Effects of stoichiometric ratio La/Mg on structures and electrochemical performances of as-cast and annealed La-Mg-Ni-based A_2B_7-type electrode alloys

In order to investigate the influences of the stoichiometric ratio of La/Mg （increasing La and decreasing Mg on the same mole ratio） on the structure and electrochemical performances of the La-Mg-Ni-based A2B7-type electrode alloy, the as-cast and the annealed ternary Lao.8＋xMgo.2_xNi3.5 （x=0-0.05） electrode alloys were prepared. The characterization of electrode alloys by X-ray diffraction （XRD） and scanning electron microscopy （SEM） shows that all the as-cast and the annealed alloys hold two major phases of （La,Mg）2Ni7 and LaNi5 as well as a residual phase of LaNi3. Moreover, the increase of La/Mg ratio brings on a decline of （La,Mg）2Ni7 phase and a rise of LaNi5 and LaNi3 phases. The variation of La/Mg ratio gives rise to an evident change of the electrochemical performances of the alloys. The discharge capacities of the as-cast and the annealed alloys evidently decrease with growing the La/Mg ratio, while the cycle stabilities of the alloys visibly augment under the same condition. Furthermore, the high rate discharge ability （HRD）, the electrochemical impedance spectrum （EIS）, the Tafel polarization curves, and the potential step measurements all indicate that the electrochemical kinetic properties of the alloy electrodes increase with the La/Mg ratio rising.

Chemical kinetic studies on interfacial reaction in SCS-6 SiC/Ti matrix composites

Interfacial reaction and its mechanism of SiC/Ti composite were revealed by chemical kinetic studies. A two-step dynamic model of interfacial reaction in SCS-6 SiC/Ti composites was built up, and the rate constant and the activation energy of the interfacial reactions were obtained based on the quantum chemistry calculation. The results show that the first step, in which the atomic Ti, C and Si are decomposed from Ti matrix and SiC fiber, respectively, is a rate-determined step because the activation energy of the step is much larger than that of the second one in which deferent interfacial reaction products form. The theoretically predicted result of the interfacial reaction is coincident with that of experimental observation.

Velocity of a Liquid Drop with a Sorption-Controlled Surfactant

The terminal velocity of a liquid droplet settling in a sulfactant solution has been studied for the non-linear adsorption Langmuir frameworks accounting for monolayer saturation and non-ideal surfactant interactions. Most prior research uses a linear adsorption model which cannot capture these effects, The Maragoni migration of a liquid drop settling through a surfactant solution is examined by using Langmuir framework. The solution concentration Ceq is assumed large enough for the surfactant mass transfer to be adsorption-controlled. Langmuir model generates non-linear Marangoni stresses which diverge in the limit of approaching ∝, strongly retarding U'.

Correlation of Cooperatively Localized Rearrangement on the ＂Fluidized Domain＂ of Polymers to Their Nonexponentially Viscoelastic Behaviors at Double Aging Processes （I）： A Set of Reduced Universal Equations on the Stress Relaxation Modulus and Creep Comp

Based on the structure of glass （or liquid） polymers consisting of α-domain, β-co-domain, and entanglement constituent chain networks, and the nonexponentially viscoelastic behavior, a “heterophase fluctuation” model was proposed. It was found that the dynamics of cooperative rearrangement on the “fluidized domain” has a great shear rate, domain size, and temperature dependences. When the shear rate, domain size, and temperature dependences were taken account into the cooperatively localized rearrangement on the fluidized domain by the degradation of primary α-domain and the reformation of secondary β-co-domain constituent chains. A new dynamic theory of cooperatively localized rearrangement on the fluidized domain constituent chains with different size and different network chain length during physical and mechanical aging was established. The total viscoelastic free en-ergy of deformation resulting from the change in conformations of α-domain, β-co-domain, crytallite, crosslinked, and trapped entanglement constituent chains during aging processes was calculated by the combining method of kinetics and statistical mechanics. The constitu- tive equations and reduced stress relaxation modulus and creep compliances for three types of polymers were also derived. Finally, two reduced universal equations on creep compliance and stress relaxation modulus with a non-linear and two nonexponential parameters α and β were theoretically derived from the dynamic theory and a statistically extended mode coupling theory for double aging effects of polymers was developed. Results show that the two reduced universal equations have the same form as Kohlraush-Williams-Watts （K-W-W） stretched exponential function. The nonlinearity and the nonexponentiality are, respectively, originated from the memory effects of nonthermal and thermal history. The correlation of nonlinearity, α and β to the aging time, aging temperature, and the mesomorphic structure of fluidized domains was also established.

