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2017


Defect chemistry and electrical properties of BiFeO3


Schrade, M; Maso, N; Perejon, A; Perez-Maqueda, LA; West, AR
Journal of Materials Chemistry C, 5 (2017) 10077-10086

ABSTRACT

BiFeO3 attracts considerable attention for its rich functional properties, including room temperature coexistence of magnetic order and ferroelectricity and more recently, the discovery of conduction pathways along ferroelectric domain walls. Here, insights into the defect chemistry and electrical properties of BiFeO3 are obtained by in situ measurements of electrical conductivity, sigma, and Seebeck coefficient, a, of undoped, cation-stoichiometric BiFeO3 and acceptor-doped Bi1-xCaxFeO3-delta ceramics as a function of temperature and oxygen partial pressure pO(2). Bi1-xCaxFeO3-delta exhibits p-type conduction; the dependencies of s and a on pO(2) show that Ca dopants are compensated mainly by oxygen vacancies. By contrast, undoped BiFeO3 shows a simultaneous increase of s and a with increasing pO(2), indicating intrinsic behavior with electrons and holes as the main defect species in almost equal concentrations. The pO(2)-dependency of s and a cannot be described by a single point defect model but instead, is quantitatively described by a combination of intrinsic and acceptor-doped characteristics attributable to parallel conduction pathways through undoped grains and defect-containing domain walls; both contribute to the total charge transport in BiFeO3. Based on this model, we discuss the charge transport mechanism and carrier mobilities of BiFeO3 and show that several previous experimental findings can readily be explained within the proposed model.


Octubre, 2017 | DOI: 10.1039/c7tc03345a

Cellulose-polyhydroxylated fatty acid ester-based bioplastics with tuning properties: Acylation via a mixed anhydride system


Heredia-Guerrero, JA; Goldoni, L; Benitez, JJ; Davis, A; Ceseracciu, L; Cingolani, R; Bayer, IS; Heinze, T; Koschella, A; Heredia, A; Athanassiou, A
Carbohydrate Polymers, 173 (2017) 312-320

ABSTRACT

The synthesis of microcrystalline cellulose (MCC) and 9,10,16-hydroxyhexadecanoic (aleuritic) acid ester-based bioplastics was investigated through acylation in a mixed anhydride (trifluoroacetic acid (TFA)/trifluoroacetic acid anhydride (TFAA)), chloroform co-solvent system. The effects of chemical interactions and the molar ratio of aleuritic acid to the anhydroglucose unit (AGU) of cellulose were investigated. The degree of substitution (DS) of new polymers were characterized by two-dimensional solution-state NMR and ranged from 0.51 to 2.60. The chemical analysis by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) confirmed the presence of aleuritate groups in the structure induces the formation of new H-bond networks. The tensile analysis and the contact angle measurement confirmed the ductile behavior and the hydrophobicity of the prepared bioplastics. By increasing the aleuritate amounts, the glass transition temperature decreased and the solubility of bioplastic films in most common solvents was improved. Furthermore, this new polymer exhibits similar properties compared to commercial cellulose derivatives.


Octubre, 2017 | DOI: 10.1016/j.carbpol.2017.05.068

HoF3 and DyF3 Nanoparticles as Contrast Agents for High-Field Magnetic Resonance Imaging


Gonzalez-Mancebo, Daniel; Becerro, Ana I.; Rojas, T. Cristina; Garcia-Martin, Maria L.; de la Fuente, Jesus M.; Ocana, Manuel
Particle & particle systems characterization, 34 (2017) art. 1700116

ABSTRACT

Clinical contrast agents (CAs) currently used in magnetic resonance imaging (MRI) at low fields are less effective at high magnetic fields. The development of new CAs is mandatory to improve diagnostic capabilities of the new generation of high field MRI scanners. The purpose of this study is to synthesize uniform, water dispersible LnF3 (Ln = Ho, Dy) nanoparticles (NPs) and to evaluate their relaxivity at high magnetic field (9.4 T) as a function of size and composition. Two different types of HoF3 NPs are obtained by homogeneous precipitation in ethylene glycol at 120 °C. The use of holmium acetate as holmium precursor leads to rhombus-like nanoparticles, while smaller, ellipsoid-like nanoparticles are obtained when nitrate is used as the holmium salt. To explain this behavior, the mechanism of formation of both kinds of particles is analyzed in detail. Likewise, rhombus-like DyF3 nanoparticles are prepared following the same method as for the rhombus-like HoF3 nanoparticles. We have found, to the best of knowledge, the highest transverse relaxivity values at 9.4 T described in the literature for this kind of CAs. Finally, the LnF3 NPs have shown negligible cytotoxicity for C6 rat glioma cells for concentrations up to 0.1 mg mL−1.


