Blends of bisphenol-A polycarbonate and acrylic polymers: III. Effect of imide concentration on compatibility

Imide units copolymerized with MMA units have been selected in order to improve compatibility between PC and acrylics through specific interaction or internal repulsion. Good dispersion of acrylic inside a PC matrix has been observed upon melt mixing, which can be partially explained by the good rheological agreement between these two polymers. Transmission electron microscopy has shown that the system remains phase separated from 5 to 95 wt % of PC. Phase diagrams for three different imide concentrations have been drawn. Results obtained by DSC (conventional and with enthalpy relaxation) are similar to those obtained by optical cloud point detection. The phase diagrams show the raise of the PC/PMMA demixtion curve (LCST type) when percentage of imide increases in the acrylic phase. Theoretical calculations on binary interaction energy density show a slight improvement of the interaction between acrylic and PC when imide percentage increases. Cloud point measurements on 50/50 PC/acrylic blends varying the imide concentration show that the improvement of compatibility deduced from the raise of the demixtion curve (LCST type) is more related to a kinetic effect (the high T_g of imidized samples is reducing macromolecule mobility) than specific interactions. The calculated favorable interactions are probably too weak to be detected with cloud point measurements. The microstructures obtained after crystallization of the PC phase under solvent vapors in phase separated PC/acrylics blends can also be explained by T_g effects. Moreover, solvent vapor exposure could be a powerful tool to determine the real thermodynamic behavior of the blends at room temperature. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 749–761, 1997     

Phase diagrams of low-density polyethylene–alkylbenzene systems

Complete phase diagrams for mixtures of low-density polyethylene with p- and m-xylene are plotted by optical means in developing the concept of which partially crystalline polymers are microstructured liquids. It is shown that in contrast to the ones presented in the literature, both diagrams contain the solubility boundary curve of the low-molecular weight component in the polymer, above which the polyethylene has the structure of a single-phase gel (crosslinks formed by crystallites and amorphous regions saturated with xylene). At the figurative point on the diagrams, a situation is observed in which the dissolution of all the liquid contained in the initial two-phase system in the polymer is accompanied by its simultaneous complete amorphization. The parameters of the figurative point allow us to estimate the thermodynamic affinity of different alkylbenzenes toward polyethylene.     

Fabrication and evaluation of self-nanoemulsifying oil formulations (SNEOFs) of Efavirenz

The current work designed to fabricate and evaluate self-nanoemulsfying oil formulations (SNEOFs) of Efavirenz (Efz) a BCS class II drug with the objective of increasing its solubility as well as in vitro dissolution rate for improvisation of bioavailability. Preliminary screening of drug which includes solubility, emulsifying ability and ternary phase diagrams was carried out to fabricate SNEOFs. Various thermodynamic stability studies were exercised to find out the stable SNEOFs. Robustness to dilution, % transmittance and turbidity, droplet size analysis, TEM study, cloud point measurement, viscosity and refractive index were executed on the stable SNEOFs to characterize the delivery system. FTIR study was adopted for the compatibility of the additives with the drug. In vitro release profiles of SNEOFs compared with Efz, percent dissolution efficiency (DE) and dissolution half-life (t₅₀) were evaluated. A low percent DE (30.12%) and high t₅₀ was obtained for Efz whereas all SNEOFs showed a DE of greater than 78.48% and less than 9?min t₅₀. The optimized SNEOFs (F8) demonstrated a significant (p?<?0.05) increase in bioavailability over Efz. Thus the designed optimized delivery system could be instrumental in increasing aqueous solubility of Efz, improving its release performance and enhancement of oral absorption.     

Phase diagrams of the KF-K<Subscript>2</Subscript>TaF<Subscript>7</Subscript> and KF-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> systems

The phase diagrams of the systems KF-K₂TaF₇ and KF-Ta₂O₅ were determined using the thermal analysis method. The phase diagrams were described by suitable thermodynamic model. In the system KF-K₂TaF₇ eutectic points at x _KF=0.716 and t=725.4°C and at x _KF=0.214 and t=712.2°C has been calculated. It was suggested that K₂TaF₇ melts incongruently at around 743°C forming two immiscible liquids. The system KF-Ta₂O₅ have been measured up to 8 mol% of Ta₂O₅. The eutectic point was estimated to be at x _KF∼0.9 and t∼816°C. The formation of KTaO₃ and K₃TaO₂F₄ compounds has been observed in the solidified samples.     

