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.

X-ray absorption spectroscopy study on La0.6Sr0.4CoO3 and La0.6Sr0.4Co1¡yFeyO3 nanotubes and nanorods for IT-SOFC cathodes.

In the last years, extensive research has been devoted to develop novel materials and structures with high electrochemical performance for intermediate-temperatures solid-oxide fuel cells (IT-SOFCs) electrodes. In recent works, we have investigated the structural and electrochemical properties of La0:6Sr0:4CoO3 (LSCO) and La0:6Sr0:4Co1¡yFeyO3 (LSCFO) nanostructured cathodes, finding that they exhibit excellent electrocatalytic properties for the oxygen reduction reaction [1,2]. These materials were prepared by a pore-wetting technique using polycarbonate porous membranes as templates. Two average pore sizes were used: 200 nm and 800 nm. Our scanning electronic microscopy (SEM) study showed that the lower pore size yielded nanorods, while nanotubes were obtained with the bigger pore size. All the samples were calcined at 1000oC in order to produce materials with the desired perovskite-type crystal structure. In this work, we analyze the oxidation states of Co and Fe and the local atomic order of LSCO and LSCFO nanotubes and nanowires for various compositions. For this pur- pose we performed XANES and EXAFS studies on both Co and Fe K edges. These measurements were carried out at the D08B-XAFS2 beamline of the Brazilian Synchrotron Light Laboratory (LNLS). XANES spectroscopy showed that Co and Fe only change slightly their oxidation state upon Fe addition. Surprisingly, XANES results indicated that the content of oxygen vacancies is low, even though it is well-known that these materials are mixed ionic-electronic conductors. EXAFS results were consistent with those expected according to the rhombohedral crystal structure determined in previous X-ray powder dffraction investigations. [1] M.G. Bellino et al, J. Am. Chem. Soc. 129 (2007) 3066 [2] J.G. Sacanell et al., J. Power Sources 195 (2010) 1786

A two-layer approximation to the Brazil Current-Intermediate Western Boundary Current System between 20 degrees S and 28 degrees S

It has been shown that the vertical structure of the Brazil Current (BC)-Intermediate Western Boundary Current (IWBC) System is dominated by the first baroclinic mode at 22 degrees S-23 degrees S. In this work, we employed the Miami Isopycnic Coordinate Ocean Model to investigate whether the rich mesoscale activity of this current system, between 20 degrees S and 28 degrees S, is reproduced by a two-layer approximation of its vertical structure. The model results showed cyclonic and anticyclonic meanders propagating southwestward along the current axis, resembling the dynamical pattern of Rossby waves superposed on a mean flow. Analysis of the upper layer zonal velocity component, using a space-time diagram, revealed a dominant wavelength of about 450 km and phase velocity of about 0.20 ms(-1) southwestward. The results also showed that the eddy-like structures slowly grew in amplitude as they moved downstream. Despite the simplified design of the numerical experiments conducted here, these results compared favorably with observations and seem to indicate that weakly unstable long baroclinic waves are responsible for most of the variability observed in the BC-IWBC system. (C) 2009 Elsevier Ltd. All rights reserved.

Periapical Tissue Response After Use of Intermediate Restorative Material, Gutta-Percha, Reinforced Zinc Oxide Cement, and Mineral Trioxide Aggregate as Retrograde Root-End Filling Materials: A Histologic Study in Dogs

Purpose: To investigate the periapical tissue response of 4 different retrograde root-filling materials, ie, intermediate restorative material, thermoplasticized gutta-percha, reinforced zinc oxide cement (Super-EBA), and mineral trioxide aggregate (MTA), in conjunction with an ultrasonic root-end preparation technique in an animal model. Materials and Methods: Vital roots of the third and fourth right mandibular premolars in 6 healthy mongrel dogs were apicectomized and sealed with 1 of the materials using a standardized surgical procedure. After 120 days, the animals were sacrificed and the specimens were analyzed radiologically, histologically, and scanning electron microscopically. The Fisher exact test was performed on the 2 outcome values. Results: Twenty-three sections were analyzed histologically. Evaluation showed better re-establishment of the periapical tissues and generally lower inflammatory infiltration in the sections from teeth treated with the intermediate restorative material and the MTA. New root cement on the resected dentin surfaces was seen on all sections regardless of the used material. New hard tissue formation, directly on the surface of the material, was seen only in the MTA sections. There was no statistical difference in outcome among the tested materials. Conclusions: The results from this dog model favor the intermediate restorative material and MTA as retrograde fillings when evaluating the bone defect regeneration. MTA has the most favorable periapical tissue response when comparing the biocompatibility of the materials tested. (C) 2012 American Association of Oral and Maxillofacial Surgeons J Oral Maxillofac Surg 70:2041-2047, 2012

