Measurement and modeling of vapor-liquid equilibrium for ternary system water + 2-propanol + 1-butyl-3-methylimidazoliumchloride简

Vapor-liquid equilibrium （VLE） data for water ＋ 2-propanol ＋ 1-butyl-3-methylimidazolium chloride （[bmim]Cl） were measured. Six sets of complete T, x, y data are reported, in which the 2-propanol mole fraction on IL-free basis is fixed separately at 0.1, 0.2, 0.4, 0.6, 0.8, and approximate 0.98, while the IL mass fraction is varied from 0.1 to 0.8, in an interval of 0.1. The non-random-two-liquid （NRTL） and electrolyte non-random-two-liquid （eNRTL） equations are used to correlate the experimental data with satisfactory results. The ternary VLE behavior is also modeled with the parameters obtained by correlating two data sets, in which the mole fraction of 2-propanol on IL-free basis is approximately 0.1 and 0.98. In this way, the six sets of data are reproduced satisfactorily. With the eNRTL model, the root-mean-square deviation for temperature is 0.82 K and that for vapor-phase mole fraction is 0.0078. The influences of IL on activity coefficients and relative volatility of the volatile components are also graphically illustrated.     

制备纳米BaSO4的W/O微乳液体系组成及稳定性

以Triton X-100/正己醇/环己烷/水制成W/O微乳反胶团体系，通过测定体系的电导率和观察液晶相的出现确定相点绘制了各体系的拟三元相图，研究了温度、盐浓度和油相组分对W/O微乳液体系稳定性的影响.实验发现助表面活性剂与表面活性剂的配比对微乳液的稳定性有显著影响.随着温度的升高，W/O微乳液稳定区域减小，可通过升高温度对微乳液进行破乳；与以纯环己烷为油相的体系相比，油相中含有少量正己烷的体系具有更优异的性质.所得结果为利用该W/O微乳液体系制备纳米颗粒提供了基础数据.     

Molecular thermodynamic analysis for phase transitions of linear and cross-linked poly(N-isopropylacrylamide) in water/2-propanol mixtures

Ternary liquid–liquid phase transitions of linear poly(N-isopropylacrylamide) (PNIPA) and the swelling behavior of cross-linked PNIPA gels in water/2-propanol mixtures were investigated using thermo-optical analysis (TOA) and a photon correlation spectroscopy (PCS) technique, respectively. Closed immiscibility gaps in ternary phase diagrams were obtained below 35 °C although all binary mixtures involved in this system were completely miscible. At a fixed concentration of PNIPA (1.0 wt%), a decrease in the lower critical solution temperature (LCST) occurred first, and with an increasing 2-propanol fraction of the solvent mixture, the upper critical solution temperature (UCST) subsequently developed. Corresponding to the linear PNIPA solution behavior, swollen PNIPA gels in pure water first shrank and then reswelled with increasing 2-propanol content in a typical reentrant transition. For theoretical treatment of the mixtures, a multi-component lattice theory of mixing and Flory–Rehner chain model for elasticity were employed for molecular thermodynamic analysis. A secondary lattice concept of specific interactions was used to model binary water/PNIPA solutions, and a temperature dependence of the intermolecular interactions for 2-propanol/PNIPA was used to describe island type ternary phase diagrams. The swelling transitions of cross-linked PNIPA gels were calculated using model parameters obtained from the ternary phase diagrams of linear PNIPA or from experimental conditions. The predicted results were in good agreement with experimental data without the need for further adjustable parameters.     

Partition of bromophenol blue in toluene/water/sodium bis(2-ethylhexyl)-sulfosuccinate water-in-oil microemulsions

The partition of bromophenol blue between oil-water interfaces and water droplets in water-in-oil microemulsions of toluene/water/sodium bis(2-ethylhexyl)sulfosuccinate was studied by a spectroscopic method at different water fractions and pH. The partition equilibrium constant, K _p , between the two domains decreased considerably with an increase in the water fraction and pH. The decrease in K _p with an increase in the water fraction suggests the retention of more dye molecules in water. The decrease in K _p with an increase in pH has been attributed to a lower tendency of the base form to associate with the anionic oil-water interface compared with that of the acid form and to an increase in the negative charge density at the oil-water interface at a higher pH.     

