Solid–liquid equilibrium, thermal, and physicochemical studies on salicylamide–4-nitrophenol and 2-cyanoacetamide–4-aminoacetophenone organic eutectic systems

The solid–liquid phase equilibrium data of two binary organic systems, namely, salicylamide–4-nitrophenol and 2-cyanoacetamide–4-aminoacetophenone show the formation of a eutectic in each case. The values of enthalpy of fusion of 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 regions of interest for microstructures were photographed.     

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.     

Thermal,physicochemical and microstructural studies of binary organic eutectic systems

Solid–liquid phase equilibrium data of three binary organic systems, namely, 3-hydroxybenzaldehyde (HB)—4-bromo-2-nitroanilne (BNA), benzoin (BN)—resorcinol (RC) and urea (U)—1,3-dinitrobenzene (DNB), were studied by the thaw–melt method. While the former two systems show the formation of simple eutectic, the third system shows the formation of a monotectic and a eutectic with a large immiscibility region where two immiscible liquid phases are in equilibrium with a liquid of single phase. Growth kinetics of the pure components, the monotectic and the eutectics, studied by measuring the rate of movement (v) of solid–liquid interface in a thin U-tube at different undercoolings (ΔT) suggests the applicability of the Hillig–Turnbull’s equation: v = u (ΔT) ⁿ , where v and n are the constants depending on the nature of the materials involved. The thermal properties of materials such as heat of mixing, entropy of fusion, roughness parameter, interfacial energy, and excess thermodynamic functions were computed from the enthalpy of fusion values, determined by differential scanning calorimeter (Mettler DSC-4000) system. The role of solid–liquid interfacial energy on morphologic change of monotectic growth has also been discussed. The microstructures of monotectic and eutectics were taken which showed lamellar and federal features.     

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.     

Physical Chemistry of Organic Eutectics

Phase diagrams of urea-α-naphthol and urea-benzoic acid systems, determined by the thaw-melt method, show the formation of simple eutectic in each case. The growth velocity data, determined at different undercooling (ΔT) by observing the rate of movement of interface in a capillary, obey the Hillig-Turnbull equation, v=u(ΔT)ⁿ, where u and n are constants depending on the nature of the materials. Using enthalpy of fusion, undercooling (ΔT) and melting point data, entropy of fusion, interfacial energy, enthalpy of mixing, critical radius size and excess thermodynamic functions were calculated. The microstructural investigations give characteristic features of the eutectics. This revised version was published online in July 2006 with corrections to the Cover Date.     

Solid–liquid equilibrium,thermal, crystallization and microstructural studies of organic monotectic alloy

A monotectic and a eutectic organic alloy have been synthesized with the help of phase diagram study. The phase diagram of an organic analogue of a metal–nonmetal system involving succinonitrile–1,4-diiodobenzene shows two immiscible liquid phases are in equilibrium with a single liquid phase. Growth behaviour of the eutectic, the monotectic and the pure components, studied at different undercooling temperatures, suggests that the data obey the square relationship between growth velocity and undercoolings. The thermal study such as heat of mixing, entropy of fusion, roughness parameter, interfacial energy and excess thermodynamic functions were calculated via the enthalpy of fusion values, determined using differential scanning calorimeter (DSC) method. The effects of solid–liquid interfacial energy on morphology of monotectic have also been discussed. The microstructures of monotectic, eutectic and pure components show their peculiar characteristic features.     

Solid–liquid equilibria, thermochemical and microstructural studies of binary organic monotectic and eutectic alloy

The phase diagram of 1,4-dibromobenzene (DBB) with pyrogallol (PG) shows the formation of a monotectic and a eutectic alloys at 0.12 and 0.99?mol fractions of DBB, respectively. The phase equilibrium shows the large miscibility gap region with the upper consolute temperature 159.0?°C at 0.55?mol fraction of DBB. Growth kinetics of pure compounds and their monotectic and eutectic at different undercooling (??T) obey Hillig?CTurnbull??s equation: v?=?u (??T) ⁿ . Thermodynamic parameters such as enthalpy of mixing, entropy of fusion, interfacial energy, roughness parameters and excess thermodynamic functions were computed based on enthalpy of fusion values obtained from DSC studies. The Cahn wetting condition is applicable for monotectic alloy. The optical microphotographs of binary alloys show lamellar and dendritic features.     

