Low-frequency Raman spectra and fragility of imidazolium ionic liquids

Raman spectra within the 5-200 cm(-1) range have been recorded as a function of temperature for different ionic liquids based on imidazolium cations. A correlation has been found between fragility and the temperature dependence of the strength of fast relaxational motions. Understanding quasielastic scattering as the relaxational contribution to ionic mean-squared displacement elucidates some effects on ionic liquids' fragility resulting from modifications in the chemical structure. (C) 2010 American Institute of Physics. [doi:10.1063/1.3462962]

The electronic states of SeF: A reinterpretation of the chemiluminescent emission of the reaction of selenium with fluorine

The low-lying doublet and quartet electronic states of the species SeF correlating with the first dissociation channel are investigated theoretically at a high-level of electronic correlation treatment, namely, the complete active space self-consistent field/multireference single and double excitations configuration interaction (CASSCF/MRSDCI) using a quintuple-zeta quality basis set including a relativistic effective core potential for the selenium atom. Potential energy curves for (Lambda+S) states and the corresponding spectroscopic properties are derived that allows for an unambiguous assignment of the only spectrum known experimentally as due to a spin-forbidden X (2)Pi-a (4)Sigma(-) transition, and not a A (2)Pi-X (2)Pi transition as assumed so far. For the bound excited doublets, yet unknown experimentally, this study is the first theoretical characterization of their spectroscopic properties. Also the spin-orbit coupling constant function for the X (2)Pi state is derived as well as the spin-orbit coupling matrix element between the X (2)Pi and a (4)Sigma(-) states. Dipole moment functions and vibrationally averaged dipole moments show SeF to be a very polar species. An overview of the lowest-lying spin-orbit (Omega) states completes this description. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3426315]

Full-dimensional analytical ab initio potential energy surface of the ground state of HOI

Extensive ab initio calculations using a complete active space second-order perturbation theory wavefunction, including scalar and spin-orbit relativistic effects with a quadruple-zeta quality basis set were used to construct an analytical potential energy surface (PES) of the ground state of the [H, O, I] system. A total of 5344 points were fit to a three-dimensional function of the internuclear distances, with a global root-mean-square error of 1.26 kcal mol(-1). The resulting PES describes accurately the main features of this system: the HOI and HIO isomers, the transition state between them, and all dissociation asymptotes. After a small adjustment, using a scaling factor on the internal coordinates of HOI, the frequencies calculated in this work agree with the experimental data available within 10 cm(-1). (C) 2011 American Institute of Physics. [doi: 10.1063/1.3615545]

Intermolecular vibrations and fast relaxations in supercooled ionic liquids

Short-time dynamics of ionic liquids has been investigated by low-frequency Raman spectroscopy (4 < omega < 100 cm(-1)) within the supercooled liquid range. Raman spectra are reported for ionic liquids with the same anion, bis(trifluoromethylsulfonyl)imide, and different cations: 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-butyl-1-methylpiperidinium, trimethylbutylammonium, and tributylmethylammonium. It is shown that low-frequency Raman spectroscopy provides similar results as optical Kerr effect (OKE) spectroscopy, which has been used to study intermolecular vibrations in ionic liquids. The comparison of ionic liquids containing aromatic and non-aromatic cations identifies the characteristic feature in Raman spectra usually assigned to librational motion of the imidazolium ring. The strength of the fast relaxations (quasi-elastic scattering, QES) and the intermolecular vibrational contribution (boson peak) of ionic liquids with non-aromatic cations are significantly lower than imidazolium ionic liquids. A correlation length assigned to the boson peak vibrations was estimated from the frequency of the maximum of the boson peak and experimental data of sound velocity. The correlation length related to the boson peak (similar to 19 angstrom) does not change with the length of the alkyl chain in imidazolium cations, in contrast to the position of the first-sharp diffraction peak observed in neutron and X-ray scattering measurements of ionic liquids. The rate of change of the QES intensity in the supercooled liquid range is compared with data of excess entropy, free volume, and mean-squared displacement recently reported for ionic liquids. The temperature dependence of the QES intensity in ionic liquids illustrates relationships between short-time dynamics and long-time structural relaxation that have been proposed for glass-forming liquids. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3604533]

Structure, stability, depolarized light scattering, and vibrational spectra of fullerenols from all-electron density-functional-theory calculations

