Zn(0.97)M(0.03)O (M = Co, Fe, and V) pigments: thermal, structural, and optical characterization

Zinc oxide is a widely used white inorganic pigment. Transition metal ions are used as chromophores and originate the ceramic pigments group. In this context, ZnO particles doped with Co, Fe, and V were synthesized by the polymeric precursors method, Pechini method. Differential scanning calorimetry (DSC) and thermogravimetry (TG) techniques were used to accurately characterize the distinct thermal events occurring during synthesis. The TG and DSC results revealed a series of decomposition temperatures due to different exothermal events, which were identified as H(2)O elimination, organic compounds degradation and phase formation. The samples were structurally characterized by X-Ray diffractometry revealing the formation of single phase, corresponding to the crystalline matrix of ZnO. The samples were optically characterized by diffuse reflectance measurements and colorimetric coordinates L*, a*, b* were calculated for the pigment powders. The pigment powders presented a variety of colors ranging from white (ZnO), green (Zn(0.97)Co(0.03)O), yellow (Zn(0.97)Fe(0.03)O), and beige (Zn(0.97)V(0.03)O).

Influence of ceria addition on thermal properties and local structure of bismuth germanate glasses

Bismuth germanate glasses are interesting materials due to their physical properties and their unique structural characteristics caused by the coordination changes of bismuth and germanium atoms. Glasses of the bismuth germanate system were prepared by melting/molding method and were investigated concerning their thermal and structural properties. The structural analysis of the samples was carried out by micro-Raman and Fourier transform infrared spectroscopes. It was observed that the glass structure is formed basically by GeO(4) tetrahedral units also having the formation of the GeO(6) octahedral units. BiO(2) was considered a network former by observing the presence of octahedral BiO(6) and pyramidal BiO(3) groups in the local structure of the samples. An absorption band observed at 1103 cm(-1) in the IR spectrum of the undoped glass was attributed to the Bi-O-Ge and/or Bi-O-Bi linkage vibration. The said band shifted to lower wavenumbers after the CeO(2) addition thus reflecting changes in the glass network. Cerium oxide was an efficient oxidant agent to prevent the darkening of the glasses which was probably associated to the reduction of Bi ions. However, CeO(2) was incorporated as a local network modifier in the glass structure even at concentrations of 0.2 mol%. (C) 2010 Elsevier B.V. All rights reserved.

Anisotropy and chemical composition of ultra-high energy cosmic rays using arrival directions measured by the Pierre Auger Observatory

The Pierre Auger Collaboration has reported. evidence for anisotropy in the distribution of arrival directions of the cosmic rays with energies E > E(th) = 5.5 x 10(19) eV. These show a correlation with the distribution of nearby extragalactic objects, including an apparent excess around the direction of Centaurus A. If the particles responsible for these excesses at E > E(th) are heavy nuclei with charge Z, the proton component of the sources should lead to excesses in the same regions at energies E/Z. We here report the lack of anisotropies in these directions at energies above E(th)/Z (for illustrative values of Z = 6, 13, 26). If the anisotropies above E(th) are due to nuclei with charge Z, and under reasonable assumptions about the acceleration process, these observations imply stringent constraints on the allowed proton fraction at the lower energies.

Polymethine cyanine dyes in beta-cyclodextrin solution: multiple equilibria and chemical oxidation

Absorption and fluorescence spectroscopy, electrochemical techniques, and semiempirical calculations were employed to characterize the multiple complexation equilibria between two polymethine cyanine dyes (IR-786 and Indocyanine green-ICG, 5) and beta-cyclodextrin (beta-CD, L), as well as the chemical reactivity of the complexed and uncomplexed species against the oxidizing agents hypochlorite (HC) and hydrogen peroxide (HP). IR-786 dimerization is favored with the increase in beta-CD concentration in the form of (SL)(2) complexes. In the case of ICG, free dimers (D) and SL complexes are favored. Both IR-786 and ICG react and discolor in the presence of HC and HP. For IR-786, the reaction with HP and HC proceeds with observed rate constants of 10(-3) and 0.28 s(-1) and second-order rate constants (k(2)) of similar to 10(-3) and 10(4) M(-1) s(-1), respectively. The intermediate species observed in the bleaching reactions of IR-786 and ICG were shown, by cyclic voltammetry and VIS absorption, to result from one electron oxidation. IR-786 complexed with beta-CD is protected against bleaching in the presence of HP and HC by factors of 20 and 4, respectively. This protection was not observed in ICG complexes. Superdelocalizability profile of both dyes and frontier orbital analysis indicates that beta-CD does not protect ICG from oxidation by HP or HC, whereas the 2:2 IR-786/beta-Cd complex is able to avoid the oxidation of IR-786. We concluded that the decrease in the chemical reactivity of the dyes against oxidant agents in the presence of beta-CD is due to the formation of (SL)(2) complexes. Copyright (C) 2010 John Wiley & Sons, Ltd.