Phenomenological theory of phase diagrams with multicritical points

The breakup of multicritical points is studied in detail within the phenomenological theory of second-order phase transitions for a thermodynamic potential invariant with respect to the C _3v (3m) group of transformations. The general conditions of this breakup are obtained and possible types of derived diagrams are plotted from a parent phase diagram containing a multicritical point. Examples of experimental phase diagrams are given that qualitatively confirm the results from theoretical and computer simulations of phase equilibria.     

Thermodynamic Model for the Solubility of TcO2⋅xH2O in Aqueous Oxalate Systems

The room temperature solubility of amorphous, hydrous technetium(IV) oxide (TcO₂⋅xH₂O) was studied across a broad range of pH values extending from 1.5 to 12 and in oxalate concentrations from dilute (10⁻⁶ mol⋅kg⁻¹) to complete saturation with respect to sodium bioxalate at lower pH values, and to saturation with respect to sodium oxalate at higher pH values. The solubility was measured to very long equilibration times (i.e., as long a 1000 days or longer). The thermodynamic modeling results show that the dominant species in solution must have at least one more hydroxyl moiety present in the complex than proposed by previous investigators (e.g., TcO(OH)Ox⁻ rather than TcO(Ox)(aq)). Inclusion of the single previously unidentified species TcO(OH)Ox⁻ in our aqueous thermodynamic model explains a wider range of observed solubility data for TcO₂⋅xH₂O(am) in the presence of oxalate and over a broad range of pH values. Inclusion of this species is also supported by the recently proposed thermodynamic data for the TcO(OH)⁺ hydrolysis species that indicates that this species is stable at pH values as low as one.     

Stability of Lead(II) Arsenates

 Predictions of lead arsenate solubility and thermodynamic stability have been based on the value of the solubility constant for a precipitate with the general composition Pb₃(AsO₄)₂. The solubility of this precipitate is high and lead arsenate is considered to be unsuitable for lead and arsenic control in the environment. Standard Gibbs energy of formation for bayldonite, duftite, mimetite, philipsbornite, and schultenite can be found in the literature from solubility studies. From these data, stability diagrams were established for the environmentally relevant lead containing solid phases – anglesite, cerussite, schultenite, and mimetite. The diagrams lead to the conclusion that mimetite is a lead arsenate that can be used for remediation techniques.     

Prediction and experimental determination of the binary and ternary phase diagrams of (±)medetomidine hydrochloride

The binary phase diagram of medetomidine hydrochloride was determined based on thermogravimetric differential thermal (TGA/DTA) measurements. The binary phase diagram presented a eutectic point in the 19:81 [(R)/(S)] composition and the ternary phase diagram in the presence of 2-propanol showed a eutectic point in the 75:25 [(S)/(R)] composition, both characterizing the product as a racemic compound forming system. The solubility of enantiomeric mixtures in 2-propanol was measured at 10, 20 and 30 °C. The ideal solubility curves of the mixtures were calculated and the activity coefficients derived. A semi-empirical thermodynamic model UNIversal QUAsi-Chemical (UNIQUAC) was used to predict the solubility of various compositions of enantiomers at different temperatures. There was good agreement between the experimental solubility data of medetomidine hydrochloride and the results obtained from the UNIQUAC equation.     

Thermodynamic study of glasses in Ag-As-Se system using EMF method with Ag<Subscript>4</Subscript>RbI<Subscript>5</Subscript> solid electrolyte

The EMF method with Ag₄RbI₅ solid electrolyte was used to study silver solubility in Ag-As-Se glasses on the basis of the cross-sections of (I) Ag-As_0.25Se_0.75, (II) Ag-As_0.33Se_0.67, (III) Ag-As_0.4Se_0.6, and (IV) Ag-As_0.5Se_0.5. It is found that silver solubility reaches 30 and 40 at % in sections (I), (IV) and (II), (III), accordingly. The data of EMF measurements were used as a basis for calculation of partial polar functions of Ag in glasses. The Gibbs-Duhem equations were integrated to calculate thermodynamic functions of silver dissolution in vitreous As _x Se_{1 − x} (x = 0.25; 0.33; 0.4; 0.5), from which the corresponding data for the latter were used to obtain the standard integral thermodynamic functions of the mixing of glasses. The obtained results were compared with the thermodynamic data for crystalline silver selenoarsenites.     

