Results of a joint trial on the method of the differential thermal analysis in the temperature range from 25 to 1000°C

For settling the question to what degree standardization of differential thermal analysis (DTA) is feasible by a joint trial of different laboratories, DTA-measurements on temperature-standard-substances have been carried out. The results are comparable with those obtained on identical substances by the International Confederation for Thermal Analysis and the National Bureau of Standards. A statistic evaluation of the DTA-procedures of the individual laboratories shows that the preponderant number of laboratories is achieving data which could be considered to belong to the same basic set. As 2 common standard deviation of the procedure of differential thermal analysis in the temperature interval of 25 to 1000°C a value of 3.6 K has been ascertained.     

Thermal characterisation of Australian oil shales

There has been a significant research effort on the development of an oil industry based on Australian oil shales. However, to date the research has been based mainly on the processing aspects of oil shale. The thermal analyses of oil shales, while having been the subject of many studies, have been limited to some extent by instrumentation and analytical techniques. This paper reports on thermal analysis studies utilising traditional thermogravimetry/differential thermal analysis (TG/DTA) and differential scanning calorimetry (DSC). The application of modern thermal analysis techniques such as high resolution TG (HRTG) and modulated differential scanning calorimetry (MDSC) is also examined and compared to the traditional methods.     

Study of the 1,4-dihydroxyanthraquinone-yttrium(III) complex in solution and in the solid state

The photometric and fluorometric characteristics of the complex formed by 1,4-dihydroxyanthraquinone with Y(III) in 20–80% water-ethanol solution are described by the study of several variables. The stoichiometry and stability constant of the complex in the solution are 1:1 and log K = 4.57, respectively. The 1,4-dihydroxyanthraquinone-Y(III) solid complex has been prepared and studied by infrared spectroscopy and thermal analysis. The thermal behavior of this compound has been studied using thermogravimetry and differential scanning calorimetry techniques and the residue verified by X-ray diffraction.     

Thermodynamic properties and thermal stability of the synthetic zinc formate dihydrate

Zinc formate dihydrate has been synthesized and characterized by powder X-ray diffraction, elemental analysis, FTIR spectra and thermal analysis. The molar heat capacity of the coordination compound was measured by a temperature modulated differential scanning calorimetry (TMDSC) over the temperature range from 200 to 330 K for the first time. The thermodynamic parameters such as entropy and enthalpy vs. 298.15 K based on the above molar heat capacity were calculated. The thermal decomposition characteristics of this compound were investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). TG curve showed that the thermal decomposition occurred in two stages. The first step was the dehydration process of the coordination compound, and the second step corresponded to the decomposition of the anhydrous zinc formate. The apparent activation energy of the dehydration step of the compound was calculated by the Kissinger method using experimental data of TG analysis. There are three sharply endothermic peaks in the temperature range from 300 to 650 K in DSC curve.     

Synthesis, crystal structure and thermal decomposition of a new copper propionate [Cu(CH3CH2COO)2]·2H2O

A new copper propionate complex was synthesised and characterized for application as precursor for CuO based oxide thin films deposition. The FT-IR and X-ray diffraction analyses have revealed the formation of a cooper propionate complex [Cu(CH₃CH₂COO)₂]·2H₂O. The crystal and molecular structure of a new copper propionate complex was determined by XRD on the copper propionate single crystal. The copper propionate complex has a binuclear structure, connected by bridging bidentate carboxylates groups and a Cu?Cu bond of 2.6 Å. The thermal decomposition of copper propionate has been investigated by thermal analysis using thermogravimetric (TG) and differential thermal analysis (DTA), differential thermal analysis coupled with quadrupole mass spectrometry-QMS, X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR) techniques. TG and XRD data indicate the reduction of Cu(II)-Cu(I,0) during the decomposition of copper propionate.     

Is there any convergence between the differential and integral procedures used in chemical kinetics,particularly in nonisothermal kinetics?

