Films of semicrystalline poly(vinylidene fluoride) (PVDF) in the βphase were studied by Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC). The main goal of this study was to improve the understanding of the structural changes that occur in β-PVDF during a mechanical deformation process. FTIR spectroscopy was used to examine the structural variations as a function of strain. DSC data allowed measurement of the melting temperatures and enthalpies of the material before and after deformation, providing information about the changes in the crystalline fraction. After the molecular vibrations were assigned to the corresponding vibrational modes, we investigated the energy and intensity variations of these vibrations at different deformations. A reorientation of the chains from perpendicular to parallel to the stress direction was observed to occur in the plastic region. During the deformation, a decrease in the degree of crystallinity of the material was observed, but the thickness of the lamellae did not change significantly.

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Abstract␤-poly(vinylidene fluoride)-␤-PVDF-exhibits ferroelectric properties due to the special arrangement of the chain units in the crystalline phase. The ferroelectric phase can be optimised by poling the original stretched film, that tends to align the randomly organised crystallites against the applied field. In this work, polarised and non-polarised ␤-PVDF from the same batch are characterised by mechanical tests and a series of thermal analysis techniques, including DMA, TMA and DSC. The films exhibit mechanical anisotropy, and in the longitudinal direction the poled film presents larger mechanical properties, due to the higher structural organisation. Poled and non-poled show similar crystallinity levels but the melting temperature probed by DSC is higher for the non-poled film; for both films the melting peak exhibits a complex shape, indicating a heterogeneous crystalline organization. Two relaxation processes were found (␤ and ␣ c ) by dynamic mechanical analysis (DMA). The ␤ process, attributed to segmental motions in the amorphous phase, appears at the same temperature in both directions, but its intensity was found to be higher for the films tested in the longitudinal direction. For a given direction, the poled films exhibit lower peaks, due to the more organised amorphous structure. At higher temperature, the ␣ c -relaxation was related to the contraction of the films in the longitudinal direction during heating, recorded by thermal mechanical analysis (TMA). The onset of molecular mobility within the crystalline phase allows for cooperative diffusion processes in the amorphous phase, generating the randomisation of the initially oriented structure.

This work is devoted to the investigation of decorative zirconium oxynitride, ZrOxNy, films prepared by dc reactive magnetron sputtering, using a 17:3 nitrogen-to-oxygen-ratio gas mixture. The color of the films changed from metallic-like, very bright yellow pale, and golden yellow, for low gas mixture flows [from 0 to about 9SCCM (SCCM denotes cubic centimeter per minute at STP)] to red brownish for intermediate gas flows (values up to 12SCCM). Associated to this color change there is a significant decrease of brightness. With further increase of the reactive gas flow, the color of the samples changed from red brownish to dark blue (samples prepared with 13 and 14SCCM). The films deposited with gas flows above 14SCCM showed only apparent colorations due to interference effects. This change in optical behavior from opaque to transparent (characteristic of a transition from metallic to insulating-type materials), promoted by the change in gas flow values, revealed that significant changes were occurring in the film structure and electronic properties, thus opening new potential applications for the films, beyond those of purely decorative ones. Taking this into account, the electrical behavior of the films was investigated as a function of the reactive gas flow and correlated with the observed chemical, electronic, and structural features. The variations in composition disclosed the existence of four different zones, which were correlated to different crystalline structures. For the so-called zone I, x-ray diffraction revealed the development of films with a B1 NaCl face-centered cubic zirconium nitride-type phase, with some texture changes. Increasing the reactive gas flow, the structure of the films is that of a poorly crystallized overstoichiometric nitride phase, which may be similar to that of Zr3N4, but with some probable oxygen inclusions within nitrogen positions. This region was characterized as zone II. Zone III was indexed as an oxynitride-type phase, similar to that of γ-Zr2ON2 with some oxygen atoms occupying some of the nitrogen positions. Finally, occurring at the highest flow rates, zone IV was assigned to a ZrO2 monoclinic-type structure. The composition∕structure variations were consistent with the chemical bonding analysis carried out by x-ray photoelectron spectroscopy, which showed oxygen doping in both Zr3N4- and ZrN-type grown films. The electronic properties of the films exhibited significant changes from zone to zone. Resistivity measurements revealed a very wide range of values, varying from relatively highly conductive materials (for zone I) with resistivity values around few hundreds of μΩcm to highly insulating films within zones III and IV, which presented resistivity values in the order of 1015μΩcm. Regarding zone II, corresponding to oxygen doped Zr3N4-type compounds, the observed behavior revealed resistivity values increasing steeply from about 103 up to 1015μΩcm, indicating a systematic transition from metallic to insulating regimes.

Titanium dioxide (TiO 2) absorbs only a small fraction of incoming sunlight in the visible region thus limiting its photocatalytic efficiency and concomitant photocatalytic ability. The large-scale application of TiO 2 nanoparticles has been limited due to the need of using an ultraviolet excitation source to achieve high photocatalytic activity. The inclusion of foreign chemical elements in the TiO 2 lattice can tune its band gap resulting in an absorption edge red-shifted to lower energies enhancing the photocatalytic performance in the visible region of the electromagnetic spectrum. In this research work, TiO 2 nanoparticles were doped with iron powder in a planetary ball-milling system using stainless steel balls. The correlation between milling rotation speeds with structural and morphologic characteristics, optical and magnetic properties, and photocatalytic abilities of bare and Fedoped TiO 2 powders was studied and discussed.

This paper reports on the preparation of TiN x thin films by d.c. reactive magnetron sputtering. The coating thickness ranged from 1.7 to 4.2 Am and the nitrogen content varied between 0 and 55 at.%. X-Ray diffraction showed the development of the hexagonal a-Ti phase, with strong [002] orientation for low nitrogen contents, where the N atoms fit into octahedral sites in the Ti lattice as the amount of nitrogen is increased. For nitrogen contents of 20 and 30 at.%, the q-Ti 2 N phase appears with [200] orientation. With further increasing the nitrogen content, the y-TiN phase becomes dominant. The electrical resistivity of the different compositions reproduces this phase behavior. The hardness of the samples varied from approximately 8 GPa for pure titanium up to 27 GPa for a nitrogen content of 30 at.%, followed by a slight decrease at the highest contents. A similar increase of stresses with nitrogen is observed. Structure and composition with the consequent changes in crystalline phases and the lattice distortion were found to be crucial in the evolution of the mechanical properties.

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In this work, tensile dynamic mechanical analysis (DMA) was used to characterise the solid-state rheological properties of a commercial ␤-polyvinylidene fluoride (PVDF) film in the two main directions (longitudinal and transversal to the stretch direction). The ␤-relaxation, assigned to the segmental motions within the amorphous phase, is observed at ∼−25 • C. The ␣ c -relaxation is observed above room temperature.This relaxation is the main responsible for the anelastic properties of the material and to the short-term creep behaviour. Longer-term creep tests along the longitudinal direction were also performed and the Eyring model was applied, in order to characterize the flow-process within the polymeric structure. The results suggest that long-term creep is mostly controlled by the deformation of amorphous tie-chains that connect adjacent crystalline lamellae.