Synthesis, characterization and thermal behaviour of solid-state compounds of benzoates with some bivalent transition metal ions

Solid-state MBz compounds, where M stands for bivalent Mn, Fe, Co, Ni, Cu and Zn and Bz is benzoate, have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), infrared spectroscopy and complexometry were used to characterize and to study the thermal behaviour of these compounds. The procedure used in the preparation of the compounds via reaction of basic carbonates with benzoic acid is not efficient in eliminating excess acid. However the TG-DTA curves permitted to verify that the binary compounds can be obtained by thermosynthesis, because the benzoic acid can be eliminated before the thermal decomposition of these compounds. The results led to information about the composition, dehydration, thermal stability, thermal decomposition and structure of the isolated compounds. On heating, these compounds decompose in two (Mn, Co, Ni, Zn) or three (Fe, Cu) steps with formation of the respective oxide (Mn3O4, Fe2O3, Co3O4, NiO, CuO and ZnO) as final residue. The theoretical and experimental spectroscopic studies suggest a covalent bidentate bond between ligand and metallic center.

Off-Diagonal Magnetoimpedance Dependence of Magnetostriction and Anisotropy in Co-Based and Fe-Based Amorphous Ribbons

The object of this work is the comparison of domain structure and off-diagonal magnetoimpedance effect in amorphous ribbons with different magnetostriction coefficient. The Co66Fe4Ni1Si15B14 and Fe80B20 samples were obtained by melt-spinning. During the quenching procedure a 0.07 T transverse magnetic field was applied to some of the samples. Domain patterns obtained by the Bitter technique confirm that the differences on the samples are related to the different anisotropy and magnetostriction coefficient, and the quenching procedure. Small changes on the anisotropy distribution and the magnetostriction coefficient can be detected by the off-diagonal impedance spectra as a consequence of the different permeability values of the samples

Estudo do efeito de tratamentos térmicos em catalisadores de PtRu/C frente à reação de oxidação de hidrogênio na presença de CO

In this work the effects of time and temperature of thermal treatments under reducing atmosphere (H2) on PtRu/C catalysts for the hydrogen oxidation reaction (HOR) in the presence of CO on a proton exchange membrane fuel cell (PEMFC) single cells have been studied. It can be seen that the increase of the treatment temperature leads to an increasing sintering of the catalyst particles with reduction of the active area, although the catalyst treated at 550 ºC presents more CO tolerance for the HOR.

Detailed crystallization study of co-precipitated Y1.47Gd1.53Fe5O12 and relevant magnetic properties

The crystallization process of co-precipitated Y1.5Gd1.5Fe5O12 powder heated up to 1000 ºC at rate of 5 °C min-1 was investigated. Above 810 ºC crystalline Y1.47Gd1.53Fe5O12 was obtained with a lattice parameter of 12.41 Å and a theoretical density of 5.84 g cm-3. Dry pressed rings were sintered at 1270 and 1320 ºC, increasing the grain-size from 3.1 to 6.5 µm, the theoretical density by 87.6 to 95.3% and decreasing Hc from 2.9725 to 1.4005 Oe. Additionally, Hc increased when the frequency of the hysteresis graph varied from 60 Hz to 10 kHz, the curie temperature was 282.4 ºC and Ms equalled 9.25 emu g-1 (0.17 kG) agreeing well with the Bs-value of the hysteresis graph and literature values.

Influência de M/C (M = Mo, Cu, Fe e W) incorporado à camada difusora do eletrodo de difusão de gás frente à reação de oxidação de hidrogênio na presença de CO

The performance of proton exchange membrane fuel cells (PEMFC) with Pt-based anodes is drastically lowered when CO-containing hydrogen is used to feed the system, because of the strong adsorption of CO on platinum. In the present work the effects of the presence of a conversion layer of CO to CO2 composed by several M/C materials (where M = Mo, Cu, Fe and W) in gas diffusion anodes formed by Pt catalysts were investigated. The diffusion layers formed by Mo/C e W/C show good CO-tolerance, and this was attributed to the CO removal by parallel occurrence of the water-gas shift reaction and the so-called bifunctional mechanism.

Cinética de redução do catalisador CuO/ZnO/Al2O3

The reduction kinetics of a CuO/ZnO/Al2O3 catalyst by hydrogen was investigated isothermally and by temperature programmed reduction (TPR). Two reducible Cu2+ species were detected; the first one was identified as CuO bulk and the other as Cu2+ strongly interacting with alumina, possibly in the form of copper aluminate. The activation energies for the reduction of these two species were 60 and 90 kJ mol-1, respectively, and the reaction order with respect to hydrogen was one. The isothermal reduction data showed that the isotropic growth model is the most appropriate to describe the reaction rate data for both Cu2+ species.