The effect ofn-butyl glycol ethers on the phase diagrams of microemulsions formulated with nonionic surfactants

The effect ofn-butyl glycol ethers used as cosurfactants on the microemulsions formulated with two nonionic surfactants, hexaoxyethylene glycol monolauryl ether and sorbitan monolaurate, is presented on ternary phase diagrams. The solubilization parameters as well as isothermal invariant points (IIP) of microemulsions were correlated with the solubility parameters of cosurfactants. An optimum solubility parameter of cosurfactants was established around 9 (cal/cm³)^1/2 where both IIP and solubilization parameters are optimal for water and oil solubilization with the lowest concentration of amphiphilic compounds. The mixture of cosurfactants can be used to obtain a certain transition on the phase diagram and so to achieve certain characteristics for microemulsions, especially to tailor the solvency of the system.On leave from the University of Bucharest Department of Physical Chemistry Bdul Republicii 13 Bucharest, Romania     

Investigation of the Hydrocortisone-<Emphasis Type="Italic">β</Emphasis>-Cyclodextrin Complex by Phase Solubility Method: Some Theoretical and Practical Considerations

Phase solubility diagrams (PSDs) and molecular mechanical (MM) modeling were used to study the complexation of hydrocortisone (HCor) with β-cyclodextrin (β-CD). The phase solubility profile of HCor with β-CD was classified as the B_s-type. PSDs revealed a six-fold increase in HCor water solubility upon addition of 7 mmol⋅dm⁻³ β-CD concentration (solubility in 7 mmol⋅dm⁻³ of β-CD/solubility in water). The thermodynamic study shows the complexation process is exothermic, with a ΔH value of −5.28 kJ⋅mol⁻¹. MM calculations were used to predict the optimal stoichiometry of the complex formed as well as the possible orientations of HCor inside the β-CD cavity. The complexes prepared were analyzed through chemical analysis, which provides evidence for the 1:1 complexation of HCor/β-CD. Electronic Supplementary Material The online version of this article () contains supplementary material, which is available to authorized users.     

Thermodynamic study of sodium-iron oxides: Part II. Ternary phase diagram of the Na-Fe-O system

Studies on ternary phase diagrams of the Na-Fe-O system have been carried out from the thermodynamic point of view. Thermodynamic data of main ternary Na-Fe oxides Na₄FeO₃(s), Na₃FeO₃(s), Na₅FeO₄(s) and Na₈Fe₂O₇(s) have been assessed. A user database has been created by reviewing literature data together with recent DSC and vapor pressure measurements by the present authors. New ternary phase diagrams of the Na-Fe-O system have been constructed from room temperature to 1000 K. Stable conditions of the ternary oxides at 800 K were presented in predominance diagram as functions of oxygen pressure and sodium pressure.     

Solubility and preferential solvation of phenacetin in methanol + water mixtures at 298.15 K

The mole fraction solubility of phenacetin (PNC) in methanol + water binary solvent mixtures at 298.15 K was determined along with density of the saturated solutions. All these solubility values were correlated with the Jouyban–Acree model. Preferential solvation parameters of PNC by methanol (δx_1,3) were derived from their thermodynamic solution properties using the inverse Kirkwood–Buff integrals (IKBI) method. δx_1,3 values are negative in water-rich mixtures but positive in methanol mole fraction of >0.32. It is conjecturable that in the former case the hydrophobic hydration around non-polar groups of PNC plays a relevant role in the solvation. The higher solvation by methanol in mixtures of similar cosolvent compositions and methanol-rich mixtures could be explained in terms of the higher basic behaviour of methanol.     

Calculation of Ln-Ba (Ln = Gd,Pr, Nd,and Sm) phase diagrams

A thermodynamic model of liquid was suggested and Ln-Ba (Ln = Gd, Pr, Nd, and Sm) phase diagrams were calculated on the basis of generalization of literature data on thermodynamic properties and phase equilibria in lanthanide-barium metallic systems. The interaction parameter of Gd_{1 ? x} Ba _x regular melt was estimated on the assumption of a proportionality between the particle-particle interaction energies of liquid lanthanide and liquid barium, on the one hand, and the lanthanide radius, on the other.     

Models of p-T-x1-x2 diagrams for ternary systems with vapor-liquid equilibria and continuous solutions in subcritical and supercritical regions

We consider model p-T-x ₁-x ₂ diagrams for ternary systems with continuous solutions in subcritical and supercritical vapor-liquid regions. Phase equilibria are analyzed with the parameters of state of the system varying as dependent on components’ volatilities. The methodology is described, and sample constructions of isobaric-isothermal diagrams and polythermal sections are made proceeding from p-T and T-x ₁-x ₂ projections of the four-dimensional diagram.     

