新戊二醇-三羟甲基甲胺二元体系相图

多元醇是一类具有技术和经济潜力的相变贮热材料［１ -３］．对多元醇及其二元体系贮热性能的研究已日趋完善,而对于其相图的研究则较少．本文采用以下三种实验技术测绘了ＮＰＧ ＴＡＭ二元体系相图：（１）热分析,以得到组成与相转变温度的关系;（２）变温红外光谱的研究,通过特征吸收峰随温度的变化,可以得到相转变温度区间,辅助相图的绘制;（３）Ｘ射线衍射,通过淬冷的方法来获得高温下的物相,测其Ｘ衍射图,进行相区分析．１实验１．１试剂ＮＰＧ：为超纯试剂,日本东京化成株式工业会社生产：ＴＡＭ：分析纯,北京化学试剂厂…     

A fast and low-cost dynamic calorimetric method for phase diagram estimation of binary systems

Journal of Thermal Analysis and Calorimetry - A dynamic calorimetric method based on infrared thermography has been used for the phase diagram estimation of binary systems of fatty organic...     

Crystalline structure of PEO-hydroquinone and PEO-2-methylresorcinol molecular complexes

This paper deals with the calorimetric study of PEO-hydroquinone and PEO-2-methylresorcinol complexes. The phase diagrams determination and the evaluation of the exact stoichiometry of both binary systems has been carried out. For the PEO-2-methylresorcinol system, WAXS experiments have been used to clarify the phase diagram.     

Temperature and composition dependence of the Soret coefficient in Lennard-Jones mixtures presenting evaporation/condensation phase transition

The thermodiffusive behavior of a Lennard-Jones binary mixture has been studied by using nonequilibrium molecular dynamics. In particular, the dependence of the Soret coefficient, S(T), on the temperature and composition has been investigated, exploring a wide range of temperatures from 1000 K to the condensation temperature of the mixture. In a previous paper the dependence of S(T) on the temperature and the composition was studied for Lennard-Jones binary mixtures presenting mixing/demixing (consolute) phase transition, and the results allowed the formulation of a very simple expression with the computed values of S(T) in the one phase region outside the critical region closely fitted by the function [T - T(c)(x(1))](-1), with T(c)(x(1)) the demixing temperature of the mixture under study. The results of the present work show that the same expression of S(T) can be found for the one phase region outside the evaporation/condensation region but now with T(c) representing the condensation temperature of the mixture under study.     

Calculation of immersion enthalpy data from adsorption isotherms

The thermodynamic equations for the calculation of binary and ternary immersion data in excess formalism are presented. Immersion enthalpies and entropies of the n-hexane/n-octane, n-octane/n-tetradecane and n-hexane/n-tetradecane binary mixtures as well as the n-hexane/n-octane/n-tetradecane ternary mixture on activated carbon are calculated from the temperature dependence of adsorption isotherms. In order to evaluate the quality of the calculations, the calculated immersion enthalpies of the binary mixtures on activated carbon are compared with those that were measured calorimetrically. It is shown that phenomenological thermodynamics can be used successfully to predict calorimetric data on the basis of adsorption excess isotherms.     

Brewster angle microscopy: A preferential method for mesoscopic characterization of monolayers at the air/water interface

Knowledge of the mesoscopic morphology of condensed phase domains formed after the main phase transition in the two-phase coexistence region of Langmuir monolayers progressed rapidly with the development of the highly-sensitive imaging techniques, particularly by Brewster angle microscopy (BAM). Latest developments of commercial BAM instruments have been developed to a high technical level and allow upgrading to imaging ellipsometers which combine optical microscopy and ellipsometry and make the assessment of small layered structures or patterned thin films possible. A large variety of condensed phase domains different in mesoscopic sizes and shapes as well as their textural features has been observed which depend sensitively on the chemical structure of the amphiphilic monolayer and the system conditions, such as surface pressure and temperature. This unsuspected morphological variety of condensed phase domains has been proven not only in Langmuir monolayers but also in adsorbed monolayers (Gibbs monolayers), in Langmuir monolayers penetrated by dissolved surfactants or in adequate molecular recognition systems. The inner textures of domains can be explained on the basis of their geometry and the two-dimensional lattice in dependence of the tilt angle of the alkyl chains and gave rise to the development of a geometric concept on the basis of the molecular packing. New knowledge has been gained about non-equilibrium structures and their transition kinetics into the equilibrium state. Combined results obtained recently by BAM have enhanced the understanding of molecular organization in phase diagrams and binary mixtures. Recent advances in model studies about chiral discrimination effects and of the highly specific structural changes of host-monolayers by recognition of non-surface active guest-components have made progress. Semi-empirical quantum chemical methods have been used to gain insight into the role of different types of interactions involved in the main characteristics of mesoscopic length scale aggregates of mimetic systems.     