Aplicação de Zr/Ti-PILC no processo de adsorção de Cu(II), Co(II) e Ni(II) utilizando modelos físico-químicos de adsorção e termodinâmica do processo

The aim of this investigation is to study how Zr/Ti-PILC adsorbs metals. The physico-chemical proprieties of Zr/Ti-PILC have been optimized with pillarization processes and Cu(II), Ni(II) and Co(II) adsorption from aqueous solution has been carried out, with maximum adsorption values of 8.85, 8.30 and 7.78 x10-1 mmol g-1, respectively. The Langmuir, Freundlich and Temkin adsorption isotherm models have been applied to fit the experimental data with a linear regression process. The energetic effect caused by metal interaction was determined through calorimetric titration at the solid-liquid interface and gave a net thermal effect that enabled the calculation of the exothermic values and the equilibrium constant.

Magnetic and transport properties of II-V diluted magnetic semiconductors doped with manganese and nickel

This thesis is devoted to investigations of three typical representatives of the II-V diluted magnetic semiconductors, Zn1-xMnxAs2, (Zn1-xMnx)3As2 and p-CdSb:Ni. When this work started the family of the II-V semiconductors was presented by only the compounds belonging to the subgroup II3-V2, as (Zn1-xMnx)3As2, whereas the rest of the materials mentioned above were not investigated at all. Pronounced low-field magnetic irreversibility, accompanied with a ferromagnetic transition, are observed in Zn1-xMnxAs2 and (Zn1-xMnx)3As2 near 300 K. These features give evidence for presence of MnAs nanosize magnetic clusters, responsible for frustrated ground magnetic state. In addition, (Zn1-xMnx)3As2 demonstrates large paramagnetic response due to considerable amount of single Mn ions and small antiferromagnetic clusters. Similar paramagnetic system existing in Zn1-xMnxAs2 is much weaker. Distinct low-field magnetic irreversibility, accompanied with a rapid saturation of the magnetization with increasing magnetic field, is observed near the room temperature in p- CdSb:Ni, as well. Such behavior is connected to the frustrated magnetic state, determined by Ni-rich magnetic Ni1-xSbx nanoclusters. Their large non-sphericity and preferable orientations are responsible for strong anisotropy of the coercivity and saturation magnetization of p- CdSb:Ni. Parameters of the Ni1-xSbx nanoclusters are estimated. Low-temperature resistivity of p-CdSb:Ni is governed by a hopping mechanism of charge transfer. The variable-range hopping conductivity, observed in zero magnetic field, demonstrates a tendency of transformation into the nearest-neighbor hopping conductivity in non-zero magnetic filed. The Hall effect in p-CdSb:Ni exhibits presence of a positive normal and a negative anomalous contributions to the Hall resistivity. The normal Hall coefficient is governed mainly by holes activated into the valence band, whereas the anomalous Hall effect, attributable to the Ni1-xSbx nanoclusters with ferromagnetically ordered internal spins, exhibits a low-temperature power-law resistivity scaling.

Co-eletrodeposição oscilatória de cobre e estanho

It is investigated in the present contribution the oscillatory co-electrodeposition of CuSn on a polycrystalline gold surface in the presence of Triton X-100 surfactant and citric acid as additive, in acidic media. The experiments were conducted under potentiostatic control and the system dynamics characterized in terms of the morphology and stability of the current oscillations. Besides modulations in the frequency and amplitude of the current oscillations, several patterned states were observed, including relaxation-like and mixed mode oscillations. The oscillations were found to be very robust and some time series presented regular motions up to about two hours.

Co-produção de lipase e biossurfactante em estado sólido para utilização em biorremediação de óleos vegetais e hidrocarbonetos

Recently lipases have been increasing in prominence due to its wide industrial application. The lipase production can be influenced by different variables such as the producing microorganism, carbon sources, aeration and agitation conditions, inductor type and the geometry of the reactor. Biosurfactants are composites of surface active produced by microbial cells which reduce superficial and interfacial tensions. The objective of this study was to verify the influence of different process variables in the lipase production during a fermentative process. The results showed that the concomitant production of lipases and biosurfactant was possible in different cultivation conditions.

Validação de metodologia analítica por cromatografia líquida de alta eficiência para quantificação de bupivacaína (S75-R25) em nanoesferas de poli(lactídeo-co-glicolídeo)

Bupivacaine (S75-R25, NovaBupi®) is an amide type local anesthetic widely used. The present work consists of the development and validation of analytical methodology for evaluation of NovaBupi® content in the poly-lactide-co-glycolide nanospheres (PLGA-NS) by high performance liquid chromatography. The separation was made using the reversed-phase column LC-18, acetonitrile/phosphate buffer 85:15 v/v as mobile phase and detection at 220 nm. The results obtained show that the analytical methodology is accurate, reproducible, robust and linear over the concentration range 10-220.0 g/mL of NovaBupi®. The method was applied to determine the encapsulation efficiency and evaluate the release profile of NovaBupi®, showing good results.