Changes in the intermediate water mass formation rates in the global ocean for the Last Glacial Maximum, mid-Holocene and pre-industrial climates

The paleoclimate version of the National Center for Atmospheric Research Community Climate System Model version 3 (NCAR-CCSM3) is used to analyze changes in the water formation rates in the Atlantic, Pacific, and Indian Oceans for the Last Glacial Maximum (LGM), mid-Holocene (MH) and pre-industrial (PI) control climate. During the MH, CCSM3 exhibits a north-south asymmetric response of intermediate water subduction changes in the Atlantic Ocean, with a reduction of 2 Sv in the North Atlantic and an increase of 2 Sv in the South Atlantic relative to PI. During the LGM, there is increased formation of intermediate water and a more stagnant deep ocean in the North Pacific. The production of North Atlantic Deep Water (NADW) is significantly weakened. The NADW is replaced in large extent by enhanced Antarctic Intermediate Water (AAIW), Glacial North Atlantic Intermediate Water (GNAIW), and also by an intensified of Antarctic Bottom Water (AABW), with the latter being a response to the enhanced salinity and ice formation around Antarctica. Most of the LGM intermediate/mode water is formed at 27.4 < sigma(theta) < 29.0 kg/m(3), while for the MH and PI most of the subduction transport occurs at 26.5 < sigma(theta) < 27.4 kg/m(3). The simulated LGM Southern Hemisphere winds are more intense by 0.2-0.4 dyne/cm(2). Consequently, increased Ekman transport drives the production of intermediate water (low salinity) at a larger rate and at higher densities when compared to the other climatic periods.

Long-Term Stability at High Temperatures for Birefringence in PAZO/PAH Layer-by-Layer Films

Optical memories with long-term stability at high temperatures have long been pursued in azopolymers with photoinduced birefringence. In this study, we show that the residual birefringence in layer-by-layer (LbL) films made with poly[1-[4-(3-carboxy-4 hydroxyphenylazo)benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) alternated with poly(allylamine hydrochloride) (PAH) can be tuned by varying the extent of electrostatic interactions with film fabrication at different pHs for PAH. The dynamics of both writing and relaxation processes could be explained with a two-stage mechanism involving the orientation of the chromophores per se and the chain movement. Upon calculating the activation energies for these processes, we demonstrate semiquantitatively that reduced electrostatic interactions in films prepared at higher pH, for which PAH is less charged, are responsible for the longer stability at high temperatures. This is attributed to orientation of PAZO chromophores via cooperative aggregation, where the presence of counterions hindered relaxation.

Investigation of a Pt3Sn/C Electro-Catalyst in a Direct Ethanol Fuel Cell Operating at Low Temperatures for Portable Applications

A 20% Pt3Sn/C catalyst was prepared by reduction with formic acid and used in a direct ethanol fuel cell at low temperatures. The electro-catalytic activity of this bimetallic catalyst was compared to that of a commercial 20% Pt/C catalyst. The PtSn catalyst showed better results in the investigated temperature range (30 degrees-70 degrees C). Generally, Sn promotes ethanol oxidation by adsorption of OH species at considerably lower potentials compared to Pt, allowing the occurrence of a bifunctional mechanism. The bimetallic catalyst was physico-chemically characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses. The presence of SnO2 in the bulk and surface of the catalyst was observed. It appears that SnO2 can enhance the ethanol electro-oxidation activity at low potentials due to the supply of oxygen-containing species for the oxidative removal of CO and CH3CO species adsorbed on adjacent Pt active sites.

Trichogramma pretiosum parasitism of Pseudoplusia includens and Anticarsia gemmatalis eggs at different temperatures

Egg parasitism of Trichogramma pretiosum strain RV when presented with eggs of Anticarsia gemmatalis and Pseudoplusia includens was investigated at 18, 20, 22, 25, 28, 30 and 32 degrees C. The number of eggs parasitized per day decreased for both hosts as a function of the age of parasitoids, reaching 80% of lifetime parasitism more rapidly as temperature increased; on the 4th day at 32 degrees C and on the 12th day at 18 degrees C. The lifetime number of parasitized P. includens eggs achieved by the parasitoid maintained at 20 degrees C (44.95 +/- 3.94) differed from the results recorded at 32 degrees C (28.5 +/- 1.33). Differently, the lifetime number of A. gemmatalis parasitized eggs did not differ among the temperatures. When T. pretiosum reached 100% of lifetime parasitism, each adult female had parasitized from 28.5 +/- 1.33 to 44.95 +/- 3.94 and from 29.58 +/- 2.80 to 45.36 +/- 4.50 P. includens and A. gemmatalis eggs, respectively. Also, the longevity of these adult T. pretiosum females, for which P. includens or A. gemmatalis eggs were offered, was inversely correlated with temperature. Not only were the survival curves of those adult T. pretiosum females of type I when they were presented with eggs of A. gemmatalis but also with eggs of P. includens, i.e., there was an increase in the mortality rate with time as the temperature increased. In conclusion, T. pretiosum strain RV parasitism was impacted by temperature when on both host eggs; however, the parasitoid still exhibited high survival and, more importantly, high number of parasitized A. gemmatalis and P. includens eggs even at the extremes tested temperatures of 18 and 32 degrees C. Those results indicate that T. pretiosum strain RV might be well adapted to this studied temperature range and, thus, be potentially suitable for use in biological control programs of P. includens and A. gemmatalis in different geographical areas that fits in this range. It is important to emphasize the results here presented are from laboratory studies and, therefore, field trials still need to be carried out in the future with this strain in order to support the full development of the technology intend to use this egg parasitoid in soybean fields worldwide. (C) 2011 Elsevier Inc. All rights reserved.

