Journal of Thermal Analysis

A series of coordination complexes with the compositions CuL, NiL×2H2 O, ML2 Cl2 (M =Pt(II), Hg(II)) and M(L-H)2 (M =Pd(II)), Cd(II)), where L =N-benzoyl-N'-2-nitro-4-methoxyphenylthiourea, were synthesized and characterized by conductance, EPR, IR and electronic spectral studies and thermogravimetric analysis. The IR and electronic spectra suggest coordination through the thiocarbonyl S and carbonyl O in the Pd(II) and Cd(II) complexes, and S bonding for the Pt(II) and Hg(II) complexes. The Cu(II) and Ni(II) complexes have polymeric structures in which the ligand is coordinated via the N, O and S atoms.

Simultaneous DTA-TG has been carried out on a set of natural vermiculite samples. Based on their dehydration behaviour the samples can be divided in two groups: (a) those with DTA endothermic peak temperatures at 140°–150°C and 240°–270°C (pure vermiculties) and (b) those with peak temperatures at 95°–115°C (vermiculite with mica or mica-vermiculite interstratifications). The low temperature at which the endothermic effect in group (b) appears is discussed on the basis of dilution due to the inert layers of mica, differences in chemical composition, and lowering of interlamellar water bond energy.

Presented work describes mechanical treatment as a non-conventional solid-state process for preparation of some functional materials. Mechanochemical syntheses may be alternative as waste-free and ecologically safer methods of preparing pigments, composites, catalysts, biomaterials, which obey main principles of Green Chemistry.

The direct production of copper sulphate from copper ore is an important route to recover copper. The condition, however, is dependant on temperature and sulphatising environment. The oxidation of chalcopyrite in static air bed condition has been studied by TG/DTA and DSC techniques. The addition of catalysts, improved the sulphation by in-situ producing better condítions. The mutual effects of sulphides were further confirmed by studying the oxidation reaction on pure copper-iron sulphides and results so obtained were corroborated with X-ray diffractrograms. With only chalcopyrite a mass gain of 8% (TG) corresponding to copper sulphate formation was observed, in the temperature range 628–738 K. The TG plots showed respective mass gain of 14, 17 and 12% in presence of Fe2O3, Na2SO4 and FeSO4 with chalcopyrite in the wider temperature range 628–923 K. As such the cupric sulphide had a negligible tendency of sulphation, which increased with the addition of ferrous sulphide mixture under the temperature range studied. At higher temperature copper ferrite formation was found.

Discontinuous isoperibolic thermal analysis (ΔITA) is a phase diagram investigation technique applicable to organic components systems (with at least one liquid phase). The elementary signal is composed by the evolution of the temperature of the system vs. time after a composition shift. A theoretical analysis and a mathematical modeling of this signal show that the overall enthalpy exchanged multiplied by a proportional factor can be obtained. From different experiments, evidence is given that this semi-quantitative calorimetric measurement is reliable. Thus, ΔITA allows consistent and accurate descriptions of phase diagrams and is a real relative calorimetric measurement technique.

Al-modified MCM-41, La-modified MCM-41, and Ce-modified MCM-41 mesoporous materials were prepared with different molar ratios (Si/M = 10; 25; 50; 100 and 200) at room temperature. The materials were characterized using XRD, BET–BJH, and TG–DTA. The XRD showed four peaks, due to the ordered hexagonal array of parallel silica tubes, which could be indexed as (100), (110), (200), and (210), assuming a hexagonal unit cell. The surface area decreased as the concentration of the metal incorporated in the material increased. The thermal stability of the materials was around 650 °C. The CeO2 phase made the mass transfer process more difficult, hindering Hofmann degradation and favoring oxidation.

Oil shale semicoke, formed in retort furnaces, is a source of severe environmental pollution and is classified as a dangerous solid waste. For the industrial application of oil shale semicoke in combustion, this present work focused on the thermal analysis of its combustion characteristics. The pyrolysis and combustion experiments of semicoke were conducted in a Pyris thermogravimetric analyzer. From the comparison of pyrolysis curves with combustion curves, the ignition mechanism of semicoke samples prepared at different carbonization temperatures was deduced, and was found to be homogeneous for semicoke samples obtained at lower carbonization temperature, shifting to heterogeneous with an increase in the carbonization temperature. The effect of carbonization temperatures and heating rates on the combustion process was studied as well. At last, combustion kinetic parameters of semicoke were calculated with the binary linear regression method, showing that activation energy will increase with increasing the heating rate.

Trong công trình này, tốc độ đóng rắn của các loại nhựa alkyd được sửa đổi bằng dầu khô oxy hóa khác nhau được khảo sát bằng phương pháp đo DSC. Chúng tôi xác định, từ phương trình Kissinger, năng lượng kích hoạt hiển nhiên của quá trình đóng rắn. Chúng tôi chỉ ra rằng năng lượng kích hoạt này phụ thuộc vào thời gian đóng rắn và rằng những biến đổi này dẫn đến việc xác định một hằng số thời gian, đặc trưng cho vật liệu.

The literature reveals that the mechanisms of some solid-state dehydrations are more complicated than has been generally accepted. Reactions at a thin advancing reactant-product interface provide the geometric models on which the most widely employed rate equations are based. For some systems, this “thin interface” model is a simplification of observed behaviour. Elimination of water from crystallographic sites may occur to a significant extent within a much thicker zone of reactant towards which the active interface is progressing. Consequently the region of chemical change may not coincide with the region of structural transformation. Limited initial dehydration may occur across all crystal faces prior to the onset of a nucleation and growth process that is usually regarded as the dominant rate process in the dehydrations of many large crystals. Experimental observations for solid-state dehydrations are discussed and reaction mechanisms with different rate controlling processes are distinguished. Studies of dehydrations have contributed substantially to the theory of solid-state reactivity, and advances in understanding may have wider application to other solid-state reactants.