Phase inversion temperatures of triton X-100/1-butanol/hydrocarbon/water systems

The formation of a water-in-oil (w/o) microemulsion in Triton X-100/1-butanol/alkane/water systems was investigated at 25.0±0.1°C. Phase inversion temperatures in hydrocarbon-water microemulsions stabilized with Triton X-100 were determined for different hydrocarbons. It was found that the more soluble the alkane (oil), functioning as a nonionic emulsifier, the lower was the phase inversion temperature, above which oil-in-water type microemulsions invert to w/o type. The effect of the presence of cosurfactant was studied. No phase inversion was observed in the absence of cosurfactant. The effect on phase inversion temperature of decreasing or increasing the temperature was evaluated. By definition, phase inversion was not affected by different temperatures.     

Microemulsions with Mixed Nonionic Surfactants and Flavor Oil

The microemulsion systems composed of water/sucrose laurate/ethoxylated mono-di-glyceride/peppermint oil were formulated and characterized using electrical conductivity and small-angle X-ray scattering. The solubilization capacity of water in the oil is dependent on the surfactant mixing ratio. A static percolation phenomenon was observed in these systems and the water volume fraction percolation threshold was determined. A progressive transformation of water-in-oil to bicontinuous microemulsions, occurring upon dilution with water was revealed for equal amounts of sucrose laurate and ethoxylated mono-di-glyceride in the microemulsions. The periodicity, that is a characteristic length for the domain size of the microemulsions, increases linearly with the increase in the water volume fraction, whereas the correlation length, that is also a characteristic length for the domain size, increases with the increase in the water volume fraction up to a certain value then decreases.     

酯类微乳液的相变过程中电导率和黏度分析

以月桂酸聚氧乙烯和聚乙二醇二油酸酯为乳化剂,以油酸酯为油相,制备了不同乳化剂配比和不同油相含量的微乳液,研究了乳液浓度对其电导率和黏度的影响。结果表明,随着微乳液浓度的增大,乳液出现由水包油（O/W）型转变为油包水（W/O）型的相变过程;其伴随的电导率变化和黏度变化有着对应的关系：当电导率升高至平稳阶段对应于黏度的缓慢上升阶段,乳液属于O/W型;当电导率急剧下降阶段对应于黏度的突变阶段,乳液处于相转变（O/W和W/O共存）阶段;当电导率很低且缓慢下降阶段对应于黏度缓慢下降的阶段,乳液属于W/O型;此外,聚醚类化合物可明显降低乳液相转变过程的黏度,其中异构醇聚醚的效果最佳,在添加量为0.5 %（质量分数,下同）时,黏度降低的程度最大。     

A STUDY OF SILICONE OIL-IN-WATER EMULSIONS

Emulsions of silicone oil-in water were formed using a Brinkmann Polytron homogenizer with Igepal CO-530 as an emulsifier. Silicone viscosities ranged from 10 to 33,000 mPa.s at 25°C. Rheological characteristics and particle size analyses of silicone oil-in-water emulsions were studied. At high volume fraction of the dispersed phase (70%-75%), silicone oil-in-water emulsions were stable. At lower volume fractions (50%-60%), emulsions formed were less stable and the two phases easily separated in a few days. The emulsions formed with high volume fraction silicone oil show highly non-Newtonian behavior (shear thinning). Emulsions made with low viscosity oils had lower viscosities than those made from high viscosity oils. Relative viscosity-concentration data could be correlated by the Frankel and Acrivos Equation. Increasing the emulsifier concentration of 70% oil-in-water emulsions resulted in a decrease in mean droplet size and an increase in emulsion viscosity. Increasing the intensity of agitation also resulted in higher viscosity and smaller droplet size until a critical energy input above which droplet size increased. Emulsification with low shear mixing provides more control in decreasing mean droplet size with time.     