We have investigated the stability, electronic properties, Rayleigh (elastic), and Raman (inelastic) depolarization ratios, infrared and Raman absorption vibrational spectra of fullerenols [C(60)(OH)(n)] with different degrees of hydroxylation by using all-electron density-functional-theory (DFT) methods. Stable arrangements of these molecules were found by means of full geometry optimizations using Becke's three-parameter exchange functional with the Lee, Yang, and Parr correlation functional. This DFT level has been combined with the 6-31G(d,p) Gaussian-type basis set, as a compromise between accuracy and capability to treat highly hydroxylated fullerenes, e.g., C(60)(OH)(36). Thus, the molecular properties of fullerenols were systematically analyzed for structures with n=1, 2, 3, 4, 8, 10, 16, 18, 24, 32, and 36. From the electronic structure analysis of these molecules, we have evidenced an important effect related to the weak chemical reactivity of a possible C(60)(OH)(24) isomer. To investigate Raman scattering and the vibrational spectra of the different fullerenols, frequency calculations are carried out within the harmonic approximation. In this case a systematic study is only performed for n=1-4, 8, 10, 16, 18, and 24. Our results give good agreements with the expected changes in the spectral absorptions due to the hydroxylation of fullerenes.

In situ infrared (FTIR) study of the mechanism of the borohydride oxidation reaction

Early reports stated that Au was a catalyst of choice for the BOR because it would yield a near complete faradaic efficiency. However, it has recently been suggested that gold could yield to some extent the heterogeneous hydrolysis of BH(4)(-),therefore lowering the electron count per BH(4)(-), especially at low potential. Actually, the blur will exist regarding the BOR mechanism on Au as long as no physical proof regarding the reaction intermediates is not put forward. In that frame, in situ physical techniques like FTIR exhibit some interest to study the BOR. Consequently, in situ infrared reflectance spectroscopy measurements (SPAIRS technique) have been performed in 1 M NaOH/1 M NaBH(4) on a gold electrode with the aim to detect the intermediate species. We monitored several bands in B-H ((nu) over bar similar to 1180,1080 and 972 cm(-1)) and B-O bond regions ((nu) over bar =1325 and similar to 1425cm(-1)), which appear sequentially as a function of the electrode polarization. These absorption bands are assigned to BH(3), BH(2) and BO(2)(-) species. At the light of the experimental results, possible initial elementary steps of the BOR on gold electrode have been proposed and discussed according to the relevant literature data.

Determination of Cr, Fe, Co, Ni, Cu, Zn, As and Pb in liquid chemical waste by energy dispersive X-ray fluorescence

A method for simultaneous determination of Cr, Fe, Co, Ni, Cu, Zn, As e Pb in liquid chemical waste using Energy Dispersive X-Ray Fluorescence (EDXRF) technique was evaluated. A small sample amount (200 mu L) was dried on a 6.35 mu m thickness Mylar film at 60 degrees C and the analyses were carried out using an EDXRF spectrometer operated with an X-ray Mo tube (Zr filter) at 30 kV/20 mA. The acquisition time was 300 s and the Ga element was utilized as internal standard at 25 mg/L for quantitative analysis. The method trueness was assessed by spiking and the detection limit for those elements ranged from 0.39 to 1.7 mg/L. This method is notable because it assists the choice of the more appropriated waste treatment procedure, in which inter elemental interference is a matter of importance. In addition, this inexpensive method allows a non-destructive determination of the elements from (19)K to (92)U simultaneously.

Biofuels and Sustainable Energy Development in Brazil

Through the assessment of three decades of the Alcohol Program in Brazil, the paper shows that adequate public policies regarding biomass production can deliver direct benefits like energy security improvement, foreign exchange savings, and local employment generation, reduced urban air pollution and avoided CO(2) emissions. Moreover, the paper shows that Brazilian produced ethanol has faced economies of scale, technical progress and productivity gains and is no longer dependent on subsidies to be competitive. The paper also examines the potential in Brazil for fostering other biofuels, namely biodiesel obtained from vegetable oils, as well as their implications on sustainable energy development. (C) 2011 Elsevier Ltd. All rights reserved.

