Low-temperature structural effects in the (TMTSF)2PF6 and AsF6 Bechgaard salts

We present a detailed low-temperature investigation of the statics and dynamics of the anions and methyl groups in the organic conductors (TMTSF) 2PF6 and (TMTSF)2AsF6 (TMTSF: tetramethyl-tetraselenafulvalene). The 4 K neutron-scattering structure refinement of the fully deuterated (TMTSF)2PF6-D12 salt allows locating precisely the methyl groups at 4 K. This structure is compared to the one of the fully hydrogenated (TMTSF)2PF6-H12 salt previously determined at the same temperature. Surprisingly, it is found that deuteration corresponds to the application of a negative pressure of 5×102 MPa to the H12 salt. Accurate measurements of the Bragg intensity show anomalous thermal variations at low temperature both in the deuterated PF 6 and AsF6 salts. Two different thermal behaviors have been distinguished. Small Bragg-angle measurements reflect the presence of low-frequency modes at characteristic energies θE = 8.3 K and θE = 6.7 K for the PF6-D12 and AsF6-D12 salts, respectively. These modes correspond to the low-temperature methyl group motion. Large Bragg-angle measurements evidence an unexpected structural change around 55 K, which probably corresponds to the linkage of the anions to the methyl groups via the formation of F...D-CD2 bonds observed in the 4 K structural refinement. Finally we show that the thermal expansion coefficient of (TMTSF)2PF6 is dominated by the librational motion of the PF6 units. We quantitatively analyze the low-temperature variation of the lattice expansion via the contribution of Einstein oscillators, which allows us to determine for the first time the characteristic frequency of the PF6 librations: θE ≈ 50 K and θE = 76 K for the PF6-D12 and PF6-H12 salts, respectively. © 2013 American Physical Society.

Effect of Low-Temperature Storage on Diaeretiella rapae (McIntosh) (Hymenoptera: Braconidae)

We evaluated the effects of constant low-temperature storage on Diaeretiella rapae (McIntosh) (Braconidae, Aphidiinae). Diaeretiella rapae mummies were stored at 5 ± 1°C for 0-36 days. The percentage of D. rapae emergence varied (100-83%) after 0-32 days of storage. After 32 days, emergence reduced to 55%. According to our Probit analysis, 50% mortality (LT50) of the population of D. rapae was reached after 40 days of storage at 5°C. Storage for up to 32 days did not negatively affect emergence and survival. Cold exposure of D. rapae for 36 days did not influence morphological malformations, sex ratio, and emergence of the F1 generation. After 4-36 days of storage, D. rapae showed a gradual decrease in emergence, longevity, reproductive capacity, and F1 sex ratio. Diaeretiella rapae can be stored for up to 24 days at 5°C, at which time the percentage of parasitism and the F1 sex ratio remain above 38% and at 0.50, respectively. © 2013 Sociedade Entomológica do Brasil.

Low-temperature degradation of a Y-TZP ceramic after surface treatments

The purpose of this study was to evaluate the influence of zirconia surface treatments on low-temperature degradation (LTD). Disc-shaped specimens were subjected to one of four surface treatments, denoted as C (controlno surface treatment), Si (air abrasion with 30 mu m silica-modified alumina particles), Al (air abrasion with 30 mu m alumina particles), and Gr (grinding with 120 grit diamond discs). Half of the samples were submitted to autoclave treatment for 12 h (127 degrees C, 1.5 bar). Samples were characterized by x-ray diffraction and profilometer analysis and were subjected to biaxial flexural strength test. All of the groups exhibited an increase in the amount of monoclinic phase (m-phase) after LTD. The tm transformation was remarkable for the specimens from the C group, which also exhibited a significant increase in strength. The Gr group also exhibited an increase in strength but lower initial roughness, which probably suppressed LTD on the zirconia surface. The specimens subjected to air abrasion exhibited higher initial amounts of m-phase and a small increase in m-phase after LTD; the strength was not affected in these groups. The effects of LTD were different with each surface treatment applied. Apparently, LTD may be suppressed by smoother surfaces or the presence of an initial amount of m-phase on zirconia surface. (c) 2013 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 101B: 1387-1392, 2013.

