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The state of the art in methane pyrolysis does not yet provide a definitive answer as to whether the concept of an elementary reaction is universally applicable to the apparently simple process of methane dissociation. Similarly, the literature currently lacks a comprehensive and unambiguous description of the methane pyrolysis process and, in particular, a single model that would well represent its course at both the micro and macro scales. Given the wide range of conditions under which this reaction can occur—whether thermal or thermo-catalytic, in solid or fluidized bed reactors—it is crucial to evaluate the usefulness of different kinetic models and their compatibility with basic thermodynamic principles and design assumptions. To address these research gaps, the authors analysed the thermodynamic and kinetic dependencies involved in the thermal decomposition of methane, using the synthesis of methane from its elemental components and its reversibility as a basis for exploring suitable kinetic models. Using experimental data available in the literature, a wide range of kinetic models have been analysed to determine how they all relate to the reaction rate constant. It was found that regardless of whether the process is catalytic or purely thermal, for temperatures above 900 °C the reversibility of the reaction has a negligible effect on the hydrogen yield. This work shows how the determined kinetic parameters are consistent with the Kinetic Compensation Effect (KCE) and, by incorporating elements of Transition State Theory (TST), the possibility of the existence of Entropy–Enthalpy Compensation (EEC). The indicated correspondence between KCE and EEC is strengthened by the calculated average activation entropy at isokinetic temperature (∆ S B = − 275.0   J · (m o l · K) − 1). Based on these results, the authors also show that changes in the activation energy (E = 20 – 421   k J · m o l − 1) can only serve as an estimate of the optimal process conditions, since the isoconversion temperature ( T i s o = 1200 − 1450   K > T e q ) is shown to depend not only on thermodynamic principles but also on the way the reaction is carried out, with temperature (T) and pressure (P) locally compensating each other. [ABSTRACT FROM AUTHOR]

Fly ash microspheres, also called cenospheres, have many valuable properties that allow them to be widely used. Some of its most important properties are its mechanical and thermal strength as well as its chemical stability. These features constitute an important commercial parameter. Refining processes aim to select the highest quality product from raw materials that meets the expectations of recipients. Generally, preparing a final product involves selecting the appropriate sequence and parameters of the grain separation process. However, the key to the optimal selection of these parameters is knowledge of the specificity of the processed raw material. Microspheres are materials that are created spontaneously, uncontrolled, and without the possibility of intentionally influencing their properties. Therefore, due to the potential directions of microsphere use, it is justified to study the relationship between density, grain size, and mechanical strength. Understanding these relationships in microspheres from various sources is particularly important at the stage of planning refining processes. This paper presents the results of research on microspheres from two different sources. The tested raw materials (microspheres) are subjected to densiometric and grain analysis. Also, mechanical strength was determined for the separated density fractions and grain classes. The test results did not show significant correlations between the tested features of the microspheres. In the case of both raw materials, the highest density was observed in the smallest grain classes, and the highest mechanical strength was determined for microspheres with grain sizes in the range of 75–100 µm. For this grain size range, the value of mechanical strength is 26 for raw Material 1 and 38 for raw Material 2. The shares of this grain fraction in the microsphere stream are 11.2% and 16%, respectively. An important difference that may significantly affect the efficiency of the refining process is the method of distribution of the primary falling parts, which affects the mechanical strength of the tested raw materials. [ABSTRACT FROM AUTHOR]

An analysis was carried out on the thermal dissociation of selected inorganic salts according to Transition-State Theory (TST). For this purpose, two possibilities were compared in the context of rate constants: in the first case using the Arrhenius constant directly from TST, and in the second, using the thermodynamic equilibrium constant of the reaction/process of active state formation. The determined relationships are presented in the form of temperature profiles. It was established that TST applies to reactions for which there is a formally and experimentally reversible reaction, in the literal sense or catalytic process. The importance of the isoequilibrium temperature, which results from the intersection of the thermodynamic temperature profile and the Gibbs free energy of activation, was demonstrated. Its values close to the equilibrium temperature are indicative of more dynamic kinetic qualities. As part of the discussion, the Kinetic Compensation Effect (KCE) was used to observe changes in the entropy of activation by comparing two kinetic characteristics of the same reaction. Enthalpy–Entropy Compensation (EEC) was shown to be the same law as KCE, just expressed differently. This was made possible by TST, specifically the entropy of activation at isokinetic temperature, by which the perspective of the relationship of energy effects changes. [ABSTRACT FROM AUTHOR]