Phase equilibria in the NaCl-NaBr-Na<Subscript>2</Subscript>MoO<Subscript>4</Subscript> system

The binary systems NaBr-Na₂MoO₄ and NaBr-Na₃ClMoO₄ and the ternary system NaCl-NaBr-Na₂MoO₄ have been studied using physicochemical methods (DTA and powder X-ray diffraction). The compositions, melting points, and heats of phase transitions have been determined for three invariant points. The liquidus surface of the ternary system consists of the fields of sodium molybdate, Na₃ClMoO₄, and sodium chloride and bromide solid solutions. The eutectics melt at 531, 612, and 524°C; the respective heats of phase transitions are 149.27, 167.55, and 215.38 J/g.     

聚乙二醇/氮化硼复合材料相变导热性能及其结晶行为

本文采用熔融共混浇筑的方法制备了聚乙二醇/氮化硼(PEG/BN)相变复合材料,并研究了不同尺度片状BN对相变复合材料导热性能和结晶行为的影响。 通过扫描电子显微镜(SEM)、热常数分析仪、红外热成像分析仪和差示扫描量热仪(DSC)研究了相变复合材料的微观形貌、导热系数和相变过程,并利用莫志深法对DSC结果进行了非等温结晶动力学分析。 结果表明,较大片状直径(50 μm)的BN可以更有效地提高聚乙二醇的导热系数,当BN填料质量分数为40%时,相变复合材料的导热系数可达到5.04 W/(m·K)。 在快速降温条件下,片径为50 μm的BN填料可以缩短PEG的半结晶时间,提高结晶速率,使相变复合材料具有较大的相变焓。     

A Raman spectroscopic study of the morphological structure of the polyethylenes

The method described by Strobl and Hagedorn to analyze the Raman spectrum internal modes of semi-crystalline polyethylene has been applied to a set of selected polyethylene samples crystallized under controlled conditions. The crystallite structure can be described in terms of the relative amounts of the crystalline orthorhombic phase, the liquid-like amorphous phase and the interfacial region. The dependence of the level of crystallinity on molecular weight and crystallization conditions is very similar to that found by other methods. However, this method allows for the quantitative determination of the interfacial content which becomes significant for molecular weights greater than about 1×10⁵ for linear polyethylene fractions, and for all the branched samples and copolymers. The degree of crystallinity determined from density measurements is equal to the sum of the crystallinity and interfacial content obtained from the Raman analysis while enthalpy of fusion measurements yield values which are equal to just the crystallinity content. The difference between the level of crystallinity obtained from density and enthalpy of fusion is thus found to be primarily due to interfacial contributions.Dedicated to Prof. Dr. F. H. Müller     

Thermodynamic Study of the Solid-Liquid Equilibria in the Systems MIPO3-Pr(PO3)3 (MI=Na,Rb, Cs OR Ag)

A previously established equation of a stoichiometric phase liquidus curve was applied to determination of the phase diagrams of the systems M^IPO₃-Pr(PO₃)₃ (with M^I=Na, Rb, Cs or Ag). The temperature, enthalpy and entropy of fusion were calculated for each solid phase with the exception of silver polyphosphate, the crystallization field of which was very limited. The enthalpy of fusion of the polyphosphate Pr(PO₃)₃ was determined from the DTA curve. The melting enthalpy of Pr(PO₃)₃ calculated from the different binary systems was approximately equal to the measured value. The calculated temperatures and compositions were in good agreement with those determined experimentally. This revised version was published online in July 2006 with corrections to the Cover Date.     