Influence of different shrinking temperatures and vacuum conditions on the ability of psychrotrophic Clostridium to cause 'blown pack' spoilage in chilled vacuum-packaged beef

This study determined the ability of psychrotrophic Clostridium strains isolated from vacuum-packaged beefs and abattoir environments to cause 'blown-pack' spoilage of vacuum-packaged beef stored at 2 and 15 degrees C. The influence of shrinking temperatures (83, 84 and 87 degrees C) and vacuum pressure (6 and 9 mbar) on the occurrence of such spoilage as well as the effects of simulated transportation (500 km) on the integrity of packages was determined. At 15 degrees C and 2 degrees C, twelve and six strains caused 'blown-pack' spoilage, respectively. The combination of vacuum pressure (9 mbar) combined with shrinking temperature (87 degrees C) retarded the occurrence of spoilage. The simulated transportation under the experimental conditions did not affect the integrity of packages. More studies that assess the factors that may contribute for the occurrence of 'blown-pack' spoilage should be performed to avoid the occurrence of such spoilage during its shelf-life. (C) 2012 Elsevier Ltd. All rights reserved.

Evaluation of corrosion resistance and cytotoxicity of electrodeposited gold on various types of intermediate layers

Gold plated surfaces are widely applied in several technical and decorative fields. The two main issues regarding the discussion on the field of precious metal coatings concern the increase in the use of thinner gold layers and 'Ni free' substrates. In order to ensure the quality of the final products, the effects of the plated surfaces on their performance require thorough and accurate research. In this paper, the corrosion resistance of gold plated nickel, copper and bronze was investigated by electrochemical methods specifically potentiodynamic polarisation and electrochemical impedance spectroscopy in phosphate buffered saline. The cytotoxicity of the gold plated substrates was also evaluated and compared. The results showed that the substrate related to the best corrosion resistance and cytotoxicity among the tested ones was bronze, and the one with the lowest performance was nickel.

CHEMICAL DEGRADATION OF ESFENVALERATE AND HPLC-UV-PAD DETECTION OF INTERMEDIATES AND BY-PRODUCTS

The impact of pyretroids, their by-products and degradation products on humans and the environment is recognized as a serious problem. Despite several studies regarding esfenvalerate toxicity and its detection in water and sediments, there is still a lack of information about its degradation intermediates and by-products in water. In this work, an HPLC method was developed to follow up the degradation of esfenvalerate and to detect the intermediates and by-products formed during the chemical degradation process. The chemical degradation was performed using an esfenvalerate suspension and different concentrations of hydrogen peroxide, temperatures, and pH. The reaction was monitored for 24 hr, and during the kinetic experiments, samples were collected at several reaction times and analyzed by HPLC-UV-PAD. In the degradation process, eleven different compounds (intermediate and by-products) were detected, among them the metabolites 3-phenoxybenzoic acid and 3-phenoxybenzaldehyde. HPLC-UV-PAD proved to be a valuable analytical technique for the rapid and reliable separation and determination of esfenvalerate, its degradation intermediates, and by-products.

Dilute Acid Hydrolysis of Sugar Cane Bagasse at High Temperatures: A Kinetic Study of Cellulose Saccharification and Glucose Decomposition. Part I: Sulfuric Acid as the Catalyst

The kinetics of sugar cane bagasse cellulose saccharification and the decomposition of glucose under extremely low acid (ELA) conditions, (0.07%), 0.14%, and 0.28% H2SO4, and at high temperatures were investigated using batch reactors. The first-order rate constants were obtained by weight loss, remaining glucose, and fitting glucose concentration profiles determined with HPLC using the Saeman model. The maximum glucose yields reached 67.6% (200 degrees C, 0.07% H2SO4, 30 min), 69.8% (210 degrees C, 0.14% H2SO4, 10 min), and 67.3% (210 degrees C, 0.28% H2SO4, 6 min). ELA conditions produced remarkable glucose yields when applied to bagasse cellulose. The first-order rate constants were used to calculate activation energies and extrathermodynamic parameters to elucidate the reaction mechanism under ELA conditions. The effect of acid concentration on cellulose hydrolysis and glucose decomposition was also investigated. The observed activation energies and reaction orders with respect to hydronium ion for cellulose hydrolysis and glucose decomposition were 184.9 and 124.5 kJ/mol and 1.27 and 0.75, respectively.

