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PLA nanocomposites containing 1 wt% ZnO nanofibers have been prepared by solvent-cast 3D printing. The ZnO nanofibers were produced by electrospinning and dispersed in PLA by ultrasound. Scanning electron microscopy revealed that the fibers were dispersed throughout the nanocomposite. Surface specimen assessment by atomic force microscopy indicated the presence of nanofibers near the surface of the nanocomposite. TGA tests showed the nanocomposite had a lower thermal stability than the neat PLA, probably induced by PLA hydrolysis catalyzed by ZnO. DSC results revealed higher crystallinity in the nanocomposite, induced both by the presence of ZnO nanofibers and by the 3D printing process, though the 3D printing process showed to be more important in increasing the crystallinity. XRD results also showed a higher crystallinity for the nanocomposite. The study opens an interesting field for the development of PLA/ZnO nanocomposites using ZnO nanofibers made by electrospinning, e.g. in medical and packaging applications.

Morphological and crystallographic characteristics of HfOx with different oxygen concentrations (0 ≤ x ≤ 2.5) and thicknesses (18 nm ≤ t ≤ 310 nm) were analyzed in this work before and after thermal annealing at 700°C in N2 atmosphere for 1h. The morphology of the as-deposited, low oxygen concentration films (t = 100 nm) is formed by a well-defined granular structure with grains around 20 nm in diameter. For higher oxygen concentration, the roughness increases, as a consequence of a very porous surface morphology. At the same time, the crystallographic structure changes from HCP with a {0002} preferred orientation to an amorphous structure as oxygen concentration increases. As the thickness of the HfO2 films increases, we also observed the formation of a high surface porosity, with pore diameter ranging from 80 nm to 120 nm. The changes observed in morphology and crystallinity of the films, as we increase the concentration of contaminants, occurs because of the lowering of the adatoms surface diffusion, which prevents them from reaching lower energy points during the formation of the microstructure of the films. Furthermore, this lowered surface diffusion favors the process of grain renucleation, which leads to roughness increasing, and to an enhancement of the formation of porous surfaces. After annealing, all films exhibit the monoclinic crystallographic phase associated with HfO2. Surface morphology of the films is consistent with a polycrystalline structure with grain diameters varying between 10 nm and 200 nm. As their size increases, the grains become very faceted, a finding consistent with the improvement in film crystallinity. Our results suggest that long-time annealing promotes the diffusion of oxygen from the SiO2-Hf interface to the film, compensating any O2 deficit in the film. Formation of the monoclinic phase is also favored by the improvement in the film stoichiometry promoted by thermal treatment. Also, the critical size of the nuclei, associated with a grain growth in a particular crystallographic orientation, decreases as a consequence of the high temperature during thermal annealing. Therefore, formation of faceted grains and increasing of surface roughness are favored in thicker films.