Search

In this work, the synthesis and catalytic activity of bimetallic Ag–Au nanoparticles (NPs) supported in TiO2 mesoporous thin films (MTFs) are presented. The composite materials were obtained through a two-step procedure, performed at room conditions. In the first step, Ag NPs were grown inside the MTFs by photoreduction. Then, a galvanic replacement reaction with Au was carried out, yielding the bimetallic NPs. The composites were characterized by UV/Vis spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray reflectometry (XRR), which show that the alloyed Ag–Au NPs are present inside the mesopores. Moreover, Ag and Au composition relationship can be controlled by adjusting the reaction times of the photoreduction and galvanic replacement reactions, respectively. Pores remain accessible after NPs synthesis, a feature that ensures their possible applications in any device that requires the contact between the NPs and the medium. Catalytic activity of the composites towards 4-nitrophenol reduction by sodium borohydride was evaluated. Although all the bimetallic systems exhibit improved catalytic properties in comparison with the monometallic Ag composite, the sample with lower Au/Ag relationship is the most effective. For the first time, to the best of our knowledge, bimetallic Au–Ag NPs are encapsulated inside mesoporous TiO2 films, paving the way towards a wide variety of applications. Fil: Coneo Rodríguez, Rusbel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina Fil: Troiani, Horacio Esteban. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Dispositivos y Sensores; Argentina Fil: Moya, Sergio Eduardo. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Departamento de Electrónica. Laboratorio de Instrumentación y Control; Argentina. CIC biomaGUNE; España Fil: Bruno, Mariano Martín. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina Fil: Angelome, Paula Cecilia. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina

In this work it is shown a precise way to optimize the heat generation in high viscosity magnetic colloids, by adjusting the Neel relaxation time in core/shell bimagnetic nanoparticles, for Magnetic Fluid Hyperthermia applications. To pursue this goal, Fe3O4/ZnxCo1-xFe2O4 core/shell nanoparticles were synthesized with 8.5 nm mean core diameter, encapsulated in a shell of ~1.1 nm of thickness, where the Zn atomic ratio (Zn/(Zn+Co) at%) changes from 33 at% to 68 at%. The magnetic measurements are consistent with a rigid interface coupling between the core and shell phases, where the effective magnetic anisotropy systematically decreases when the Zn concentration increases, without a significant change of the saturation magnetization. Experiments of magnetic fluid hyperthermia of 0.1 wt% of these particles dispersed in water, DMEM (Dulbecco modified Eagles minimal essential medium) and a high viscosity butter oil, result in a large specific loss power (SLP), up to 150 W/g, when the experiments are performed at 571 kHz and 200 Oe. The SLP was optimized adjusting the shell composition, showing a maximum for intermediate Zn concentration. This study shows a way to maximize the heat generation in viscous media like cytosol, for those biomedical applications that requiere smaller particle sizes .

In this work, we studied the cation occupancy of bimagnetic CoO/Co1−xZnxFe2O4 core/shell nanoparticles by means of X-ray absorption and Mossbauer spectroscopies, which provide element-sensitive information at the atomic scale. Our results indicate that, although the spinel ferrite forms a multi-grain shell, the Zn cations occupy solely tetrahedral sites, while the Co cations are mostly in the octahedral site. On the other hand, the Fe cations are distributed in both tetrahedral and octahedral sites for all concentrations. Also the results provide evidence for a Zn-deficient spinel with an excess of Co cations in the shell, whose origin is further rationalized in terms of the two-step synthesis process. In overall, this work gives a description of the cation occupancy in the core/shell nanoparticles and can serve as a guide to the interpretation of the magnetic properties of complex bimagnetic systems for future technological applications.

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.

In Specific Power Absorption (SPA) models for Magnetic Fluid Hyperthermia (MFH) experiments, the magnetic relaxation time of the nanoparticles (NPs) is known to be a fundamental descriptor of the heating mechanisms. The relaxation time is mainly determined by the interplay between the magnetic properties of the NPs and the rheological properties of NPs environment. Although the role of magnetism in MFH has been extensively studied, the thermal properties of the NPs medium and their changes during of MFH experiments have been so far underrated. Here, we show that ZnxFe3-xO4 NPs dispersed through different with phase transition in the temperature range of the experiment: clarified butter oil (CBO) and paraffin. These systems show non-linear behavior of the heating rate within the temperature range of the MFH experiments. For CBO, a fast increase at $306 K$ associated to changes in the viscosity (\texteta(T)) and specific heat (c_p(T)) of the medium below and above its melting temperature. This increment in the heating rate takes place around $318 K$ for paraffin. Magnetic and morphological characterizations of NPs together with the observed agglomeration of the nanoparticles above $306 K$ indicate that the fast increase in MFH curves could not be associated to a change in the magnetic relaxation mechanism, with N\'eel relaxation being dominant. In fact, successive experiment runs performed up to temperatures below and above the CBO melting point resulted in different MFH curves due to agglomeration of NPs driven by magnetic field inhomogeneity during the experiments. Similar effects were observed for paraffin. Our results highlight the relevance of the NPs medium's thermodynamic properties for an accurate measurement of the heating efficiency for in vitro and in vivo environments, where the thermal properties are largely variable within the temperature window of MFH experiments., Comment: 36 pages, 8 figures

We report the precise control of tunneling magnetoresistance (TMR) in devices of self-assembled core/shell Fe$_3$O$_4$/Co$_{1-x}$Zn$_x$Fe$_2$O$_4$ nanoparticles ($0\leq x\leq 1$). Adjusting the magnetic anisotropy through the content of Co$^{2+}$ in the shell, provides an accurate tool to control the switching field between the bistable states of the TMR. In this way, different combinations of soft/hard and hard/soft core/shell configurations can be envisaged for optimizing devices with the required magnetotransport response., Comment: 25 pages, 7 figures

