Ternary Solutions Research Articles

Precision Polymer Particles by Flash Nanoprecipitation and Microfluidic Droplet Extraction

We comparatively review two versatile approaches employed in the precise formation of polymer particles, with length scales from 10s of nm to to 100s μm, from ternary polymer(s), solvent and nonsolvent mixtures. Flash nanoprecipitation (FNP) utilizes an opposing jet arrangement to mix a dilute polymer solution and a nonsolvent in confinement, inducing a rapid (∼millisecond) chain collapse and eventual precipitation of nanoparticles (NPs) of 10–1000 nm diameters. FNP of polymer mixtures and block copolymers can yield a range of multiphase morphologies with various functionalities. While droplet solvent extraction (DSE) also involves the exposure of a polymer solution to a nonsolvent, in this case the polymer solution is templated into a droplet prior to solvent extraction, often using microfluidics, resulting in polymer particles of 1–1000 μm diameter. Droplet shrinkage and solvent exchange are generally accompanied by a series of processes including demixing, coarsening, phase inversion, skin formation, and kinetic arrest, which lead to a plethora of possible internal and external particle morphologies. In the absence of external flow fields, DSE corresponds effectively to nonsolvent induced phase separation (NIPS) in a spherical geometry. In this review, we discuss the requirements to implement both approaches, detailing consequences of ternary solution phase behavior and the interplay of the various processes underpinning particle formation and highlighting the similarities, differences, and complementarity of FNP and DSE. In addition to reviewing previous work in the field, we report comparative experimental results on the formation of polystyrene particles by both approaches, emphasizing the importance of solution phase behavior in process design.

Ternary Hybrid Perovskite Solid Solution Single Crystals: Growth, Composition Determination and Phase Stability in Highly Moist Atmosphere.

Ternary hybrid perovskite solid solutions have shown superior optoelectronic properties and better stability than their ABX3 simple perovskite counterparts under ambient conditions. However, crystal growth and identification of the accurate composition of these complex crystalline compounds remain challenging, and their stability under extreme conditions such as in highly moist atmosphere is unknown. Herein, large-size (up to 2 cm) single crystals of ternary perovskite 0.80FAPbI3 ⋅ x'FAPbBr3 ⋅ y'CsPbI3 (x'+y'=0.20) are grown. An elemental analysis method based on wavelength dispersive X-ray fluorescence is proposed to determine their accurate compositions. Among these single crystals, the composition with y'=0.12 shows the best moisture stability at 90 % relative humidity for 15 days. Other components with richer or poorer Cs+ ions undergo different phase segregation behaviours. The performance and stability of photodetectors based on these single crystals are tested. This work offers a deeper insight into phase stability of ternary hybrid perovskite solid solution crystals in highly moist atmosphere.

Osmotic dehydration kinetics of fresh and frozen blueberries considering volume shrinkage in a novel ternary solution

Osmotic dehydration is a nonthermal processing technology, that is limited in blueberries because of the osmotic agent, temperature and efficiency. This study was to prepare a novel ternary solution considering low-sugar, low-salt and low-viscosity requirements and to dehydrate blueberries at 20 °C. The mass transfer kinetics of fresh and frozen blueberries were explored in ternary solution considering the volume shrinkage of blueberries. The results showed that the 40%/50% xylitol solution had the lowest viscosity in polyols at 20 °C. The addition of 5%/10% CaCl2 had no significant effect on the viscosity of the ternary solution. Frozen blueberries had higher OD efficiency and less equilibrium time than fresh blueberries at 600 rpm vibration speed and 50%xylitol/10%CaCl2 concentration. There was competition between xylitol and CaCl2 transfer at shorter dehydration times for fresh blueberries, which was not significant in frozen blueberries and with longer times. Considering volume shrinkage of the blueberries, the effective diffusion coefficient of water and solute was calculated. The vibration speed had a significant effect on the effective diffusion coefficient, which governed the mass transfer efficiencies of the blueberries in the ternary solution.