T-x1-x2 model phase diagrams with upper and lower critical stratification temperatures in the starting binary systems

T-x ₁-x ₂ model phase diagrams have been developed under the condition that the component binary systems had closed regions with upper and lower critical stratification temperatures, as well as monotectic equilibria. Isothermal sections in different interinvariant intervals are given.     

Prediction of phase equilibria and thermodynamic properties of refrigerant/oil solutions

A method for estimation of the phase equilibrium, density, enthalpy, heat of vaporization and molecular weight of refrigerant/oil solutions (ROS) is proposed in this paper. The method is based on the theory of thermodynamic similarity, since refrigerant/oil solutions appear to be thermodynamically similar in the region of the refrigerant mass concentrations: 0.3≤w_R≤1.0. The initial information is the concentration dependence of the temperature of the normal boiling point, the concentration dependence of the density in very narrow temperature ranges, and the temperature dependence of the isobaric heat capacity of the liquid phase of the pure oil. On the basis of this information, the proposed method allows calculation of all the above-mentioned properties. Modeling of thermodynamic properties of the ROS requires data on pseudocritical properties and molar weight. Hence, the method of estimation of these properties is proposed.     

Density and phase diagram of the magnesium–lead system in the region of Mg2Pb intermetallic compound

The phase diagram of magnesium–lead system has been investigated by a new method for phase analysis on the basis of a strong penetrating radiation. The measurements have shown that the standard phase diagram of this system contains inaccuracy in the region of the Mg₂Pb intermetallic compound. New data on the temperature dependences of the solid and the melt densities have been obtained. The density change during the phase transitions has been directly measured.     

Phase stratification in disordered metallic systems

Phase stratification in a series of binary melts (AlBi, AlCd, AlIn, AlPb, CdGa, CrSn, and CuTl) and an amorphous NiZr alloy was studied. Equations describing the main stratification parameters in the liquid phase (the enthalpy ΔH, the relative volume change of melt formation ΔV/V ₀, and the highest temperature T _k at which phase stratification occurs) were obtained. An equation describing the concentration dependence of the relative integral Gibbs energy in the amorphous (liquid) phase was found. This equation took into account the influence of volume changes caused by melt formation on its entropy. The equations obtained were shown to qualitatively correctly describe phase stratification and the subsequent growth of crystalline phases in NiZr system alloys.     

Phase transitions and low-frequency dielectric dispersion in the solid phase of bromoform

Phase transitions in the solid phase of bromoform have been studied by dielectric and differential scanning calorimetric techniques. Two modifications of the solid phase, solid I and solid II, have been observed above and below about ?35°C respectively. Solid phase I exhibits clear Debye-type dispersion in the 0.5 to 100 kHz frequency region, while solid phase II exhibits complete dipole freezing.     

On the compatibility of binary and ternary random copolymers of acrylonitrile with vinyl acetate and/or α-methylstyrene—II: The influence of the time factor

The time dependence of the microscopical aspect, crystallinity, viscosity of the spinning solutions and the thermal and tinctorial properties of films formed from binary, ternary copolymers and binary copolymer mixtures of acrylonitrile with vinyl acetate and χ-methylstyrene have been compared. The characteristics of binary copolymers and incompatible mixtures are stable with time, while those of ternary copolymers and pseudocompatible mixtures evolve towards a limiting state. with phase separation.     

Some physical properties of polyorganosiloxanes. I. Linear polyorganosiloxanes

Some physical properties of linear polydimethylsiloxanes have been studied. The states and transitions in polydimethylsiloxanes have been investigated by using the method of dynamic heat capacity and a thermomechanic method in the temperature range from ?150 to +200°C. The temperature dependence of primary and secondary crystallization has been studied by optical, calorimetric, and x-ray methods.     

Phase equilibria in phospholipid-water systems

This work is a critical account of phase studies of phospholipid-water mixtures. The Phase Rule and equations of thermodynamics of heterogeneous systems are applied in the analysis of calorimetric and dilatometric results for these systems. It is inferred that the approach in which a lipid-water mixture of low lipid content is regarded as a one-component system is misleading and unhelpful. A mixture containing water and a pure synthetic phospholipid is a binary system, and the Phase Rule can be applied to it in a straightforward manner. Non-isothermal transitions and invariant three-phase reactions of the eutectic, peritectic and polytectic type can be encountered in lipid-water systems, like in other binary mixtures. The concentration dependence of the enthalpy of the isothermal three-phase transition yields a well-known Tammann triangle. For the volume change at such transition an analog of the Tammann triangle can be drafted which can be useful in interpretation of dilatometric and densitometric data for heterogeneous binary systems.The literature thermodynamic data for the aqueous lipids are analyzed on the basis of the phase diagram of the DPPC-water system. The measured values of the transition enthalpy and volume change at the pre- and main transitions refer to invariant phase reactions. The measured heat capacities and thermal coefficients of expansion actually characterize the biphasic lipid-water mixtures and may reflect phenomena specific for heterogeneous binary systems only. A reinterpretation of the literature DSC data for the DPPC-water system at temperatures below zero is suggested.Experience gained in the study of equilibrium phase diagram, kinetic and colloidal aspects of phase behaviour of dioctadecyldimethylammonium chloride-water system indicates that the common procedures of the sample preparation of lipid-water mixtures may lead to the states which are non-equilibrium in two respects: the system contains a metastable phase, and the phase is dispersed to such an extent that an irreversible colloidal structure is formed. Definitive phase studies of the phase behaviour of phospholipid-water systems in the whole concentration range are urgently needed.     

