Electric field-assisted sintering (gadolinia-doped ceria/alkali salts) composite membranes

Composite ceramic membranes were prepared according to two routes: (i) vacuum impregnation of molten eutectic sodium-lithium carbonates (NLC) into porous ceria-20 mol% gadolinia (20GDC) solid electrolytes; (ii) electric field-assisted sintering of a 25 wt% NLC/75 wt% 20GDC mixture. Porous 20GDC ceramics were obtained by controlled thermal removal of 40 vol% KCl added as pore former. Electric field-assisted (flash) sintering was carried out monitoring thickness during application of 200 V cm−1 to the specimen positioned in a sample chamber inserted in a vertical dilatometer. The surfaces of the sintered membranes were observed in a scanning electron microscope. Electrochemical impedance spectroscopy measurements were performed in the 5 Hz to 13 MHz frequency range in the 280–580°C range. Arrhenius plots showed the transition from oxide ion conduction (due to the solid electrolyte) to carbonate ion conduction (due to the molten NLC). Membranes flash sintered at 420°C in 2 min showed electrical conductivity similar to membranes conventionally sintered at 690°C for 2 h.publishe

Ionic and Electronic Conductivity of Nanostructured, Samaria-Doped Ceria

The ionic and electronic conductivities of samaria doped ceria electrolytes, Ce_(0.85)Sm_(0.15)O_(1.925−δ), with nanometric grain size have been evaluated. Nanostructured bulk specimens were obtained using a combination of high specific-surface-area starting materials and suitable sintering profiles under conventional, pressureless conditions. Bulk specimens with relatively high density (≥92% of theoretical density) and low medium grain size (as small as 33 nm) were achieved. Electrical A.C. impedance spectra were recorded over wide temperature (150 to 650°C) and oxygen partial pressure ranges (0.21 to 10^(−31) atm). Under all measurement conditions the total conductivity decreased monotonically with decreasing grain size. In both the electrolytic and mixed conducting regimes this behavior is attributed to the high number density of high resistance grain boundaries. The results suggest a possible variation in effective grain boundary width with grain size, as well as a possible variation in specific grain boundary resistance with decreasing oxygen partial pressure. No evidence appears for either enhanced reducibility or enhanced electronic conductivity upon nanostructuring

Ac and dc magnetotransport properties of the phase-separated La 0.6 Y 0.1 Ca 0.3 MnO 3 manganite

Abstract The physical properties of the La 0.6 Y 0.1 Ca 0.3 MnO 3 compound have been investigated, focusing on the magnetoresistance phenomenon studied by both dc and ac electrical transport measurements. X-ray diffraction and scanning electron microscopy analysis of ceramic samples prepared by the sol-gel method revealed that specimens are single phase and have average grain size of~0.5 lm. Magnetization and 4-probe dc electrical resistivity q(T,H) experiments showed that a ferromagnetic transition at T C~1 70 K is closely related to a metal-insulator (MI) transition occurring at essentially the same temperature T MI . The magnetoresistance effect was found to be more pronounced at low applied fields (H £ 2.5 T) and temperatures close to the MI transition. The ac electrical transport was investigated by impedance spectroscopy Z(f,T,H) under applied magnetic field H up to 1 T. The Z(f,T,H) data exhibited two well-defined relaxation processes that exhibit different behaviors depending on the temperature and applied magnetic field. Pronounced effects were observed close to T C and were associated with the coexistence of clusters with different electronic and magnetic properties. In addition, the appreciable decrease of the electrical permittivity e¢(T,H) is consistent with changes in the concentration of e g mobile holes, a feature much more pronounced close to T C

Use of SSR and retrotransposon-based markers to interpret the population structure of native grapevines from Southern Italy

Native grapevines are the quintessential ele- ments of Southern Italy winemaking, and genomic char- acterization plays a role of primary importance for preservation and sustainable use of these unexploited genetic resources. Among the various molecular techniques available, SSR and retrotransposons-based markers result to be the most valuable for cultivars and biotypes distinc- tiveness. A total of 62 accessions including 38 local grape cultivars were analyzed with 30 SSR, four REMAP and one IRAP markers to assess their genetic diversity and obtain a complete genomic profiling. The use of VrZAG79, VrZAG112, VVS2, VVMD25 and VVMD5 combined with retrotransposon-based markers proved to be the most dis- criminating and polymorphic markers for the rapid and unambiguous identification of minority grapevines from Campania region, which is considered one of the most appreciated Italian districts for wine production. Results revealed 58 SSR marker-specific alleles, 22 genotype- specific SSR alleles, and four REMAP and IRAP private bands. Cases of synonymy and homonymy were discov- ered. In conclusion, we provided evidences that the inte- grating SSR and retrotransposon-based markers is an effective strategy to assess the genetic diversity of autochthonous grapes, allowing their easy identification