Octubre, 2017 | DOI: 10.1002/ppsc.201700116

Dense graphene nanoplatelet/yttria tetragonal zirconia composites: Processing, hardness and electrical conductivity


Gallardo-Lopez, A; Marquez-Abril, I; Morales-Rodriguez, A; Munoz, A; Poyato, R
Ceramics International, 43 (2017) 11743-11752

ABSTRACT

Yttria tetragonal zirconia ceramic composites with 1, 2.5, 5 and 10 vol% nominal contents of graphene nanoplatelets (GNPs) were fabricated and characterized. First, the GNP dispersion in isopropanol was optimized to de-agglomerate the GNPs without damaging their structure. Then, submicrometric fully dense composites were obtained via spark plasma sintering (SPS) at 1250 degrees C with a 5 min holding time. The processing routine produced a nearly homogeneous GNP dispersion in the ceramic matrix, and the GNPs preferential orientation was perpendicular to the sintering compression axis. A ceramic grain refinement due to the GNPs was also detected. The Vickers hardness measured on the plane perpendicular to the sintering compression axis (basal plane) was lower than on the cross sections. This anisotropy increased with the increasing GNP content, while the average hardness decreased. The electrical conductivity was also highly anisotropic, up to seven times higher for the basal planes. The electrical percolation threshold for these composites was estimated to be between 2.2 and 4.4 vol% of the GNP measured content.


Octubre, 2017 | DOI: 10.1016/j.ceramint.2017.06.007

Incorporation of Calcium Containing Mesoporous (MCM-41-Type) Particles in Electrospun PCL Fibers by Using Benign Solvents


Liverani, L.;Boccardi, E.; Beltrán, A.M.; Boccaccini, A.R.
Polymers, 9 (2017) 487

ABSTRACT

The electrospinning technique is a versatile method for the production of fibrous scaffolds able to resemble the morphology of the native extra cellular matrix. In the present paper, electrospinning is used to fabricate novel SiO2particles (type MCM-41) containing poly(epsilon-caprolactone) (PCL) fibers. The main aims of the present work are both the optimization of the particle synthesis and the fabrication of composite fibers, obtained using benign solvents, suitable as drug delivery systems and scaffolds for soft tissue engineering applications. The optimized synthesis and characterization of calcium-containing MCM-41 particles are reported. Homogeneous bead-free composite electrospun mats were obtained by using acetic acid and formic acid as solvents; neat PCL electrospun mats were used as control. Initially, an optimization of the electrospinning environmental parameters, like relative humidity, was performed. The obtained composite nanofibers were characterized from the morphological, chemical and mechanical points of view, the acellular bioactivity of the composite nanofibers was also investigated. Positive results were obtained in terms of mesoporous particle incorporation in the fibers and no significant differences in terms of average fiber diameter were detected between the neat and composite electrospun fibers. Even if the Ca-containing MCM-41 particles are bioactive, this property is not preserved in the composite fibers. In fact, during the bioactivity assessment, the particles were released confirming the potential application of the composite fibers as a drug delivery system. Preliminary in vitro tests with bone marrow stromal cells were performed to investigate cell adhesion on the fabricated composite mats, the positive obtained results confirmed the suitability of the composite fibers as scaffolds for soft tissue engineering.


