Measurement and prediction of gas hydrate and hydrated salt equilibria in aqueous ethylene glycol and electrolyte solutions

A recently developed method in modelling electrolyte solutions is extended to include phase behaviour of aqueous solutions containing hydrated salts (e.g., calcium chloride) and organic hydrate inhibitors (e.g., ethylene glycol). A novel salt precipitation model applicable to various hydrated salts is presented. The precipitation model takes into account various precipitates of hydrated salts over a wide range of temperature (i.e., -20-120 ^°C). Due to lack of the required experimental data in the literature, new experimental data have been generated. These data, which have been used in determining the binary interaction parameters between salts and organic inhibitors, include; freezing point depression, boiling point elevation, and salt solubility in the aqueous solutions containing salts and organic inhibitors. The extended thermodynamic model is capable of predicting complex vapour-liquid-solid equilibria (VLSE) for aqueous electrolytes and/or organic inhibitor solutions over a wide range of pressure, temperature and inhibitor concentration.In addition, in order to establish the effect of a combination of salts and organic inhibitors on the locus of incipient hydrate-liquid water-vapour (H-L_W-V) curve, reliable equilibrium data have been generated for one quaternary system, methane/water/calcium chloride/ ethylene glycol at pressures up to 50 MPa. These data along with various independent literature data are used to validate the predictive capabilities of the model for phase behaviour and hydrate equilibria. Good agreement between experimental data and predictions is observed, demonstrating the reliability of the developed model.     

Extending the range of COSMO‐SAC to high temperatures and high pressures

The range of the predictive Gibbs energy of solvation model, COSMO‐SAC, is extended to large ranges of density, pressure, and temperature for very nonideal mixtures by combining it with an equation of state (EOS) using the Wong‐Sandler mixing rule. The accuracy of isothermal vapor‐liquid equilibria (VLE) calculations based on using the predictive COSMO‐SAC model and separately the correlative NRTL model is compared, each combined with three different forms of the Peng‐Robinson equation of state. All the models considered require the value of the EOS mixing rule binary parameter k_ij. The NRTL model also requires three other parameters obtained from correlation low pressure VLE data. The PRSV + COSMO‐SAC model is showed, with its one adjustable parameter obtained from low temperature data leads good predictions at much higher temperatures and pressures. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1806–1813, 2018     

A Novel Predictive Technique for Estimating the Hydrate Inhibition Effects of Single and Mixed Thermodynamic Inhibitors

A new correlation has been developed for predicting hydrate inhibition characteristics, as well as water freezing point depression of aqueous solutions containing salts and/or organic inhibitors. The correlation has been developed using hydrate inhibition/freezing point depression data at different concentrations of salt and/or organic inhibitor generated using a previously reported thermodynamic model. Independent data have been used in examining the reliability of this method. The predictions of this correlation are in acceptable agreement with the independent experimental data, demonstrating the reliability of this predictive technique for estimating the hydrate inhibition effects of salts and/or organic inhibitors.     

Modeling high pressure vapor–liquid equilibrium of ternary systems containing supercritical CO2 and mixed organic solvents using Peng–Robinson equation of state

High pressure vapor–liquid equilibrium (VLE) of CO₂-expanded organic solvents was investigated using Peng–Robinson-LCVM-UNIFAC equation of state. Bubble pressure of several ternary mixtures was predicted using this model and correlations were developed based only on binary experimental data. A sensitivity study of the LCVM parameter numerical value was done by considering the coherence between the mathematical features of the mixing rule and the quality of the simulation. The results provided by PR-LCVM-UNIFAC were compared with those ones given by Peng–Robinson equation of state using the classical quadratic mixing rules (PR-CMR). Despite the use of two adjustable parameters for each binary system, PR-CMR is not able to provide good results when applied to ternary systems. The capability of PR-LCVM-UNIFAC model to predict liquid mixture density for ternary systems using parameters regressed only from bubble pressure experimental data was also investigated. Due to the lack of liquid density experimental data, it was possible to perform only a qualitative assessment of the density curves calculated by this equation of state.     

