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The characterization of polymers by size-exclusion chromatography basically consists of the determination of the weight-average molar mass (Mw), number-average molar mass (Mn), and polydispersity index (I). An accurate estimation of these magnitudes requires the use of a reliable and trusted calibration curve. Three procedures for building up a calibration curve are analyzed in this work. The first is the classical universal calibration (UC), based on the elution of tetrahydrofuran-polystyrene in a system as reference. The second is based on the proper calibration curve made with standards of the sample under study. However, two main drawbacks arise when using these methodologies: the nonfulfilment of the UC when secondary mechanisms, other than pure size-exclusion, are present in the separation process; and the lack of a broad set of narrow standards of the sample under analysis in the second procedure. In order to circumvent these difficulties, a third, recently-proposed approach based on fractal considerations is applied. The accuracy and reliability of this method is proven through the calculation of the deviations observed in the estimation of the Mw values for polymer samples in different solvent-gel chromatographic systems. Whereas the classical UC shows a mean deviation of approximately 80% relative to the values given by the manufacturer, the fractal calibration yields a mean deviation of approximately 16%, similar to that obtained from the proper calibration. Moreover, the fractal procedure only needs one polymeric sample to generate the calibration curve.

A recent theoretical approach based on the coupling of both the Flory-Huggins (FH) and the Association Equilibria thermodynamic (AET) theories was modified and adapted to study the miscibility properties of a multicomponent system formed by two polymers (a proton-donor and a proton-acceptor) and a proton-acceptor solvent, named copolymer(A)/solvent(B)/polymer(C). Compatibility between polymers was mainly attained by hydrogenbonding between the hydroxyl group on the phenol unit of the poly(styrene-co-vinyl phenol) (PSVPh) and the carbonyl group of the biodegradable and environmentally friendly poly(3-hydroxybutyrate) (PHB). However, the selfassociation of PSVPh and specific interactions between the PSVPh and the H-acceptor group (an ether oxygen atom) of the epichlorohydrin (ECH) solvent were also established in a lower extension, which competed with the polymer-polymer association. All the binary specific interactions and their dependence with the system composition as well as with the copolymer content were evaluated and quantified by means of two excess functions of the Gibbs free energy, Δg A Band Δg A C . Experimental results from fluorescence spectroscopy were consistent with the theoretical simulations derived with the model, which could also be applied and extended to predict the miscibility in solution of any polymer blend with specific interactions.