Octubre, 2017 | DOI: 10.3390/polym9100487

Microstructure characterization of multifunctional As4S4/Fe3O4 nanocomposites prepared by high-energy mechanical milling


Shpotyuk, O; Bujnakova, Z; Sayagues, MJ; Balaz, P; Ingram, A; Shpotyuk, Y; Demchenko, P
Materials Characterization, 132 (20187) 303-311

ABSTRACT

Multifunctional As4S4/Fe3O4 nanocomposites prepared by high-energy mechanical milling are probed by complementary methods of positron annihilation lifetime (PAL) spectroscopy, supported by microstructure characterization using X-ray powder diffraction (XRPD) with analysis applied to the first sharp diffraction peak (FSDP), morphology studies by transmission electron microscopy (TEM) with energy-dispersive spectroscopy (EDS) and high-resolution TEM (HRTEM). 
These nanocomposites are shown to consist of Fe3O4 crystallites with particle sizes of 8-21 nm, and far separated beta-As4S4 crystallites surrounded by amorphous As-S phase. In respect to PAL data, the effect of milling is identified as possible conversion from Ps traps to positron-trapping sites depending on preferential chemistry of atomic surrounding. So, the interfacial triple junctions at the intersections of Fe3O4 crystallites are identified as principal positron traps in As4S4/Fe3O4 nanocomposites with competitive influence from free-volume defects of amorphous As-S phase.


Octubre, 2017 | DOI: 10.1016/j.matchar.2017.08.028

Vapor and liquid optical monitoring with sculptured Bragg microcavities


Oliva-Ramirez, M; Gil-Rostra, J; Lopez-Santos, MC; Gonzalez-Elipe, AR; Yubero, F
Journal of Nanophotonics, 11 (2017) 046009

ABSTRACT

Sculptured porous Bragg microcavities (BMs) formed by the successive stacking of columnar SiO2 and TiO2 thin films with a zig-zag columnar microstructure are prepared by glancing angle deposition. These BMs act as wavelength-dependent optical retarders. This optical behavior is attributed to a self-structuration of the stacked layers involving the lateral association of nanocolumns in the direction perpendicular to the main flux of particles during the multilayer film growth, as observed by focused ion beam scanning electron microscopy. The retardance of these optically active BMs can be modulated by dynamic infiltration of their open porosity with vapors, liquids, or solutions with different refractive indices. The tunable birefringence of these nanostructured photonic systems has been successfully simulated with a simple model that assumes that each layer within the BMs stack has uniaxial birefringence. The sculptured BMs have been incorporated as microfluidic chips for optical transduction for label-free vapor and liquid sensing. Several examples of the detection performance of these chips, working either in reflection or transmission configuration, for the optical monitoring of vapor and liquids of different refractive indices and aqueous solutions of glucose flowing through the microfluidic chips are described.


Octubre, 2017 | DOI: 10.1117/1.JNP.11.046009

Synthesis and characterization of Rh/MnO2-CeO2/Al2O3 catalysts for CO-PrOx reaction


Martinez, TLM; Laguna, OH; Lopez-Cartes, C; Centeno, MA
Molecular Catalysis, 440 (2017) 9-18

ABSTRACT

Rh/MnO2-CeO2/Al2O3 catalysts with different manganese-to-ceria ratios have been synthesized, characterized and tested in CO-PrOx reaction. The physicochemical properties of the solids were studied by XRD, Raman spectroscopy, BET surface area, H-2-TPR, TGA-DTG and TEM. The differences observed in the textural, structural and redox properties were related to the Mn-to-ceria ratio of the samples. The segregation of Mn species was observed at high Mn-to-Ce ratios. In opposite way, MnO2-CeO2 solid solutions were obtained at low Mn to Ce ones. In this last case, the physicochemical properties of the solids were favored by the intimate Rh-Ce-Mn contact. The effect of the Mn-Ce presence on Rh catalysts which promotes the catalytic behavior towards selective CO oxidation was observed to be better at low temperatures. At higher temperatures, Mn species promote the Reverse Water Gas Shift reaction, whilst ceria promotes the H-2 oxidation in the whole range of working temperatures.