Evaluation of possible interactions for ionic liquids [Emim][HSO4] and [Bmim][BF4] in aqueous sorbitol solutions at T = (293.15–313.15) K by volumetric data

Our systematic volumetric studies on the aqueous solutions containing ionic liquids and carbohydrates is followed in this research by consideration of the ternary (1-butyl-3-methylimidazolium tetrafluoroborate or 1-ethyl-3-methylimidazolium hydrogen sulfate + sorbitol + water) mixtures. For this purpose, via the measured density data, apparent molar volumes, their values at infinite dilution and apparent molar expansibility for these ionic liquids (ILs) in aqueous sorbitol solutions have been calculated. By means of these information, as where as possible, solute =solvent and solute-solute interactions in these systems are discussed. Hydrophilic–hydrophobic hydrophobic–ionic and hydrophobic–hydrophobic interactions are governing in the considered ternary solutions. Both ionic liquids act as structure maker in these solutions.

Thermal Conductivity of Disordered Continuous Ternary Solid Solutions of Semiconductor Compounds PbTe–PbSe–PbS

Thermal Conductivity of Disordered Continuous Ternary Solid Solutions of Semiconductor Compounds PbTe–PbSe–PbS

Improvement in Solubility and Absorption of Nifedipine Using Solid Solution: Correlations between Surface Free Energy and Drug Dissolution.

Ternary solid solutions composed of nifedipine (NDP), amino methacrylate copolymer (AMCP), and polysorbate (PS) 20, 60, or 65 were prepared using a solvent evaporation method. The dissolution profiles of NDP were used to study the effect of the addition of polysorbate based on hydrophilic properties. A solid solution of NDP and AMCP was recently developed; however, the dissolution of NDP was <70%. In the present study, polysorbate was added to improve the dissolution of the drug by altering its hydrophilicity. The suitable formulation contained NDP and AMCP at a ratio of 1:4 and polysorbate at a concentration of 0.1%, 0.3%, or 0.6%. Differential scanning calorimetry and powder X-ray diffraction were used to examine the solid solutions. No peak representing crystalline NDP was observed in any solid solution samples, suggesting that the drug was molecularly dispersed in AMCP. The NDP dissolution from NDP powder and solid solution without PS were 16.82% and 58.19%, respectively. The highest dissolution of NDP of approximately 95.25% was noted at 120 min for the formulation containing 0.6% PS20. Linear correlations were observed between the surface free energy and percentages of dissolved NDP (R2 = 0.7115–0.9315). Cellular uptake across Caco-2 was selected to determine the drug permeability. The percentages of cellular uptake from the NDP powder, solid solution without and with PS20 were 0.25%, 3.60%, and 7.27%, respectively.

CO2 absorption mechanism in aqueous ternary solutions of alkanolamines: Experimental and thermodynamic modeling approaches

The absorption mechanism of CO2 in an aqueous solution containing three alkanolamines was analyzed experimentally and theoretically. The vapor–liquid equilibrium of a CO2–monoethanolamine (MEA)–diisopropanolamine (DIPA)–2-amino-2-methyl-propanol (AMP)–H2O system was evaluated experimentally over a wide temperature range (323.15–393.15 K) at several MEA:DIPA:AMP:H2O blending ratios (15:10:5:70, 10:10:10:70, 7.5:7.5:15:70, and 5:15:10:70 wt%). The successive substitution method was used to calculate the concentrations of five molecules (CO2, MEA, DIPA, AMP, and H2O) and nine electrolytes (four cations and five anions) in the liquid phase by solving eight equilibrium equations, four mass balance equations, and one charge balance equation. The Deshmukh–Mather model, which is based on an activity coefficient approach, and the fugacity coefficient model were used to evaluate the nonideality of the liquid and vapor phases, respectively. Thereafter, the effect of the MEA:DIPA:AMP blending ratio was evaluated using the triangular diagrams of the carbamate, bicarbonate and carbonate molar fractions in liquid phase, CO2 loading ratio, CO2 cyclic capacity, and heat of CO2 absorption.