Kinetics and Mechanism of Decomposition of Nano-sized Calcium Carbonate under Non-isothermal Condition

Experiments on thermal decomposition of nano-sized calcium carbonate were carried out in a thermo-gravimetric analyzer under non-isothermal condition of different heating rates (5 to 20K·min-1). The Coats and Redfern's equation was used to determine the apparent activation energy and the pre-exponential factors. The mechanism of thermal decomposition was evaluated using the master plots, Coats and Redfern's equation and the kinetic compensation law. It was found that the thermal decomposition property of nano-sized calcium carbonate was different from that of bulk calcite. Nano-sized calcium carbonate began to decompose at 640℃, which was 180℃lower than the reported value for calcite. The experimental results of kinetics were compatible with the mechanism of one-dimensional phase boundary movement. The apparent activation energy of nano-sized calcium carbonate was estimated to be 151kJ·mol-1 while the literature value for normal calcite was approximately 200kJ·mol-1. The order of magnitude of pre-exponential factors was estimated to be 10~9 s-1.

Kinetic mechanism of magnesium production by silicothermic reduction of CaO·MgO in vacuum

The investigation of silicothermic reduction of CaO·MgO was carried out using a self-developed thermogravimetric analysis(TGA)instrument under vacuum and high temperature conditions.The TG data of pellets prepared with calcined dolomite,ferrosilicon and fluorite were determined at the heating rates of 1.5,2.0,2.5 and 3.0℃/min in 5 Pa vacuum at 300−1400℃,respectively.Model-free analysis and model-based analysis were applied for simulating the kinetic mechanism.By analyzing the characteristics of the initial and final reaction temperatures of TG curve,ratio of half-width of derivative TG curve and kinetic parameters,a conclusion was made that the most probable mechanism function is the first order formal chemical reaction with activation energy of 233.42 kJ/mol and pre-exponential factor of 5.14×1010 s−1.This study provides the basic data of dynamics of silicothermic magnesium production under vacuum conditions.

Differential Cross Sections and Collision-Induced Rotational Alignment in Inelastic Scattering of NO(X)by Xe

Fully A-doublet resolved differential cross sections and collision-induced rotational alignment moments have been measured for the NO(X)-Xe collision system at a collision energy of 519 cm^-1.The experiments combine initial quantum state selection,employing a hexapole inhomogeneous electric field,with quantum state resolved detection,using(1+1')resonantly enhanced multiphoton ionization and velocity map ion imaging.The differential cross sections and polarization dependent differential cross sections are shown to agree well with quantum mechanical scattering calculations performed on ab initio potential energy surfaces[J.Klos et al.J.Chem.Phys.137,014312(2012)].By comparison with quasi-classical trajectory calculations,quantum mechanical scattering calculations on a hard-shell potential,and kinematic apse model calculations,the effects of the attractive part of the potential on the measured differential cross sections and collision-induced rotational alignment moments are assessed.

Susceptibilities of QCD Vacuum from Renormalized Dyson-Schwinger Equations]

The pion and tensor vacuum susceptibilities are calculated in the framework of the renormalizable DysonSchwinger equations. A comparison with the results of other nonperturbative QCD approaches is given.

