Synthesis, characterization, thermal studies, and DFT calculations on Pd(II) complexes containing N-methylbenzylamine

This work describes the synthesis, characterization, and the thermal behavior investigation of four palladium(II) complexes with general formulae [PdX(2)(mba)(2)], in which mba = N-methylbenzylamine and X = OAc(-) (1), Cl(-) (2), Br(-) (3) or I(-) (4). The complexes were characterized by elemental analysis, infrared vibrational spectroscopy, and (1)H nuclear magnetic resonance. The stoichiometry of the complexes was established by means of elemental analysis and thermogravimetry (TG). TG/DTA curves showed that the thermodecomposition of the four complexes occurred in 3-4 steps, leading to metallic palladium as final residue. The palladium content found in all curves was in agreement with the mass percentages calculated for the complexes. The following thermal stability sequence was found: 3 > 2 > 4 > 1. The geometry optimization of 1, 2, 3, and 4, calculated using the DFT/B3LYP method, yielded a slightly distorted square planar environment around the Pd(II) ion made by two anionic groups and two nitrogen atoms from the mba ligand (N1 and N2), in a trans-relationship.

Structural and optical properties of GdAlO3:RE3+ (RE = Eu or Tb) prepared by the Pechini method for application as X-ray phosphors

In this work, GdAlO3:RE3+ (RE = Eu or Tb) was successfully prepared by the Pechini method at lower temperatures when compared to others methods as solid-state synthesis and sol-gel process. In accordance to the XRD data, the fully crystalline single-phase GdAlO3 could be obtained at 900 degrees C. The differential thermal analysis (DTA) shows a crystallization peak at 850 degrees C. The samples are composed by monocrystalline particles (50-120 nm) exhibiting the formation of aggregates among them, which indicates the beginning of the sinterization process. This feature indicates a strong tendency to the formation of aggregates, which is a suitable ability for the close-packing of particles, and hence a potential application in X-ray intensifying screens. Luminescence measurements indicate Gd3+ -> RE3+ energy transfer. The Eu3+ emission spectra exhibit all the characteristics D-5(0) -> F-7(j) transitions and the observed profile suggests that RE3+ ions occupy at least one site without center of symmetry. For terbium-doped samples, the D-5(3) -> F-7(j) (blue emission) and D-5(4) -> F-7(j) (green emission) transitions were observed and the ratio between them may depend on the Tb3+ content due to cross-relaxation processes. (C) 2009 Elsevier B.V. All rights reserved.

Crystallization study of molybdate phosphate glasses by thermal analysis

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

Thermal Constant of an Experimental Population of Muscina stabulans (Fallén 1817) (Diptera:Muscidae) in the Laboratory

A study was conducted to investigate the thermal constant in an experimental population of Muscina stabulans (Fallén 1817). A natural population was obtained from a livestock and their F1 generations were maintained at four constant temperatures (16°C, 20°C, 26°C and 31°C). The thermal constant was calculated by the hyperbole method using the base temperature, tb = 4.4°C and the thermal constant K = 35.3 GD. Ricker's geometric regression, considering tb = 7.8°C and K = 28.9 GD was also calculated.

Hydrolysis rates of TMOS catalyzed by oxalic acid and stimulated by ultrasound

A simple calorimetric method was employed to study the kinetics of the hydrolysis of the solventless TMOS-water mixtures, under ultrasound stimulation, as a function of the concentration of oxalic acid. The reaction rates were obtained, in relative units, from the measured thermal peak of the reaction as a non-separated function of both the sonication time and the instantaneous temperature of the medium. For concentrations of oxalic acid below 0.01 M, polycondensation reaction starts before complete hydrolysis. For concentrations of oxalic acid above 0.01 M, hydrolysis is complete and, in addition, the inverse of the time, as measured from the starting of ultrasound action until the maximum hydrolysis heat release, was found to be a reasonable relative measure of the average hydrolysis rate constant. The average hydrolysis rate constant was found to be proportional to the square root of the molar concentration of the oxalic acid. This result is in agreement with the literature if we assume small dissociation degree for the catalyst in such a solventless alkoxyde-water medium.

Ferroelectric and microstructural characteristics of SrBi2Ta2O9 thin films crystallized by the rapid thermal annealing process

Ferroelectric SrBi2Ta2O9 thin films on Pt/Ti/SiO2/Si were successfully synthesized by the modified polymeric precursor method. The films were deposited by spin coating and crystallized by rapid thermal annealing in a halogen lamp furnace, followed by postannealing at temperatures ranging from 700 degreesC to 800 degreesC in an oxygen atmosphere. Microstructural and phase evaluations were followed by x-ray diffraction and atomic force microscopy. The films displayed spherical grain structures with a superficial roughness of approximately 3-6 nm. The dielectric constant values were 121 and 248 for films treated at 700 degreesC and 800 degreesC, respectively. The P-E curve showed a voltage shift toward the positive side, which was attributed to crystallization under the halogen illumination. The remanent polarization (2P(r)) and coercive field (E-c) were 7.1 muC/cm(2) and 113 kV/cm, and 18.8 muC/cm(2) and 93 kV/cm for the films treated at 700 degreesC and 800 degreesC, respectively. (C) 2001 American Institute of Physics.