Electronic structure and chemical bonding in W(2) molecule

The electronic structure of the lowest-lying electronic states of W(2) were investigated at the CASPT2 level. The ground state is a X(1)Sigma(+)(g) state, followed by the a(3)Delta(u), b(3)Sigma(+)(u) and A(1)Delta(u) electronic states. Seven low-lying Omega-states were computed: (1)0(g)(+), (2)3(u), (3)2(u), (4)1(u), (5)0(u)(-), (6)1(u), and (7)2(u), with the ground state corresponding to the (1)0(g)(+)(X(1)Sigma(+)(g)) state. Comparison with the other VIB transition metal group dimers indicates a common pattern of electronic structure and spectroscopic properties. (C) 2010 Elsevier B.V. All rights reserved.

Electronic Structure and Chemical Bonding in the Lowest Electronic States of TcN

Multiconfiguration second-order perturbation theory, with the inclusion of relativistic effects and spin-orbit Coupling, was employed to investigate the nature of the ground and low-lying Lambda-S and Omega states of the TcN molecule. Spectroscopic constants, effective bond order, and potential energy curves for 13 low-lying Lambda-S states and 5 Omega states are given, The computed ground state of TcN is of Omega = 3 symmetry (R(e) = 1.605 angstrom and omega(e) = 1085 cm(-1)), originating mainly from the (3)Delta Lambda-S ground state. This result is contrasted with the nature of the ground state for other VIIB transtion-metal mononitrides, including X(3)Sigma(-) symmetry for MnN and Omega = 0(+) symmetry for ReN, derived also from a X(3)Sigma(-) state.

Thermal analysis and compatibility studies of prednicarbate with excipients used in semi solid pharmaceutical form

Differential Scanning Calorimetry (DSC), thermogravimetry/derivative thermogravimetry (TG/DTG) and infrared spectroscopy (IR) techniques were used to investigate the compatibility between prednicarbate and several excipients commonly used in semi solid pharmaceutical form. The thermoanalytical studies of 1:1 (m/m) drug/excipient physical mixtures showed that the beginning of the first thermal decomposition stage of the prednicarbate (T (onset) value) was decreased in the presence of stearyl alcohol and glyceryl stearate compared to the drug alone. For the binary mixture of drug/sodium pirrolidone carboxilate the first thermal decomposition stage was not changed, however the DTG peak temperature (T (peak DTG)) decreased. The comparison of the IR spectra of the drug, the physical mixtures and of the thermally treated samples confirmed the thermal decomposition of prednicarbate. By the comparison of the thermal profiles of 1:1 prednicarbate:excipients mixtures (methylparaben, propylparaben, carbomer 940, acrylate crosspolymer, lactic acid, light liquid paraffin, isopropyl palmitate, myristyl lactate and cetyl alcohol) no interaction was observed.

Electronic structure and chemical bonding in the ground states of Tc(2) and Re(2)

Multiconfiguration second-order perturbation theory, including relativistic effects and spin-orbit coupling, has been employed to investigate the nature of the chemical bonding in the ground state of Tc(2) and Re(2). The Tc(2) ground state is found to be a 0(g)(+) state, with an effective bond order (EBO) of 4.4, and a dissociation energy of 3.25 eV. The Re(2) ground state is a 1(g) state, with EBO = 4.3. Almost degenerate to it, is a 0(g)(+) state (T(e) = 77 cm(-1)), with EBO = 4.1. Experimental evidence also indicates that the ground state is of 1(g) nature. The dissociation energy is computed to be 5.0 eV in agreement with an experimental estimate of 4 +/- 1 eV.