Predicting the thermodynamic properties and dielectric behavior of electrolyte solutions using the SAFT‐VR+DE equation of state

We extend the SAFT‐VR+DE equation of state to describe 19 aqueous electrolyte solutions with both a fully dissociated and a partially dissociated model. The approach is found to predict thermodynamic properties such as the osmotic coefficient, water activity coefficient, and solution density, across different salt concentrations at room temperature and pressure in good agreement with experiment using only one or two fitted parameters. At higher temperatures and pressures, without any additional fitting, the theory is found to be in qualitative agreement with experimental mean ionic activities and osmotic coefficients. The behavior of the dielectric constant as a function of salt concentration is also reported for the first time using a statistical associating fluid theory (SAFT)‐based equation of state. At high salt concentrations, the stronger electrostatic interactions between the ionic species due to the dielectric decrement, is captured through the inclusion of ion association. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3053–3072, 2015     

A modification of Wong-Sandler mixing rule for the prediction of vapor-liquid equilibria in binary asymmetric systems

Systems consisting of light components and heavy hydrocarbons are highly asymmetric and industrially important. Design and control of facilities for separation and purification of such mixtures require vapor-liquid equilibrium data. Coupling of the cubic equation of state (EOS) with excess Gibbs energy models (EOS/G ^ex models) failed to represent the vapor-liquid equilibria (VLE) of such systems accurately. The main purpose of this work is to present a modification of Wong-Sandler mixing rule with using the composition dependent binary interaction parameter. Vaporliquid equilibria for 30 binary systems are calculated using the SRK equation of state with proposed model and Wong-Sandler mixing rule. Calculated pressures and mole fractions of vapor phase are compared with experimental data. The average absolute percentage deviation indicates that error involved in the application of modified Wong-Sandler model is less than Wong-Sandler model in most cases.     

Extension of Valderrama-Patel-Teja equation of state to modelling single and mixed electrolyte solutions

The Valderrama modification of Patel-Teja equation of state (VPT EoS) has been extended to predicting fluid phase equilibria in the presence of single and mixed electrolyte solutions at high-pressure conditions. Salts have been introduced as components in the EoS by calculating their EoS parameters from corresponding cation and anion parameters. A non-density dependent mixing rule is used for calculating a, b, and c parameters of the EoS. The inclusion of salts in the EoS resulted in the omission of the Debye-Hückel electrostatic contribution term in the fugacity coefficient calculations. Water-salt binary interaction parameters (BIPs) are optimised using freezing point depression and boiling point elevation data of aqueous electrolyte solutions. Gas solubility data in aqueous electrolyte solution are used for optimising salt-gas BIPs. The predictions of the model have been compared with independent experimental data, demonstrating the reliability of the approach.     

Application of peng-Robinson equation to high-pressure aqueous systems containing gases and sodium chloride

A novel approach is proposed for modeling vapor-liquid equilibria in systems containing aqueous NaCl and supercritical gases. The Peng-Robinson equation of state is used for all species, with the salt treated as a hypothetical liquid component. To correctly model the highly non-ideal liquid solution, a two-fluid model is used for the mixing rules in the equation of state. Effective pure-component parameters are reported for NaCl as well as binary interaction parameters for all possible binaries. Representation of high-pressure phase equilibria data show good agreement with experimental data. The principal advantage of this approach is the ability to treat high pressure systems containing non-volatile salts, while maintaining the simplicity of a cubic equation of state.     

A GE/Equation of State Mixing Rule for Vapor-Liquid Equilibria

A new excess Gibbs free energy/equation of state type mixing 0rule was derived byremoving the infinite pressure boundary condition imposed by Wong and Sandler.The mixing rulewas extensively tested in terms of a comprehensive data base,consisting of 52 simple nonpolar-nonpolar,carbon dioxide containing,hydrocarbon-hydrocarbon,CFC,polar-polar,nonpolar-polarbinary and multicomponent systems.Focused on the complete predictive capability,a comparisonbetween the Wong-Sandler and the mixing rule proposed was conducted.The results indicate that thenew mixing rule is in general superior to the Wong-Sandler's,and the binary interaction parameteras required by the latter is removed,which reduces computing effort and is reliable in predictions ofvapor-liquid equilibria from low pressures to high pressures.     