High-P/T experimental studies and water in the silicate mantle

Water(or H) in the silicate mantle is a key element in influencing Earth's climate, habitability, geochemical evolution, geophysical properties and geodynamical processes, and has received increasing attention in the past decades. Experimental work under simulated high-pressure and high-temperature conditions is a powerful tool in characterizing the species, distribution, storage capacity and various physicochemical impacts of water in the mantle. In recent years, significant approaches have been acquired about some key physical, chemical and dynamical properties of water in the mantle and their various impacts, as a result of extensive studies by high-pressure and temperature experiments, and our knowledge of Earth's water cycle, especially the deep water cycle, on both temporal and spatial scales has been greatly enhanced. In this paper, a brief review based mainly on experimental studies is presented concerning the current understanding and some recent approaches of water in the silicate mantle, such as the possible origin, amount, storage and the effect on mantle properties.

Equations of state for aqueous solutions under mantle conditions

With unique physical and chemical properties, aqueous solutions in the mantle may play important roles for a number of geochemical and geodynamical processes. However, since experimental data available are very limited, people still know little about the aqueous solutions and their interactions with surrounding rocks and melts. From the perspective of thermodynamics, equation of state(EOS) is the key to push forward the modeling of aqueous solutions. Nevertheless, up to now accurate EOSs suitable for the mantle conditions are still in shortage. With discussions over several recognized EOSs, we summarize several ways to enhance the predictability of EOS: utilizing high quality data from molecular simulations, choosing functions with sound physical background, and improving the regression procedures for the empirical parameters. In the meantime, we find that the ion-bearing systems are still the focus of challenges in this area. New developments of experiments and computer simulations effectively deal with these challenges and in-depth understandings of aqueous solutions in the mantle are expected in the near future.

Adsorption behavior of uranium on polyvinyl alcohol-g-amidoxime:Physicochemical properties, kinetic and thermodynamic aspects

Amidoxime-based adsorbents are widely studied as the main adsorbent in the recovery of uranium from seawater. However, the adsorption rate and loading capacity of such adsorbents should be further improved due to the economic viability consider- ation. In this paper, polyvinyl alcohol functionalized with amidoxime （PVA-g-AO） has been prepared as a new adsorbent for uranium （VI） adsorption from aqueous solution. The physicochemical properties of PVA-g-AO were investigated using infra- red spectroscopy （IR）, scanning electron microscope （SEM）, X-ray diffraction （XRD）, and X-ray photoelectron spectroscopy （XPS）. Results showed that the ligand monomers were successfully grafted onto the matrixes. The XRD and XPS analysis showed that uranium was adsorbed in metal ionic form rather than in crystal form. Uranyl （U （VI）） adsorption properties onto PVA-g-AO were evaluated. The adsorption of U （VI） by PVA-g-AO was fast, with an equilibrium time of less than 50 rnin. Additionally the maximum adsorption capacity reached 42.84 mg/g at pH 4.0.

Modeling an Evolving Complex Supply Network

Building a good supply network has a competitive advantage in every part of business. However, people rarely know the principles from which supply chain with complex organizational structure and function arise and develop. In this paper, we develop an evolving supply network model by using complex network theory. We mainly consider three kinds of firms＇ behaviors： entering of new firms, adding new relationships and rewiring of relationships among firms. By analyzing the statistical characteristics of the evolutionary dynamics of supply network, we find that the degree distribution follows a power-law distribution. Therefore, a supply network is a scale-free network where few but significant firms have lots of connections （called ＂hub＂ or core firm）, while most firms have few connections. These results are consistent with the results in empirical researches, which will be very useful for designing a robust and effective supply network.