Ascorbic acid oxidation in SDS micellar systems

In this contribution the results of atmospheric and electrochemical oxidation of AA in the SDS micellar solutions and in the microemulsions pentanol/water stabilized by SDS are presented. The hydrophilic vitamin C readily dissolves in water and O/W microemulsions as well as undergoes the irreversible two-electron oxidation reaction. It was found that the atmospheric oxidation of AA is accelerated by the SDS up to the CMC and inhibited in the concentrated SDS solutions. We also found that the rate of atmospheric oxidation of ascorbic acid is higher in the water-in-oil (W/O) than in the oil-in-water (O/W) microemulsions and increases with the increasing oil content. The influence of the SDS on the electrochemical behavior of vitamin C was also studied. The general conclusion emerging from this investigation is that the increasing surfactant concentration shifts the ascorbic acid oxidation potential to higher values whereas the corresponding peak current values diminish. In the microemulsions the AA oxidation is slowed down by increasing the pentanol amount in the system.     

Phase behavior and structural properties for the triton X-100/<Emphasis Type="Italic">n</Emphasis>-C<Subscript>n</Subscript>H<Subscript>2n+1</Subscript>COOH/H<Subscript>2</Subscript>O system

In the Triton X-100/n-C_nH_2n+1COOH/H₂O system, n-C_nH_2n+1COOH can be used as a cosurfactant. As its chain length increases, the regions of the microemulsions showing oil-in-water (O/W), water-in-oil (W/O), and bicontinuous structures decrease and at the same time, the region of the lamellar liquid crystal increases. In the O/W region, the distribution coefficient K of n-C_nH_2n+1COOH between Triton X-100 micellar phase and water phase increases with the chain length of saturated unbranched monocarboxylic acid. The relationship between the standard solubilization Gibbs free energy of saturated unbranched monocarboxylic acid and the number of methylene groups in the saturated unbranched monocarboxylic acid is given by the equation: ΔG _m ⁰=−2.364−2.818 n(CH₂) kJ·mol⁻¹ in the Triton X-100 micellar system. In the lamellar liquid crystal region, small-angle X-ray diffraction shows that the thickness of the bilayer d ₀ is independent of the weight ratio of n-C_nH_2n+1COOH to Triton X-100, but the volume of the solvent penetrating from the solvent layer to the amphiphilic bilayer increases with the weight ratio of n-C_nH_2n+1COOH to Triton X-100. Furthermore, the d ₀ value increases with the chain length of saturated unbranched monocarboxylic acid, which will contribute to the formation and stabilization of the lamellar liquid crystal.     

Application of artificial neural network for vapor liquid equilibrium calculation of ternary system including ionic liquid: Water, ethanol and 1-butyl-3-methylimidazolium acetate

A feed forward three-layer artificial neural network (ANN) model was developed for VLE prediction of ternary systems including ionic liquid (IL) (water+ethanol+1-butyl-3- methyl-imidazolium acetate), in a relatively wide range of IL mass fractions up to 0.8, with the mole fractions of ethanol on IL-free basis fixed separately at 0.1, 0.2, 0.4, 0.6, 0.8, and 0.98. The output results of the ANN were the mole fraction of ethanol in vapor phase and the equilibrium temperature. The validity of the model was evaluated through a test data set, which were not employed in the training case of the network. The performance of the ANN model for estimating the mole fraction and temperature in the ternary system including IL was compared with the non-random-two-liquid (NRTL) and electrolyte non-random-two-liquid (eNRTL) models. The results of this comparison show that the ANN model has a superior performance in predicting the VLE of ternary systems including ionic liquid.     

Preparation and characterization of platinum-ruthenium bimetallic nanoparticles using reverse microemulsions for fuel cell catalyst

Platinum-ruthenium bimetallic nanoparticles are prepared by chemical reduction using sodium borohydride in reverse microemulsions of water/isooctane/Igepal CA-630/2-propanol for fuel cell catalysts. The prepared nanoparticles are characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and energy-dispersive X-ray analysis. The average size and morphology of nanoparticles are dependent on the water volume fraction in reverse microemulsion system in the range of ca. 2-4 nm. The morphology of particles is related with the percolation behavior of water droplets in reverse microemulsions. By the pretreatment of water phase using a hydrochloric acid, the particles of a homogeneous solid solution state can be obtained. The CO stripping cyclovoltammetry and the electrochemical measurements compared with commercial catalyst show that the prepared particles have a high electrochemically active surface area and a stable and high catalytic activity for reformate gas oxidation.     