Thiourea complexes in synthesis of Cd1 ? xZnxS solid solutions

Solid solutions of the CdS-ZnS system deposited as polycrystalline films by aerosol pyrolysis from aqueous solutions of cadmium and zinc thiourea complexes have been studied. The phase composition and solid-phase solubility are dictated by the nature of initial complexes. From solutions of [M(thio)₂(CH₃COO)₂] complexes, sphalerite sulfides are precipitated, which form a continuous solid solution s-Cd_1−x Zn _x S, whereas the use of the [M(thio)₂Cl₂] precursor leads to crystallization of the wurtzite w-Cd_1−x Zn _x S solid solution based on CdS (the homogeneity range 0–20 mol % ZnS) and the s-Cd_1−x Zn _x S solid solution based on zinc sulfide (50–100 mol % ZnS). The structure of the solid phase in the sulfide system is attributed to the specific features of the stereochemistry of complex precursors.     

Rigorous nonlinear regression analysis of phase solubility diagrams to obtain complex stoichiometry and true thermodynamic drug-cyclodextrin complexation parameters

This work reports rigorous nonlinear regression procedures aimed at analyzing various types of phase solubility diagrams (PSDs) corresponding to the different soluble and insoluble complex stoichiometries, which are generally encountered in drug-cyclodextrin (CD) complexation studies. These are depicted in final equations that can be modeled to fit experimental data of measured drug solubility against CD concentration utilizing simple spreadsheet software available for all PCs (i.e., the Solver Add-in in Microsoft Excel). They cover all types of guest/host phase solubility diagrams (A-, B_S-and B_I-types) allowing accurate estimation of soluble and insoluble complex stoichiometries generally encountered in drug/CD complexes (1:1, 2:1, 1:2, 2:2, 2:3, 3:2), the corresponding thermodynamic complex formation constants (K₁₁, K₂₁, K₁₂, K₂₂, K₂₃, K₃₂) and solubility product constants (K_sp) of saturated complexes.     

Liquid-solid equilibrium for the NaCl-NaHCO3-Na2CO3-H2O system at 45°C. Validation of mixed solvent electrolyte model

The main objective of this work was to verify the mixed solvent electrolyte (MSE) thermodynamic model for the prediction of the liquid-solid equilibrium in the soda system. The full quaternary system NaCl-NaHCO₃-Na₂CO₃-H₂O and its three subsystems were considered. Validation of the thermodynamic model was based on experimental data from literature. Phase diagrams for the soda system are plotted for isotherms of 45°C. Good agreement of the MSE results with those from experiments was found at 45°C. Similar phase diagrams for other temperature levels can be constructed based on the validated MSE model.     

Analysis of thermodynamic properties and phase equilibria in the Si-P system

A self-consistent analysis of the available data on thermodynamic properties and phase equilibria in the Si-P system is performed. Thermodynamic properties of solid and liquid solutions of phosphorus in silicon are approximated on the basis of the concepts of dilute and ideal associated solutions. The thermodynamic properties and phase boundaries in the range of compositions 0 ≤ x(P) ≤ 0.5 are adequately described.     

Solid–Liquid Equilibrium for the Ternary System 2-Methyl-4-Nitroaniline + 2-Methyl-6-Nitroaniline + Ethyl Acetate: Determination and Modelling

The solid–liquid phase equilibria for the ternary system 2-methyl-4-nitroaniline + 2-methyl-6-nitroaniline + ethyl acetate was determined experimentally by the method of isothermal solution saturation at temperatures of (293.15, 303.15 and 313.15) K under the pressure of 101.2 kPa. Based on the obtained solubility data, the isothermal phase diagrams of the system were constructed. At each temperature, there are two pure solid phases formed, which correspond to pure 2-methyl-4-nitroaniline and pure 2-methyl-6-nitroaniline, which was confirmed by Schreinemakers’ wet residue method and X-ray powder diffraction. The crystallization regions of pure 2-methyl-4-nitroaniline and pure 2-methyl-6-nitroaniline increased with decreasing temperature. The crystalline region of 2-methyl-4-nitroaniline was larger than that of 2-methyl-6-nitroaniline at a fixed temperature. The solubility data were correlated with the NRTL and Wilson models. The values of the root-mean-square deviations are 5.01 × 10^?3 for the NRTL model, and 6.43 × 10^?3 for the Wilson model. The solid–liquid equilibria, phase diagrams and the thermodynamic models for the ternary system can provide the foundation for separating 2-methyl-6-nitroaniline or 2-methyl-4-nitroaniline from its mixtures.