Pseudocapacitive sodium storage of Fe1-xS@N-doped carbon for low-temperature operation

Constructing potential anodes for sodium-ion batteries(SIBs)with a wide temperature property has captured enormous interests in recent years.Fe1-xS,a zero-band gap material confirmed by density states calculation,is an ideal electrode for fast energy storage on account of its low cost and high theoretical capacity.Herein,Fe1-xS nanosheet wrapped by nitrogen-doped carbon(Fe1-xS@NC)is engineered through a post-sulfidation strategy using Fe-based metal-organic framework(Fe-MOF)as the precursor.The obtained Fe1-xS@NC agaric-like structure can well shorten the charge diffusion pathway,and significantly enhance the ionic/electronic conductivities and the reaction kinetics.As expected,the Fe1-xS@NC electrode,as a prospective SIB anode,delivers a desirable capacity up to 510.2 mA h g^-1 at a high rate of8000 mA g^-1.Additionally,even operated at low temperatures of 0 and-25°C,high reversible capacities of 387.1 and 223.4 mA h g^-1 can still be obtained at 2000 mA g^-1,respectively,indicating its huge potential use at harsh temperatures.More noticeably,the full battery made by the Fe1-xS@NC anode and Na3 V2(PO4)2 O2 F cathode achieves a remarkable rate capacity(186.8 mA h g^-1 at 2000 m A g^-1)and an impressive cycle performance(183.6 m A h g^-1 after 100 cycles at700 mA g^-1)between 0.3 and 3.8 V.Such excellent electrochemical performance is mainly contributed by its pseudocapacitive-dominated behavior,which brings fast electrode kinetics and robust structural stability to the whole electrode.

Numerical simulation of turbulent combustion: Scientific challenges

Predictive simulation of engine combustion is key to understanding the underlying complicated physicochemical processes,improving engine performance,and reducing pollutant emissions.Critical issues as turbulence modeling,turbulence-chemistry interaction,and accommodation of detailed chemical kinetics in complex flows remain challenging and essential for highfidelity combustion simulation.This paper reviews the current status of the state-of-the-art large eddy simulation(LES)/probability density function(PDF)/detailed chemistry approach that can address the three challenging modelling issues.PDF as a subgrid model for LES is formulated and the hybrid mesh-particle method for LES/PDF simulations is described.Then the development need in micro-mixing models for the PDF simulations of turbulent premixed combustion is identified.Finally the different acceleration methods for detailed chemistry are reviewed and a combined strategy is proposed for further development.

Hydrogen bonding mediated ion pairs of some aprotic ionic liquids and their structural transition in aqueous solution

Ion pair speciation of ionic liquids(ILs) has an important effect on the physical and chemical properties of ILs and recognition of the structure of ion pairs in solution is essential. It has been reported that ion pairs of some ILs can be formed by hydrogen bonding interactions between cations and anions of them. Considering the fact that far-IR(FIR) spectroscopy is a powerful tool in indicating the intermolecular and intramolecular hydrogen bonding, in this work, this spectroscopic technique has been combined with molecular dynamic(MD) simulation and nuclear magnetic resonance hydrogen spectroscopy(~1H NMR) to investigate ion pairs of aprotic ILs [Bmim][NO_3], [BuPy][NO_3], [Pyr_(14)][NO_3], [PP_(14)][NO_3] and [Bu-choline][NO_3] in aqueous IL mixtures. The FIR spectra have been assigned with the aid of density functional theory(DFT) calculations, and the results are used to understand the effect of cationic nature on the structure of ion pairs. It is found that contact ion pairs formed in the neat aprotic ILs by hydrogen bonding interactions between cation and anion, were still maintained in aqueous solutions up to high water mole fraction(say 0.80 for [BuPy][NO3]). When water content was increased to a critical mole fraction of water(say 0.83 for [BuPy][NO3]), the contact ion pairs could be transformed into solvent-separated ion pairs due to the formation of the hydrogen bonding between ions and water. With the further dilution of the aqueous ILs solution, the solvent-separated ion pairs was finally turned into free cations and free anions(fully hydrated cations or anions). The concentrations of the ILs at which the contact ion pairs were transformed into solvent-separated ion pairs and solvent-separated ion pairs were transformed into free ions(fully hydrated ion) were dependent on the cationic structures. These information provides direct spectral evidence for ion pair structures of the aprotic ILs in aqueous solution. MD simulation and ~1H NMR results support the conclusion drawn from FIR spectra investigations.