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Oxides with proton conductivity have a great potential for applications in environmental energy technology. Despite the BaCe0.4Zr0.4Y0.2O3−δ (BCZY) perovskites being well-known proton conductors, it is a challenge to determine the optimal operating temperature range where the energy applications benefit most from this unique property. The protonic transport properties strongly depend on crystal structure and local distortions in the participating cation coordination sphere, according to related temperatures and gas feed. The transport and crystallographic properties of BCZY were simultaneously studied by impedance spectroscopy (IS) and synchrotron X-ray diffraction (S-XRD). A strong correlation between conductivity and the lattice parameter, corresponding in principle to a cubic symmetry, was observed, mainly between 400 and 700 °C. The protonic conductivity range was analyzed by the H/D isotopic effect on the impedance spectra, which helped to identify protonic conduction as the governing transport mechanism below 600 °C, while the transport via oxygen vacancies dominates above this temperature. In order to assess the real crystallographic structure, the simultaneous refinement of laboratory XRD and neutron diffraction (ND) patterns was performed. According to this, BCZY changes from rhombohedral symmetry below 400 °C to cubic at 600 °C in a second-order phase transition. Complementary quasielastic neutron scattering (QENS) enables us to determine a protonic jump length of 3.1 Å, which matches the O–O distances in the octahedral oxygen coordination sphere around the cations. These results support the protonic self-diffusion through proton hopping between intraoctahedral O sites as the main transport mechanism up to 600 °C., This work was supported by Agencia Nacional de Promocion de Ciencia y Tecnologia (ANPCyT) PICT-2016-2965 and PICT2014-1849, CONICET PIP-2015-0565, LNLS (Brazil), under proposals 20150099 and 20170278, and ILL (France) under proposal 7-03-168. L. Giebeler is grateful to the German Federal Ministry of Education and Research (BMBF) and the Argentinian Ministry of Science and Technology (MinCyT) for funding in the bilateral project DeFLeST (01DN14002). J. A. Alonso thanks the Spanish Ministry for Science, Innovation and Universities for funding the Project MAT2017-84496-R.

Conjugation of optical and magnetic responses in a unique system at the nanoscale emerges as a powerful tool for several applications. Here, we fabricated bifunctional CoFe2O4-core/ZnO-shell nanoparticles with simultaneous photoluminescence in the visible range and ac magnetic losses suitable for hyperthermia. The structural characterization confirms that the system is formed by a ≈7 nm CoFe2O4 core encapsulated in a ≈1.5-nm-thick semiconducting ZnO shell. As expected from its high anisotropy, the magnetic losses in an ac magnetic field are dominated by the Brown relaxation mechanism. The ac magnetic response of the core/shell system can be accurately predicted by the linear response theory and differs from that one of bare CoFe2O4 nanoparticles as a consequence of changes in the viscous relaxation process due to the effect of the magnetostatic interactions. Concerning the optical properties, by comparing core/shell CoFe2O4/ZnO and single-phase ZnO nanoparticles, we found that the former exhibits a broader optical absorption and photoluminescence, both shifted to the visible range, indicating that the optical properties are closely associated with the shell-morphology of ZnO. Being focused on bifunctional nanoparticles with an optical response in the visible range and a tunable hyperthermia output, our results can help to address current open questions on magnetic fluid hyperthermia. Fil: Lavorato, Gabriel Carlos. Centro Brasileiro de Pesquisas Físicas; Brasil. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina Fil: Lima, Enio Junior. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina Fil: Vasquez Mansilla, Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina Fil: Troiani, Horacio Esteban. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina Fil: Zysler, Roberto Daniel. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina Fil: Winkler, Elin Lilian. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina

In this work, we studied the dynamic and static magnetic properties of ZnO-core/CoFe2O4-shell and CoO-core/CoFe2O4-shell nanoparticles. Both systems are formed by a core of ∼4 nm of diameter encapsulated in a shell of ∼2 nm of thickness. The mean blocking temperature changes from 106(7) to 276(5) K when the core is diamagnetic or antiferromagnetic, respectively. Magnetic remanence studies revealed the presence of weak dipolar interparticle interactions, where Hint is approximately -0.1 kOe for ZnO/CoFe2O4 and -0.9 kOe for CoO/CoFe2O4, playing a minor role in the magnetic behavior of the materials. Relaxation experiments provided evidence that the magnetization reversal process of CoFe2O4 is strongly dependent on the magnetic order of the core. At 10 K, activation volumes of ∼46(6) and ∼69(5) nm3 were found for CoO/CoFe2O4 and ZnO/CoFe2O4 nanoparticles, respectively, corresponding to one-third and one-fifth of the total shell volume. While the magnetic behavior of ZnO/CoFe2O4 nanoparticles is strongly affected by the surface disorder, the exchange coupling at the CoO/CoFe2O4 interface rules the magnetization reversal and the nanoparticles' thermal stability by inducing a larger energy barrier and promoting smaller switching volume. Fil: Lavorato, Gabriel Carlos. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Resonancias Magnéticas; Argentina. Argentine Italian Joint Laboratory of Nanomagnetism; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Consiglio Nazionale delle Ricerche; Italia Fil: Peddis, Davide. Argentine Italian Joint Laboratory of Nanomagnetism; Argentina. Consiglio Nazionale delle Ricerche; Italia Fil: Lima, Enio Junior. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Resonancias Magnéticas; Argentina. Argentine Italian Joint Laboratory of Nanomagnetism; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina Fil: Troiani, Horacio Esteban. Comisión Nacional de Energía Atómica. Gerencia del Área de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina Fil: Agostinelli, Elisabetta. Argentine Italian Joint Laboratory of Nanomagnetism; Argentina. Consiglio Nazionale delle Ricerche; Italia Fil: Fiorani, Dino. Argentine Italian Joint Laboratory of Nanomagnetism; Argentina. Consiglio Nazionale delle Ricerche; Italia Fil: Zysler, Roberto Daniel. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Resonancias Magnéticas; Argentina. Argentine Italian Joint Laboratory of Nanomagnetism; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina Fil: Winkler, Elin Lilian. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Resonancias Magnéticas; Argentina. Argentine Italian Joint Laboratory of Nanomagnetism; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina

Metal-porous oxide nanocomposites present great interest in optical devices and heterogeneous catalysis. For these applications, particle shape and size control, as well as accessibility, are critical aspects. In this work, gold nanoparticles (NPs) were infiltrated into mesoporous TiO2 thin films (MTTF) by an impregnation-reduction method. In situ ellipsometry measurements were performed during thermal treatment to follow in real time the changes in the optical constants and thickness of the composites systems while being submitted to continuous heating at different rates, from room temperature up to 600 °C. Complementary characterization by UV–visible spectrophotometry, grazing incident wide angle scattering (GIWAXS), and X-ray reflectometry (XRR) were performed. TEM microscopy was used to analyze the morphological changes in the composite films after the thermal treatment. Our experiments demonstrate that particle coarsening starts at temperatures below 200 °C through the processes of ripening and particle migration, leading to changes in the particle size distribution (PSD) until a mechanical restriction, due to the porous geometry, induces a change of the particle shape from spherical to ellipsoidal. This results in an internal stress that swells the mesoporous film. The effect of the gold filling fraction and the heating ramp was analyzed. A mechanism based on the kinetics of particle migration and coalescence, through the modeling of the localized surface plasmon resonance under the dipolar approximation, is proposed to explain the changes in the optical properties of these composites materials and unravel the thermal activated processes occurring in metal crystallites supported on porous oxide frameworks. Fil: Martínez, Eduardo David. Comisión Nacional de Energía Atómica. Gerencia del Área de Seguridad Nuclear y Ambiente. Gerencia de Química (CAC); Argentina Fil: Cédric, Boissiere. College de France; Francia Fil: Grosso, David. College de France; Francia Fil: Sanchez, Clément. College de France; Francia Fil: Troiani, Horacio Esteban. Comision Nacional de Energia Atomica. Gerencia D/area de Energia Nuclear; Argentina Fil: Galo, J. A. A. Soler Illia. Comisión Nacional de Energía Atómica. Gerencia del Área de Seguridad Nuclear y Ambiente. Gerencia de Química (CAC); Argentina

Starting from an amorphous C film, single-walled carbon nanotubes were obtained in situ in a high-resolution electron microscope by the combined effect of irradiation and axial strain. Ductile nanotubes developed either a junction or a linear chain of C atoms before failure. These facts have been put in direct evidence for the first time. Tight-binding calculations indicate that the bonding in the linear chain is of a cumulene type., This work was supported by the CONYCYT, Argentina, by special funds from Texas Materials Institute and the Center for Nano and Molecular Technology (UT-Austin), CONACYT, México, the University of the Basque Country, DGES, and by the EU research training network NANOPHASE (HPRN-CT-2000-00167).