Octubre, 2017 | DOI: 10.1016/j.mcat.2017.06.018

High performance novel gadolinium doped ceria/yttria stabilized zirconia/nickel layered and hybrid thin film anodes for application in solid oxide fuel cells


Garcia-Garcia, FJ; Beltran, AM; Yubero, E; Gonzalez-Elipe, AR; Lambert, RM
Journal of Power Sources, 363 (2017) 251-259

ABSTRACT

Magnetron sputtering under oblique angle deposition was used to produce Ni-containing ultra thin film anodes comprising alternating layers of,gadolinium doped ceria (GDC) and yttria stabilized zirconia (YSZ) of either 200 nm or 1000 nm thickness. The evolution of film structure from initial deposition, through calcination and final reduction was examined by XRD, SEM, TEM and TOF-SIMS. After subsequent fuel cell usage, the porous columnar architecture of the two-component layered thin film anodes was maintained and their resistance to delamination from the underlying YSZ electrolyte was superior to that of corresponding single component Ni-YSZ and Ni-GDC thin films. Moreover, the fuel cell performance of the 200 nm layered anodes compared favorably with conventional commercially available thick anodes. The observed dependence of fuel cell performance on individual layer thicknesses prompted study of equivalent but more easily fabricated hybrid anodes consisting of simultaneously deposited Ni-GDC and Ni-YSZ, which procedure resulted in exceptionally intimate mixing and interaction of the components. The hybrids exhibited very unusual and favorable I-V characteristics, along with exceptionally high power densities at high currents. Their discovery is the principal contribution of the present work. 


Septiembre, 2017 | DOI: 10.1016/j.jpowsour.2017.07.085

Rare earth based nanostructured materials: synthesis, functionalization, properties and bioimaging and biosensing applications


Escudero, Alberto; Becerro, Ana I.; Carrillo-Carrion, Carolina; Nunez, Nuria O.; Zyuzin, Mikhail V.; Laguna, Mariano; Gonzalez-Mancebo, Daniel; Ocana, Manuel; Parak, Wolfgang J.
Nanophotonics, 6 (2017) 881-921

ABSTRACT

Rare earth based nanostructures constitute a type of functional materials widely used and studied in the recent literature. The purpose of this review is to provide a general and comprehensive overview of the current state of the art, with special focus on the commonly employed synthesis methods and functionalization strategies of rare earth based nanoparticles and on their different bioimaging and biosensing applications. The luminescent (including downconversion, upconversion and permanent luminescence) and magnetic properties of rare earth based nanoparticles, as well as their ability to absorb X-rays, will also be explained and connected with their luminescent, magnetic resonance and X-ray computed tomography bioimaging applications, respectively. This review is not only restricted to nanoparticles, and recent advances reported for in other nanostructures containing rare earths, such as metal organic frameworks and lanthanide complexes conjugated with biological structures, will also be commented on.


Septiembre, 2017 | DOI: 10.1515/nanoph-2017-0007

Multicycle activity of natural CaCO3 minerals for thermochemical energy storage in Concentrated Solar Power plants


Benitez-Guerrero, M; Valverde, JM; Sanchez-Jimenez, PE; Perejon, A; Perez-Maqueda, LA
Solar Energy, 153 (2017) 188-199

ABSTRACT

Thermochemical energy storage in Concentrated Solar Power plants by means of the Calcium-Looping process is a promising novel technology that would allow for a higher share of renewables. A main benefit of this technology is the use of widely available, non-toxic and environmentally friendly calcium carbonate minerals as raw materials to store energy. Efficient integration of the Calcium-Looping process into Concentrated Solar Power plants involves the endothermic calcination of CaCO3 in the solar receiver while the exothermic carbonation of CaO is carried out at high temperature under high CO2 partial pressure. The heat released by this reaction is carried out by the excess CO2 and employed for power generation by means of a closed CO2 cycle. This work explores the multicycle Calcium-Looping performance of naturally occurring CaCO3 minerals such as limestone, chalk and marble for thermochemical energy storage in Concentrated Solar Power plants. Despite their similar composition (almost pure CaCO3), these minerals exhibit a significant difference in their Calcium-Looping multicycle activity, which may be attributed to differences in particle size and microstructure. Pore plugging at the Calcium-Looping conditions for thermochemical energy storage tested in our work is a main limiting mechanism on the multicycle CaO carbonation activity.