Chemometric optimization of solid-liquid extraction with low-temperature partition (SLE-LTP) for determination of persistent organic pollutants in Caiman yacare eggs

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Platinum-Group Minerals in Chromitites of the Niquelandia Layered Intrusion (Central Goias, Brazil): Their Magmatic Origin and Low-Temperature Reworking during Serpentinization and Lateritic Weathering

A variety of platinum-group-minerals (PGM) have been found to occur associated with the chromitite and dunite layers in the Niquelandia igneous complex. Two genetically distinct populations of PGM have been identified corresponding to phases crystallized at high temperatures (primary), and others formed or modified during post-magmatic serpentinization and lateritic weathering (secondary). Primary PGM have been found in moderately serpentinized chromitite and dunite, usually included in fresh chromite grains or partially oxidized interstitial sulfides. Due to topographically controlled lateritic weathering, the silicate rocks are totally transformed to a smectite-kaolinite-garnierite-amorphous silica assemblage, while the chromite is changed into a massive aggregate of a spinel phase having low-Mg and a low Fe3+/Fe2+ ratio, intimately associated with Ti-minerals, amorphous Fe-hydroxides, goethite, hematite and magnetite. The PGM in part survive alteration, and in part are corroded as a result of deep chemical weathering. Laurite is altered to Ru-oxides or re-crystallizes together with secondary Mg-ilmenite. Other PGM, especially the Pt-Fe alloys, re-precipitate within the altered chromite together with kaolinite and Fe-hydroxides. Textural evidence suggests that re-deposition of secondary PGM took place during chromite alteration, controlled by variation of the redox conditions on a microscopic scale.

Effect of low-temperature aging on the mechanical behavior of ground Y-TZP

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Innovative low temperature plasma approach for deposition of alumina films

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Low-temperature plasma: an effective approach against Candida albicans biofilm

This study evaluated the antifungal potential of low-temperature plasma (LTP) on a 72-hour Candida albicans biofilm. A growth inhibition zone test was conducted with agar plates inoculated with C. albicans and submitted to LTP and argon application at 3 and 10 mm for 10, 30, 60, 90, and 120 seconds. The groups for biofilm assays were 60 seconds of LTP application with a tip-to-sample distance of 3 mm (LTP-3) and 10 mm (LTP-10); –application of only argon gas for 60 seconds with a tip-to-sample distance of 3 mm (Ar-3) and 10 mm (Ar-10); and no treatment. The C. albicans biofilm was grown on saliva-coated discs. The medium was replaced every 24 hours. Confocal laser scanning microscopy revealed the proportion of live and dead cells, and variable pressure scanning electron microscopy (VPSEM) showed biofilm/cell structure. No inhibition zone was observed for control and either Ar groups. For the LTP groups, a progressively increasing of inhibition zone diameter was observed for different treatment durations. The LTP-3 and LTP-10 groups presented higher proportions of dead cells compared with the Ar-3 and Ar-10 groups. VPSEM revealed cell perforations in the LTP-3 and LTP-10 groups. A short period of LTP exposure demonstrated an antifungal effect on C. albicans biofilm.

An Estuarine Low Temperature Fish Kill in Mississippi, with Remarks on Restricted Necropsies

In January 1973, large numbers of Mugil cephalus (striped mullet), weighing approximately 250 gm each, died in two freshwater localities in tidewater bayous of Jackson County, Mississippi. Fish identified as Mugil curema, M. cephalus, Megalops atlantica, Dormitator maculatus, and Fundulus grandis were found dead in other low saline estuarine areas. Fish-kills during cold periods are less commonly encountered in Mississippi than in Texas or Florida. This particular incident is attributed to conditions of stress for fishes incompletely acclimated to the encountered low temperatures. The most deleterious stress was the low saline water which probably allowed a breakdown in the fishes' ion-osmoregulatory mechanisms. Striped mullet and other euryhaline fishes in salinities greater than 6 ppt survived, as did freshwater centrarchids and ictalurids in areas with dying mullet. Other stresses thought to contribute to the weakening of striped mullet in Paige Bayou during the period of rapidly decreasing temperatures include starvation and high levels of pesticide residues. In examined fish, the alimentary tracts were devoid of food, the gall bladders were distended and leaking bile, the livers contained excess lipid material and were often stained throughout with bile pigments, and the levels of DDT metabolites and endrin residues in the liver were higher than in control fish. Stress caused by low levels of dissolved oxygen, toxic substances in the water, or disease was discounted as a cause of death.