Photoacoustic procedure for measuring thermal parameters of transparent solids

An application of photoacoustic technique is developed for determining the thermal diffusivity coefficient and the thermal conductivity of transparent materials. The backing material which supports the sample is made optically opaque, i.e., it entirely absorbs the incident light, and the converted heat diffuses through the sample heating the gas in contact with its opposite surface. The method is illustrated by fitting voltage amplitude and phase signals versus the chopping frequency in the photoacoustic cell, according to a theoretical model of heat diffusion. Thermal parameters obtained for three polymers compare very well with results from the literature. (C) 1995 American Institute of Physics.

Influence of the precursor salts in the synthesis of CaSnO3 by the polymeric precursor method

CaSnO3 was synthesized by the polymeric precursor method, using different precursor salts as (CH3COO)(2)Ca. H2O, Ca(NO3)(2). 4H(2)O, CaCl2. 2H(2)O and CaCO3, leading to different results. Powder precursor was characterized using thermal analysis. Depending on the precursor different thermal behaviors were obtained. Results also indicate the formation of carbonates, confirmed by IR spectra. After calcination and characterization by XRD, the formation of perovskite as single phase was only identified when calcium acetate was used as precursor. For other precursors, tin oxide was observed as secondary phase.

Effect of modifiers on thermal behaviour of Se in acid digestates and slurries of vegetables by graphite furnace atomic absorption spectrometry

The influence of sample preparation strategy of vegetables on the electrothermal behaviour of Se without and with chemical modifiers such as Pd(NO3)(2), Pd(NO3)(2) + Mg(NO3)(2), Pd(NO3)(2) + Cd(NO3)(2), pre-reduced Pd, Mg(NO3)(2), and Ni(NO3)(2) was investigated. Acid digestates and slurries of vegetables (0.1% m/v in 1% m/v HNO3 + 0.005% v/v of Triton X-100) were used to prepare reference solutions or slurries. For 10 mul of each modifier tested, pyrolysis and atomization temperatures were evaluated using pyrolysis and atomization curves, respectively. Best conditions, such as thermal stability, signal profile, repeatability and sensitivity were attained using Pd(NO3)(2) as chemical modifier. The following heating program (temperature, ramp/hold time) of the graphite tube of the Varian SpectrAA-800Z atomic absorption spectrometer was used: dry step (85 degreesC, 5/0 s; 95 degreesC, 40/0 s; 120 degreesC, 10/.5 s); pyrolysis step (1400 degreesC, 10/3s); atomization step (2200 degreesC, 1/2 s); clean step (2600 degreesC, 2/0 s). This pyrolysis temperature is 800 degreesC higher than when measuring without any modifier. For 20 muL sample volume and 10 mug Pd(NO3)(2), analytical curves in the 3.0-30 mug Se 1(-1) range were obtained. The method was applied for Se determination in acid digestates and slurries of 10 vegetable samples and one standard reference material (rice flower) and results were in agreement at 95% confidence level. Recoveries varied from 89 to 95% for spiked samples. The lifetime of the graphite tube was ca. 250 firings and the relative standard deviations (n = 12) for a typical acid digestate and slurry containing 20 mug Se 1(-1) were 3.8% and 8.3%, respectively. The limits of detection were 2.0 mug Se 1(-1) and 0.6 mug Se 1(-1) Se for digestates and slurries, respectively. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Characterization of methylcellulose produced from sugar cane bagasse cellulose: Crystallinity and thermal properties

In the present work, methylcellulose produced from sugar cane bagasse was characterized by FTIR, WAXD, DTA and TGA techniques. Two samples were synthesized: methylcellulose A and rnethylcellulose B. The only difference in the process was the addition of fresh reactants during the preparation of methylcellulose B. The ratio between the absorption intensities of the C-H stretching band at around 2900 cm(-1) and C-H stretching at around 3400 cm(-1) for methylcellulose B is higher than for methylcellulose A, indicating that methylcellulose B showed an increase in the degree of substitution (DS). Methylcellulose A presents a more heterogeneous structure, which is similar to the original cellulose as seen through FTIR and DTA. Methylcellulose B showed thermal properties similar to commercial methylcellulose. The modification of rnethylcellulose preparation method allows the production of a material with higher DS, crystallinity and thermal stability in relation to the original cellulose and to methylcellulose A. (c) 2006 Elsevier Ltd. All rights reserved.