Thermodynamic Optimization of the Ternary Ga-Sn-Te System Using Modified Quasichemical Model

Thermoelectric (TE) materials are of great interest to many researchers because they directly convert electric and thermal energy in a solid state. Various materials such as chalcogenides, clathrates, skutterudites, eutectic alloys, and intermetallic alloys have been explored for TE applications. The Ga-Sn-Te system exhibits promising potential as an alternative to the lead telluride (PbTe) based alloys, which are harmful to environments because of Pb toxicity. Therefore, in this study, thermodynamic optimization and critical evaluation of binary Ga-Sn, binary Sn-Te, and ternary Ga-Sn-Te systems have been carried out over the whole composition range from room temperature to above liquidus temperature using the CALPHAD method. It is observed that Sn-Te and Ga-Te liquids show the strong negative deviation from the ideal solution behavior. In contrast, the Ga-Sn liquid solution has a positive mixing enthalpy. These different thermodynamic properties of liquid solution were explicitly described using Modified Quasichemical Model (MQM) in the pair approximation. The asymmetry of ternary liquid solution in the Ga-Sn-Te system was considered by adopting the toop-like interpolation method based on the intrinsic property of each binary. The solid phase of SnTe was optimized using Compound Energy Formalism (CEF) to explain the high temperature homogeneity range, whereas solid solution, Body-Centered Tetragonal (BCT) was optimized using a regular solution model. Thermodynamic properties and phase diagram in the Ga-Sn-Te and its sub-systems were reproduced successfully by the optimized model parameters. Using the developed database, we also suggested several ternary eutectic compositions for designing TE alloy with improved properties.

Thermal stability of CrAlN/AlCrN nanolaminate coating deposited by hybrid dcMS/HPPMS after heat treatment with continuous-wave laser

Nanolaminate coatings consisting of hundreds of alternating CrN and AlN nanolayers can be used as protective coatings on various manufacturing technology tools. In this work, a coating is investigated, which is deposited using a hybrid direct current and high power pulse magnetron sputtering technology. The coating exhibits a nanolaminate architecture and its nanolayers consist of cubic CrAlN and AlCrN ternary solid solution phases. In order to study the thermal stability especially in the near-surface area of the coating, it is heat treated by using a continuous-wave laser at two different laser power densities. Laser induced heat-affected zone as well as punctual Al-rich precipitates, which are formed at the interface between the Al–rich AlCrN nanolayers and the column boundaries, are investigated using transmission electron microscopy. Moreover, it is demonstrated that the indentation hardness and indentation modulus of the coating are affected only to a small extent by the continuous-wave laser heat treatment.

Phase Separation of an Evaporating Ternary Solution in a Hele-Shaw Cell.

In the present work, we investigate the dynamic phenomena induced by solvent evaporation from ternary solutions confined in a Hele-Shaw cell. The model solutions consist of ethanol, water, and oil, and with the decrease in ethanol concentration by selective evaporation, they may undergo microdroplet formation via the ouzo effect or macroscopic liquid–liquid phase separation. We varied the initial concentration of the three components of the solutions. For all ternary solutions, evaporation of the good solvent ethanol from the gas–liquid interface, aligned with one side of the cell, leads to a Marangoni instability at the early stage of the evaporation process. The presence of the Marangoni instability is in agreement with our recent predictions based on linear stability analysis of binary systems. However, the location and onset of subsequent microdroplet formation and phase separation are the result of the interplay between the Marangoni instability and the initial composition of the ternary mixtures. We classified the ternary solutions into different groups according to the initial concentration of oil. For each group, based on the ternary diagram of the mixture, we offer a rationale for the way phase separation takes place and discuss how the instability influences droplet nucleation. Our work helps us to understand under what conditions and where droplet nucleation can take place when advection is present during phase separation inside a microfluidic device.

