0000000000139815

AUTHOR

Sabine Enders

Phase separation of blends of polydisperse polymers: Comparison between experiment and theory for the system poly(dimethylsiloxane)/poly(ethylmethylsiloxane)

Cloud point curves were measured turbidimetrically for blends (upper critical solution temperatures ; UCSTs) of poly(ethylmethylsiloxane) (PEMS) and four different samples of poly(dimethylsiloxane) (PDMS) ; the weight average molar masses in kg/mol are 31.2 for PEMS and 10.4, 15.5, 18.1 and 24.0 for PDMS ; all components have polydispersity indices D (= M w /M n ) within the range from 1.82 to 2.67. Corresponding calculations on the basis of the Flory-Huggins theory (three adjustable parameters) account for the polydispersity; molecular weight distributions are represented by the generalized Schulz-Flory equation. Calculated cloud point curves agree very well with those measured, if individ…

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Influence of Molar Mass Distribution on the Compatibility of Polymers

Abstract Phase equilibria were calculated by means of a new method (direct minimization of the Gibbs energy of mixing) for polymer blends consisting of monodisperse polymer A and polydisperse polymer B. The results obtained for a Schulz-Flory distribution of B (molecular nonuniformity U = (M w/M n) −1 = 1 and 100 components of model B) agree quantitatively with that of computations on the basis of continuous thermodynamics. The influence of U B on the miscibility of A and B in 1:1 mixtures was studied for constant M w of B, quantifying the incompatibility of the polymers by the length of the tie lines. The outcome of these calculations demonstrates that the typical effect of an augmentation…

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Polydispersity effects on the phase diagram of the system chloroform/poly-l-(lactic acid)/poly(methyl methacrylate) and morphology of PLA/PMMA films

Abstract Cloud point curve, critical composition and several critical coexistence curves were measured at 25°C for the ternary system poly- l -(lactic acid) (PLA), poly(methyl methacrylate) (PMMA) — where both polymers exhibit broad molecular weight distributions — and the common solvent chloroform. In contrast to the situation encountered in the absence of the second polymer both branches of the critical coexistence curves are located without any doubt inside the miscibility gap as defined by the cloud point curve. This unexpected experimental finding is corroborated by model calculations on the basis of continuous thermodynamics. The removal of solvent from the ternary mixtures yields fil…

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Interfacial tension and interaction parameters

In view of various contradictory theoretical equations relating the interfacial tension σ between phase-separated polymer solutions to the Flory-Huggins interaction parameter of the system, the idea that σ should depend on the extent of the ‘hump’ in the concentration dependence of the Gibbs energy of mixing was studied. This investigation is based on 12 series of σ( T ) measurements reported in the literature and on additional experiments for the system cyclohexane/polystyrene. To quantify the extent of the ‘hump’, a reduced ‘hump energy’ ɛ was introduced and its value calculated for different temperatures from the measured critical data of the systems. The analysis of the entire experimen…

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