Gravitational quasinormal modes of AdS black branes in d spacetime dimensions

The AdS/CFT duality has established a mapping between quantities in the bulk AdS black-hole physics and observables in a boundary finite-temperature field theory. Such a relationship appears to be valid for an arbitrary number of spacetime dimensions, extrapolating the original formulations of Maldacena`s correspondence. In the same sense properties like the hydrodynamic behavior of AdS black-hole fluctuations have been proved to be universal. We investigate in this work the complete quasinormal spectra of gravitational perturbations of d-dimensional plane-symmetric AdS black holes (black branes). Holographically the frequencies of the quasinormal modes correspond to the poles of two-point correlation functions of the field-theory stress-energy tensor. The important issue of the correct boundary condition to be imposed on the gauge-invariant perturbation fields at the AdS boundary is studied and elucidated in a fully d-dimensional context. We obtain the dispersion relations of the first few modes in the low-, intermediate- and high-wavenumber regimes. The sound-wave (shear-mode) behavior of scalar (vector)-type low- frequency quasinormal mode is analytically and numerically confirmed. These results are found employing both a power series method and a direct numerical integration scheme.

Energy systems contributions in 2,000 m race simulation: a comparison among rowing ergometers and water

This study investigated the energy system contributions of rowers in three different conditions: rowing on an ergometer without and with the slide and rowing in the water. For this purpose, eight rowers were submitted to 2,000 m race simulations in each of the situations defined above. The fractions of the aerobic (W(AER)), anaerobic alactic (W(PCR)) and anaerobic lactic (W([La-])) systems were calculated based on the oxygen uptake, the fast component of excess post-exercise oxygen uptake and changes in net blood lactate, respectively. In the water, the metabolic work was significantly higher [(851 (82) kJ] than during both ergometer [674 (60) kJ] and ergometer with slide [663 (65) kJ] (P <= 0.05). The time in the water [515 (11) s] was higher (P < 0.001) than in the ergometers with [398 (10) s] and without the slide [402 (15) s], resulting in no difference when relative energy expenditure was considered: in the water [99 (9) kJ min(-1)], ergometer without the slide [99.6 (9) kJ min(-1)] and ergometer with the slide [100.2 (9.6) kJ min(-1)]. The respective contributions of the WAER, WPCR and W[La-] systems were water = 87 (2), 7 (2) and 6 (2)%, ergometer = 84 (2), 7 (2) and 9 (2)%, and ergometer with the slide = 84 (2), 7 (2) and 9 (1)%. (V) over dotO(2), HR and lactate were not different among conditions. These results seem to indicate that the ergometer braking system simulates conditions of a bigger and faster boat and not a single scull. Probably, a 2,500 m test should be used to properly simulate in the water single-scull race.

Acute high-intensity exercise with low energy expenditure reduced LDL-c and total cholesterol in men

A reduction in LDL cholesterol and an increase in HDL cholesterol levels are clinically relevant parameters for the treatment of dyslipidaemia, and exercise is often recommended as an intervention. This study aimed to examine the effects of acute, high-intensity exercise (similar to 90% VO(2max)) and varying carbohydrate levels (control, low and high) on the blood lipid profile. Six male subjects were distributed randomly into exercise groups, based on the carbohydrate diets (control, low and high) to which the subjects were restricted before each exercise session. The lipid profile (triglycerides, VLDL, HDL cholesterol, LDL cholesterol and total cholesterol) was determined at rest, and immediately and 1 h after exercise bouts. There were no changes in the time exhaustion (8.00 +/- A 1.83; 7.82 +/- A 2.66; and 9.09 +/- A 3.51 min) and energy expenditure (496.0 +/- A 224.8; 411.5 +/- A 223.1; and 592.1 +/- A 369.9 kJ) parameters with the three varying carbohydrate intake (control, low and high). Glucose and insulin levels did not show time-dependent changes under the different conditions (P > 0.05). Total cholesterol and LDL cholesterol were reduced after the exhaustion and 1 h recovery periods when compared with rest periods only in the control carbohydrate intake group (P < 0.05), although this relation failed when the diet was manipulated. These results indicate that acute, high-intensity exercise with low energy expenditure induces changes in the cholesterol profile, and that influences of carbohydrate level corresponding to these modifications fail when carbohydrate (low and high) intake is manipulated.