Electronic Structure and Chemical Bonding in the Ground and Low-Lying Electronic States of Ta(2)

The electronic structure and chemical bonding of the ground and low-lying Lambda - S and Omega states of Ta(2) were investigated at the multiconfiguration second-order perturbation theory (CASSCF//CASPT2) level. The ground state of Ta(2) is computed to be a X(3)Sigma(-)(g) state (R(e) = 2.120 angstrom, omega(e) = 323 cm(-1), and D(e) = 4.65 eV), with two low-lying singlet states close to it (a(1) Sigma(+)(g) : T(e) = 409 cm(-1), R(e) = 2.131 angstrom, and omega(e) = 313 cm(-1); b(1) Gamma(g): T(e) = 1, 038 cm(-1), R(e) = 2.127 angstrom, and omega(e) = 316 cm(-1)). These electronic states are derived from the same electronic configuration: vertical bar 13 sigma(2)(g)14 sigma(2)(g)7 delta(2)(g)13 pi(4)(u)>. The effective bond order of the X(3) Sigma(-)(g) state is 4.52, which indicates that the Ta atoms are bound by a quintuple chemical bond. The a(1) Sigma(+)(g) state interacts strongly with the X(3)Sigma(-)(g) g ground state by a second-order spin-orbit interaction, giving rise to the (1)0(g)(+) (ground state) (dominated by the X(3)Sigma(-)(g) Lambda - S ground state) and (9)0(g)(+) (dominated by the a(1) Sigma(+)(g) Lambda - S state) Omega states. These results are in line with those reported for the group 5B homonuclear transition metal diatomics. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1306-1315, 2011

Thermal behavior and structural properites of plant-derived eugenyl acetate

Eugenol is an allyl chain-substituted guaiacol in the biosynthesized phenylpropanoid compound class derived from Syzygium aromaticum L. and widely used in folk medicine. Nonetheless, its pharmacological use is limited by some problems, such as instability when exposed to light and high temperature. In order to enhance stability, the eugenol molecule was structurally modified, resulting in eugenyl acetate. The eugenyl acetate`s thermal behavior and crystal structure was then characterized by differential scanning calorimetry (DSC) and X-ray diffraction (XRD) and compared to a commercial sample.

Wettability, Shrinkage and Color Changes of Araucaria angustifolia After Heating Treatment

The effects of thermal treatment on the wettability and shrink resistance of Araucaria angustifolia (Parana pine) were studied from 20 to 200 °C. The contact angles of water droplets on untreated and heat-treated samples were measured by the sessile drop method in the grain of heartwood and sapwood cut in the radial, longitudinal, and tangential directions. A significant increase of the contact angles was verified for the samples from room temperature to 120 °C, in particular in the radial and tangential directions; at higher temperatures, the contact angles assumed almost constant values. From 120 to 200 °C, the sapwood of Araucaria angustifolia showed better dimensional stability and lower thermal resistance when compared to the heartwood. Variations of color were also studied by using the CIELab system, which showed to be capable of accurately distinguishing samples treated at different temperatures.

Comparative study of chemical and mechanical retentive systems for bonding of indirect composite resin to commercially pure titanium

This study evaluated the effect of chemical and mechanical surface treatments for cast metal alloys on the bond strength of an indirect composite resin (Artglass) to commercially pure titanium (cpTi). Thirty cylindrical metal rods (3 mm diameter x 60 mm long) were cast in grade-1 cpTi and randomly assigned to 6 groups (n=5) according to the received surface treatment: sandblasting; chemical treatment; mechanical treatment - 0.4 mm beads; mechanical treatment - 0.6 mm beads; chemical/mechanical treatment - 0.4 mm; and chemical/mechanical treatment - 0.6 mm beads. Artglass rings (6.0 mm diameter x 2.0 mm thick) were light cured around the cpTi rods, according manufacturer's specifications. The specimens were invested in hard gypsum and their bond strength (in MPa) to the rods was measured at fracture with a universal testing machine at a crosshead speed of 2.0 mm/min and 500 kgf load cell. Data were analyzed statistically by one-way ANOVA and Tukey test (a=5%). The surface treatments differed significantly from each other (p<0.05) regarding the recorded bond strengths. Chemical retention and sandblasting showed statistically similar results to each other (p=0.139) and both had significantly lower bond strengths (p<0.05) than the other treatments. In conclusion, mechanical retention, either associated or not to chemical treatment, provided higher bond strength of the indirect composite resin to cpTi.