Some contradictions concerning the classification of the methods to evaluate nonisothermal kinetic parameters into differential and integral ones are analyzed. Using the theorem of media for integrals, the equivalence between the methods that use the integration on low ranges of variables and the differential methods is shown. Concerning the magnitude of the range of change of variables on which the integration of the rate equation is performed, the applicability of the isoconversional methods that use approximate expressions of the temperature integral (Simpson's formula, formula based on the theorem of media for integrals) was analyzed. Our results were verified for simulated data (which are not affected by the experimental errors) as well as for the nonisothermal data for the thermal decomposition of ammonium perchlorate. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 339–344, 2006     

Thermal behaviour and kinetic study of some triazoles as potential anti-inflammatory agents

Thermogravimetric (TG), differential thermogravimetric analysis and differential scanning calorimetry had been used to characterize the thermal stability of four new heterocyclic compounds with triazolic structure. The four analysed compounds have similar thermal behaviours, namely the thermal mal curves of these new compounds show three thermal events. These compounds were thermally stable up to 110 °C. Above this temperature, the evolution of hydrochloric acid took place as observed by EGA. Identification and the monitoring of gaseous species released during thermal decomposition of pure triazoles in air atmosphere have been carried out by coupled TG–FTIR. Between 110 and 220 °C the main gaseous product is HCl which was identified on the basis of these FTIR spectra. Arguments for a rapid thermooxidation of the four molecules were brought by EGA by identifying the substances which arise from both the destruction of side chains and of triazolic ring. The kinetic analysis of the destruction process of triazolic structure was investigated using the TG data in air for the substance’s decomposition in non-isothermal conditions. The isoconversional methods, Kissinger–Akahira–Sunose, Flynn–Wall–Ozawa and Friedman, were applied to determine the activation energy from the analysis of four curves measured at different heating rates. In order to obtain realistic kinetic parameters, even if the decomposition process is a complex one, the non-parametric kinetics method was also used. A good agreement between the data obtained from the four applied methods was found.     

Polycycloalkylene-siloxane polymers: Synthesis and thermal study

Based on dicyclopentadiene and silacyclopentene, two linear polycycloalkylene-siloxane polymer systems have been synthesized and the thermal stability of the raw polymers evaluated by differential scanning calorimetry and thermal gravimetric analysis. The DSC data in nitrogen indicate that both polymer systems have excellent thermal stability. In air, these polymers begin to oxidize at approximately 150°C, with catastrophic oxidation occurring at about 400°C.     

Experimental investigations and thermodynamic description of the PbO−Bi2O3 system

In the present work, the experimental characterization of the pseudo-binary PbO–Bi₂O₃ cut has been performed by differential thermal analysis (DTA), isothermal annealing, powder X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), and electron probe microanalysis (EPMA). A thermodynamic assessment according to the Calphad method was also performed based on the present results as well as previous experimental data using the ThermoCalc software.     

Evaluation of the degree of hydration of synthetic alites by quantitative differential thermal analysis

The degree of hydration of synthetic alites has been determined by quantitative differential thermal analysis, using strong signals related to the polymorphic transformations of alites. The conditions suitable for noting the various reference signals, obtained with maximum apparatus sensibility, have been described and the data derived from differential thermal test with those obtained by analysis of the liquid phase in contact with the hydrating solid are correlated.     

Comparative thermal analysis study of two biopolymers, starch and cellulose

The degradation of cellulose and starch samples in air and nitrogen has been investigated by thermal analysis techniques. The techniques employed were differential thermal analysis, rising temperature and temperature jump thermogravimetry. Rate data were obtained from these experiments and Arrhenius parameters calculated from these values. This data was used to determine the mechanism by which the cellulose and starch samples degraded. The Arrhenius parameters were also calculated. The behavior of starch and cellulose upon thermal analysis were compared and are reported.E _act for corn starch was found to be 474 kJ mol^–1 and for a cellulose 242 kJ mol^–1.Dedicated to Prof. Menachem Steinberg on the occasion of his 65th birthday     

Preparation and degradation of copolymers of methyl methacrylate with alkali metal methacrylates—II: Thermal analysis of the copolymers,nature of the degradation products and general characteristics of the degradation reaction

Three series of copolymers, each spanning the composition range from alkali metal methacrylate homopolymer to methyl methacrylate homopolymer, have been prepared; their degradations have been studied under programmed heating conditions, by means of simultaneous thermogravimetry and thermal volatilization analysis (TVA) in a vacuum system and by differential thermal analysis in dynamic nitrogen. Total volatile products have been characterised by infrared spectroscopy, subambient TVA and GLC. The thermal analysis data suggest that the two types of monomer unit tend to participate in degradation processes in different temperature ranges. However, in addition to those products characteristic of the degradation of each homopolymer, the copolymers give substantial amounts of methanol; this product must arise from a reaction specific to the copolymer structure.     