Liquid-vapor phase transition in a stratifying lead-zinc system upon a reduction in pressure

The boundaries of the liquid-vapor phase transition at 101325, 100, and 10 Pa were calculated on the basis of the values of the vapor pressure of the components in a lead-zinc system as determined by the boiling point method. It was shown that at low pressures the region of the coexistence of the liquid and vapor is superimposed on the stratification region of the state diagram.     

Modeling of overloaded gradient elution of nociceptin/orphanin FQ in reversed-phase liquid chromatography

The Reversed-phase (RP) gradient elution chromatography of nociceptin/orphanin FQ (N/OFQ), a neuropeptide with many biological effects, has been modeled under linear and non-linear conditions. In order to do this, the chromatographic behavior has been studied under both linear and nonliner conditions under isocratic mode at different mobile phase compositions--ranging from 16 to 19% (v/v) acetonitrile (ACN) in aqueous trifluoracetic acid (TFA) 0.1% (v/v)-on a C-8 column. Although the range of mobile phase compositions investigated was quite narrow, the retention factor of this relatively small polypeptide (N/OFQ is a heptadecapeptide) has been found to change by more than 400%. In these conditions, gradient operation resulted thus to be the optimum approach for non-linear elution. As the available amount of N/OFQ was extremely reduced (only a few milligrams), the adsorption isotherms of the peptide, at the different mobile phase compositions examined, have been measured through the so-called inverse method (IM) on a 5 cm long column. The adsorption data at different mobile phase compositions have been fitted to several models of adsorption. The dependence of the isotherm parameters on the mobile phase composition was modeled by using the linear solvent strength (LSS) model and a generalized Langmuir isotherm that includes the mobile phase composition dependence. The overloaded gradient separation of N/OFQ has been modeled by numerically solving the equilibrium-dispersive (ED) model of chromatography under a selected gradient elution mode, on the basis of the previously determined generalized Langmuir isotherm. The agreement between theoretical calculations and experimental overloaded band profiles appeared reasonably accurate.     

线性和非线性聚合物的相分离

分子共混物从20世纪60年代开始,引起很多科学家的兴趣.加工过程中,聚合物相分离过程中的热力学和动力学起了重要的作用,赋予了共混物一定的形貌,提供了很多人们需要的功能.关于聚合物的相分离问题,近年来无论在实验还是在理论上都得到了很大的发展.聚合物相分离的热力学是以Flory-Huggins的平均场理论为基础,动力学以CHC(Cahn-Hilliard-Cook)的线性理论为基础.在本文中,我们对亚稳相分离SD(Spinodal Decomposition)的热力学和动力学都进行了考察.描述了测量二元共混物的浓度涨落的静态散射实验,给出了在二元共混物体系的SD的近期理论计算.首先,从普适的Langevin方程推导CHC理论,从而给出CHC的唯象的平均场理论的微观图象.然后介绍模式耦合计算,从而将SD理论扩展到非线性区域.通过将短期SD分解与高分子共混物的对比揭示了定量计算的本质.最后,讨论了一些近年来在剪切场下相行为的研究以及该领域可能的发展方向.     

N.M.R. investigations and the molecular field theory of nematic mixtures

N.M.R. measurements have shown that the mixture E5 can be described by a single order parameter. Based on molecular field theory the nematic-isotropic transition and the temperature dependence of the order parameter in the nematic phase are considered for a binary mixture of nematogens. Guided by the results of the N.M.R. measurements the binary mixture is treated as an effective medium characterized by a single order parameter. Soft attractive forces are taken into account as well as the excluded volume. The coexistence of nematic and isotropic phases in the phase transition region is discussed in detail.     

The phase behavior of dodecylsulfonic acid with water: A reinterpretation

Data from visual inspection, microscopic observations through a polarizing microscope, and dilatometry on sealed samples have been used to draw a phase diagram for this two-component system that differs from the one originally published on the basis of the same data. The difference lies in the recognition of a mesophase existing in a composition region intermediate between that of the cylindrical (middle) and lamellar (neat) phases. The problems of accounting for these three types of structures include their very narrow miscibility gaps with each other, their extraordinary thermal stability, and the possible absence of any region of direct binary equilibrium between the middle and neat phases.