Urea-Based Synthesis of Zinc Oxide Nanostructures at Low Temperature

The preparation of nanometer-sized structures of zinc oxide (ZnO) from zinc acetate and urea as raw materials was performed using conventional water bath heating and a microwave hydrothermal (MH) method in an aqueous solution. The oxide formation is controlled by decomposition of the added urea in the sealed autoclave. The influence of urea and the synthesis method on the final product formation are discussed. Broadband photoluminescence (PL) behavior in visible-range spectra was observed with a maximum peak centered in the green region which was attributed to different defects and the structural changes involved with ZnO crystals which were produced during the nucleation process.

Nanosized precipitates in H13 tool steel low temperature plasma nitriding

A comprehensive study of pulsed nitriding in AISI H13 tool steel at low temperature (400 degrees C) is reported for several durations. X-ray diffraction results reveal that a nitrogen enriched compound (epsilon-Fe2-3N, iron nitride) builds up on the surface within the first process hour despite the low process temperature. Beneath the surface, X-ray Wavelength Dispersive Spectroscopy (WDS) in a Scanning Electron Microscope (SEM) indicates relatively higher nitrogen concentrations (up to 12 at.%) within the diffusion layer while microscopic nitrides are not formed and existing carbides are not dissolved. Moreover, in the diffusion layer, nitrogen is found to be dispersed in the matrix and forming nanosized precipitates. The small coherent precipitates are observed by High-Resolution Transmission Electron Microscopy (HR-TEM) while the presence of nitrogen is confirmed by electron energy loss spectroscopy (EELS). Hardness tests show that the material hardness increases linearly with the nitrogen concentration, reaching up to 14.5 GPa in the surface while the Young Modulus remains essentially unaffected. Indeed, the original steel microstructure is well preserved even in the nitrogen diffusion layer. Nitrogen profiles show a case depth of about similar to 43 mu m after nine hours of nitriding process. These results indicate that pulsed plasma nitriding is highly efficient even at such low temperatures and that at this process temperature it is possible to form thick and hard nitrided layers with satisfactory mechanical properties. This process can be particularly interesting to enhance the surface hardness of tool steels without exposing the workpiece to high temperatures and altering its bulk microstructure. (c) 2012 Elsevier B.V. All rights reserved.

Low-temperature thermodynamic properties near the field-induced quantum critical point in NiCl2-4SC(NH2)(2)

We present a comprehensive experimental and theoretical investigation of the thermodynamic properties: specific heat, magnetization, and thermal expansion in the vicinity of the field-induced quantum critical point (QCP) around the lower critical field H-c1 approximate to 2 T in NiCl2-4SC(NH2)(2). A T-3/2 behavior in the specific heat and magnetization is observed at very low temperatures at H = H-c1, which is consistent with the universality class of Bose-Einstein condensation of magnons. The temperature dependence of the thermal expansion coefficient at H-c1 shows minor deviations from the expected T-1/2 behavior. Our experimental study is complemented by analytical calculations and quantum Monte Carlo simulations, which reproduce nicely the measured quantities. We analyze the thermal and the magnetic Gruneisen parameters, which are ideal quantities to identify QCPs. Both parameters diverge at H-c1 with the expected T-1 power law. By using the Ehrenfest relations at the second-order phase transition, we are able to estimate the pressure dependencies of the characteristic temperature and field scales.