Experimental determination of the H2SO4/(NH4)2SO4/H2O phase diagram

We have experimentally investigated the water and sulfuric acid-rich regions of the H2SO4/(NH4)2SO4/H2O ternary liquid/solid phase diagram using differential scanning calorimetry (DSC) and infrared spectroscopy of thin films. We present the liquid/solid ternary phase diagram for temperatures below 373 K and H2SO4 concentrations below 60 wt %. We have determined two ternary eutectics and two tributary reaction points for this system in the regions studied. It is also seen that sulfuric acid tetrahydrate (SAT) forms as a metastable solid over a large concentration range. Two true binary systems have been identified: ice/letovicite and SAT/ammonium bisulfate. Finally, we have compared our results to the predictions of the aerosol inorganics model and have found significant differences both in the final melting points and in the location of some of the phase boundaries including a significant discrepancy in the invariant points predicted versus those observed.     

Solubility of phosphonium ionic liquid in alcohols, benzene, and alkylbenzenes

The (solid + liquid) phase equilibria and (liquid + liquid) phase equilibria of binary mixtures containing quaternary phosphonium salt-tetrabutylphosphonium methanesulfonate and alcohols or alkylbenzenes were investigated. The systems {[(CH(3)CH(2)CH(2)CH(2))4P][CH(3)SO(3)] + 1-butanol, or 1-hexanol, 1-octanol, 1-decanol, or 1-dodecanol} and {[(CH(3)CH(2)CH(2)CH(2))4P][CH(3)SO(3)] + benzene, or toluene, ethylbenzene, or propylbenzene} have been measured by a dynamic method at a wide range of temperatures from 220 to 386 K. Solid-liquid equilibria with immiscibility in the liquid phase were detected with the aromatic hydrocarbons ethylbenzene and propylbenzene. The basic thermodynamic properties of pure ionic liquid--the melting point, enthalpy of fusion, enthalpy of solid-solid-phase transition, and glass transition--have been determined by differential scanning calorimetry. The experimental data of systems with alcohols were correlated by means of the UNIQUAC ASM and NRTL1 equations and of systems with alkylbenzenes with Wilson and NRTL equations utilizing parameters derived from the (solid + liquid) equilibrium. The root-mean-square deviations of the solubility temperatures for all calculated data are dependent upon the particular system and the particular equation used.     

Diagrammes de Phase R(+)-Chlorhydrate d'Éfaroxan - R(+)-Bromhydrate d'Éfaroxan et Modélisation

We have shown that efaxoran hydrochloride and efaxoran hydrobromide form solid solution over the entire range of compositions. The small values of enthalpy of mixing indicate that the system is close to ideality. Consequently, Oonk's method was used for its modelling, assuming that the liquid phase is ideal and the departure of the solid phase from ideality was expressed by the excess free enthalpy gE. The results obtained agreed with experience. This revised version was published online in July 2006 with corrections to the Cover Date.     

Physicochemical interactions in the GeSb2Te4-GeBi2Te4 system

The GeSb₂Te₄-GeBi₂Te₄ system has been studied for the first time using a complex of physicochemical methods, and its phase diagram has been constructed. When the component ratio in the GeSb₂Te₄-GeBi₂Te₄ system is 1: 1, a quaternary compound GeSbBiTe₄ is formed; it melts congruently at 850 K. A GeBi₂Te₄-based solid solution region has been discovered; its boundary at 300 K reaches 5 mol % GeSb₂Te₄. The compositions and melting temperatures of eutectics have been determined.     

In Situ Solid‐State Generation of (BN)2‐Pyrenes and Electroluminescent Devices

New BN‐heterocyclic compounds have been found to undergo double arene photoelimination, forming rare yellow fluorescent BN‐pyrenes that contain two B? N units. Most significant is the discovery that the double arene elimination can also be driven by excitons generated electrically within electroluminescent (EL) devices, enabling the in situ solid‐state conversion of BN‐heterocycles to BN‐pyrenes and the use of BN‐pyrenes as emitters for EL devices. The in situ exciton‐driven elimination (EDE) phenomenon has also been observed for other BN‐heterocycles.     

