Journal of Thermal Analysis

During the heating of YBCO a peritectic reaction takes place at 1020‡C, which can be described by: 2YBa2Cu3O7−x⇄Y2BaCuO5+L+(1-2x)/2O2 (1) whereL = 3BaCuO2 +2CuO is a fluid with limited amount of yttrium. It has been reported, that many parameters can influence the reaction. From one side not only the starting size of grains but also the heating rate have an influence on the resulting Y2BaCuO5-phase. From the other side, there is a change of the peritectical temperature caused by changing of the partial pressure of O2 and the presence of parasitic phase. From general kinetic consideration one can draw the conclusion, that different mechanisms (nucleation, phase-boundary reaction and diffusion) can control the reaction. Using DTA/TG measurements, the peritectic reaction has been examined. Classical kinetic methods (Kissinger and Friedman) has been used. The Friedman method has given the dependence of the activation energy from reaction degree. This suggests many steps reactions. The dependence of the DTA-peaks from the heat rate suggest a parallel steps of reaction. This assumption can be motivated by evaluation of free O2, one solid and liquid phase formation. Amount of this phases depends on the heating rate. Additionally X-ray and microscopic methods has been used. In this way was shown, that the perovskit structure is stable up to peritectical temperature and than is dramatically destroyed. From microscopic observations has been got information about shape and size of solid phase and it's creation as a function of temperature, time and starting grain size.

The thermal behaviour of 6-amino-5-formyluracil (HFU), 6-amino-1-methyl-5-formyluracil (1-MFU), 6-amino-3-methyl-5-formyluracil (3-HFU) and 6-amino-1,3-dimethyl-5-formyluracil (HDFU) is described. Only HDFU is shown to contain crystallization water. Dehydration and fusion enthalpy values have been calculated from the DSC curves. Likewise, the thermal behaviour of new complexes obtained by reaction between the above pyrimidine derivatives and Ni(II), Cu(II) and Pd(II) ions is reported.

Various ways of thermodynamic evaluations can yield different results, contradicting to one another. Such a case is considered a paradox, with the attempts to solve it. This is because thermodynamics is thought to be the science established on solid conceptual ground, with accurate mathematical evaluations. Recently, we faced similar problem, when the relationship between heat capacity and pressure is described by two different equations, predicting opposite behavior. Both equations are free of evident errors. In searching for the reason of the discrepancy, we found out that it is common practice in thermodynamic evaluations to tune the mathematical operations in order to receive the necessary result. It is typical of empirical science, but inappropriate for the fundamental knowledge based on axiomatic background. Short historical survey on experimental data and theoretical concepts dealing with the relation between heat capacity and pressure proves that the thermodynamics is very flexible and effective tool for the solution of the problems in the field of relationships among P–V–T parameters and thermophysical properties of matter. One should not consider the solutions as the universal laws.

The thermal properties of KTN crystal were investigated at low temperatures by DSC and TM. The phase transition enthalpies and the average specific heats of the crystal were measured. Results are analyzed and discussed.

The relaxation spectra in polymers arise from the existence of many possible modes for dissipating the strain energy raised by the imposed force. These modes are made up by coupling the simplest and fastest mode of relaxation involving the rotation of a conformer, typically represented by the picosecond rotation of the carbon to carbon bond. This fast relaxation process cannot take place easily in the condensed state crowded by the densely packed conformers, necessitating cooperativity among them. The domain of cooperativity grows at lower temperatures, toward the infinite size at the Kauzman zero entropy temperature. From the temperature dependence of the domain size, the well-known Vogel equation is derived, which is numerically equivalent to the empirical WLF and free volume equations. The molar volume is a crucial factor in determining the molar free volume and, therefore, in determining theT g of a material. The molar ΔC P is proportional to the logarithmic molar volume, and is greater for a polymer with a higherT g, but ΔC P per gram for it is smaller, as it is proportional to (logM) divided byM, whereM is the molecular weight of the conformer. From this theory, it is possible to predict the dependence of the characteristic relaxation time on temperature if eitherT g or the conformer size is known, since one can be derived from the other. From the Vogel equation with all parameters thus derived, it is possible to obtain a master relaxation curve and the spectrum from one set of dynamic mechanical data taken at one frequency over a range of temperatures. Whereas the linear viscoelastic principle is limited to small strains only, a real polymer is often deformed well beyond such a limit. Above a certain limit of strain energy level, linear viscoelastic deformation is no longer possible and the plastic deformation takes over. However, because a polymer typically manifests a spectrum of relaxation times, its behavior is a combination of viscoelastic and plastic behaviors. The ratio between the two behaviors depend on the rate of deformation, and can be precisely predicted from the linear viscoelastic relaxation spectrum. The combined behavior is termed viscoplasticity, and it applies to a wide range of practically important mechanical behaviors from the flow of the melt to the yield and fracture of glassy and crystalline solids.

The hydrazinium(1+) metal acetates and malonate dihydrates of the molecular formula [(N2H5)2M(CH3COO)4] and (N2H5)2[M(OOCCH2COO)2(H2O)2] respectively, whereM=Co, Ni or Zn, have been prepared and characterized by chemical analyses, conductance, magnetic, spectral, thermal and X-ray powder diffraction studies. The magnetic moments and electronic spectra indicate that these complexes are of high-spin octahedral variety. The infrared spectra show that the hydrazinium ions are coordinated in the case of acetate complexes, whereas in the malonate complexes the hydrazinium ions are out side the coordination sphere. These complexes undergo exothermic decomposition in the temperature range 150–450°C to give the respective metal oxide as the final residue. The X-ray powder diffraction patterns of the malonate complexes indicate isomorphism among them.

In order to explore the influence of CeO2 on the structure and surface characteristics of molybdena, an investigation was undertaken by using N2 adsorption (BET method), thermal analysis and in-situ diffuse reflectance infrared (DRIFT) techniques. In this work, the Mo/CeO2 and Ce-Mo/Al2O3 samples were prepared by impregnation and co-precipitation methods with high Mo loadings. Combining the results one may notice that the presence of ceria led to the increase of polymerized surface Mo species so as to forming Mo-O-Ce linkages besides the formation of coupled O=Mo=O bonds indicative of polymeric MoO3. From thermal analysis, it can be inferred that Mo/Al2O3 is the thermally most stable material in the temperature range used in the experiment (up to 900°C), whereas Ce-Mo/Al2O3 and Mo/CeO2 samples undergo morphological modifications above 700°C resulting in lattice defects, which motivate the mobility of Mo and Ce ions and thus enhance the possibility of interaction between them. Additionally, their activity towards CO adsorption needs reduced ceria and molybdena containing coordinatively unsaturated sites (CUS), oxygen vacancies and hydroxyl groups to form various carbonate species.