scholarly journals Thermodynamic Modeling and Validation of the Temperature Influence in Ternary Phase Polymer Systems

Polymers ◽  
2021 ◽  
Vol 13 (5) ◽  
pp. 678
Author(s):  
Marta Romay ◽  
Nazely Diban ◽  
Ane Urtiaga

The effect of the temperature, as a process variable in the fabrication of polymeric membranes by the non-solvent induced phase separation (NIPS) technique, has been scarcely studied. In the present work, we studied the influence of temperature, working at 293, 313 and 333 K, on the experimental binodal curves of four ternary systems composed of PVDF and PES as the polymers, DMAc and NMP as the solvents and water as the non-solvent. The increase of the temperature caused an increase on the solubility gap of the ternary system, as expected. The shift of the binodal curve with the temperature was more evident in PVDF systems than in PES systems indicating the influence of the rubbery or glassy state of the polymer on the thermodynamics of phase separation. As a novelty, the present work has introduced the temperature influence on the Flory–Huggins model to fit the experimental cloud points. Binary interaction parameters were calculated as a function of the temperature: (i) non-solvent/solvent (g12) expressions with UNIFAC-Dortmund methodology and (ii) non-solvent/polymer (χ13) and solvent/polymer (χ23) using Hansen solubility parameters. Additionally, the effect of the ternary interaction term was not negligible in the model. Estimated ternary interaction parameters (χ123) presented a linear relation with temperature and negative values, indicating that the solubility of the polymers in mixtures of solvent/non-solvent was higher than expected for single binary interaction. Finally, PES ternary systems exhibited higher influence of the ternary interaction parameter than PVDF systems.

Author(s):  
Ю.И. Цой

Задача получения однородного состава ЛКМ сводится к правильному выбору пленкообразователей и соответствующих растворителей и, в случае необходимости, разбавителей и добавок. На основе положений теории растворимости была проведена оценка совместимости компонентов и стабильности таких систем. Критериями оценки были приняты параметры растворимости и термодинамического взаимодействия. Исследовали совместимость алкидных лаков с аминоформальдегидными смолами в бутаноле, и результаты этих исследований представлены в треугольной фазовой диаграмме. Для оценки совместимости смол по результатам расчета параметров термодинамического взаимодействия были построены спинодали для тройных систем. Как показывает анализ результатов проведенных исследований, даже при большой разности ?? = |?12 – ?13| = 0,2 наблюдается небольшая область несовместимости. С уменьшением разности ?? область несовместимости сужается. При ?23 > ?с область несовместимости расширяется как для ? = 0,2, так и для ?? = 0,1 и ?? = 0. Таким образом, для таких систем на совместимость компонентов, в первую очередь, влияет их взаимодействие между собой – чем оно больше, тем лучше они совместимы. Проведенные исследования показали, что парциальные параметры растворимости, учитывающие природу когезионных сил, более объективно характеризуют растворимость пленкообразующих смол в органических растворителях, чем их общий параметр растворимости. Растворимость пленкообразующих алкидных и этерифицированных аминоформальдегидных смол в органических растворителях обусловлена термодинамическим взаимодействием молекулярных сил различной природы. Стабильность смеси алкидной и этерифицированной аминоформальдегидной смолы в бутаноле обусловлена в большей степени термодинамическим взаимодействием молекулярных сил; при этом степень бутанолизации меламиноформальдегидной смолы оказывает наибольшее влияние на стабильность cистемы. Проведенные исследования по стабильности лакокрасочных смесей из различных пленкообразующих смол на основе рассмотренных критериев оценки могут быть использованы для совершенствования технологии защитно-декоративной отделки древесины. The problem of obtaining a homogeneous composition of the coatings is reduced to the proper selection of film-forming agents, and diluent and, if appropriate, diluents and additives. On the basis of the theory of solubility, we have carried out the assessment of the compatibility of the components and stability of such systems. The evaluation criteria were adopted the parameters of the solubility and thermodynamic interaction. Researched the compatibility with alkyd varnishes aminoformaldehyde resin in butanol, and the results of these studies are presented in the triangular phase diagram. To evaluate the compatibility of the resins according to the results of calculation of thermodynamic parameters of interaction were built spinodal for ternary systems. As the analysis of the results of the studies, even when the difference ??|?12 – ?13| = 0,2 there is a small area of incompatibility. With the decrease of the difference ? ? region incompatibility narrows. When ?23> ?с region incompatibility extends to ?? = 0,2, and for ?? = 0.1 and ?? = 0. Thus, for such systems, compatibility of components, primarily, affects their interaction with each other – the further away it is, the better they are compatible. Studies have shown that the partial solubility parameters, which take into account the nature of cohesive forces, more objectively characterize the solubility of film-forming resins in organic solvents than their total solubility parameter. The solubility and film-forming aminoformaldehyde esterified alkyd resins in organic solvents due to thermodynamic interaction of molecular forces of different nature. Тhe stability of the mixture and aminoformaldehyde esterified alkyd resin in butanol is generated largely by thermodynamic forces of molecular interaction; the degree of butanolate melamine-formaldehyde resin has the greatest effect on the stability of the system. Conducted research on the stability of the paint mixtures of various film-forming resins on the basis of the evaluation criteria can be used to improve the technology of protective and decorative wood finish.


Burns ◽  
2021 ◽  
Author(s):  
Maryam Hosseini ◽  
Michael S. Roberts ◽  
Reza Aboofazeli ◽  
Hamid R. Moghimi

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3091
Author(s):  
Mohammed Ghazwani ◽  
Prawez Alam ◽  
Mohammed H. Alqarni ◽  
Hasan S. Yusufoglu ◽  
Faiyaz Shakeel

This research deals with the determination of solubility, Hansen solubility parameters, dissolution properties, enthalpy–entropy compensation, and computational modeling of a naturally-derived bioactive compound trans-resveratrol (TRV) in water, methanol, ethanol, n-propanol, n-butanol, propylene glycol (PG), and various PG + water mixtures. The solubility of TRV in six different mono-solvents and various PG + water mixtures was determined at 298.2–318.2 K and 0.1 MPa. The measured experimental solubility values of TRV were regressed using six different computational/theoretical models, including van’t Hoff, Apelblat, Buchowski–Ksiazczak λh, Yalkowsly–Roseman, Jouyban–Acree, and van’t Hoff–Jouyban–Acree models, with average uncertainties of less than 3.0%. The maxima of TRV solubility in mole fraction was obtained in neat PG (2.62 × 10−2) at 318.2 K. However, the minima of TRV solubility in the mole fraction was recorded in neat water (3.12 × 10−6) at 298.2 K. Thermodynamic calculation of TRV dissolution properties suggested an endothermic and entropy-driven dissolution of TRV in all studied mono-solvents and various PG + water mixtures. Solvation behavior evaluation indicated an enthalpy-driven mechanism as the main mechanism for TRV solvation. Based on these data and observations, PG has been chosen as the best mono-solvent for TRV solubilization.


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