Mixed ionic and electronic conductor (MIEC) oxides have been proposed as candidates to replace Ni/YSZ composites as anodes for Solid Oxide Fuel Cells (SOFC) due to their good stability under C-based fuels. Some MIECs have also demonstrated a good electro-catalytic activity both for oxygen reduction and hydrogen oxidation, making them suitable for symmetric configurations (S-SOFC). This approach presents remarkable advantages for reducing manufacturing and operational costs, as well as for extending the cell’s lifetime by reversing gas flows and thus partially reversing the negative effects of sulphur poisoning and carbon deposition that may happen during operation. Also, the catalytic activity of MIEC electrodes can be improved by functionalizing the oxide surface with active nanoparticles. In this work, we study the formation of Ni-Fe alloy nanoparticles by exsolution from a Sr0.93(Ti0.3Fe0.63Ni0.07)O3-δ (STFN) perovskite in reducing atmospheres, and also the process of reoxidation when the exsolved material is exposed to an oxidizing atmosphere. The initial Sr-deficient composition was chosen to alleviate the segregation of Sr [1], which typically can occur in these materials. Exsolution has previously been reported to improve the electrochemical performance of STFN anodes [2], but the mechanisms underlying the exsolution process and the solid/gas interface are still not well understood. The possibility of using S-SOFC materials that undergo exsolution also raises the question of whether the material is regenerated during reoxidation. While oxidation-induced redissolution of exsolved nanoparticles has been observed for Fe-Co exsolution on La0.8Sr1.2Fe0.9Co0.1O4−δ perovskites [3], for the Ni-Fe exsolution in Sr2(Fe1.4Ni0.1Mo0.5)O6− δ, nanoparticles remained at the surface even after reoxidation [4]. The first case is a very interesting result to achieve larger cell lifetimes, and the latter case is interesting as it opens an additional route to increase the cathode performance. In fact, in ref. [5] Ni exsolution in SrTi0.1Fe0.85Ni0.05O3− δ is deliberately employed as design strategy, fully exploiting the non-reversibility of the exsolution of nanoparticles. However, it is not clear whether Ni-Fe nanoparticles oxidize to form a (Ni,Fe)Ox phase or if Fe is reincorporated into the lattice leaving only NiO particles at the surface. It is also not clear how Sr segregation is affected by the exsolution/reoxidation treatments, or how the reoxidized STFN perovskite is modified compared to the pristine sample. To address these questions directly, ambient pressure X-ray photoelectron and near-edge X-ray absorption fine structure spectroscopy (AP-XPS and NEXAFS) is used to study the chemical structure of STFN in a complete redox cycle in-situ. Based on the measurements, we can provide insights into the chemical states of Fe and Ni and can differentiate the surface and bulk species for Sr and O in each stage of the cycle. We observe that Ni exsolves readily, but we also note that the amount of surface Fe0 increases with increasing H2 content in the reducing atmosphere; Fe0 also increases with the reduction time following an exponential trend until a plateau value is reached within ~1h. Further, we find a significant Sr segregation in reducing atmospheres, which we presume occurs to compensate for the B-site cation exsolution. The amount of Sr segregation remains constant in the nearest surface after reoxidation, but is partially reversed for larger penetration depths; there is also a rapid reversibility in the Fe oxidation state during reoxidation. These observations were complemented with transmission (TEM) and scanning electron microscopy (SEM) studies, with simultaneous energy dispersive spectroscopy (EDS) analysis. In conclusion, we propose a reoxidation-induced reconstruction which forms a Fe- and Sr-rich STF perovskite in the near-surface region, leaving the Ni segregated from the perovskite. Finally, we link the results to the electrochemical impedance spectroscopy (EIS) response of the STFN electrode, observing that this STFN-reoxidized sample shows a significant improvement in its cathode performance compared to the pristine STFN. [1] Fagg, D. P. et al, J. Eur. Ceram. Soc. 21, 1831–1835 (2001). [2] Zhu, T., Troiani, H. E., Mogni, L. V, Han, M. & Barnett, S. A. Joule 2, 478–496 (2018). [3] Zhou, J. et al. Chem. Mater. 28, 2981–2993 (2016). [4] Liu, T. et al. J. Mater. Chem. A 8, 582–591 (2020). [5] Yang, G., Zhou, W., Liu, M. & Shao, Z. ACS Appl. Mater. Interfaces 8, 35308-35314 (2016). Figure 1

The modification of surface composition after long-term operation is one of the most reported degradation mechanisms of (La,Sr)(Co,Fe)O3-δ (LSCFO) cathodes for Solid Oxide Fuel Cells (SOFCs). Nevertheless, its effect on the oxygen reduction reaction kinetics of porous LSCFO cathodes has not been yet reliably established. In this work, La- and Sr-enrichment at the LSCFO surface of porous cathodes has been induced after 50 h aging at 800 °C under air. Such cation redistribution can extend up to ∼400 nm depth under the LSCFO surface as detected by high resolution Scanning Transmission Electron Microscopy-Energy Dispersive Spectroscopy maps acquired inside the cathode pores. The observed surface chemical changes hamper the oxygen surface exchange reaction at the LSCFO/gas interface. Accordingly, a suitable Electrochemical Impedance Spectroscopy analysis revealed that the oxygen ion conductivity remains practically unaltered during the aging treatment while the oxygen surface exchange resistance increases up to 1.8 times. As a result, the cathode impedance response deteriorates within the 10–0.1 Hz frequency range during the aging treatment, resulting in a total cathode area specific resistance increase of 150%. The methodology adopted has demonstrated to be very valuable for studying the degradation of SOFC cathodes produced by the modification of surface composition.

We report the critical current density Jc and the vortex dynamics in phase-separated Tl0.58Rb0.42Fe1.72Se2 crystals by performing magnetization measurements. Structural investigation reveals micro- and nanoscopic phase separation between 122 (superconducting) and 245 (not superconducting) phases. Micrometric phase separation refers to 245 islands with typical diameters of 2 µm embedded in a multiply-connected 122 superconducting network. Nanoscopic phase separation refers to 245 nanoprecipitates embedded in the 122 superconducting paths. The 245 nanoprecipitates with size comparable to the coherence length produce strong vortex pinning. It was observed that the temperature dependence of the flux creep rate presents a peak at intermediate temperatures and magnetic fields lower than 0.5 T. The peak is systematically suppressed as the magnetic field is increased, and it could be related with relaxation generated by double-kink excitations. Double-kinks are low-energy depinning excitations usually associated with strong pinning produced by correlated disorder. Fil: Haberkorn, Nestor Fabian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina Fil: Troiani, Horacio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina Fil: Condo, Adriana Maria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina Fil: Wang, Hangdong. Zhejiang University; China. Hangzhou Normal University; China Fil: Mao, Qianhui. Zhejiang University; China Fil: Fang, Minghu. Zhejiang University; China. Collaborative Innovation Center of Advanced Microstructures; China

We report a fast method of producing rhodium-decorated platinum nanoparticles (NPs) containing iridium oxides (IrOx) to be used in the glycerol electrooxidation reaction. We synthesize PtIrOx/C electrocatalysts of different atomic compositions dispersed on Carbon Vulcan XC-72R® by using the fast polyol method assisted by microwaves. Afterwards, PtIrOx/C was potentiodynamically decorated by Rh (Rh/PtIrOx/C). The NPs are characterized by energy dispersive X-ray analysis, X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. The electrooxidation of glycerol was investigated in acid medium by cyclic voltammetry and chronoamperometry. The electrochemical stability of Rh/PtIrOx/C NPs was evaluated by following a degradation test protocol, which consists in exhaustive cyclic voltammetries. Our results show that the presence of iridium oxides in the architecture of platinum enhances the electrochemical stability of the catalyst by avoiding agglomeration effects. Moreover, the presence of rhodium catalyzes the glycerol electrooxidation reaction. These results help understanding the role of Rh and IrOx in the glycerol electrooxidation and provide new insights for designing nanomaterials with improved stability and activity.

