Boosting the “Solid–Liquid–Solid” Conversion Reaction via Bifunctional Carbonate-Based Electrolyte for Ultra-long-life Potassium–Sulfur Batteries

Potassium–sulfur (K−S) batteries have attracted wide attention owing to their high theoretical energy density and low cost. However, the intractable shuttle effect of K polysulfides results in poor cyclability of K−S batteries, which severely limits their practical application. Herein, a bifunctional concentrated electrolyte (3 mol L⁻¹ potassium bis(trifluoromethanesulfonyl)imide in ethylene carbonate (EC)) with high ionic conductivity and low viscosity is developed to regulate the dissolution behavior of polysulfides and induce uniform K deposition. The organic groups in the cathode electrolyte interphase layer derived from EC can effectively block the polysulfide shuttle and realize a “solid–liquid–solid” reaction mechanism. The KF-riched solid-electrolyte interphase inhibits K dendrite growth during cycling. As a result, the achieved K−S batteries display a high reversible capacity of 654 mAh g⁻¹ at 0.5 A g⁻¹ after 800 cycles and a long lifespan over 2000 cycles at 1 A g⁻¹.     

Solid–liquid phase diagrams of binary mixtures

This study investigates the sorption of toluene and naphthalene by a sodium bentonite (BFN), an organoclay (WS35) and by their respective iron oxide hydrate composites Mag_BFN and Mag_S35. The organic matter content of WS35 and Mag_S35, determined by thermogravimetry, was used to obtain their organic matter sorption coefficients, which show that they are effective sorbents to remove organic contaminants from water, with a higher selectivity for naphthalene than for toluene sorption. The main iron oxide phase present in Mag_BFN and Mag_S35 is maghemite (γ-Fe₂O₃), which allows these sorbents to be separated from the effluent by a magnetic separation process after use.     

Activity Measurements of Solid Ni–In Alloys by EMF Method with Zirconia Solid Electrolyte

Summary. The EMF of galvanic cells with stabilized zirconia solid electrolyte was measured to determine the activity of indium in solid Ni–In alloys in the temperature range of 970–1170 K and composition range of 5–55 mol% In. Activity of indium increases sharply in the ζ phase and Ni₁₃In₉ phase. The activity values are compared with literature data.     

X-Ray Photoelectron Spectra in TiC–NbC Solid Solutions

The inner-level and valence-band X-ray photoelectron spectra of TiC–NbC solid solutions have been studied. The TiL, NbL_2,15, and CK X-ray emission spectra and the valence-band photoelectron spectra were fitted to a single energy scale relative to the Fermi level, and the results of the fitting are analyzed. It is shown that formation of the electronic structure of these mixed carbides is strongly affected by the variation of the lattice parameters and also by the mutual effects of the Ti and Nb atoms on charge redistribution between them.     

Proton Conductor of Propylene Carbonate–Plasticized Carboxyl Methylcellulose–Based Solid Polymer Electrolyte

Carboxyl methylcellulose (CMC) solid polymer electrolytes were prepared by utilizing oleic acid (OA) and different wt.% of propylene carbonate (PC) by using the solution casting technique. An ionic conductivity study of the films was done by using impedance spectroscopy. The highest ionic conductivity gained is 2.52 × 10^?7 S cm^?1 at ambient temperature for sample CMC-OA-PC 10 wt.%. From transference number measurement (TNM), the value of cation diffusion coefficient, D₊, and ionic mobility, μ₊, was higher than the value of anion diffusion coefficient, D_?, and ionic mobility, μ_?. Thus, the results prove that the present samples were proton conductors.     

Solid–liquid equilibria in the acetic acid–propanoic acid and propanoic acid–trifluoroacetic acid systems

Solid–liquid equilibria in the binary systems, propanoic acid–acetic acid and propanoic acid–trifluoroacetic acid, were measured by a synthetic method. A solid compound (1:1) was found in the propanoic acid–trifluoroacetic acid system. The obtained activity coefficients were successfully fitted by the Wilson equation.     