Materials with required dielectric properties: Computational development and production of polymer‐ceramic composites

Many applications in wireless communication, microelectronics, and microwave power engineering rely on dielectrics with particular dielectric properties. This article proposes an original approach that can be used for producing materials with required complex permittivity. The technique is based on an inverted power‐law mixing rule model computing volume fractions in which three or more prime materials should be taken to get in the resulting homogeneous mixture the required dielectric properties. Functionality of the approach is demonstrated by production of composites from a polymer matrix (polymethyl methacrylate) and two inorganic fillers (silicon and alumina). The composites are made by mechanically mixing the powders and axially hot‐pressing and cooling the mixture. Complex permittivity of the samples is measured by a split‐post resonator method. Experimental data on dielectric properties of the samples help calibrate the technique; for the used powders, the Looyenga power‐law model is found to be most adequate. In the produced samples, the target values of dielectric constant are reached with a higher precision than the ones of the loss factor; however, analysis of the production process and error propagation in the computations suggest that deviations of the resultant complex permittivity fall in the anticipated ranges. Features and issues of both computational and production parts of the technique are finally discussed. POLYM. ENG. SCI., 58:319–326, 2018. © 2017 Society of Plastics Engineers     

Cyclic interaction between normal and shear stresses of an epoxy polymer—Experiments and model predictions

This investigation focuses on the axial‐torsional loading interaction of an epoxy polymer, Epon 826/Epi‐Cure Curing Agent 9551. Thin‐walled tubular specimens were subjected to combined constant tensile (or shear) stress and cyclic shear (or tension) loading schemes. Pure tensile creep and shear creep tests were also performed to compare the creep deformation to that with superimposed cyclic shear or cyclic tension. Test data clearly showed that cyclic shear (or cyclic tension) have a readily discernible effect on the tensile (or shear) creep deformation. Similarly, a superimposed constant tensile (or shear) load affects the hysteresis responses in cyclic shear (or cyclic tension). A nonlinear constitutive model developed by the authors was used to simulate the observed normal‐shear stress interaction. Due to the inclusion of an effective stress parameter in its nonlinear function, this model was able to account for the normal‐shear coupling effect. However, the incorporation of a general loading/unloading rule led to inaccurate simulation of the observed oscillatory creep response. A modification of the general rule was proposed and better predictions on both the cyclic and the creep responses could be obtained. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

A modified Kurihara mixing rule and a comparison of density-independent mixing rules

A modified density-independent Kurihara mixing rule is developed by introducing the low density limit condition into the excess Helmholtz free-energy function at infinite pressure. A parallel comparison of the new mixing rule and existing density-independent mixing rules was performed using the same equation of state and excess function and the same experimental data sets. Five existing density-independent mixing rules were examined: Huron and Vidal (1979), Kurihara et al. (1987), Wong and Sandler (1992) and van der Waals mixing rules with one or two binary interaction coefficients. Non-polar, non-polar-polar and polar-polar binary and ternary systems have been tested.     

醋酸甲酯-甲醇-水体系的盐效应

在20℃的条件下研究了加入氯化钙对醋酸甲酯-甲醇-水体系产生的盐效应。实验结果表明,随着初始水相中氯化钙质量分数的增加,两相区逐渐扩大,醋酸甲酯在水相的溶解度和水在有机相中的溶解度均有所降低。在有机相中甲醇质量分数一定的条件下,随着初始水相中氯化钙质量分数的增加,甲醇在有机相和水相间的分配系数减小,甲醇的选择性系数而增大。这些结论表明,采用加盐萃取对醋酸甲酯和甲醇进行分离十分有利。对该含盐体系的液—液平衡数据采用Eisen-Joffe方程进行了关联,关联值与实验值的平均相对偏差为4 08%。     