Non-isothermal kinetic applied to thermal decomposition of commercial alkyd varnish

Samples of commercial alkyd resin varnish were spread in a film form on slides, dried at room temperature and exposed to solar radiation from one day up to seven months.Thermogravimetric measurements have been done. Based on the TG data, the Flynn-Wall isoconversional method was applied. The activation energy varied between 176-154 kJ mol(-1) and logA was between 15.5-12.9 min(-1) for A, B and C samples at 95% confidence level.

Thermal degradation of a composite solid propellant examined by DSC - Kinetic study

The thermal decomposition of ammonium perchlorate (AP)/hydroxyl-terminated-polybutadiene (HTPB), the AP/HTPB solid propellant, was studied at different heating rates in dynamic nitrogen atmosphere. The exothermic reaction kinetics was studied by differential scanning calorimetry (DSC) in non-isothermal conditions. The Arrhenius Parameters were estimated according to the Ozawa method. The calculated activation energy was 134.5 W mol(-1), the pre-exponential factor, A, was 2.04.10(10) min(-1) and the reaction order for the global composite decomposition was estimated in 0.7 by the kinetic Shimadzu software based on the Ozawa method. The Kissinger method for obtaining the activation energy value was also used for comparison. These results are discussed here.

Calorimetric study of the effect of water quantity on tetramethoxysilane hydrolysis under ultrasound stimulation

The ultrasound stimulated and oxalic acid-catalyzed hydrolysis of tetramethoxysilane (TMOS) was studied by means of a heat flux calorimetric method as a function of the initial water/TMOS molar ratio (r) ranging from 2 to 10. The method is based on the time recording of the hydrolysis exothermic heat peak. which takes place in acidulated heterogeneous water-TMOS mixtures under ultrasonic stimulation, accounting for the instantaneous hydrolysis rate. The hydrolysis rate increases from zero up to a maximum value during the heterogeneous step of the process and then diminishes naturally according to the reactant consumption. The total hydrolyzed quantity was found to be slightly increasing with r. The immiscibility gap of the TMOS- water system in the presence of the hydrolysis products has been inferred from the evaluation of the reacted quantity during the heterogeneous step of the reaction and it has been represented in a ternary diagram in the studied r-range.

Structural carbon/epoxy prepregs properties comparison by thermal and rheological analyses

Two different carbon/epoxy prepreg materials were characterized and compared using thermal (DSC, TGA, and DMA) and rheological analyses. A prepreg system (carbon fiber preimpregnated with epoxy resin F584) that is currently used in the commercial airplane industry was compared with a prepreg system that is a prospective candidate for the same applications (carbon fiber prepreg/epoxy resin 8552). The differences in the curing kinetics mechanisms of both prepreg systems were identified through the DSC, TGA, DMA, and rheological analyses. Based on these thermal analysis techniques, it was verified that the curing of both epoxy resin systems follow a cure kinetic of n order. Even though their reaction heats were found to be slightly different, the kinetics of these systems were nevertheless very similar. The activation energies for both prepreg systems were determined by DSC analysis, using Arrhenius's method, and were found to be quite similar. DMA measurements of the cured prepregs demonstrated that they exhibited similar degrees of cure and different glass transition temperatures. Furthermore, the use of the rheological analysis revealed small differences in the gel temperatures of the two prepreg systems that were examined.

Study of the hydrolysis of TEOS-TMOS mixtures under ultrasound stimulation

Pure and mixed tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS) were hydrolyzed at 35 degrees C, using oxalic acid as a catalyst and ultrasound stimulation. The hydrolysis reaction was carried out in a specially designed device, in which a heat flow steady state, between the ultrasound source and an external thermostatic bath, was maintained, in the absence of reactions. The exothermic hydrolysis causes a time dependent thermal peak. An induction time is apparent in pure TEOS before the hydrolysis peaks starts, which has been explained by the initial immiscibility gap of the TEOS-water system. The induction time was found to be approximately of the same magnitude as in the HCl catalyzed hydrolysis, in spite of the uncertainty accompanying the peak definition. No induction period is apparent in pure TMOS, so that the hydrolysis starts with its maximum rate. Two independent thermal peaks in the mixed TMOS-TEOS samples were found, both associated to the respective hydrolyses of the pure component. The induction time for the TEOS hydrolysis is decreased as more alcohol (and silanol) is produced in the earlier TMOS hydrolysis. This effect is explained by improvement of homogenization by alcohol.