Liquid–Solid Phase Diagrams of PrOH–Water and BuOH–Water Systems from Differential Scanning Calorimetry

The freezing process in i-PrOH- and tert-BuOH-water systems were investigatedto obtain reliable liquid=nsolid phase diagrams by differential scanning calorimetry(DSC), especially focusing on formation of metastable solid phases. In addition,n-BuOH, sec-BuOH, and i-BuOH were studied within their solubility limits. Inmost systems studied, there exist metastable solid phases and, with increasingbranching of alkyl groups, the number of metstable solid phases increases. Themost complicated is i-PrOH-water where curious phenomena were found,probably because of the abnormally high viscosity of the solution at low temperatures.The relation between hydration in the liquid and formation of solid phases isdiscussed. It is suggested that the positional relation between methyl groups andalcoholic OH groups plays an important role; the increase in number ofalphamethyl group seems to strengthen hydration and stabilizes solid hydrates.     

Solid–liquid equilibria in the NaCl–SrCl2–H2O system at 288.15 K

The phase equilibria in the ternary system NaCl–SrCl₂–H₂O at 288.15 K were studied with the isothermal equilibrium solution method. The phase diagram and refractive index diagram were plotted for this system at 288.15 K. The phase diagram contains one invariant solubility point, two univariant solubility curves, and two crystallization fields of NaCl and SrCl₂ · 6H₂O. The refractive indices of the equilibrium solution change regularly with w(NaCl) increase. The calculated refractive index data are in good agreement with the experimental data. Combining the experimental solubility data of the ternary system, the Pitzer binary parameters for NaCl at 288.15 K and SrCl₂ at 298.15 K, the Pitzer mixing parameters θ_{Na, Sr}, Ψ_{Na, Sr, Cl} and the solubility equilibrium constants Ksp of solid phases existing in the ternary system at 288.15 K were fitted using the Pitzer and Harvie-Weare (HW) models. The mean activity coefficients of sodium chloride and strontium chloride, and the solubilities for the ternary system at 288.15 K were presented. A comparison between the calculated and measured solubilities shows that the predicted data agree well with the experimental results.     

Solid–liquid equilibrium and thermochemical studies of organic analogue of metal–nonmetal system: Succinonitrile–pentachloronitrobenzene

The phase diagram of an organic analogue of a metal–nonmetal system, involving succinonitrile–pentachloronitrobenzene, shows the formation of a eutectic and a monotectic. The two immiscible liquid phases are in equilibrium with a single liquid phase and the consolute temperature being 53.5 °C above the monotectic horizontal. The phase equilibrium study confirms the alloy composition of monotectic and eutectic at 0.150 and 0.985 mol fractions of succinonitrile, respectively. The solidification behaviour shows the validity of Hilling–Turnbull equation. The thermal properties such as heat of mixing, entropy of fusion, roughness parameter, interfacial energy, grain boundary energy and excess thermodynamic functions for parent components, monotectic and eutectic have been studied using their enthalpy of fusion values. The effects of solid–liquid interfacial energy on morphological change of monotectic have also been discussed. The microstructure of monotectic shows the lamellar growth along with droplets, however, eutectic infers the vertical growth of lamella.     

Determination of Pyrethroids in Dendrobium officinale by Ultrasound/Microwave-Assisted Solid–Liquid–Solid Dispersive Extraction,Gas Chromatography,and Triple-Quadrupole Mass Spectrometry

An ultrasound/microwave-assisted solid–liquid–solid dispersive extraction method was developed for the determination of 16 pyrethroid insecticides in Dendrobium officinale. The extraction and purification were performed in one step. The pyrethroids were extracted with 8:2 acetone:hexane and purified with a mixture of primary secondary amine, Florisil, C18, and graphitized carbon black. The extraction temperature, extraction time, and ultrasound power were optimized. Trans-cyfluthrin-d₆ was used as the internal standard to improve the accuracy. Under the optimized conditions, the recoveries of the pyrethroids were from 72.2 to 113.9% with the limits of detection between 0.29 and 9.38?µg?kg^?1. The optimized method was successfully used for the determination of pyrethroids in commercial D. officinale samples and may allow monitoring pyrethroids in herbal products.     

