Variation of the physicochemical and morphological characteristics of solvent casted poly(vinylidene fluoride) along its binary phase diagram with dimethylformamide

Poly(vinylidene fluoride), PVDF, films and membranes were prepared by solvent casting from dimethylformamide, DMF, by systematically varying polymer/solvent ratio and solvent evaporation temperature. The effect of the processing conditions on the morphology, degree of porosity, mechanical and thermal properties and crystalline phase of the polymer were evaluated. The obtained microstructure is explained by the Flory-Huggins theory. For the binary system, the porous membrane formation is attributed to a spinodal decomposition of the liquid-liquid phase separation. The morphological features were simulated through the correlation between the Gibbs total free energy and the Flory-Huggins theory. This correlation allowed the calculation of the PVDF/DMF phase diagram and the evolution of the microstructure in different regions of the phase diagram. Varying preparation conditions allow tailoring polymer 2 microstructure while maintaining a high degree of crystallinity and a large β crystalline phase content. Further, the membranes show adequate mechanical properties for applications in filtration or battery separator membranes.

Ion exchange dependent electroactive phase content and electrical properties of poly(vinylidene fluoride)/Na(M)Y composites

Different metal-ion exchanged NaY zeolite, Na(M)Y, were used to prepare poly(vinylidene fluoride) based composites by solvent casting and melting crystallization. The effect of different metal ion-exchanged zeolites on polymer crystallization and electrical properties was reported. Cation-framework interactions and hydration energy of the cations determined that K+ is the most efficient exchanged ion in NaY zeolite, followed by Cs+ and Li+. The electroactive phase crystallization strongly depends on the ions present in the zeolite, leading to variations of the surface energy characteristics of the Na(M)Y zeolites and the polymer chain ability of penetration in the zeolite. Thus, Na(Li)Y and NaY induces the complete electroactive -phase crystallization of the crystalline phase of PVDF, while Na(K)Y only induces it partly and Na(Cs)Y is not able to promote the crystallization of the electroactive phase. Furthermore, different ion size/weigh and different interaction with the zeolite framework results in significant variations in the electrical response of the composite. In this way, iinterfacial polarization effects in the zeolite cavities and zeolite-polymer interface, leads to strong increases of the dielectric constant on the composites with lightest ions weakly bound to the zeolite framework. Polymer composite with Na(Li)Y show the highest dielectric response, followed by NaY and Na(K)Y. Zeolite Na(Cs)Y contribute to a decrease of the dielectric constant of the composite. The results show the relevance of the materials for sensor development.

Nonsolvent induced phase separation preparation of poly(vinylidene fluoride-co-chlorotrifluoroethylene) membranes with tailored morphology, piezoelectric phase content and mechanical properties

Poly(vinylidene fluoride-co-chlorotrifluoroethylene) – P(VDF-CTFE) membranes are increasingly interesting for a wide range of applications, including battery separators, filtration membranes and biomedical applications. This work reports on the morphology, hydrophobicity, thermal and mechanical properties variation of P(VDF-CTFE) membranes processed by nonsolvent induced phase separation technique (NIPS) as a function of the main processing parameters. All membranes show a porous structure composed of large spherulites, (interconnected) micropores and/or microvoids depending on the processing conditions used that in turn affect their hydrophobicity and mechanical properties. The degree of crystallinity of the membranes remains approximately constant with a value of about 15 %, except for the membranes immediately immersed in ethanol, which is of about 23 %. In turn, the crystalline phases present in the copolymer is mainly affected by the temperature and nonsolvent characteristics of the coagulation bath, the β-phase content ranging from 33 to 100 %, depending on those processing parameters. It was show that the temperature of water-based coagulation bath plays an important role in order to produce structurally uniform and homogeneous porous membranes, which is particularly important from the point of view of technological applications.

Tailoring poly(vinylidene fluoride-co-chlorotrifluoroethylene) microstructure and physicochemical properties by exploring its binary phase diagram with dimethylformamide

Poly(vinylidene fluoride-co-chlorotrifluoroethylene), PVDF-CTFE, membranes were prepared by solven casting from dimethylformamide, DMF. The preparation conditions involved a systematic variation of polymer/solvent ratio and solvent evaporation temperature. The microstructural variations of the PVDF-CTFE membranes depend on the different regions of the PVDF-CTFE/DMF phase diagram, explained by the Flory-Huggins theory. The effect of the polymer/solvent ratio and solvent evaporation temperature on the morphology, degree of porosity, β-phase content, degree of crystallinity, mechanical, dielectric and piezoelectric properties of the PVDF-CTFE polymer were evaluated. In this binary system, the porous microstructure is attributed to a spinodal decomposition of the liquid-liquid phase separation. For a given polymer/solvent ratio, 20 wt%, and higher evaporation solvent temperature, the β-phase content is around 82% and the piezoelectric coefficient, d33, is - 4 pC/N.

Structure dependent resistivity and dielectric characteristics of tantalum oxynitride thin films produced by magnetron sputtering

tThe main purpose of this work is to present and to interpret the change of electrical properties of TaxNyOzthin films, produced by DC reactive magnetron sputtering. Some parameters were varied during deposi-tion: the flow of the reactive gases mixture (N2and O2, with a constant concentration ratio of 17:3); thesubstrate voltage bias (grounded, −50 V or −100 V) and the substrate (glass, (1 0 0) Si or high speed steel).The obtained films exhibit significant differences. The variation of the deposition parameters inducesvariations of the composition, microstructure and morphology. These differences cause variation of theelectrical resistivity essentially correlated with the composition and structural changes. The gradualdecrease of the Ta concentration in the films induces amorphization and causes a raise of the resistivity.The dielectric characteristics of some of the high resistance TaxNyOzfilms were obtained in the sampleswith a capacitor-like design (deposited onto high speed steel, with gold pads deposited on the dielectricTaxNyOzfilms). Some of these films exhibited dielectric constant values higher than those reported forother tantalum based dielectric films.

Interrelationship between partition behavior of organic compounds and proteins in aqueous dextran-Polyethylene glycol and Polyethylene glycol-sodium sulfate two-phase systems

Partition behavior of adenosine and guanine mononucleotides was examined in aqueous dextran-polyethylene glycol (PEG) and PEG-sodium sulfate two-phase systems. The partition coefficients for each series of mononucleotides were analyzed as a functions of the number of phosphate groups and found to be dependent on the nature of nucleic base and on the type of \ATPS\ utilized. It was concluded that an average contribution of a phosphate group into logarithm of partition coefficient of a mononucleotide cannot be used to estimate the difference between the electrostatic properties of the coexisting phases of ATPS. The data obtained in this study were considered together with those for other organic compounds and proteins reported previously, and the linear interrelationship between logarithms of partition coefficients in dextran-PEG, PEG-Na2SO4 and PEG-Na2SO4-0.215 M NaCl (all in 0.01 M Na- or K/Na-phosphate buffer, pH 7.4 or 6.8) was established. Similar relationship was found for the previously reported data for proteins in Dex-PEG, PEG-600-Na2SO4, and PEG-8000-Na2SO4 ATPS. It is suggested that the linear relationships of the kind established in \ATPS\ may be observed for biological properties of compounds as well.

Incorporation of hybrid phase change materials in plastering mortars for increased energy efficiency in buildings

Tese de Doutoramento em Engenharia Civil.