Flash point measurement and prediction of dodecane + ethanol + FAEE systems

As interest in biofuel blends has grown through the years, especially in terms of jet fuel blend development, it has become more and more important to be aware of their physical chemical properties. One of them is the Flash Point (FP), which is intimately related to the flammability of the blend. With this in mind, the aim of this study was to determine experimentally and also mathematically new FP data on binary and ternary solutions containing ethanol, fatty acid ethyl esters (FAEE), and dodecane, as a way of providing data for flammability evaluation of jet fuels based on surrogates. Therefore, FPs of seventeen binary systems and eight ternary systems were measured. A vapor pressure approach was employed to FP prediction with NRTL and original UNIFAC activity coefficient models in order to further analyze flammability in terms of solution behavior, while providing guidance for FP prediction of these systems, needed for fuel development. NRTL binary interaction parameters were adjusted from FP data, as these parameters are not available in the literature for FAEE multicomponent systems. It was observed that addition of ethanol to dodecane or FAEEs steeply decreases FP. On the other hand, addition of FAEEs to dodecane does not affect FP as drastically, which implies an almost ideal behavior for these systems. Both the original UNIFAC and NRTL models were able to improve FP prediction in comparison to the ideal model for all ternary systems with RMSDs ranging from 4.6 K to 0.5 K and 1.3 K to 0.3 K respectively, which points to the validity of the adjusted NRTL parameters.

Cu2MoS4-based magnetic composites as effective adsorbent and photocatalyst for removal of organic contaminants in water

The wastewater containing pharmaceutical and personal care products (PPCPs) could not be removed effectively by traditional sewage treatment technologies and was directly discharged into the natural environment, causing serious threats to environment and human health. In this study, polypyrrole-functionalized Cu2MoS4 magnetic composites (Cu2MoS4-Fe3O4@PPy) were prepared and applied as an adsorbent for the removal of PPCPs from aqueous solution. Cu2MoS4-Fe3O4@PPy exhibited synergistic effects and showed excellent adsorption performances for indomethacin (IDM) and ketoprofen (KET) with removal efficiencies of 97.1% and 88.6% at initial pollutant concentration of 10 mg/L, respectively. It was also found that IDM and KET could be effectively removed by Cu2MoS4-Fe3O4@PPy in a wider pH range (5.0-11.0). Cu2MoS4-Fe3O4@PPy could be separated easily with a magnet and possessed the removal efficiency up to 83% even after eight adsorption-desorption cycles. Furthermore, the potential applications of Cu2MoS4-Fe3O4@PPy as a photocatalyst after the deposition of silver nanoparticles were further explored. Under visible-light irradiation, the Cu2MoS4-Fe3O4@PPy-Ag could quickly degrade malachite green (MG) with 94.8% removal within 60 min and had higher selectivity for MG in dual and ternary dye solutions. Due to excellent performances in adsorption and photocatalysis, Cu2MoS4-based magnetic composites had great potential application in the treatment of wastewater containing organic pollutants.

Intrinsic Pseudocapacitive Affinity in Manganese Spinel Ferrite Nanospheres for High-Performance Selective Capacitive Removal of Ca2+ and Mg2.

Pseudocapacitor-type hybrid capacitive deionization (PHCDI) has been developed extensively for deionization, which enables to address the worldwide freshwater shortage. However, the exploitation of selective hardness ion removal in resourceful hard water via the intrinsic pseudocapacitive effect, rather than the ion-sieving or ion-swapping effect based on the electric double layer (EDL) of porous carbon, is basically blank and urgent. Herein, manganese spinel ferrite (MFO) nanospheres were successfully fabricated by one-step solvothermal synthesis and used as the cathode for PHCDI assembled with commercial activated carbon. The MFO electrode exhibited prominent capacities of 534.6 μmol g-1 (CaCl2) and 980.4 μmol g-1 (MgCl2), outperforming those of other materials ever reported in the literature. Fascinatingly, systematic investigation of binary and ternary ion solutions showed the high electro-affinity of hardness ions (Ca2+ and Mg2+) toward Na+, especially the leading affinity of Mg2+, in which the superhigh hardness selectivity of 34.76 was achieved in the ternary solution with a molar ratio of Na-Ca-Mg as 20:1:1. Unexpectedly, the ion-swapping trace in a multi-ion environment was also first detected in our pseudocapacitive-based electrode. The electrochemical response in unary and multiple electrolytes disclosed that the unique pseudocapacitive affinity based on the cation (de)intercalation-redox mechanism was from the synergistic effect of the relative redox potential, ionic radius, and valence, in which the redox potential was the dominant factor.

Separation and Recovery of Gold(III), Palladium(II) and Platinum(IV) by Solvent Extraction Using a New β-Diketone Derivative from Acidic Solutions.