High‐k dielectric composites of poly(2‐cyanoethyl vinyl ether) and barium titanate for flexible electronics

High‐k dielectric composite material for electronic applications was obtained by mixing a polymer with high dielectric constant, poly(2‐cyanoethyl vinyl ether) (CEPVA), and highly crystalline barium titanate (BT). Barium titanate nanoparticles of a size in the range 40–90 nm were prepared by the solvothermal method. By optimizing the reaction conditions, the formation of carbonate impurities and the agglomeration of formed nanoparticles were significantly reduced compared to state‐of‐the‐art procedures. Dielectric spectroscopy was measured in the range of 0.01 Hz to 10 MHz and showed the dielectric constant to be ?′ ～ 35–40 with only 30 vol % content of BT in the composite. Extrapolating to 100% BT nanoparticle concentration and using the Lichtenecker model, the dielectric constant ?′ = 365 ± 27 at 10 kHz was obtained. The relaxation and electrical properties were investigated in depth, and a new relaxation phenomenon was revealed. CEPVA/BT composite is considered suitable for electronic applications, in which high ?′ together with a good mechanical flexibility are required, such as organic field effect transistors. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45236.     

Electrochemical synthesis of tetra-alkylthiuram disulphides in emulsions

Sodium dimethyldithiocarbamate, NaDTC, was electrochemically oxidized to tetramethylthiuram disulphide, TMT, in an univided electrolytic cell using a couple of rhutenized titanium electrodes; in earlier work the electrodes were platinum. The reaction was carried out in an emulsion formed by mixing saturated aqueous sodium chloride solution containing the substrate with a suitable organic solvent at constant current density. The product was obtained with a high yield and high degree of purity after the passage of the theoretical amount of charge. It was found that at a high current density and a high reactant concentration the product solubility in the organic solvent used determines the success of the electrochemical reaction. Possible reaction mechanisms are also discussed.     

Fabrication of barium titanate nanoparticles‐polymethylmethacrylate composite films and their dielectric properties

A method for incorporating barium titanate (BT) nanoparticles into polymethylmethacrylate (PMMA) is proposed to prepare composite films with a high dielectric constant and high transparency. BT particles with particle sizes of 7.8–24.0 nm and crystal sizes of 8.60–17.7 nm were synthesized with a complex alkoxide method. Surface of the BT particles was modified with 3‐methacryloxypropyltrimethoxysilane to introduce double bonds that was grafted with PMMA. The PMMA‐grafted BT particles were suspended in PMMA/N‐methyl‐2‐pyrrodinone solution and spin‐coated onto glass substrates to prepare the PMMA/BT composite films. The surface modification gave composite films having smooth surfaces and high transparency. An increase in BT particle size and BT volume fraction in the film tended to increase the dielectric constant while keeping the dissipation factor around 5%. The dielectric constant of the film prepared for a particle size of 24.0 nm at 39 vol% attained a value of 19.8 that was around four times higher than that of the pure PMMA film. The dielectric constants of the BT particles estimated by the application of Lichtenecker's mixing model to the composite films were 75.3, 105.1, and 166.3 for particle sizes of 7.8, 11.0, and 24.0 nm, respectively. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Crystallization Kinetics and Properties of Nonstoichiometric Cordierite-Based Thick-Film Dielectrics

Dielectric thick films based on a nonstoichiometric cordierite (2.4MgO·2Al₂O₃·5SiO₂, containing 3 wt% B₂O₃, 3 wt% P₂O₅, and 3 wt% PbO) were investigated, in regard to their microstructure, crystallization kinetics, and properties. A stable glass-ceramic thick-film microstructure that was formed on a 96% alumina substrate was observed after firing at a temperature of 915°C for 30 min in a nitrogen atmosphere. No µ-cordierite was observed in the X-ray diffraction (XRD) patterns of the thick film. The crystallization kinetics were studied via quantitative XRD analysis using the Avrami equation, and the rate constant increased as the temperature increased. The decreasing tendency of the Avrami parameter, relative to temperature, suggested a change in growth directionality during crystallization. The activation energy for crystallization of the thick film was determined to be ~83 kcal/mol (~350 kJ/mol). The coefficient of thermal expansion (CTE) and the dielectric constant of the glass phase were evaluated using the bulk-sample data. For the case of a 3-wt%-PbO sample fired at 950°C for 30 min in a nitrogen atmosphere, the remaining glass was estimated, using the parallel mixing rule, to have a dielectric constant of 15.3 at 1 MHz. The dielectric constant of the remaining glass was dependent on the PbO content and the heat-treatment temperature. The estimated CTE of the remaining glass for the 3-wt%-PbO sample was 19 × 10^-6/°C.     