Some thermochemical studies on binary faceted organic eutecitcs and 1∶1 molecular complexes

The phase diagrams of binary organic systems of benzidine with pyrogallol andp-nitrophenol give a double simple eutectic type phase diagram showing formation of a 1∶1 molecular complex with congruent melting point and two eutectics. The growth data on the pure components, the eutectics and the molecular complexes, determined by measuring the rate of movement of growth front in a capillary, justify the square relationship between growth velocity and undercooling. While enthalpy of mixing values suggest intermolecular hydrogen bonding, the excess thermodynamic functions reveal strong interactions among the components forming eutectics and addition compounds.     

微乳液的热力学性质 I: 芳烃类的侧链链长对微乳液热力学函数影响

本文研究以非离子型表面活性剂-正辛醇-水-芳烃类所组成的微乳液, 探讨醇从油相转移到界面相时的自由能变化, 以及温度对自由能的影响。计算出熵和焓的变化, 发现在实验范围内, 上述热力学函数的对数值与芳烃侧链的碳原子数(n)呈线性关系。这些关系式对微乳液的构成和稳定性的讨论是重要的, 还对几种芳烃异构体所构成的微乳液的热力学函数进行了实验和讨论。     

Anisotropically Electrochemical–Mechanical Evolution in Solid‐State Batteries and Interfacial Tailored Strategy

All‐solid‐state batteries have attracted attention owing to the potential high energy density and safety; however, little success has been made on practical applications of solid‐state batteries, which is largely attributed to the solid–solid interface issues. A fundamental elucidation of electrode–electrolyte interface behaviors is of crucial significance but has proven difficult. The interfacial resistance and capacity fading issues in a solid‐state battery were probed, revealing a heterogeneous phase transition evolution at solid–solid interfaces. The strain‐induced interfacial change and the contact loss, as well as a dense metallic surface phase, deteriorate the electrochemical reaction in solid‐state batteries. Furthermore, the in situ growth of electrolytes on secondary particles is proposed to fabricate robust solid–solid interface. Our study enlightens new insights into the mechanism behind solid–solid interfacial reaction for optimizing advanced solid‐state batteries.     

Thermal energy storage and retrieval properties of form-stable phase change nanofibrous mats based on ternary fatty acid eutectics/polyacrylonitrile composite by magnetron sputtering of silver

This paper demonstrated a novel magnetron sputtering method used for the improvement in thermal energy storage and retrieval rates of phase change materials (PCMs). The ten types of ternary fatty acid eutectics (i.e., CA–LA–MA, CA–LA–PA, CA–LA–SA, CA–MA–PA, CA–MA–SA, CA–PA–SA, LA–MA–PA, LA–MA–SA, LA–PA–SA and MA–PA–SA) were firstly prepared using five fatty acids such as capric acid (CA), lauric acid (LA), myristic acid (MA), palmitic acid (PA) and stearic acid (SA) and then selected as solid–liquid PCMs. Thereafter, magnetron sputter coating was used to deposit the functional silver (Ag) nanolayers onto the surface of electrospun polyacrylonitrile (PAN) nanofibrous mats serving as supporting skeleton. Finally, a series of composite PCMs were fabricated by adsorbing the prepared ternary eutectics into three-dimensional porous network structures of Ag-coated PAN membranes. The observations by EDX determined the formation of Ag nanolayers on the PAN nanofibers surface after magnetron sputtering. The SEM images illustrated that the Ag-coated PAN nanofibers appeared to have larger fiber diameter and rougher surface. Ag-coated PAN nanofibrous mats could effectively prevent the leakage of molten ternary eutectics and help maintain form-stable structure due to surface tension forces, capillary and nanoconfinement effects. The DSC results suggested that the phase change temperatures of the ternary fatty acid eutectics were obviously lower than those of individual fatty acids and their binary eutectics. The adsorption rates of ternary fatty acid eutectics in the composite PCMs were determined to be about 89–98 %. The thermal performance test indicated that the metallic coating of Ag dramatically improved the thermal energy storage and retrieval rates of the composite PCMs.