This study indicates that a new amine derivative of β-diketone (EDAB-acac) can be successfully used in an acidic medium (HCl) to separate a mixture containing Au(III), Pd(II), and Pt(IV) ions using solvent extraction. The study was conducted in single and ternary model solutions. The impact of acid concentration and the type of solvent (toluene, chloroform, methylene chloride, 2-ethylhexanol) on separation efficiency was discussed. It has been shown that increasing the HCl concentration in the aqueous phase does not favor extraction. In contrast, solvents with high donor numbers (methylene chloride, 2-ethylhexanol) increase both the extraction percentage of Pd and Au as well as the separation coefficients of Pd in relation to Au and Pt. The palladium(II) and gold(III) (which form 4-coordinated planar [MCl4]2− complexes) are extracted most efficiently, Pd(II) (87–93%) and Au(III) (56–62%). The stripping of Au(III), Pd(II), and Pt(IV) ions from the EDAB-acac-methylene chloride phase was also investigated using 0.5 M ammonia aq., mineral acid (5 M HCl, 5 M HNO3), 0.1 M thiourea in HCl and 0.5 M ammonium thiocyanate. A 3-step stripping process was proposed for the recovery of Pd(II), Au(III), and Pt(IV) from the Pd-Au-Pt mixture in the EDAB-acac-methylene chloride system. In the first stage, the aqueous phase is treated with 5 M HNO3 (Pt separation), followed by the application of 0.5 M ammonia (Pd separation) and, finally, 0.1 M thiourea in HCl (Au separation). The solvent extraction with EDAB-acac in acidic medium (HCl) can be used for separation of Pd(II) and Au(III) ions from e-waste leach solutions.

Surface tension of binary and ternary polymer solutions: Experimental data of poly(vinyl acetate), poly(vinyl alcohol) and polyethylene glycol solutions and mixing rule evaluation over the entire concentration range

In order to assess the driving forces of Marangoni instabilities in drying polymer solution films, surface tension data over a wide concentration are necessary. While experimental data and mixing rule equations for the surface tension of liquid-liquid mixtures are readily available, data for polymer solutions are scarce. The aim of this work is to report surface tension data of methanol-toluene-poly(vinyl acetate), methanol-water-polyethylene glycol and water-poly(vinyl alcohol) solutions as well as to evaluate the applicability of available liquid-liquid mixing rule equations on polymer solutions despite an inevitable data gap at low solvent concentrations due to viscosity increase and solidification. The fit quality was assessed by calculating the averaged deviation as well as by manually checking for implausible curve shapes in the respective concentration data gaps. Several available but slightly modified equations are well equipped to describe the concentration and temperature dependent surface tension of the material systems under investigation. Recommendations are given for binary and ternary solutions.

Resistive Switching Effect of Multiferroic Complex Oxide Solid Solution Thin Films

Resistive switching in multiferroics has attracted increasing attention due to the potential application for next-generation nonvolatile memory and could lead to forms of computing. However, the resistive switching mechanism in solid solution oxides is unclear. In this article, we have successfully fabricated binary 0.72BiTi0.27Fe0.46Mg0.27O3-0.28LaFeO3 (BTFM-LFO) and ternary 0.625BiTi0.27Fe0.46Mg0.27O3-0.25LaFeO3-0.125La2MgTiO6 (BTFM-LFO-LMT) thin films with precise component control by the spin coating method. The solid solution films exhibit obvious ferroelectricity and magnetism at room temperature. Both binary and ternary solid solution films show switchable polarization, weak magnetism, and reversible and repeatable resistive switching effects. Multistage resistive switching behavior was observed. Four resistive switching states were obtained in the binary film; the highest Ion/off is up to 106. The influence of the film composition on the resistive switching effect was discussed. It is considered that the oxide vacancy/valance exchange-induced defects play a dominant role in the resistive switching effect of complex oxide thin films. This work provides an alternative pathway to explore the resistive switching in multiferroic oxides by fabrication of complex solid solution films.