Do Higher Temperatures Increase Growth in the Nocturnal Gecko Homonota darwini (Gekkota: Phyllodactylidae)? A Skeletochronological Assessment Analyzed at Temporal and Geographic Scales

Recent studies predict that several lineages of tropical animals are at particular risk given current estimates of global climate change. Yet, much uncertainty exists on the effects of climate shifts in ectothermic species from cool temperate regions such as Patagonia. In this study, we focus on the impact of environmental temperature on growth, age at sexual maturity, and life-span of the Patagonian gecko Homonota darwini. Skeletochronological methods were used to assess the bone growth rates Of individuals from three populations at different geographic and temporal scales: two populations from Chubut (warm site; 1941 and 2010) and one population from Rio Negro (cold site; 1997-1998). Populations displayed similar bone arrangement and the growth patterns fit a von Bertalanffy curve. Three populations attained reproductive size at a minimum age of 3 yr, but at the cold site two specimens were shown to mature in 4 yr. We found no differences in juvenile growth rates in body size or bone zone width between juveniles of 1 to 3 yr of age from the 1941 warm site and the 2010 warm site. However, these traits appeared to be higher at these two warm sites than at the cold site, which is consistent with the climatic differences among the three localities. Our results suggest that higher temperatures positively affect growth, denoting that global warming might benefit H. darwini, especially the southern populations.

Considerations for Assessing Maximum Critical Temperatures in Small Ectothermic Animals: Insights from Leaf-Cutting Ants

The thermal limits of individual animals were originally proposed as a link between animal physiology and thermal ecology. Although this link is valid in theory, the evaluation of physiological tolerances involves some problems that are the focus of this study. One rationale was that heating rates shall influence upper critical limits, so that ecological thermal limits need to consider experimental heating rates. In addition, if thermal limits are not surpassed in experiments, subsequent tests of the same individual should yield similar results or produce evidence of hardening. Finally, several non-controlled variables such as time under experimental conditions and procedures may affect results. To analyze these issues we conducted an integrative study of upper critical temperatures in a single species, the ant Atta sexdens rubropiosa, an animal model providing large numbers of individuals of diverse sizes but similar genetic makeup. Our specific aims were to test the 1) influence of heating rates in the experimental evaluation of upper critical temperature, 2) assumptions of absence of physical damage and reproducibility, and 3) sources of variance often overlooked in the thermal-limits literature; and 4) to introduce some experimental approaches that may help researchers to separate physiological and methodological issues. The upper thermal limits were influenced by both heating rates and body mass. In the latter case, the effect was physiological rather than methodological. The critical temperature decreased during subsequent tests performed on the same individual ants, even one week after the initial test. Accordingly, upper thermal limits may have been overestimated by our (and typical) protocols. Heating rates, body mass, procedures independent of temperature and other variables may affect the estimation of upper critical temperatures. Therefore, based on our data, we offer suggestions to enhance the quality of measurements, and offer recommendations to authors aiming to compile and analyze databases from the literature.

Multivariate analysis of fresh-cut carambola slices stored under different temperatures

Quality of fresh-cut carambola (Averrhoa carambola L) is related to many chemical and biochemical variables especially those involved with softening and browning, both influenced by storage temperature. To study these effects, a multivariate analysis was used to evaluate slices packaged in vacuum-sealed polyolefin bags, and stored at 2.5 degrees C, 5 degrees C and 10 degrees C, for up to 16 d. The quality of slices at each temperature was correlated with the duration of storage, O(2) and CO(2) concentration in the package, physical chemical constituents, and activity of enzymes involved in softening (PG) and browning (PPO) metabolism. Three quality groups were identified by hierarchical cluster analysis, and the classification of the components within each of these groups was obtained from a principal component analysis (PCA). The characterization of samples by PCA clearly distinguished acceptable and non-acceptable slices. According to PCA, acceptable slices presented higher ascorbic acid content, greater hue angles ((o)h) and final lightness (L-5) in the first principal component (PC1). On the other hand, non-acceptable slices presented higher total pectin content. PPO activity in the PC1. Non-acceptable slices also presented higher soluble pectin content, increased pectin solubilisation and higher CO(2) concentration in the second principal component (PC2) whereas acceptable slices showed lower total sugar content. The hierarchical cluster and PCA analyses were useful for discriminating the quality of slices stored at different temperatures. (C) 2011 Elsevier B.V. All rights reserved.