Polymerization of acrylamide in single-phase in-verse dispersion systems at high volume fractions of dispersed phase

The preparation of single-phase inverse microemulsions of toluene/sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/water/acrylamide (AAm) is described and their properties prior to polymerization (macro and microviscosity as a function of volume fraction Φ_aw of the dispersed aqueous (water + acrylamide) phase, of the [to-luene]/[AOT] molar ratio and of the acrylamide/water mass ratio) were studied. The polymerization of acrylamide in dispersion systems was initiated by the oilsoluble initiator dibenzoyl peroxide at 60°C. The polymerization rate of acrylamide for a given [toluene]/[AOT] molar ratio and AAm/water mass ratio monotonically decreases beyond a Φ_aw value of 20%. The polymer particle size in polymerized systems as well as the molecular mass of polymer in the polymer particles increase on increasing the acrylamide concentration in the aqueous phase and/or the Φ_aw values of the dispersion system. On increasing the surfactant AOT concentration both polymer particle size and polymer molecular mass decrease for a given set of other relevant parameters of the dispersion system (i.e. [toluene]/[AOT] and AAm/water ratios). The polymerized inverse dispersion system can be converted to an oil-in-water dispersion by addition of water.     

吐温-80/正丁醇/环己烷/水系微乳液性能及对木材的渗透能力

考察了吐温-80/正丁醇/环己烷/水系微乳液各组分及其质量比对其形成的影响,通过电导率、表面张力和动态光散射(DLS)表征体系的物化性质。结果表明,以吐温-80为表面活性剂,正丁醇为助表面活性剂,环己烷为油相形成的微乳区较大。微乳体系的电导率随含水量的增加呈现规律性变化,可以判断微乳液的3种类型(油包水型、双连续型和水包油型);不同类型的微乳液均具有较低的表面张力(约24.6 mN/m)和粒径(小于100nm),且粒径随体系含水量的增加而增大。此外,采用液体吸收法考察了微乳液对木材的渗透能力,与普通溶剂相比,微乳液具有很强的渗透能力,特别是对于双连续型微乳液,10 min时,对马尾松和桉木的渗透能力分别达70%和50%。     

Olive oil microemulsions as a biomimetic medium for enzymatic studies: Oxidation of oleuropein

Microemulsions consisting of olive oil as the non-polar solvent, lecithin as surfactant, 1-propanol as cosurfactant, and water were prepared. The choice of the compositions of the microemulsions used was based on the pseudo-ternary phase diagrams of the system determined at 30°C, for different weight ratios of lecithin/olive oil. Lecithin solubilization and water incorporation in these microemulsion systems was limited. Tyrosinase, an oxidizing enzyme present in olives, was successfully incorporated in the water core of these microemulsions. Enzymatic oxidation of oleuropein, the most abundant olive phenolic compound, in the restricted aqueous environment of olive oil microemulsions was studied. Formation of oleuropein oxidation products was followed spectrophotometrically at 30°C for several minutes. An absorption maximum was observed at 415 nm. When the enzymatic reaction was considered at different tyrosinase and oleuropein concentrations, a rapid inactivation of the enzyme was observed. Addition of l-proline as a coupling reactor did not succeed in preventing enzyme inactivation in the microemulsions, probably owing to substrate localization and product accumulation around the entrapped enzyme molecules in the micellar interface.     

Particle-Inhibited Grain Growth in AI2O3-SiC: I, Experimental Results

An extensive experimental study has been conducted to examine the influence of ultraflne SiC particles on grain growth in A1₂O₃. Grain growth has been studied as a function of annealing time, particle volume fraction, and annealing temperature. The SiC particles reduce the grain-growth rate of A1₂O₃ by >3 orders of magnitude, resulting in final grain sizes that decrease with increasing particle volume fraction. The fraction of SiC particles on grain boundaries, φ, has been measured as a function of annealing time, particle volume fraction, and annealing temperature. φ decreases during grain-growth anneals, implying that grain boundaries are able to break free from particles and this is true to a greater extent for smaller volume fractions of particles. Further, it has been discovered that φ and average grain size, G , are strongly correlated, such that any increase in G results in a predictable decrease in pH. This new finding has revealed a path for microstructure development in this system that proves to be critical in the equilibrium and kinetic analyses described in a companion paper.     