New LT-SOFC cathodes with La0.5-xPrxBa0.5CoO3-δ (0 ≤ x ≤ 0.5) compositions were studied. The La-rich compounds exhibit an inter-growing cubic and tetragonal structure whereas the Pr-rich show a tetragonal structure. Cathode polarization resistances, estimated from electrochemical impedance (EIS), take values around 0.15 and 0.04 Ω cm2 in air at 600 and 700 °C, respectively. The O2-reduction mechanism and its kinetic coefficients, O-ion diffusion (Dchem) and O-surface exchange (kchem), were studied by applying the ALS model for macro homogenous porous electrodes to the EIS data, in combination with microstructural parameters obtained from three-dimensional tomography using focused ion beam-scanning electron microscopy (3D FIB-SEM). The diffusion coefficients for samples with mixing of phases take values of Dchem ∼ 10-6 cm2 s-1, at 700 °C in air, whereas the pure tetragonal phases present lower values Dchem ∼ 10-8 cm2 s-1. On the contrary the kchem for all samples takes values ranging between 0.4 and 1 × 10-4 cm s-1 at 700 °C in air. In addition, the origin of time evolution of polarization at 700 °C in air was evaluated by combining the EIS spectra as a function of time and the ex situ sample characterization of fresh and tested samples by 3D FIB-SEM tomography and inductively coupled plasma-optical emission spectrometry (ICP-OES). Little changes of microstructures were detected, whereas an increasing of the amount of a water-soluble Ba surface species in comparison with total cation surface segregation was observed for all samples after the ageing. This may constitute the main reason causing the polarization resistance degradation. However, the analysis of time evolution shows, that contrary to the situations reported for SrO segregation in Sr-based perovskites, the Dchem is the coefficient mainly affected for compositions with inter-grown phases. At the same time, both Dchem and kchem decreases with time when only the tetragonal phase is present. Fil: Garcés, D.. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina Fil: Wang, H.. Northwestern University; Estados Unidos Fil: Barnett, S.A.. Northwestern University; Estados Unidos Fil: Leyva, Adelma Graciela. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Napolitano, Federico Ricardo. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina Fil: Fuentes, Rodolfo Oscar. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; 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: Mogni, Liliana Verónica. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina

A mixed conducting oxide with a nominal composition Sr(Ti0.3Fe0.7Ru0.07)O3-δ (STFRu) is studied, in comparison with SrTi0.3Fe0.7O3-δ (STF) oxide, as an anode for solid oxide fuel cells. Exposing STFRu to reducing fuel conditions at 800 °C for 4 h results in the exsolution of essentially all of the Ru and a small fraction of the Fe from the oxide, and the formation of Ru1-xFex nanoparticles on the oxide surfaces. Most of the nanoparticles have the hexagonal structure expected for Ru-rich alloys, and thermogravimetric analysis suggests the composition x ∼ 0.2. A small fraction of bcc-structure, presumably Fe-rich, nanoparticles are also detected. Comparison of cells with STFRu and STF anodes shows that the presence of Ru induces a reduced polarization resistance and increases the maximum power density under most cell operating conditions, particularly at lower temperatures and hydrogen partial pressures. For example, at 700 °C and 30% H2 fuel, the maximum power density is 0.1 W cm-2 for STF compared to 0.3 W cm-2 for STFRu. There is also a significant change in the shape of the current-voltage curves and the pH2-dependence of the anode polarization resistances RP,A ∝ (pH2)-m, from m ∼ 0.5-1.0 for STF to m ∼ 0.11-0.29 for STFRu; these suggest that Ru1-xFex nanoparticles improve anode performance by promoting hydrogen adsorption. Fil: Glaser, R.. Northwestern University; Estados Unidos Fil: Zhu, T.. Northwestern University; Estados Unidos Fil: Troiani, Horacio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Gerencia de Área de Aplicaciones de la Tecnología Nuclear. Gerencia de Investigación Aplicada; Argentina Fil: Caneiro, Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. YPF - Tecnología; Argentina Fil: Mogni, Liliana Verónica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Gerencia de Área de Aplicaciones de la Tecnología Nuclear. Gerencia de Investigación Aplicada; Argentina Fil: Barnett, S.. Northwestern University; Estados Unidos

Electrically conducting oxides have been proposed as alternatives to Ni-based cermet anodes for solid oxide fuel cells (SOFCs) to overcome issues such as coking and impurity poisoning, but their electrochemical performance is typically inferior to that of Ni-based cermets. Here we show that a new oxide composition, Sr0.95(Ti0.3Fe0.63Ni0.07)O3−δ, yields anode polarization resistance competitive with Ni cermets, and substantially better than that of the corresponding Ni-free compound, SrTi0.3Fe0.7O3−δ. Exposure to fuel results in exsolution and nucleation of Ni0.5Fe0.5 nanoparticles uniformly dispersed on the Ni-substituted perovskite surface, whereas no nanoparticles are observed on SrTi0.3Fe0.7O3−δ. A general thermodynamic model is developed that quantitatively predicts exsolved nanoparticle composition. The reduction in anode polarization resistance by the nanoparticles, by as much as 4 times, is most pronounced at cell operating temperatures below 800°C and low H2 partial pressures, suggesting that the nanoparticles improve performance by promoting H2 adsorption. Mixed conducting perovskite oxides are proposed as alternatives for solid oxide fuel cell anodes, and in situ metallic nanoparticle precipitation/exsolution is considered to improve their performance. However, understanding of exsolution is still lacking, such as the reason why specific cations exsolve from an oxide anode and what determines the exsolved phase composition under various anode conditions. Here we directly compare Sr(Ti,Fe)O3-based anodes with and without exsolved metallic nanoparticles, showing their impact on electrochemical characteristics especially under low anode hydrogen concentrations and low temperatures. Three different methods are used to quantitatively determine the composition of the exsolved (Ni,Fe) nanoparticles, and for the first time demonstrate that this can be achieved through thermogravimetric analysis. This work is the first to propose a detailed thermodynamic theory predicting the exsolved nanoparticle composition with successful experimental verification. Ni-Fe nanoparticles are observed to exsolve from Ni-substituted Sr0.95(Ti0.3Fe0.63Ni0.07)O3−δ anode. The exsolved nanoparticles act to enhance hydrogen dissociative adsorption, yielding much lower anode polarization resistance and higher cell performance, especially under low pH2 and temperatures, which is comparable with the current Ni-based cermets. Fil: Zhu, Tenglong. Northwestern University; Estados Unidos. Nanjing University of Science and Technology; China Fil: Troiani, Horacio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Gerencia de Área de Aplicaciones de la Tecnología Nuclear. Gerencia de Investigación Aplicada; Argentina Fil: Mogni, Liliana Verónica. Comisión Nacional de Energía Atómica. Gerencia de Área de Aplicaciones de la Tecnología Nuclear. Gerencia de Investigación Aplicada; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina Fil: Han, Minfang. Tsinghua University; China Fil: Barnett, Scott A.. Northwestern University; Estados Unidos

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 study we demonstrate that the effective coupling of the magnetic phases in core/shell nanoparticles can be promoted by an appropriate thermal annealing. In this way, the magnetization thermal stability of the hard ferrimagnetic CoFe2O4 oxide can be increased up to room temperature when coupled to a CoO antiferromagnetic core in an inverse core/shell structure. In addition, the results show that, being encapsulated in a ∼2 nm thick CoFe2O4 shell, the CoO core is successfully protected against oxidation which is crucial for the effectiveness of the magnetic coupling at the interface. Fil: Lavorato, Gabriel Carlos. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Lima, Enio Junior. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Troiani, Horacio Esteban. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Zysler, Roberto Daniel. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Winkler, Elin Lilian. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina

Lithium reactive hydride composite 2LiBH4 + MgH2 (Li-RHC) has been lately investigated owing to its potential as hydrogen storage medium for mobile applications. However, the main problem associated with this material is its sluggish kinetic behavior. Thus, aiming to improve the kinetic properties, in the present work the effect of the addition of Fe to Li-RHC is investigated. The addition of Fe lowers the starting decomposition temperature of Li-RHC about 30 °C and leads to a considerably faster isothermal dehydrogenation rate during the first hydrogen sorption cycle. Upon hydrogenation, MgH2 and LiBH4 are formed whereas Fe appears not to take part in any reaction. Upon the first dehydrogenation, the formation of nanocrystalline, well distributed FeB reduces the overall hydrogen storage capacity of the system. Throughout cycling, the agglomeration of FeB particles causes a kinetic deterioration. An analysis of the hydrogen kinetic mechanism during cycling shows that the hydrogenation and dehydrogenation behavior is influenced by the activity of FeB as heterogeneous nucleation center for MgB2 and its non-homogenous distribution in the Li-RHC matrix. Fil: Puszkiel, Julián Atilio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh; Fil: Gennari, Fabiana Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Centro Atómico Bariloche; Argentina Fil: Arneodo Larochette, Pierre Paul. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Centro Atómico Bariloche; Argentina Fil: Ramallo Lopez, Jose Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina Fil: Vainio, U.. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh; . Deutsches Elektronen-Synchrotron; Alemania Fil: Karimi, F.. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh; Fil: Pranzas, P. K.. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh; Fil: Troiani, Horacio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Centro Atómico Bariloche; Argentina Fil: Pistidda, C.. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh; Fil: Jepsen, J.. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh; Fil: Tolkiehn, M.. Deutsches Elektronen-Synchrotron; Alemania Fil: Welter, E.. Deutsches Elektronen-Synchrotron; Alemania Fil: Klassen, T.. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh; Fil: Bellosta Von Colbe, J.. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh; Fil: Dornheim, M.. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh

A scalable, simple, robust and reproducible method is presented for the preparation of chemically homogeneous and ordered nanocrystalline and mesoporous Zr1-xCexO2 thin films. The method utilizes widely available commercial block copolymers as templates. We show how the preparation conditions, film compositions and thermal treatments determine the mesoporous and crystalline structure. Through the scanning of the synthetic process, it was possible to arrive at an optimized and very reproducible method which allows the preparation of high quality, transparent, nanocrystalline and ordered Zr1-xCexO2 mesoporous thin films with different compositions. Fil: Violi, Ianina Lucila. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias "Elizabeth Jares Erijman"; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Seguridad Nuclear y Ambiente. Gerencia de Química (CAC); Argentina Fil: Luca, Vittorio. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina Fil: Soldati, Analía Leticia. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia de Área de Aplicaciones de la Tecnología Nuclear. Gerencia de Investigación Aplicada; Argentina Fil: Troiani, Horacio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Gerencia de Área de Aplicaciones de la Tecnología Nuclear. Gerencia de Investigación Aplicada; Argentina Fil: Soler Illia, Galo Juan de Avila Arturo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área Investigaciones y Aplicaciones no Nucleares; Argentina. Universidad Nacional de San Martin. Instituto de Nanosistemas; Argentina Fil: Zelcer, Andrés. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias "Elizabeth Jares Erijman"; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Seguridad Nuclear y Ambiente. Gerencia de Química (CAC); Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina

The Focused Ion Beam (FIB) technique was used to prepare site-specific samples from interfacial regions of different solid oxide fuel cells assemblies. Transmission and Scanning Electron Microscopy on the FIB foils combined with Electrochemical Impedance Spectroscopy (EIS) allowed the characterization of the electrode/electrolyte interphases and the determination of its influence on the cell performance after long-term operation conditions. This work reviews two cases: on one hand, Ln2NiO4+d (Ln= La, Nd) cathodes deposited on both Y0.08Zr0.92O1.96 and Ce0.9Gd0.1O1.95 electrolytes, that react at 900 °C during the adhesion treatment and at temperatures higher than 650 °C during the EIS measurements. These samples present a reaction layer of 10 nm thickness, which contains elements of both phases and was found responsible of the cell performance degradation. On the other hand, La0.4Sr0.6Co0.8Fe0.2O3-δ cathodes showed excelent performance on Ceria electrolytes, even after 1 000 h at operation conditions. In that case, the microscopic analyses of FIB foils showed a semi-coherent interphase growth. Fil: Soldati, Analía Leticia. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Montenegro Hernandez, Alejandra. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Baque, Laura Cecilia. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Troiani, Horacio Esteban. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Mogni, Liliana Verónica. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Schreiber, Anja. Helmholtz-Zentrum Potsdam; Alemania Fil: Serquis, Adriana Cristina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina

The Fe-rich corner of the Fe-Al-V system has shown phase separation into disordered A2 and ordered L21 phases. In a former work we model this ordering reaction by using ab-initio thermodynamics. The approach is now employed to suggest the Fe1-2xAlxVx alloys in order to reduce the Al content by increasing the addition of vanadium looking for a better ductility of the solid solution which can be afterwards strengthened by coherent L21 precipitates. Four alloys with compositions in the range 0.08 < X < 0.15 were studied. The phase transition temperatures and microstructures of the alloys were characterized by differential scanning calorimetry (DSC) and transmission electron microscopy (TEM), respectively. The region (A2 + L21) occurs for 0.10 < X < 0.15 up to maximum temperature of 720 C, higher temperatures causes the appearance of (A2 + B2), B2 and (B2 + L21) regions. The microstructure in the (A2 + L21) region consists of nanosized precipitates of L21 phase in A2 matrix which morphology evolutes with temperature and ageing time. The hardness values, measured at room temperature, for the alloys with X < 0.125 and ageing temperature between 650 and 700 C are comparable to those obtained with other Fe-Al based alloys. Fil: Ferreirós, Pedro Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Unidad de Actividad de Materiales (CAC); Argentina. Universidad Nacional de San Martín. Instituto Sabato; Argentina Fil: Alonso, Paula Regina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Martín. Instituto Sabato; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Unidad de Actividad de Materiales (CAC); Argentina Fil: Gargano, Pablo Hugo. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Unidad de Actividad de Materiales (CAC); Argentina. Universidad Nacional de San Martín. Instituto Sabato; Argentina Fil: Bozzano, Patricia Beatriz. Universidad Nacional de San Martín. Instituto Sabato; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Unidad de Actividad de Materiales (CAC); Argentina Fil: Troiani, Horacio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina Fil: Baruj, Alberto Leonardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina Fil: Rubiolo, Gerardo Hector. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Martín. Instituto Sabato; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Unidad de Actividad de Materiales (CAC); Argentina

In the last decades ethanol and glycerol arose as potential fuels for fuel cells. Based on their importance to the field and molecular similarity, here we compare the electrooxidation of ethanol and glycerol on platinum nanoparticles as an attempt to learn about their differences and similarities in terms of oxidation pathways. By using in situ FTIR we interpret the electrochemical behavior in terms of different pathways involving the production of carboxylic acids for both alcohols. For ethanol, CO2 is produced from CO in a direct pathway involving several electrons, while acetic acid is produced through a parallel pathway. Conversely, for glycerol CO2 seems to be mainly produced through a sequential pathway involving carboxylic acids, each one involving few electrons. The results suggest that glycerol demands surfaces that speed up the oxidation of partially oxidized species formed at intermediate potentials., Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas

The exsolution of metal cations from oxides under reducing fuel conditions results in the formation of surface metallic nanoparticles, which can reduce Solid Oxide Fuel Cell anode polarization resistance. However, the loss of the B-site cations shifts the stoichiometry of the perovskite oxide. Depending on the amount exsolved and the initial stoichiometry, the exsolution can presumably shift the oxide away from its single-phase perovskite region. Herein, the direct comparison of initially stoichiometric composition Sr(Ti0.3Fe0.63Ni0.07)O3-δ (STFN0) with initially A-site deficient Sr0.95(Ti0.3Fe0.63Ni0.07)O3-δ (STFN5) is conducted and reported. X-ray diffraction along with scanning and transmission electron microscopy analysis of the oxides, which are both reduced at 850 °C in H2/H2O/Ar, shows a similar size and density of exsolved Fe–Ni alloy nanoparticles, albeit with slightly different alloy compositions. Whereas the oxide phase in reduced STFN5 shows a well-ordered perovskite structure, the greater B-site deficiency in reduced STFN0 results in a highly disordered and strained structure. The electrochemical performance of STFN0 anodes is inferior to that of STFN5 anodes, and even worse than SrTi0.3Fe0.7O3-δ (Ni-free) anodes. It appears that an initial Sr deficiency is important to avoid a too-high B-site deficiency after exsolution, which distorts the perovskite structure and impairs electrochemical processes.

Pure-phase La0.75Sr0.25Cr0.5Mn0.5O3-δ (LSCM) nanocrystallites have been successfully synthesized by the combustion method, employing glycine as fuel and complexing agent, and ammonium nitrate as combustion trigger. A detailed morphological and structural characterization is performed, by using of X-ray diffraction, N2 physisorption and electron microscopy. The LSCM material consists in interconnected nanocrystallites (∼30 nm) forming a sponge-like structure with meso and macropores, being its specific surface area around 10 m2 g-1. Crystalline structural analyses show that the LSCM nanopowder has trigonal/rhombohedral symmetry in the R-3c space group. By employing the spin coating technique and quick-stuck thermal treatments of the ink-electrolyte, electrodes with different crystallite size (95, 160 and 325 nm) are built onto both sides of the La0.8Sr0.2Ga0.8Mg0.2O3-δ-disk electrolyte. To test the influence of the electrode crystallite size on the electrocatalytic behavior of the symmetrical cells, electrochemical impedance spectroscopy measurements at 800 ºC were performed. When the electrode crystallite size becomes smaller, the area specific resistance decreases from 3.6 to 1.31 Ω cm2 under 0.2O2-0.8Ar atmosphere, possibly due to the enlarging of the triple phase boundary, while this value increases from 7.04 to 13.78 Ω cm2 under 0.17H2-0.03H2O-0.8Ar atmosphere, probably due to thermodynamic instability of the LSCM nanocrystallites. Fil: Chanquia, Corina Mercedes. Comisión Nacional de Energía Atómica. Gerencia de Area de Aplicaciones de la Tecnología Nuclear. Gerencia de Investigación Aplicada; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Montenegro Hernandez, Alejandra. Comisión Nacional de Energía Atómica. Gerencia de Area de Aplicaciones de la Tecnología Nuclear. Gerencia de Investigación Aplicada; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Troiani, Horacio Esteban. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Física de Metales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Caneiro, Alberto. Comisión Nacional de Energía Atómica. Gerencia de Area de Aplicaciones de la Tecnología Nuclear. Gerencia de Investigación Aplicada; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina

International audience; In the past decade, the surprising magnetic behavior of gold nanoparticles has been reported. This unexpected property is mainly attributed both to size and surface effects. Mesoporous thin films are ideal matrices for metallic nanoparticles inclusion, because of their highly accessible and tailorable pore systems that lead to completely tunable chemical environments. Exploiting these features, we synthesized Au nanoparticles within mesoporous titania thin films (film thickness of ∼150 nm and pore diameter of ∼5 nm), and we studied their magnetic properties under confinement. Here, we present the results of the magnetization as a function of temperature and magnetic field for this system, which are consistent with the previously reported for free (unconfined) thiol-capped gold nanoparticles. The successful inclusion of stable magnetic Au nanoparticles within transparent mesoporous thin films opens the gates for the application of these nanocomposites in two-dimensional (2D) microdevices technology and magneto-optical devices.

Nanoparticles (NPs) with magnetic properties based on magnetite (Fe3O4, MAG) modified with oleic acid (OA), chitosan (CS) and bovine serum albumin (BSA) have been prepared. A versatile method of synthesis was employed, involving two steps: (i) co-precipitation of MAG; and (ii) nanoprecipitation of macromolecules on as-formed MAG NPs. Experimental variables have been explored to determine the set of conditions that ensure suitable properties of NPs in terms of their size, functionality and magnetic properties. It was found that the presence of OA in Fe+2/Fe+3 solutions yields MAG NPs with lower aggregation levels, while increasing initial amounts of OA may change the capability of NPs to disperse in aqueous or organic media by modifying the stabilization mechanism. Incorporation of CS was verified through Fourier transform IR spectroscopy. This biopolymer stabilizes NPs by electrostatic repulsions leading to stable ferrofluids and minimal fraction of recoverable solid NPs. BSA was successfully added to NP formulations, increasing their functionality and probably their biocompatibility. In this case too stable ferrofluids were obtained, where BSA acts as a polyelectrolyte. From the proposed methodology it is possible to achieve a wide range of NPs magnetically active intended for several applications. The required properties may be obtained by varying experimental conditions. Fil: Nicolás, Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Planta Piloto de Ingeniería Química (i); Argentina. Universidad Nacional del Sur; Argentina Fil: Saleta, Martin Eduardo. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina Fil: Troiani, Horacio Esteban. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina Fil: Zysler, Roberto Daniel. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina Fil: Lassalle, Verónica Leticia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Química del Sur; Argentina. Universidad Nacional del Sur; Argentina Fil: Ferreira, Maria Lujan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Planta Piloto de Ingeniería Química (i); Argentina. Universidad Nacional del Sur; Argentina