Long-term stability of hydrogen and organic acids production in an anaerobic fluidized-bed reactor using heat treated anaerobic sludge inoculum

This study evaluates the stability of hydrogen and organic acids production in an anaerobic fluidized-bed reactor (AFBR) that contains expanded clay (2.8-3.35 mm in diameter) as a support medium and is operated on a long-term basis. The reactor was inoculated with thermally pre-treated anaerobic sludge and operated with decreasing hydraulic retention time (HRT), from 8 h to 1 h, at a controlled temperature of 30 degrees C and a pH of about 3.8. Glucose (2000 mg L(-1)) was used as the substrate, generating conversion rates of 92-98%. Decreasing the HRT from 8 h to 1 h led to an increase in average hydrogen-production rates, with a maximum value of 1.28 L h(-1) L(-1) for an HRT of 1 h. In general, hydrogen yield production increased as HRT decreased, reaching 2.29 mol of H(2)/mol glucose at an HRT of 2 h and yielding a maximum hydrogen content of 37% in the biogas. No methane was detected in the biogas throughout the period of operation. The main soluble metabolites (SMP) were acetic acid (46.94-53.84% of SMP) and butyric acid (34.51-42.16% of SMP), with less than 15.49% ethanol. The steady performance of the AFBR may be attributed to adequate thermal treatment of the inoculum, the selection of a suitable support medium for microbial adhesion, and the choice of satisfactory environmental conditions imposed on the system. The results show that stable hydrogen production and organic acids production were maintained in the AFBR over a period of 178 days. (C) 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Effect of Different Cooking Conditions on Phenolic Compounds and Antioxidant Capacity of Some Selected Brazilian Bean (Phaseolus vulgaris L.) Cultivars

The effects of different cooking conditions such as soaking, atmospheric (100 degrees C) or pressure boiling (121 degrees C), and draining of cooking water following thermal treatment on phenolic compounds and the DPPH radical scavenging capacity from two selected Brazilian bean cultivars (black and yellow-brown seed coat color) were investigated using a factorial design (2(3)). Factors that significantly reduced the total phenolic contents and antioxidant capacity in both cultivars were the soaking and draining stage. Independent of cooking temperature, total phenolics and antioxidant capacities were enhanced in treatments without soaking and where cooking water was not discarded, and this was likely linked to an increase of specific phenolic compounds detected by high performance liquid chromatography such as flavonols and free phenolic acids in both cultivars. Cooking of beans either at 100 or 121 degrees C, without a soaking stage and keeping the cooking water, would be recommendable for retaining antioxidant phenolic compounds.

The RAINY3D Code: The Treatment of Condensation in Nova Remnants during Nebular Phase

Classical nova remnants are important scenarios for improving the photoionization modeling. This work describes the pseudo-three-dimensional code RAINY3D, which drives the photoionization code Cloudy as a subroutine. Photoionization simulations of old nova remnants are also presented and discussed. In these simulations we analyze the effect of condensation in the remnant spectra. The condensed mass fraction affects the Balmer lines by a factor of greater than 4 when compared with homogeneous models, and this directly impacts the shell mass determination. The He II 4686/H beta ratio decreases by a factor of 10 in clumpy shells. These lines are also affected by the clump size and density distributions. The behavior of the strongest nebular line observed in nova remnants is also analyzed for heterogeneous shells. The gas diagnoses in novae ejecta are thought to be more accurate during the nebular phase, but we have determined that at this phase the matter distribution can strongly affect the derived shell physical properties and chemical abundances.