The spin label amino acid TOAC and its uses in studies of peptides: chemical, physicochemical, spectroscopic, and conformational aspects

We review work on the paramagnetic amino acid 2,2,6,6-tetramethyl-N-oxyl-4-amino-4-carboxylic acid, TOAC, and its applications in studies of peptides and peptide synthesis. TOAC was the first spin label probe incorporated in peptides by means of a peptide bond. In view of the rigid character of this cyclic molecule and its attachment to the peptide backbone via a peptide bond, TOAC incorporation has been very useful to analyze backbone dynamics and peptide secondary structure. Many of these studies were performed making use of EPR spectroscopy, but other physical techniques, such as X-ray crystallography, CD, fluorescence, NMR, and FT-IR, have been employed. The use of double-labeled synthetic peptides has allowed the investigation of their secondary structure. A large number of studies have focused on the interaction of peptides, both synthetic and biologically active, with membranes. In the latter case, work has been reported on ligands and fragments of GPCR, host defense peptides, phospholamban, and β-amyloid. EPR studies of macroscopically aligned samples have provided information on the orientation of peptides in membranes. More recent studies have focused on peptide–protein and peptide–nucleic acid interactions. Moreover, TOAC has been shown to be a valuable probe for paramagnetic relaxation enhancement NMR studies of the interaction of labeled peptides with proteins. The growth of the number of TOAC-related publications suggests that this unnatural amino acid will find increasing applications in the future

Pesquisa e desenvolvimento em cerâmicas eletro-eletrônicas no IPEN

O Grupo de Cerâmicas Eletro-eletrônicas do IPEN desenvolve trabalhos de pesquisa em materiais cerâmicos avançados para utilização em dispositivos sensores de espécies químicas e em células de combustíveis a eletrólitos sólidos. As principais áreas de atuação do grupo são em 1) síntese, processamento e caracterização elétrica de materiais cerâmicos, 2) estudo de correlação microestrutura-propriedades elétricas de materiais cerâmicos, 3) projeto, desenvolvimento, montagem e testes de sensores eletroquímicos de espécies químicas. Os principais materiais estudados são condutores iônicos (à base de ZrO2, ThO2 e outros), protônicos (à base de BaCeO3), varistores à base de SnO2, supercondutores cerâmicos de alta temperatura crítica (das famílias Y-Ba-Cu-O e Bi-Sr-Ca-Cu-O) e compósitos de matriz cerâmica (dos tipos isolante em matriz condutora iônica e condutor iônico em matriz supercondutora). A infra-estrutura experimental dispõe de analisador de impedância, difratômetro de raios X, equipamento de análise térmica simultânea, fornos para sinterização e laboratório químico. O trabalho de pesquisa do Grupo é financiado por projetos FAPESP e PRONEX

Densification and enhancement of the grain boundary conductivity of gadolinium-doped barium cerate by ultra fast flash grain welding

Doped barium cerate is a promising solid electrolyte for intermediate temperature fuel cells as a protonic conductor. However, it is difficult to sinter it to high density at a reasonable temperature. Moreover, it presents a high grain boundary resistivity at intermediate temperatures. Flash grain welding was applied to compacted samples, starting from a temperature of 910 degrees C and applying, for a short time, an ac electric polarization of 40 V, 1000 Hz. At that frequency, the resulting current flows through the grain boundaries promoting a welding via a local Joule heating. A large decrease of the grain boundary resistivity was observed by impedance spectroscopy. Scanning electron microscopy observations of polished and etched surfaces revealed highly sintered regions. Attempts were also made to combine flash grain welding with conventional sintering. (C) 2012 Elsevier Ltd. All rights reserved.FAPESP [Proc. 05/53241-9, Proc. 2010/51293-0