Alternative formalism for the evaluation of the activity coefficients on ternary electrolyte solutions from osmotic coefficient data

An alternative method is presented, which is independent of any physicochemical model of the electrolyte solution, for the evaluation of the mean ionic activity coefficient in molal scale, γ±i (i: 2,3), of the solutes of a ternary solution (1–2–3), starting from experimental data of the osmotic coefficient on composition ϕexp(m,xi). It is based on the dependence of ln γ±i on ϕ originally derived by H.A.C. McKay and confirmed by S.G. Canagaratna and M. Maheswaran as a particular solution of Gibbs-Duhem equation for multicomponent systems. Its application involves the integration of both ϕ and its derivative ∂ϕ/∂mi, so that it requires a very precise correlation of the dependence ϕexp(m,xi). Therefore, in order to achieve the required precision, the theoretical expression ϕ(m,xi) is developed as the sum of three contributions, (i) ϕDH: the limiting behaviour given by the Debye-Hückel equation for multicomponent systems, (ii) ΔϕDDH: the sum of the deviations to the Debye-Hückel behaviour of the corresponding binary solutions (1–2 and 1–3) and (iii) ΔϕM: a contribution of mixing effect. Finally, introducing the resulting ϕ(m,xi) into the Gibbs-Duhem equation and operating, the corresponding expression of ln γ±i (m,xi) is derived. The capacity of the ϕ(m,xi) equation to correlate the dependence ϕexp(m,xi), the methodology employed to obtain the parameters values, as well as the ln γ±i (m,xi) resulting dependence are illustrated through its application to the analysis of two ternary systems.

Investigation of molecular interactions insight into some biologically active amino acids and aqueous solutions of an anti-malarial drug by physicochemical and theoretical approach

Herein we have made a comprehensive analysis of the mode of interactions between the L-Alanine/L-Valine and Chloroquine diphosphate in aqueous solution. Evaluation of different Physico-chemical parameters like density, viscosity, refractive index, conductance study (at three different temperatures), and surface tension (at 298.15 K) at atmospheric pressure have used to help in the gathering of knowledge about the existence of plausible intermolecular interactions in the ternary (Drug + Water + Amino acid) solution. Furthermore, apparent molar volume, limiting apparent molar volume, viscosity B-coefficient, and molar refraction, limiting molar refraction all support the idea that the leading solute–solvent interaction is influenced by the solute concentration and temperature. In addition, in aqueous Chloroquine diphosphate, both amino acids showed structure-breaking activities. The system's Gibbs free energy change was measured, suggesting its spontaneity. The 1H NMR spectroscopy results showed significance changes in the shifting of aromatic protons of CDP and protons of amino acids indicating that a strong interaction (hydrophobic-hydrophobic) takes place among them which is further supported by our theoretical observations. L-Valine-Drug interactions were found to be more predominating over L-Alanine-Drug interactions, according to both experiment and theory. Models for mixtures of drug molecules and amino acids could be developed using the experimental and correlated results.

Densities and Viscosities of Binary and Ternary Solutions of Triethylenetetramine, 2-Amino-2-methyl-1-propanol, and Water for Carbon Dioxide Capture

Densities and Viscosities of Binary and Ternary Solutions of Triethylenetetramine, 2-Amino-2-methyl-1-propanol, and Water for Carbon Dioxide Capture

General Counteraction Exerted by Sugars against Denaturants.

The conformational stability of globular proteins is strongly influenced by the addition to water of different co-solutes. Some of the latter destabilize the native state, while others stabilize it. It is emerging that stabilizing agents are able to counteract the action of destabilizing agents. We have already provided experimental evidence that this counteraction is a general phenomenon and offered a rationalization. In the present work, we show that four different sugars, namely fructose, glucose, sucrose, and trehalose, counteract the effect of urea, tetramethylurea, sodium perchlorate, guanidinium chloride, and guanidinium thiocyanate despite the chemical and structural differences of those destabilizing agents. The rationalization we provide is as follows: (a) the solvent-excluded volume effect, a purely entropic effect, stabilizes the native state, whose solvent-accessible surface area is smaller than the one of denatured conformations; (b) the magnitude of the solvent-excluded volume effect increases markedly in ternary solutions because the experimental density of such solutions is larger than that of pure water.