Regioregular improvement on the oxidative polymerization of poly-3-octylthiophenes by slow addition of oxidant at low temperature

Many pathways can be used to synthesize polythiophenes derivatives. The polycondensation reactions performed with organometallics are preferred since they lead to regioregular polymers (with high content of heat-to-tail coupling) which have enhanced conductivity and luminescence. However, these pathways have several steps; the reactants are highly moisture sensitive and expensive. On the other hand, the oxidative polymerization using FeCl3 is a one-pot reaction that requires less moisture sensitive reactants with lower cost, although the most common reaction conditions lead to polymers with low regioregularity. Here, we report that by changing the reaction conditions, such as FeCl3 addition rate and reaction temperature, poly-3-octylthiophenes with different the regioregularities can be obtained, reaching about 80% of heat-to-tail coupling. Different molar mass distributions and polydispersivities were obtained. The preliminary results suggest that the oxidative polymerization process could be improved to yield polythiophenes with higher regioregularity degree and narrower molar mass distributions by just setting some reaction conditions. We also verified that it is possible to solvent extract part of the lower regioregular fraction of the polymer further improving the regioregularity degree. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Study of La2-xCaxCuO4 perovskites for the low temperature water gas shift reaction

The effects of small fractions of calcium (x = 0, 0.05, 0.1, 0.15, and 0.20) on the structure and the catalytic properties of La2-xCaxCuO4 peroviskites have been investigated. The samples have been synthesized using the co-precipitation method. Perovskite-type oxides were characterized by XRD, TPR, XPS, XANES, SEM, and TEM. Catalytic tests for the water gas shift reaction (WGSR) were carried out in a tubular reactor at 290 degrees C. All samples showed a well-defined perovskite structure with surface areas between 6 and 18 m(2) g(-1). The partial substitution of La by Ca enhanced the stability of the perovskites and increased their reduction temperature. All catalysts were actives for WGSR, and the best catalytic performance was obtained for the La1.85Ca0.15CuO4 catalyst, but the samples with 5 and 10% of Ca had the best TOF values for reaction. These results can be associated to promoter effect of calcium, the high surface area, and the reducible species Cu-0 and Cu1+. (C) 2011 Elsevier B.V. All rights reserved.

Low-temperature thermochronological evolution of the Menderes and Alanya massifs (Turkey)

The application of two low-temperature thermochronometers [fission-track analysis and (U-Th)/He analyses, both on apatite] to various tectonostratigraphic units of the Menderes and Alanya Massifs of Turkey has provided significant new constraints to the understanding of their structural evolution. The Menderes Massif of western Anatolia is one of the largest metamorphic core complexes on Earth. The integration of the geochronometric dataset presented in this dissertation with preexisting ones from the literature delineates three groups of samples within the Menderes Massif. In the northern and southern region the massif experienced a Late Oligocene-Early Miocene tectonic denudation and surface uplift; whereas data from the central region are younger, with most ages ranging between the Middle-Late Miocene. The results of this study are consistent with the interpretation for a symmetric exhumation of the Menderes Massif. The Alanya Massif of SW Anatolia presents a typical nappe pile consisting of thrust sheets with contrasting metamorphic histories. Petrological and geochronological data clearly indicate that the tectonometamorphic evolution Alanya started from Late Cretaceous with the northward subduction of an ‘Alanya ocean’ under the Tauride plate. As an effect of the closure of the İzmir–Ankara–Erzincan ocean, northward backthrusting during the Paleocene-Early Eocene created the present stacking order. Apatite fission-track ages from this study range from 31.8 to 26.8 Ma (Late Rupelian-Early Chattian) and point to a previously unrecognized mid-Oligocene cooling/exhumation episode. (U-Th)/He analysis on zircon crystals obtained from the island of Cyprus evidentiate that the Late Cretaceous trondhjemites of the Troodos Massif not recorded a significant cooling event. Instead results for the Late Triassic turbiditic sandstones of the Vlambouros Formation show that the Mamonia mélange was never buried enough to reach the closure temperature of the ZHe radiometric system (ca. 200°C), thus retaining the Paleozoic signature of a previous sedimentary cycle.