Septiembre, 2017 | DOI: 10.1016/j.solener.2017.05.068

Europium-doped NaGd(WO4)(2) nanophosphors: synthesis, luminescence and their coating with fluorescein for pH sensing


Laguna, M; Escudero, A; Nuñez, NO; Becerro, AI; Ocaña, M
Dalton Transactions, 46 (2017) 11575-11583

ABSTRACT

Uniform Eu-doped NaGd(WO4)(2) nanophosphors with a spherical shape have been synthesized for the first time by using a wet chemistry method based on a homogeneous precipitation process at low temperature (120 degrees C) in ethylene glycol/water mixtures. The obtained nanoparticles crystallized into the tetragonal structure and presented polycrystalline character. The europium content in such phosphors has been optimized through the analysis of the luminescence dynamics (lifetime measurements). By coating the Eu3+-doped wolframate based nanoparticles with fluorescein through a layer-by-layer (LbL) approach, a wide range (4-10) ratiometric pH-sensitive sensor has been developed, which uses the pH insensitive emission of Eu3+ as a reference.

 


Septiembre, 2017 | DOI: 10.1039/c7dt01986f

Carbon nanofibers replacing graphene oxide in ceramic composites as a reinforcing-phase: Is it feasible?


Cano-Crespo, Rafael; Malmal Moshtaghioun, Bibi; Gomez-Garcia, Diego; Dominguez-Rodriguez, Arturo; Moreno, Rodrigo
Journal of the European Ceramic Society, 37 (2017) 3791-3796

ABSTRACT

In recent years, the interest of graphene and graphene-oxide has increased extraordinarily due to the outstanding properties concurring in this material. In ceramic science, the possibility of combining excellent electrical conductivities together with an enhancement of mechanical properties has motivated the research in fabrication of graphene oxide-reinforced ceramic composites despite the intrinsic difficulties for sintering. In this work a comparison is made between graphene oxide-reinforced alumina composites and carbon nanofiber-reinforced alumina ones. It will be concluded that the improvement of mechanical properties is scarce, if any. Since carbon nanofibers have also a good electrical conductivity their importance for future applications as a replacement of more sophisticated but expensive graphene-based ceramic composites will be stressed.


Septiembre, 2017 | DOI: 10.1016/j.jeurceramsoc.2017.03.027

Enhanced green fluorescent protein in optofluidic Fabry-Perot microcavity to detect laser induced temperature changes in a bacterial culture


Lahoz, F; Martin, IR; Walo, D; Freire, R; Gil-Rostra, J; Yubero, F; Gonzalez-Elipe, AR
Applied Physics Letters, 111 (2017) 111103

ABSTRACT

Thermal therapy using laser sources can be used in combination with other cancer therapies to eliminate tumors. However, high precision temperature control is required to avoid damage in healthy surrounding tissues. Therefore, in order to detect laser induced temperature changes, we have used the fluorescence signal of the enhanced Green Fluorescent Protein (eGFP) over-expressed in an E. coli bacterial culture. For that purpose, the bacteria expressing eGFP are injected in a Fabry-Perot (FP) optofluidic planar microcavity. In order to locally heat the bacterial culture, external infrared or ultraviolet lasers were used. Shifts in the wavelengths of the resonant FP modes are used to determine the temperature increase as a function of the heating laser pump power. Laser induced local temperature increments up to 6-7 degrees C were measured. These results show a relatively easy way to measure laser induced local temperature changes using a FP microcavity and using eGFP as a molecular probe instead of external nanoparticles, which could damage/alter the cell. Therefore, we believe that this approach can be of interest for the study of thermal effects in laser induced thermal therapies. 


Septiembre, 2017 | DOI: 10.1063/1.4990870

Influence of milling parameters on the solid-gas synthesis of TiCxN1-x by mechanically induced self-sustaining reaction


Chicardi, E; Gotor, FJ; Alcala, MD; Cordoba, JM
Powder Technology, 319 (2017) 12-18

ABSTRACT

The synthesis of a titanium carbonitride solid solution (TiCxN1 − x) performed in a high-energy planetary mill by a solid-gas Mechanically induced Self-sustaining Reaction (MSR) was used to study the influence of a full set of experimental milling parameters on the ignition time (tig) as a measure of the mechanical dose rate provided by the mill. The highly exothermic Ti-C-N mixture was selected to ensure no competitiveness between MSR and diffusion-controlled routes under the milling conditions employed. The results showed that the dependence of tig on the spinning rate followed a potential function, with a potential factor higher than the value of 3 that would be obtained if a perfect collision model is assumed. The scalability of milling processes performed using planetary mills was confirmed. The results suggested that to define a milling experiment, it is necessary to provide not only the Ball-to-Powder mass Ratio (BPR) and spinning rate values, as is usually performed, but also the full set of milling parameters including the nature of the milling media (vial and balls), the number and size of balls, the mass of the powder charge, the pressure of the reactive gas and even the volume of the vial.