Bimagnetic nanoparticles have been proposed for the design of new materials with controlled properties, which requires a comprehensive investigation of their magnetic behavior due to multiple effects arising from their complex structure. In this work we fabricated bimagnetic core/shell nanoparticles formed by an $\ensuremath{\sim}3$-nm antiferromagnetic (AFM) CoO core encapsulated within an $\ensuremath{\sim}1.5$-nm ferrimagnetic (FiM) ${\mathrm{Co}}_{0.5}{\mathrm{Ni}}_{0.5}{\mathrm{Fe}}_{2}{\mathrm{O}}_{4}$ shell, aiming at studying the enhancement of the magnetic anisotropy and the surface effects of a ferrimagnetic oxide shell. The magnetic properties of as-synthesized and annealed samples were analyzed by ac and dc magnetization measurements. The results indicate that the magnetic response of the as-synthesized particles is governed by the superparamagnetic behavior of the interacting nanoaggregates of spins that constitute the disordered ferrimagnetic shell, whose total moments block at $\ensuremath{\langle}{T}_{B}\ensuremath{\rangle}=49$ K and collectively freeze in a superspin-glass-type state at $\ensuremath{\langle}{T}_{g}\ensuremath{\rangle}=3$ K. On the other hand, annealed nanoparticles are superparamagnetic at room temperature and behave as an exchange-coupled system below the blocking temperature $\ensuremath{\langle}{T}_{B}\ensuremath{\rangle}=70$ K, with enhanced coercivity ${H}_{C}(10\phantom{\rule{4.pt}{0ex}}\text{K})\ensuremath{\sim}14.6$ kOe and exchange bias field ${H}_{EB}(10\phantom{\rule{4.pt}{0ex}}\text{K})\ensuremath{\sim}2.3$ kOe, compared with the as-synthesized system where ${H}_{C}(10\phantom{\rule{4.pt}{0ex}}\text{K})\ensuremath{\sim}5.5$ kOe and ${H}_{EB}(10\phantom{\rule{4.pt}{0ex}}\text{K})\ensuremath{\sim}0.8$ kOe. Our results, interpreted using different models for thermally activated and surface relaxation processes, can help clarify the complex magnetic behavior of many core/shell and hollow nanoparticle systems.

The co-condensation in situ of tetraethoxysilane (TEOS) and mercaptopropyltrimethoxysilane (MPTMS) using cetyltrimethylammonium bromide (CTAB) as a template results in the synthesis of multilayered mesoporous structured SiO2 colloids with “onion-like” chemical environments. Thiol groups were anchored to an inner selected SiO2 porous layer in a bilayered core shell particle producing different chemical regions inside the colloidal layered structure. X-Ray Photoelectron Spectroscopy (XPS) shows a preferential anchoring of the –SH groups in the double layer shell system, while porosimetry and simple chemical modifications confirm that pores are accessible. We can envision the synthesis of interesting colloidal objects with defined chemical environments with highly controlled properties.

This paper presents a study of the mechanical properties of pseudoelastic Cu-Zn-Al foams. Foams of different densities were cycled in compression. The paper shows the retained/dissipated energy by the material, i.e. the area of the compression cycle, as a function of the material density. The frequency and strain amplitude, usual parameters that may influence the damping properties, are studied by evaluating the dissipated energy and the specific damping capacity. Samples cyclically tested under constrained compression conditions show a remarkable mechanical stability and reproducibility. The material does not appreciably degrade after 1000 compression cycles at room temperature. We emphasize the material does not need any thermomechanical processing or training treatment in order to present the mechanical properties detailed in the present paper.

In this work, the mechanical behavior of Fe–28Mn–6Si–5Cr (wt.%) shape memory alloy subjected to a simple thermomechanical treatment consisting in rolling at 600 °C and subsequent aging at 800 °C for 10 min is studied. Martensite can be stress-induced in this material up to 110 °C. No stress-induced martensite was detected at temperatures above 150 °C. Extrapolating the mechanical testing data a yield stress for the austenite at room temperature σ y = 450 MPa was calculated. In addition, a relatively large pseudoelastic behavior was observed at the temperature range between 90 and 110 °C. This effect is discussed on the basis of the formation of stacking faults and the reversible movement of their associated partial dislocations.

Subjecting Cu–Zn samples to annealing under dynamical vacuum produces the evaporation of Zn, a process known as dezincification. Here, we study the phase transitions related to dezincification of Cu–48 at.% Zn (bcc, Beta phase) single crystalline surfaces with residual stresses due to mechanical polishing. In order to identify different steps in the dezincification process of these deformed samples we apply a combination of in situ optical microscopy and transmission electron microscopy (TEM) observations. The former allows us to control and stop the dezincification process at a specific stage of evolution while the latter allows relating surface features with structure and composition changes. Due to dezincification, the formation of an on average 4H hexagonal phase and the fcc equilibrium phase take place. TEM observations show that the bcc to 4H phase transformation occurs by a mechanism of nucleation and growth. In particular, we show evidence of the mechanism of embryo formation for the first time. During the subsequent growth process, the coalescence of transformed zones defines regions in the micron range which after subsequent prolonged dezincification transform to the final fcc equilibrium structure. These experiments provide an insight on the reason for the formation of the non-equilibrium hexagonal phase during the dezincification of electropolished (non-deformed) samples. The new experimental results evidence the heterogeneous character of the dezincification.

Magnetic properties of a single nanotube whose walls are constituted by nanograins of La2/3Sr1/3MnO3 are studied by means of Monte Carlo (MC) simulation. The system is considered as composed by ferromagnetic grains which couple via dipolar interaction. The grain size distribution is obtained from experimental measurements and the inter-grain distance distribution is obtained from a study of distance distribution among magnetic particles distributed in the tube walls. We show the magnetization behavior for a tube of 700 nm of diameter and 3.5 μm length. We discuss the simulation for different temperatures and external fields. As a main result, we show that the distribution of inter-granular distances has a unique behavior for tubular structures of similar diameter/length aspect ratio, independent of their sizes. This scaling relation allows us to perform the simulations using a tube of smaller dimensions. We succeed in explaining the magnetization curves, finding that dipolar interaction is necessary to explain the experimental behavior and that the grains behave as having magnetic dead layers.

Advanced Functional Materials Vol. 17 (8), p. 1247 - 1254, Environment-sensitive Bragg reflectors are built using functional mesoporous thin films as building blocks. Tuning of optical properties is achieved by changing the composition or porosity of the slabs or the introduction of planar defects. Sorption or capillary condensation of molecules into the pore system results in a 10-40 nm photonic bandgap (PBG) shift. Organic functions added to the pore surface change the response, permitting tailoring of the selectivity towards small-size molecules.

Since the discovery of carbon nanotubes (CNT), transmission electron microscopy (TEM) has been the most important tool in their investigation. It is possible to use electron irradiation in a TEM to construct a single-walled carbon nanotube (SWCNT) from an amorphous carbon film. Here we show that such a synthesis method creates a large number of carbon ad-atoms, which after some critical amount of radiation act to restore the system by reconstructing the carbon film. The behavior of the ad-atoms can be controlled by adjusting the current density in the microscope, suggesting that carbon nanomaterials can be tailored by electron irradiation., R.C. thanks the University of Texas at Austin for their fellowship support.

Molecular dynamics simulations and high resolution TEM experiments are performed to assess the fracture of nanotubes under high stretching conditions. Brittle or plastic response is controlled by the rate of applied strain to the tube as well as by the number of defects (in particular vacancies). Simulations predict that under high temperatures and presence of defects (as induced under the high-energy electron beam of the TEM) the tubes exhibit mainly plastic deformation, with the appearance of medium size carbon chains as the latest stage before fracture. These results are in agreement with in-situ TEM observation. Carbon exhibits a very rich dynamics of bond-breaking and bond-reconstruction that allows transformations from fullerenes to tubes to chains., This work was supported by the ECRTNs NANOPHASE (HPRN-CT-2000-00167), COMELCAN (HPRN-CT-2000-00128), EXC!TiNG (HPRN-CT- 2002-00317), by Spanish MCyT(MAT2001-0946) and University of the Basque Country (9/UPV 00206.215-13639/2001).

