Milica Vasić

Thermal stability and degradation of binuclear hexaaqua-bis(ethylenediamine)-( μ 2 -pyromellitato)dinickel(II) tetrahydrate

Thermal degradation of ternary transition metal complex containing tetraanion of pyromellitic acid, pyr, and ethylenediamine, en, [Ni2(en)2(H2O)6(pyr)]·4H2O, 1, was investigated under non-isothermal conditions. The mechanism of thermal degradation, which occurs in three steps, was clarified by TG/DSC measurements in conjunction with FT-IR spectroscopy and XRPD analysis. The complexity of all degradation steps has been revealed using isoconversional methods. Dehydration comprises the loss of ten water molecules in a relatively narrow temperature interval, resulting in a very complicated reaction mechanism. In addition, density functional theory calculations have been applied for better understanding of dehydration. The second degradation step, related to loss of en, was separated into two single-step processes with Fraser–Suzuki function. The obtained individual steps were described by Johnson–Mehl–Avrami A2 model and Šesták–Berggren model, respectively. Validation of the proposed kinetic triplets for individual steps was performed using master plot and Pérez-Maqueda criteria. The third degradation step is related to the fragmentation of pyr ion most likely followed with the release of a number of gaseous products.

Synthesis and thermal stability of cis -dichloro[ (E) -ethyl-2-(2-((8-hydroxyquinolin-2-il)methylene)hidrazinyl)acetate-κ 2 N ]-palladium(II) complex

The structure of new cis-dichloro[(E)-ethyl-2-(2-((8-hydroxyquinolin-2-il)methylene)hidrazinyl)acetate-κ2N]-palladium(II) complex was determined using a combination of XRD and IR measurements and DFT calculations. Inherent flexibility of its structure is evident from the complexity of its IR spectrum, which could only be theoretically reproduced as a combination of several closely related structures, involving rotation around C–O bond and changes in hydrogen interactions of its –OH group. Its thermal stability and decomposition were studied non-isothermally, and the thermal decomposition mechanism was proposed using correlation with DFT calculations at the molecular level. It was determined that the initial degradation step consists of the release of Cl free radical, which then reacts with both the initial compound and the degradation products. Besides the endothermic steps, there are exothermic ones, contributing to the complex shape of the DSC curve, consisted of overlapping endothermic and exothermic peaks. Deconvolution of DTG curve allowed identification of primary fragments of the initial degradation process and, in conjunction with DFT calculations, construction of the most likely reaction mechanism.

Thermally Induced Structural Transformations of Fe40Ni40P14B6 Amorphous Alloy

Thermal stability and thermally induced structural transformations of Fe40Ni40P14B6 amorphous alloy were examined under non-isothermal and isothermal conditions. Formation of metastable α-(Fe,Ni), and stable γ-(Fe,Ni) and (Fe,Ni)3(P,B) crystalline phases as the main crystallization products was observed, while the presence of small amounts of other crystalline phases like Fe23B6 and Fe2NiB was indicated by electron diffraction in HRTEM. Thermomagnetic curve indicated that Fe content in different crystalline phases is very different, resulting in markedly different Curie temperatures after crystallization. Transmission electron microscopy and atomic force microscopy study suggested multiple-layered platelet-shaped morphology, both on the surface and in the bulk of the crystallized alloy sample. The thermal treatment heating rate and maximum temperature affected surface roughness and grain size inhomogeneity.