Solid–liquid–gas equilibrium of the naphthalene–biphenyl–CO2 system: Measurement and modeling

The first and last melting points (FLMP) method was employed to measure the melting temperature–composition (T–w$T–w$) data at solid–liquid–gas (SLG) equilibrium for the naphthalene–biphenyl–CO₂ system. Results show that the system's phase diagram is simple eutectic under all investigated pressures (0.1, 3.0, 6.0 and 8.0 MPa), and the system's eutectic composition is almost constant. The (T–w$T–w$) data measured with a high-pressure differential scanning calorimetry are in good agreement with these from FLMP. The semi-predictive model using solubility data (SMS) and the calculation model combining with G^E models (CMG) for binary systems were extended to this ternary system. For the SMS model, the Peng–Robinson equation of state (PR-EoS) with the van der Waals one-fluid mixing rule was used to correlate the solubility data of the two solutes in CO₂ to obtain the two interaction parameters k₁₂ and k₁₃ and calculate the fugacity coefficients of the solutes in the liquid and vapor phases; the UNIFAC method was also applied to the activity coefficient of the solutes in the liquid phase. For the CMG model, the PR-EoS combining respectively the MHV1, LCVM, and modified LCVM (mLCVM) mixing rules was applied to the fugacity coefficients of the solutes. Results show that the CMG model with MHV1 gives the best prediction of the system's SLG equilibrium, while the SMS model and the CMG model with mLCVM provide comparable and acceptable results.     

X–ray Spectroscopic Analysis of Solid State Reaction during Mechanical Alloying

Niobium or tungsten and graphite powders were mechanically alloyed. Carbon K X–ray spectra of the mechanically alloyed powders were measured using an electron probe microanalyzer (EPMA) in order to investigate the solid state reaction process. In the early stage of the mechanical alloying (10 hours), graphite did not react with metal, but particle size of graphite became smaller. In the next stage of the mechanical alloying (2–4 hours), micro–crystalline graphite powder reacted with metal. Polarization of the X–rays were measured for Nb₂C and W₂C, because a single crystal WC emitted polarized X–rays. The measurement of X–ray emission spectra was useful for the structural and chemical analysis of mechanical alloying reaction processes.     

Solid–liquid equilibria for systems containing 1-butyl-3-methylimidazolium chloride

The solubility of 1-butyl-3-methylimidazolium chloride [C₄mim][Cl] in alcohols {ethanol, 1-butanol, 1-hexanol, 1-octanol, 1-decanol, 1-dodecanol, 2-butanol, 2-methyl-2-propanol (tert-butanol)} has been measured by a dynamic method from 270 K to the melting point of the ionic liquid or to the boiling point of the solvent. The melting point, enthalpy of fusion, and the temperature of the glass phase transition were determined by differential scanning calorimetry.The solubility data were correlated by means of the Wilson, UNIQUAC ASM and modified NRTL1 equations utilizing parameters derived from the solid–liquid equilibrium data. The root-mean-square deviations of the solubility temperatures for all calculated data were higher than 0.9 K and depended on the particular equation used.     

Solid–liquid equilibrium,thermal and physicochemical studies of organic eutectics

The solid–liquid phase equilibrium data of two binary organic systems, namely, urea (U)–3-aminophenol (AP) and 3-hydroxybenzaldehyde (HB)–β-napthaol (BN) show formation of a eutectic in each case. The enthalpies of fusion of the pure components and binary eutectics have been determined using differential scanning calorimeter (Mettler DSC-4000) system. The thermal properties of the materials such as heat of mixing, entropy of fusion, roughness parameter, interfacial energy and excess thermodynamic functions were computed using the enthalpy of fusion values. The microstructures of eutectics were developed using unidirectional thermal gradient and interested region were photographed.     

A Dissipative Reaction Network Drives Transient Solid–Liquid and Liquid–Liquid Phase Cycling of Nanoparticles

Transient states maintained by energy dissipation are an essential feature of dynamic systems where structures and functions are regulated by fluxes of energy and matter through chemical reaction networks. Perfected in biology, chemically fueled dissipative networks incorporating nanoscale components allow the unique properties of nanomaterials to be bestowed with spatiotemporal adaptability and chemical responsiveness. We report the transient dispersion of gold nanoparticles in water, powered by dissipation of a chemical fuel. A dispersed state that is generated under non-equilibrium conditions permits fully reversible solid–liquid or liquid–liquid phase transfer. The molecular basis of the out-of-equilibrium process is reversible covalent modification of nanoparticle-bound ligands by a simple inorganic activator. Activator consumption by a coupled dissipative reaction network leads to autonomous cycling between phases. The out-of-equilibrium lifetime is tunable by adjusting the pH value, and reversible phase cycling is reproducible over several cycles.     