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

Carbon-supported platinum nanoparticles Pt/C (NPs) are used in many fields of science. These kinds of materials have been extensively studied in electrochemistry due to the fact that they are applied in fuel cell technology. Although there are a myriad of methods for Pt NP synthesis, the need for obtaining Pt/C NPs with a good dispersion (covering over the entire support), a narrow size distribution, and clean surface (among other parameters) is far to be overcome. On this sense herein we describe a very easy and quick method of synthesis of highly dispersed Pt NPs followed by a simple electrochemical cleaning step. The catalysts were electrochemically characterized by studying their behavior in 0.5 M H2SO4 and also by using CO as a probe during the CO electro-oxidation reaction (COEOR). This paper shows how to obtain highly dispersed and clean Pt/C NPs that produce very reproducible results. Besides, we demonstrate how the presence of impurities negatively affects the electrochemical reproducibility of Pt NPs with a clear impact on their catalytic activity., Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas

We introduce a nanoparticle-mesoporous oxide thin film composite (NP-MOTF) as low-cost and straightforward sensing platforms for surface-enhanced Raman Spectroscopy (SERS). Titania, zirconia, and silica mesoporous matrices templated with Pluronics F-127 were synthesized via evaporation-induced self-assembly and loaded with homogeneously dispersed Ag nanoparticles by soft reduction or photoreduction. Both methods give rise to uniform and reproducible Raman signals using 4-mercaptopyridine as a probe molecule. Details on stability and reproducibility of the Raman enhancement are discussed. Extensions in the design of these composite structures were explored including detection of nonthiolated molecules, such as rhodamine 6-G or salicylic acid, patterning techniques for locating the enhancement regions and bilayered mesoporous structures to provide additional control on the environment, and potential size-selective filtration. These inorganic oxide–metal composites stand as extremely simple, reproducible, and versatile platforms for Raman spectroscopy analysis. Fil: Wolosiuk, Alejandro. Comisión Nacional de Energía Atómica. Gerencia del Área de Seguridad Nuclear y Ambiente. Gerencia de Química (CAC); Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Tognalli, Nicolas Gerardo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Centro de Innovación Tecnológica Empresarial y Social S.A.; Argentina Fil: Martínez, Eduardo David. Comisión Nacional de Energía Atómica. Gerencia del Área de Seguridad Nuclear y Ambiente. Gerencia de Química (CAC); Argentina. Universidad Nacional de San Martín. Instituto Sabato; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Granada, Mara. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Constituyentes); Argentina Fil: Fuertes, María Cecilia. Universidad Nacional de San Martín. Instituto Sabato; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Seguridad Nuclear y Ambiente. Gerencia de Química (CAC); Argentina Fil: Troiani, Horacio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina Fil: Bilmes, Sara A.. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina Fil: Fainstein, Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Seguridad Nuclear y Ambiente. Gerencia de Química (CAC); Argentina Fil: Soler Illia, Galo Juan de Avila Arturo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Seguridad Nuclear y Ambiente. Gerencia de Química (CAC); Argentina

Since reactor pressure vessel steels are ferromagnetic, provide a convenient means to monitor changes in the mechanical properties of the material upon irradiation with high energy particles, by measuring their magnetic properties. Here, we discuss the correlation between mechanical and magnetic properties and microstructure, by studying the flux effect on the nuclear pressure vessel steel used in reactors currently under construction in Argentina. Charpy-V notched specimens of this steel were irradiated in the RA1 experimental reactor at 275 C with two lead factors (LFs), 93 and 183. The magnetic properties were studied by means of DC magnetometry and ferromagnetic resonance. The results show that the coercive field and magnetic anisotropy spatial distribution are sensitive to the LF and can be explained by taking into account the evolution of the microstructure with this parameter. The saturation magnetization shows a dominant dependence on the accumulated damage. Consequently, the mentioned techniques are suitable to estimate the degradation of the reactor vessel steel. Fil: Kempf, Rodolfo A.. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes. Gerencia de Investigación y Aplicaciones; Argentina Fil: Sacanell, Joaquin Gonzalo. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes. Gerencia de Investigación y Aplicaciones; Argentina Fil: Milano, Julian. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Resonancias Magnéticas; Argentina Fil: Guerra Mendez, Nicolas. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes. Gerencia de Investigación y Aplicaciones; 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 Fil: Butera, Alejandro Ricardo. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Resonancias Magnéticas; Argentina Fil: Troiani, Horacio Esteban. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Resonancias Magnéticas; Argentina Fil: Saleta, Martin Eduardo. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Resonancias Magnéticas; Argentina Fil: Fortis, Ana Maria. Comisión Nacional de Energía Atómica; Argentina

Chemical reactivity between Ln2NiO4+δ (Ln: La, Nd) electrodes and Y0.08Zr0.92O1.96 (YSZ) and Ce0.9Gd0.1O1.95 (CGO) electrolytes was analyzed by Electrochemical Impedance Spectroscopy (EIS) and Focused Ion Beam-Transmission Electron Microscopy (FIB-TEM) techniques. Ln2NiO4+δ electrodes were deposited onto CGO and YSZ electrolytes by aerography and treated at 900 °C during 1 h in order to promote electrode adhesion. EIS spectra were collected between 500 and 800 °C in dry air. The Polarization Resistances (PR) values for La2NiO4/CGO/La2NiO4 cell are higher than those of La2NiO4/YSZ/La2NiO4. The PR for both cells and its evolution in time suggest that chemical reactivity is developed at 900 °C during the adhesion treatment and at T higher than 650 °C during the EIS measurements. The PR for Nd2NiO4/CGO/Nd2NiO4 and Nd2NiO4/YSZ/Nd2NiO4 are much lower than those of La2NiO4/CGO/La2NiO4 and La2NiO4/YSZ/La2NiO4 cells. These values and the slight increase of PR with time for Nd2NiO4 (NNO) electrodes indicate that the strength of chemical reactivity is much lower than that of La2NiO4 (LNO). TEM results confirmed that reactivity between CGO and LNO is much higher than that of YSZ and LNO and also confirm that the strength of reactivity is appreciably lower for NNO as electrode material.

Controlling the structures of supports and supported phases is important for catalytic applications where synergic effects can play a main role. In this context, we present versatile methods for suitable microstructurization of CeO2 support and improved dispersion of supported Pt crystallites in a Pt/CeO2 system for enhanced catalytic oxidation of CO. The physicochemical properties investigated using SEM, BET, visible Raman, H2-TPR and OSC measurements demonstrated the important role played by the precursor on the properties of CeO2. Further, 0.5 wt% Pt deposited over CeO2 via ethylene glycol assisted reduction (EGR) was found to be more advantageous than conventional impregnation (IMP) in producing very finely dispersed Pt particles that did not noticeably sinter even after thermal treatment at 500 ◦C for longer duration. H2-chemisorption and H2-TPR experiments further substantiated better Pt dispersion on CeO2 prepared in the presence of Cl− ions regardless of the method employed, thus suggesting a strong microstructural effect of support during growth and anti-sintering activity of Pt crystallites. The CO oxidation activity additionally demonstrates that samples prepared by EGR method show remarkably better performance (100% conversion in

The increasing global energy requirements and the growing environmental conscience demand high performance technology for energy production, storage and transport. Fuel cells (FCs) have reached a recognized place within the potentially efficient devices to convert chemical energy into electricity. First developed by William Grove in 1835 [1], FCs had a profound impact in the aerospatial industry and more recently gained special attention for wider application, because they are considered as environmentally friendly devices. Some advantages of FCs include, that their efficiency is independent of the Carnot cycle for thermal machines [2], and that they can be designed for mobile and stationary applications. These devices also produce only water as residue when Hydrogen is used as fuel, without undesired residual emissions and consequently has no impact on the greenhouse effect.