Assessing land availability to produce biomass for energy: The case of Brazilian charcoal for steel making

The paper discusses the availability of biomass in Brazil to supply charcoal to the steel industry on the bases of an initial global assessment of land potentially available for plantations and of Brazilian data that allows refining the assessment and specifying the issue of practical availability. Technical potentials are first assessed through a series of simple rules against direct competition with agriculture, forests and protected areas, and of quantitative criteria, whether geo-climatic (rainfall), demographic (population density) or legal (reserves). Institutional, social and economic factors are then identified and discussed so as to account for the practical availability of Brazilian biomass through six criteria. The ranking of nine Brazilian States according to these criteria brings out the necessary trade-offs in the selection of land for plantations that would efficiently supply charcoal to the steel industry. (C) 2008 Elsevier Ltd. All rights reserved.

Flux Pinning Optimization of MgB(2) Bulk Samples Prepared Using High-Energy Ball Milling and Addition of TaB(2)

MgB(2) is considered to be an important conductor for applications. Optimizing flux pinning in these conductors can improve their critical currents. Doping can influence flux pinning efficiency and grain connectivity, and also affect the resistivity, upper critical field and critical temperature. This study was designed to attempt the doping of MgB(2) on the Mg sites with metal-diborides using high-energy ball milling. MgB(2) samples were prepared by milling pre-reacted MgB(2) and TaB(2) powders using a Spex 8000M mill with WC jars and balls in a nitrogen-filled glove box. The mixing concentration in (Mg(1-x)Ta(x))B(2) was up to x = 0.10. Samples were removed from the WC jars after milling times up to 4000 minutes and formed into pellets using cold isostatic pressing. The pellets were heat treated in a hot isostatic press (HIP) at 1000 degrees C under a pressure of 30 kpsi for 24 hours. The influence that milling time and TaB(2) addition had on the microstructure and the resulting superconducting properties of TaB(2)-added MgB(2) is discussed. Improvement J(c) of at high magnetic fields and of pinning could be obtained in milled samples with added TaB(2) The sample with added 5at.% TaB(2) and milled for 300 minutes showed values of J(c) similar to 7 x 10(5) A/cm(2) and F(p) similar to 14 GN/m(3) at 2T, 4.2 K. The milled and TaB(2)-mixed samples showed higher values of mu(0)H(irr) than the unmilled-unmixed sample.

The influence of microstructure on the maximum load and fracture energy of refractory castables

Refractory castables are composed of fractions of fine to fairly coarse particles. The fine fraction is constituted primarily of raw materials and calcium aluminate cement, which becomes hydrated, forming chemical bonds that stiffen the concrete during the curing process. The present study focused on an evaluation of several characteristics of two refractory castables with similar chemical compositions but containing aggregates of different sizes. The features evaluated were the maximum load, the fracture energy, and the ""relative crack-propagation work"" of the two castables heat-treated at 110, 650, 1100 and 1550 degrees C. The results enabled us to draw the following conclusions: the heat treatment temperature exerts a significant influence on the matrix/aggregate interaction, different microstructures form in the castables with temperature, and a relationship was noted between the maximum load and the fracture energy. (C) 2009 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Properties of Y-TZP/Al(2)O(3) ceramic nanocomposites obtained by high-energy ball milling

In this work, the synthesis of Y(2)O(3) stabilized tetragonal zirconia polycrystals (Y-TZP)-alumina (Al(2)O(3)) powder mixture was performed by high-energy ball milling and the sintering behavior of this composite was investigated. In order to understand the phase transformations occurring during ball milling, samples were collected after different milling times, from 1 to 60 h. The milled powders were compacted by cold uniaxial pressing and sintered at 1400 and 1600 degrees C. Both powders and sintered samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometry analysis (EDS) and mechanical properties. Fully dense samples were obtained after sintering at 1600 degrees C, while the samples sintered at 1400 degrees C presented a full density for powder mixtures milled for 30 and 60 h. Fracture toughness and Vickers hardnessvalues of the Y-T-ZP/Al(2)O(3) nanocomposite were improved due to dispersed Al(2)O(3) grains and reduced ZrO(2) grain size. Samples sintered at 1400 degrees C, based on powders milled for 60 h, presented high K(IC) and hardness values near to 8.0 Mpan(1/2) and 15 GPa, respectively (C) 2008 Elsevier B.V. All rights reserved