Calculation of the solid solubilities in supercritical carbon dioxide using a new G mixing rule

The aim of this study is to develop a new EOS/G^ex-type mixing rule with special attention to calculating the solid solubilities of aromatic hydrocarbons, aliphatic carboxylic acids, aromatic acids, and heavy aliphatic and aromatic alcohols in supercritical carbon dioxide. A volume correction term is applied with a combination of second and third virial coefficients which the equation for the third virial coefficient is quadratic, according to the suggestion by Hall and Iglesias-Silva. In this study, the cubic Peng-Robinson (PR) and Soave-Redlich-Kwong (SRK) equations of state have been used to calculate the solid solubilities of 23 solutes in supercritical CO₂, by using six mixing rules, namely, the Wong-Sandler (WS) rule, the Orbey-Sandler (OS) rule, the van der Waals one fluid rule with one (VDW1) and two (VDW2) adjustable parameters, the covolume dependent (CVD) rule and the new mixing rule. In all cases, the NRTL model was chosen as the excess Gibbs free energy model. The coefficients of the NRTL model and the binary interaction parameters of six mixing rules with two EOSs (PR and SRK EOSs) have been determined for 100 data sets of 23 binary systems over a wide range of temperatures and pressures covering more than 970 experimental data points which are reported in the literature. The results show that the PR EOS with the new mixing rule model is more accurate than the PR and SRK EOSs with the other mixing rules for solid solubility calculations in supercritical carbon dioxide.The regressed interaction parameters of the binary system, without any further modification, were then extended to four ternary mixtures, giving satisfactory results of the solid solubilities in supercritical CO₂.     

Cloud‐point measurements for salt + poly(ethylene glycol) + water systems by viscometry and laser beam scattering methods

The phase separation of salt + poly(ethylene glycol) + water systems was studied by cloud‐point measurements using viscometry and laser beam scattering methods. The Flory–Huggins model was applied to determinate the condition for salt‐induced liquid–liquid phase separation in the system. A temperature‐ and concentration‐dependent interaction parameter was employed to fit the phase diagrams for the systems. The temperature and concentration functionality of the interaction parameter was determined and used to predict cloud‐point curves for the systems. The cloud‐point curves were found to be in quantitative agreement with experimental data. Also, the effect of various salts on the measured cloud points was studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1983–1990, 2003     

Photoinduced mesoporosity of Tert‐butoxycarbonyl acrylic photosensitive material with low dielectric constant

We have developed a photosensitive system having low dielectric constant with mesoporous. The photosensitive system we developed is patternable and the mesoporosity is generated through the combination of photo exposure and thermal treatment. The mesopores were formed in a photosensitive material to reduce its dielectric constant. Tert‐butoxycarbonyl (t‐BOC) containing acrylic copolymer was activated as a photosensitive material via photochemical reactions. Iodonium salt as a photo acid generator was exposed to ultraviolet light with a wavelength of under 365 nm to form the corresponding Lewis acid. The side chains of t‐BOC were cleaved by this Lewis acid to yield isobutylene and acrylic acid groups. The small molecules thus formed were further heated in the polymer matrix to generate mesopores. Notably, the t‐BOC content and heat affect the dimensions and number of mesopores. The dielectric constant decreased as the density of mesopores increases. The formation of mesopores was observed by transmission electron microscope and scanning electron microscopy. We have also studied the mechanisms of formation of mesopores and their effects on the dielectric constant. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013