M/CeO2/YSZ nanocomposites (M = Ru, Pd, Ag) were prepared by successive impregnation and tested in the ethanol steam reforming (ESR). Ru/CeO2/YSZ demonstrated good activity and stability under reaction conditions. Pd/CeO2/YSZ shows good initial activity but suffers of significant deactivation while the performances of the Ag-based sample were rather poor. A plethora of different structural (Powder XRD), microstructural (HR-TEM), morphological (surface area, CO chemisorption) and thermal analysis characterization techniques were used to evidence the modification of the samples induced by prolonged exposure to the reaction mixture. The promising performances of Ru/CeO2/YSZ were associated to the combination of the positive action of the metal selectivity to syn-gas and of CeO2 in metal dispersion stabilization and coke deactivation prevention. (C) 2011 Elsevier B.V. All rights reserved.

FeMn based alloys are a low cost alternative to traditional SMAs due to their convenient one-way shape memory effect. While alloy systems containing several elements have received considerable attention along the last few years, namely FeMnSiCr, FeMnSiCrNi and modifications of these two containing precipitates, there is still scarce information about some of the related ternary systems. An important example is the FeMnCr system. Information about phase stability and transformation temperatures in this ternary system would be useful as input data for higher order alloy design. We present experimental fcc/hcp martensitic transformation temperatures of selected FeMnCr alloys measured by means of dilatometry and electrical resistivity. We have found that these transformation temperatures suffer an evolution when samples are thermally cycled, up to an asymptotic state. In the case of the studied samples, this asymptotic state is reached after a small number of cycles (n < 5). TEM observations aimed at elucidating the origin of this behavior found two main microstructural features: 1) the presence of very small precipitates in the alloy matrix, and 2) a tendency to form mono-oriented martensite inside each grain.

Heavy metals from mining, smelting operations and other industrial processing facilities pollute wastewaters worldwide. Extraction of metals from industrial effluents has been widely studied due to the economic advantages and the relative ease of technical implementation. Consequently, the search for new and improved methodologies for the recovery of gold has increased. In this particular research, the use of cone hops biomass (Humulus lupulus) was investigated as a new option for gold recovery. The results showed that the gold binding to native hops biomass was pH dependent from pH 2 to pH 6, with a maximum percentage binding at pH 3. Time dependency studies demonstrated that Au(III) binding to native and modified cone hops biomasses was found to be time independent at pH 2 while at pH 5, it was time dependent. Capacity experiments demonstrated that at pH 2, esterified hops biomass bound 33.4 mg Au/g of biomass, while native and hydrolyzed hops biomasses bound 28.2 and 12.0 mg Au/g of biomass, respectively. However, at pH 5 the binding capacities were 38.9, 37.8 and 11.4 mg of Au per gram of native, esterified and hydrolyzed hops biomasses, respectively.

We report on energetic surface reconstruction phenomena observed on bimetallic nanoparticle systems of AuPd and AuCu, similar to a resolidification effect observed during the cooling process in lead clusters. These binary alloy nanoparticles show the fivefold edges truncated, resulting in { 100 } facets on decahedral structures, an effect largely envisioned and reported theoretically, with no experimental evidence so far. We demonstrate experimentally as well as by computational simulations that this new eutectic structure is favored in such nanoalloy systems. Fil: Rodríguez López J. L.. Instituto Potosino de Investigación Científica y Tecnológica ; México Fil: Montejano Carrizales, J. M.. Universidad Autónoma de San Luis Potosí; México Fil: Pal, U.. Universidad Auto´noma de Puebla; México Fil: Sánchez Ramírez, J. F.. Universidad Auto´noma de Puebla; México Fil: Troiani, Horacio Esteban. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Física de Metales; Argentina Fil: García, D.. The University of Texas; Estados Unidos Fil: Miki Yoshida, M.. The University of Texas; Estados Unidos Fil: José Yacamán, Miguel. The University of Texas; Estados Unidos

The synthesis method for obtaining sub-micrometric structures of rare earth manganese-based mixed oxide compounds is described. Pore wetting of porous polycarbonate templates with the liquid precursor was followed by a two-stage thermal treatment to obtain single phase La0.325Pr0.300Ca0.375MnO3 hollow and solid structures, with external diameter determined by the sacrificial template pore size. The first thermal stage, a microwave assisted denitration process, determines the shape of the structures. The second treatment, performed at 1073 K, allows to obtain the crystallographic structure of the compound. A variety of techniques (scanning and transmission electron microscopy, scanning probe microscopy) allowed to fully characterize the microstructure and morphology of these self-standing manganite nanostructures. For 1 mum pore size templates we obtained tubes, with external diameter around 800 nm and wall thickness around 150 nm; densely packed nanoparticles sized 20-50 nm are the building blocks of the walls. For pore size below 0. 1 mum, solid nanowires were obtained, the size of constituent crystallites being around 10 nm. Overall obtained material exhibits ferromagnetic ordering below 200 K.

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).

La1-xSrxCo1-yFeyO3-? oxides are good candidates for solid oxide fuel cell (SOFC) cathodes because these materials present high ionic and electronic conductivity, and compatibility with Cerium Gadolinium Oxide (CGO) electrolytes allowing a lower operation temperature. In this work, we report the synthesis of La0.4Sr0.6Co0.8Fe0.2O3-? (LSCF) nanotubes prepared by a porous polycarbonate membrane approach, obtaining different microstructures depending on sintering conditions. The structure and morphology of the nanotubes and deposited films were characterized by X-ray diffraction, transmission and scanning microscopy. Finally, we obtained nanostructured films of vertically aligned LSCF tubes deposited over the whole surface of CGO pellets with diameter up to 2.5cm in a direct and single step process.

In this work we describe the synthesis and characterization of maghemite nanoparticles obtained by a new synthetic route. The material was synthesized using triethylamine as a coprecipitation agent in the presence of the organic ligand N , N′ -bis(3,5-di-tert-butyl-catechol)-2,4-diaminotoluene (LCH 3 ). Mossbauer spectrum at 4 K shows typical hyperfine parameters of maghemite and Transmission Electron Microscopy images reveal that the nanoparticles have a mean diameter of 3.9 nm and a narrow size distribution. AC magnetic susceptibility in zero field presents an Arrhenius behavior with unreasonable relaxation parameters due to the strong influence of dipolar interaction. In contrast when the measurements are performed in a 1 kOe field, the effect of dipolar interactions becomes negligible and the obtained parameters are in good agreement with the static magnetic properties. The dynamic energy barrier obtained from the AC susceptibility results is larger than the expected from the average size observed by HRTEM results, evidencing the strong influence of the surface contribution to the anisotropy.