Septiembre, 2017 | DOI: 10.1016/j.powtec.2017.06.035

High-temperature thermal conductivity of biomorphic SiC/Si ceramics


Ramirez-Rico, J.; Singh, M.; Zhu, D.; Martinez-Fernandez, J.
Journal of Materials Science, 52 (2017) 10038-10046

ABSTRACT

Thermal conductivity of biomorphic SiC/Si, a silicon carbide + silicon containing two phase material, was evaluated using the laser steady-state heat flux method. These materials were processed via silicon melt infiltration of wood-derived carbon scaffolds. In this approach, heat flux was measured through the thickness when one side of the specimen was heated with a 10.6-A mu m CO2 laser. A thin mullite layer was applied to the heated surface to ensure absorption and minimize reflection losses, as well as to ensure a consistent emissivity to facilitate radiative loss corrections. The influence of the mullite layer was accounted for in the thermal conductivity calculations. The effect of microstructure and composition (inherited from the wood carbonaceous performs) on measured conductivity was evaluated. To establish a baseline for comparison, a dense, commercially available sintered SiC ceramic was also evaluated. It was observed that at a given temperature, thermal conductivity falls between that of single-crystal silicon and fine-grained polycrystalline SiC and can be rationalized in terms of the SiC volume fraction in biomorphic SiC/Si material.


Septiembre, 2017 | DOI: 10.1007/s10853-017-1199-y

In Vitro and in Vivo Study of Poly(Lactic-co-Glycolic) (PLGA) Membranes Treated with Oxygen Plasma and Coated with Nanostructured Hydroxyapatite Ultrathin Films for Guided Bone Regeneration Processes


Torres-Lagares, D; Castellanos-Cosano, L; Serrera-Figallo, MA; Garcia-Garcia, FJ; Lopez-Santos, C; Barranco, A; Elipe, ARG; Rivera-Jimenez, C; Gutierrez-Perez, JL
Polymers, 9 (2017) art. 410

ABSTRACT

The novelty of this study is the addition of an ultrathin layer of nanostructured hydroxyapatite (HA) on oxygen plasmamodified poly(lactic-co-glycolic) (PLGA) membranes (PO2) in order to evaluate the efficiency of this novel material in bone regeneration. Methods: Two groups of regenerative membranes were prepared: PLGA (control) and PLGA/PO2/HA (experimental). These membranes were subjected to cell cultures and then used to cover bone defects prepared on the skulls of eight experimental rabbits. Results: Cell morphology and adhesion of the osteoblasts to the membranes showed that the osteoblasts bound to PLGA were smaller and with a lower number of adhered cells than the osteoblasts bound to the PLGA/PO2/HA membrane (p < 0.05). The PLGA/PO2/HA membrane had a higher percentage of viable cells bound than the control membrane (p < 0.05). Both micro-CT and histological evaluation confirmed that PLGA/PO2/HA membranes enhance bone regeneration. A statistically significant difference in the percentage of osteoid area in relation to the total area between both groups was found. Conclusions: The incorporation of nanometric layers of nanostructured HA into PLGA membranes modified with PO2 might be considered for the regeneration of bone defects. PLGA/PO2/HA membranes promote higher osteosynthetic activity, new bone formation, and mineralisation than the PLGA control group.