柴油微乳液拟三元相图的研究

绘制了复合表面活性剂(D0821/Tx-4/AEO-3)/正戊醇/柴油/水体系在不同温度及不同正戊醇质量分数时的一系列拟三元相图。结果表明,正戊醇质量分数及温度对拟三元相图及水最大增溶量有很大影响,醇量太大或太小形成的微乳区面积均较小;温度升高,微乳区面积及水最大增溶量也大大减少;随着正戊醇质量分数的增大,每一个温度下的微乳区及其最大增溶水量都逐渐向AEO-3/正戊醇/油角漂移。     

水-乙醇-1-丁基-3-甲基咪唑乙酸盐三元体系汽液平衡测定及模型

Vapor-liquid equilibrium (VLE) data were measured for ternary system water + ethanol + 1-butyl-3- methylimidazolium acetate ([bmim][OAc]), in a relatively wide range of ionic liquid (IL) mass fractions up to 0.8. Six sets of complete T-x-y data were obtained, in which the mole fraction of ethanol on IL-free basis was fixed separately at 0.1, 0.2, 0.4, 0.6, 0.8, and approximate 0.98. The non-random-two-liquid (NRTL) and electrolyte non-random-two-liquid (eNRTL) equations were used for correlation, showing similar deviations. The ternary VLE was also modeled with the correlation from two data sets, with the mole fractions of ethanol on IL-free basis being 0.1 and approximate 0.98. The VLE data were also reproduced satisfactorily. With the eNRTL model, the root-mean-square deviation for temperature is 0.79 K and that for vapor-phase mole fraction is 0.0094. The calculations are in good agreement with experimental data. The effect of the IL on the VLE behavior of the volatile components is also illustrated.     

Soybean oil microemulsions with oleic acid/glycols as cosurfactants

The preparation of biocompatible microemulsions of soybean oil in systems made of anionic surfactant, oleic acid, water, and several glycols was considered. The selected glycols were ether derivatives (methyl, ethyl, dimethyl, and diethyl ether) of ethylene glycol and diethylene glycol. The study was performed using pseudoternary phase diagrams in which the three apexes were occupied by soybean oil, a combination of surfactant/oleic acid, and a combination of water/glycol, respectively. The widest regions of microemulsions were obtained for systems containing methyl ether and especially ethyl ether of both ethylene glycol and diethylene glycol. The two latter compounds allowed the preparation of oil-in-water, bicontinuous, and water-in-oil microemulsions with final surfactant contents of 3–4%.     

Elastic and Anelastic Response of Polycrystalline UO2-PuO2

A sonic resonance technique was used to investigate the room-temperature elastic and anelastic properties of physically mixed U_0.8PU_0.2O₂ as a function of density, stoichiometry, and cation homogeneity. The effect of porosity on the elastic moduli was linear and is described by E =2102.7 (1–2.03 P )± 13.5 Kbars for the Young's modulus, G =823.5(1–2.05 P )± 9.1 kbars for the shear modulus, and B = 1584.8(1–1.89 P )± 59.1 kbars for the bulk modulus, where P is the volume fraction porosity. Poisson's ratio was 0.28 and was not a function of porosity. The Debye temperature of U_0.8Pu_0.2O₂ computed from the Young's and shear moduli for theoretically dense specimens was 379°K. Variation of the O/M ratio from 1.968 to 2.006 produced no significant change in either the damping capacity or the elastic moduli of single-phase 80%UO₂-20% PuO₂ solid solutions. An approximate 24% decrease of the room-temperature Young's and shear moduli and an approximate increase by a factor of 14 in the internal friction were observed with gross modifications of plutonium cation homogeneity. Preliminary results suggest that internal friction measurements might be used to assay the homogeneity of UO₂-PuO₂ solid solutions.