Solid–liquid interface growth of Cu50Ni50 under deep undercoolings

Molecular dynamics simulations have been performed to explore interface growth of liquid Cu₅₀Ni₅₀ alloy by using an embedded atom potential, namely due to Zhou. The simulated melting temperature is 1585 K in agreement well with the experimental value of 1600 K. The calculated interface velocity increases with decreasing temperature ranging from 1585 K to 1100 K, where the calculated values are a little higher than the experimental ones at higher temperatures, and in agreement with the experimental ones at lower temperatures; while the calculated interface velocity decreases with decreasing temperature lower than 1100 K. The activation energy of atom is 0.0048 eV, almost close to zero under deep undercoolings, although the crystal growth still proceeds with the speed ranging from 50 m s^?1 to 10 m s^?1. The crystal growth of Cu₅₀Ni₅₀ is not controlled by diffusion mechanism under deep undercoolings.     

Solid–solvent molecular interactions observed in crystal structures of β-chitin complexes

Three β-chitin structures [anhydrous, di-hydrate, mono-ethylenediamine (EDA)] recently determined by synchrotron X-ray and neutron fiber diffraction were reviewed from the viewpoint of molecular interactions. Both water and EDA molecules interact with the chitin chains through multiple hydrogen bonds. When water complexes with chitin, the hydrogen bonding pattern rearranges with the replacement of an intrachain chitin hydrogen bond by a stronger hydrogen bond between chitin and water, with an associated reduction in the degrees of freedom; the water oxygen is a much stronger acceptor than the O5 ring atom. The behavior of hydrogen exchange by deuterium supports this interpretation. EDA-molecules change the conformation of hydroxymethyl group from gg to gt, accompanied by changes in hydrogen bonds due to the strong accepting ability of the EDA nitrogen atoms. Some important interactions are in common with experimental crystallographic results of cellulosic crystals and of molecular dynamics studies. These new insights into solid–solvent interactions are valuable in understanding molecular interactions in other polysaccharides-solvents system in solution or on surface.     

Evaluation of Target Efficiencies for Solid–Liquid Separation Steps in Biofuels Production

Development of liquid biofuels has entered a new phase of large scale pilot demonstration. A number of plants that are in operation or under construction face the task of addressing the engineering challenges of creating a viable plant design, scaling up and optimizing various unit operations. It is well-known that separation technologies account for 50–70% of both capital and operating cost. Additionally, reduction of environmental impact creates technological challenges that increase project cost without adding to the bottom line. Different technologies vary in terms of selection of unit operations; however, solid–liquid separations are likely to be a major contributor to the overall project cost. Despite the differences in pretreatment approaches, similar challenges arise for solid–liquid separation unit operations. A typical process for ethanol production from biomass includes several solid–liquid separation steps, depending on which particular stream is targeted for downstream processing. The nature of biomass-derived materials makes it either difficult or uneconomical to accomplish complete separation in a single step. Therefore, setting realistic efficiency targets for solid–liquid separations is an important task that influences overall process recovery and economics. Experimental data will be presented showing typical characteristics for pretreated cane bagasse at various stages of processing into cellulosic ethanol. Results of generic material balance calculations will be presented to illustrate the influence of separation target efficiencies on overall process recoveries and characteristics of waste streams.     

Solid–liquid phase equilibria for binary mixtures of propellant’s stabilizers

Solid–liquid equilibria for three binary mixtures of N-(2-acetoxyethyl)-p-nitroaniline (1) + 2-nitrodiphenylamine (2), N-(2-acetoxyethyl)-p-nitroaniline (1) + ethyl centralite (2) and N-(2-acetoxyethyl)-p-nitroaniline (1) + methyl centralite (2) have been determined experimentally using differential scanning calorimeter (DSC). Simple eutectic behaviours for these systems have been observed. The experimental results have been correlated by means of NRTL and UNIQUAC equations. The root-mean-square deviations of the solubility temperatures for all measured data vary from 0.61 to 3.32 K and depend on the particular model used. The best solubility correlation has been obtained with the UNIQUAC model.     

Solid–liquid equilibria of long chain n-alkanes (C18–C28) in N,N-dimethylacetamide

Solid–liquid equilibria (SLE) of the n-alkanes (octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane and octacosane) in N,N-dimethylacetamide (DMA) are reported. The data has been measured by the dynamic method from 275 K to the melting temperatures of the n-alkane. The experimental results have been correlated by the Redlich–Kister equation with two and three parameters and the NRTL equation.