Septiembre, 2017 | DOI: 10.3390/polym9090410

Lead-Free Polycrystalline Ferroelectric Nanowires with Enhanced Curie Temperature


Datta, Anuja; Sanchez-Jimenez, Pedro E.; Al Orabi, Rabih Al Rahal; Calahorra, Yonatan; Ou, Canlin; Sahonta, Suman-Lata; Fornari, Marco; Kar-Narayan, Sohini
Advanced Functional Materials, 27 (2017) 1701169

ABSTRACT

Ferroelectrics are important technological materials with wide-ranging applications in electronics, communication, health, and energy. While lead-based ferroelectrics have remained the predominant mainstay of industry for decades, environmentally friendly lead-free alternatives are limited due to relatively low Curie temperatures (T-C) and/or high cost in many cases. Efforts have been made to enhance T-C through strain engineering, often involving energy-intensive and expensive fabrication of thin epitaxial films on lattice-mismatched substrates. Here, a relatively simple and scalable sol-gel synthesis route to fabricate polycrystalline (Ba0.85Ca0.15)(Zr0.1Ti0.9)O-3 nanowires within porous templates is presented, with an observed enhancement of T-C up to similar to 300 degrees C as compared to similar to 90 degrees C in the bulk. By combining experiments and theoretical calculations, this effect is attributed to the volume reduction in the template-grown nanowires that modifies the balance between different structural instabilities. The results offer a cost-effective solution-based approach for strain-tuning in a promising lead-free ferroelectric system, thus widening their current applicability.


Agosto, 2017 | DOI: 10.1002/adfm.201701169

Biomorphic ceramics from wood-derived precursors


Ramirez-Rico, J.; Martinez-Fernandez, J.; Singh, M.
International Materials Reviews, 62 (2017) Issue 8

ABSTRACT

Materials development is driven by microstructural complexity and, in many cases, inspired by biological systems such as bones, shells and wood. In one approach, one selects the main microstructural features responsible for improved properties and design processes to obtain materials with such microstructures (continuous-fibre-reinforced ceramics, porous ceramics, fibrous ceramic monoliths, etc.). In a different approach, it is possible to use natural materials directly as microstructural templates. Biomorphic ceramics are produced from natural and renewable resources (wood or wood-derived products). A wide variety of SiC-based ceramics can be fabricated by infiltration of silicon or silicon alloys into cellulose-derived carbonaceous templates, providing a low-cost route to advanced ceramic materials with near-net shape potential and amenable to rapid prototyping. These materials have tailorable microstructure and properties, and behave like ceramic materials manufactured by advanced ceramic processing approaches. This review aims to be a comprehensive description of the development of bioSiC ceramics: from wood templates and their microstructure to potential applications of bioSiC materials.


Agosto, 2017 | DOI: 10.1080/09506608.2017.1354429

The role of cobalt hydroxide in deactivation of thin film Co-based catalysts for sodium borohydride hydrolysis


Paladini, M; Arzac, GM; Godinho, V; Hufschmidt, D; de Haro, MCJ; Beltran, AM; Fernandez, A
Applied Catalysis B-Environmental, 210 (2017) 342-351

ABSTRACT

Deactivation of a Co catalyst prepared as thin film by magnetron sputtering was studied for the sodium borohydride (SB) hydrolysis reaction under different conditions. Under high SB concentration in single run experiments, the formation of a B-O passivating layer was observed after 1.5 and 24 h use. This layer was not responsible for the catalyst deactivation. Instead, a peeling-off mechanism produced the loss of cobalt. This peeling-off mechanism was further studied in cycling experiments (14 cycles) under low SB concentrations. Ex-situ study of catalyst surface after use and solid reaction products (precipitates) was performed by X-Ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). The presence of cobalt hydroxide and oxyhydroxide was detected as major components on the catalyst surface after use and as precipitates in the supernatant solutions after washing. Cobalt borate, cobalt carbonate and oxycarbonate were also formed but in lesser amounts. These oxidized cobalt species were formed and further detached from the catalyst at the end of the reaction and/or during catalyst washing by decomposition of the unstable in-situ formed cobalt boride. Leaching of cobalt soluble species was negligible. Thin film mechanical detachment was also found but in a smaller extent. To study the influence of catalyst composition on deactivation processes, cycling experiments were performed with Co-B and Co-C catalysts, also prepared as thin films. We found that the deactivation mechanism proposed by us for the pure Co catalyst also occurred for a different pure Co (prepared at higher pressure) and the Co-B and Co-C samples in our experimental conditions. 


Agosto, 2017 | DOI: 10.1016/j.apcatb.2017.04.005

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