregation using traffic density and adjacency connectivity, respectively. Thereafter we apply our spectral theory based graph cut (referred as α-Cut) to partition the DPG and obtain the different sub-networks. Thus the framework applies the locally distributed computations of density based clustering to improve efficiency and the centralized global computations of spectral clustering to improve accuracy. We perform extensive experiments on real as well as synthetic datasets, and compare its performance with that of an existing road network partitioning method. Our results show that the proposed method outperforms the existing normalized cut based method for small road networks and provides impressive results for much larger networks, where other methods may face serious problems of time and space complexities.