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Purpose: The main objective of this study was to obtain single-phase ß-ZrO2 powders with so-called soft agglomerates reproducibile morphology with acetyl-acetone as a chelating-agent. To the best of our knowledge there is no avaiable data which determine the effect of acetyl acetone on the phase composition and morphology of ceria-doped ZrO2 powders for biomedical applications. Methods: Twenty variants of powders with different water to zirconia precursor and acetylacetone to zirconia precursor molar ratios were prepared. 0.9ZrO20.1CeO2 powders were obtained by a hydrolysis and condensation and further calcination of zirconium n-propoxide in a simple one-step sol-gel process. Influence of acetyloacetone to zirconia precursor on the phase composition ratio and water to zirconia precursor was investigated. Samples have been characterized by X-ray diffraction (XRD), Raman spectroscopy (RS), thermal analysis (TGA/DTA) and scanning electron microscopy (SEM) measurements. Results: Ceramic powders prepared by sol-gel process, according to the various concentration of chelating agent and water show different morphology and phase composition. Conclusions: Higher molar ratios of AcAc in range with smaller amounts of water cause hard agglomerates, obtained powders are characterized by highly thermally stable behaviour and various phase composition. With higher molar ratios of water to zirconium-n-propoxide so-called soft agglomerates and one phase powders are obtained. [ABSTRACT FROM AUTHOR]

Purpose: High purity, fine crystalline, degradation-free at low temperature powders have attracted special interest in CAD/CAM prosthetic dentistry full ceramic restorations. This study reports the preparation and characterisation of zirconia-ceria (0.9 ZrO2 0.1 CeO2) powders. Materials were obtained from zirconium-n-alkoxide and cerium nitrate hexahydrate in the pH 2-4 and 8-10., Methods: Zirconia- ceria powders were obtained with the sol-gel method in a humid-free environment. Thermal analysis (TGA/DTA) of the as-prepared materials was made for an assessment of its behaviour at elevated temperatures. Specimens were dried at 80 °C and calcinated in two stages: at 300 °C with soaking time 2.5 h and 850 °C with holding time 2.5 h, in order to evaluate the phase transformations. Thermal analyses of the as-dried powders were made for an assessment of its thermal behaviour during heat treatment up to 1000 °C. By X-ray diffraction (XRD), polymorphs of ZrO2 were identified. Additionally, scanning electron microscopy (SEM) and laser particle size distribution (PSD) were involved for characterisation of morphology of the powders., Results: A correlation between the pH of the colloidal system and the morphology of the as-obtained powders were found. Based on analysis (SEM, PSD), structures were identified known as soft and hard agglomerates., Conclusions: It can be stated that differences found between powder morphology were dependent on the value pH used, which can be crucial for powder densification during sintering and compacting green bodies which, as a consequence, may be crucial for the lifetime of zirconia prostheses. Correlations between phase composition and pH are difficult to grasp, and require further, more sophisticated, studies.

Purpose: The main objective of this study was to obtain single-phase β-ZrO2 powders with so-called soft agglomerates reproducibile morphology with acetyl-acetone as a chelating-agent. To the best of our knowledge there is no avaiable data which determine the effect of acetyl acetone on the phase composition and morphology of ceria-doped ZrO2 powders for biomedical applications., Methods: Twenty variants of powders with different water to zirconia precursor and acetylacetone to zirconia precursor molar ratios were prepared. 0.9ZrO20.1CeO2 powders were obtained by a hydrolysis and condensation and further calcination of zirconium n-propoxide in a simple one-step sol-gel process. Influence of acetyloacetone to zirconia precursor on the phase composition ratio and water to zirconia precursor was investigated. Samples have been characterized by X-ray diffraction (XRD), Raman spectroscopy (RS), thermal analysis (TGA/DTA) and scanning electron microscopy (SEM) measurements., Results: Ceramic powders prepared by sol-gel process, according to the various concentration of chelating agent and water show different morphology and phase composition., Conclusions: Higher molar ratios of AcAc in range with smaller amounts of water cause hard agglomerates, obtained powders are characterized by highly thermally stable behaviour and various phase composition. With higher molar ratios of water to zirconium-n-propoxide so-called soft agglomerates and one phase powders are obtained.