The application of artificial neural networks for the selection of key thermoanalytical parameters in medicinal plants analysis

In the present study three thermoanalytical methods: differential thermal analysis (DTA), thermogravimetric analysis (TGA), and derivative thermogravimetric analysis (DTG) were used to investigate the thermal behavior of medicinal plant raw materials. In order to describe DTA curve, designation of the onset T(i), and peak T(p), temperatures was required. In TGA the mass losses Delta(m), and in DTG the temperature range of peak DeltaT, peak temperature T(p), and peak height h, were recorded. All parameters were read for three stages of the thermal decomposition of plant samples which resulted in obtaining eighteen thermal variables for each sample. Some similarities in the course of thermal decomposition of the same plant organs were recognized, but complexity of the obtained data made it very difficult to determine if they could differentiate between medicinal plant materials and which of them encode the most valuable information about the studied herbals. In order to confirm the existence of any relations between the chemical composition of medicinal plants and their thermal decomposition and to find out which thermoanalytical variables or decomposition stages can be considered as the most significant in terms of their evaluation, it was decided to apply fully connected feed-forward artificial neural networks (ANN). Two different training algorithms were used to address the problem: back-propagation of error and conjugate gradient descent. To verify the results two-dimensional (2-D) Kohonen self-organizing feature maps (SOFMs) were employed. Two alternative datasets of thirteen key variables discriminating plant samples have been proposed.     

Differential thermal analysis of porous silicon

Porous silicon materials, macro- and mesoporous silicon, obtained by electrochemical anodic etching of n- and p-Si were studied by differential thermal analysis at a steady temperature rise and under isothermal conditions in nitrogen atmosphere and in air. The method was used to estimate the presence and amount of phases of surface volatile compounds. The possibility was studied to perform a comparative estimate of the specific surface area of different types of porous silicon from data on the surface oxidation kinetics determined by the dynamic differential thermal analysis in air.     

Thermal and sorption behavior of polyacrylonitrile supported hydrous titanium dioxide

Summary Modification of the physico-chemical properties of hydrous titanium dioxide (TiO₂) was conducted by using binding polyacrylonitrile (PAN) for the preparation of larger size particles having higher granular strength. The thermal behavior of the obtained composite has been studied by thermogravimetric and differential thermal analysis (TG/DTA). Sorption behavior of the TiO₂-PAN composite for removal of some hazardous radionuclides has been studied at different conditions such as, pH, contact time, ion concentrations and reaction temperature as well as the drying temperature. The effects of interfering ions as well as some complexing agents on the distribution ratio of the sorption process have been determined. As a result of the obtained data the optimum conditions for the removal of the studied radionuclides were recommended.     

Selected thermoanalytical methods and their applications from medicine to construction

There are many thermoanalytical techniques but only several of them such as thermogravimetric analysis (TG), high resolution thermogravimetric analysis (Hi-Res™ TG), derivative thermogravimetry (DTG), differential thermal analysis (DTA), calorimetry, differential scanning calorimetry (DSC), modulated differential scanning calorimetry (MDSC), evolved gas analysis (EGA), transient thermal analysis (TTA) and thermal conductivity (k) have selected to be discussed in this paper. Simultaneous thermal analysis (STA) is ideal for investigating issues such as the glass transition of modified glasses, binder burnout, dehydration of ceramic materials or decomposition behaviour of inorganic building materials, also with gas analysis. Selected applications of various thermoanalytical techniques from medicine to construction have also been discussed in this paper.     

Chemistry and thermal decomposition of trinitropyrazoles

New energetic compounds-3,4,5-1H-trinitropyrazole (TNP), 1-methyl-3,4,5-1H-trinitropyrazole (MTNP) and ammonium 3,4,5-1H-TNP have been synthesized and characterized by thermal analysis. These new compounds can be considered as promising since the high heat of formation for them. To estimate the process of their thermal decomposition, the original technique for computer simulation was used. We generated the models for the mechanisms of thermal decay of synthesized compounds which allowed obtaining comprehensive spectrum of transformations of intermediates on the way to the final products of thermolysis. The preferred pathways were determined based on the results of activation energy (E _a) calculations (DFT 6-311⁺⁺G** method) of thermal decay reactions for each generated pathways. The thermal decomposition has been studied also experimentally by thermogravimetry (TG) and differential scanning calorimetry. Kinetic parameters of thermolysis were evaluated by model-free and -fitting methods using TG data. Model-free method has given not reliable data for TNP and MTNP compounds, whereas model-fitting yields kinetic equations with the good correlation with experimental TG data.     

Imaging mass spectrometry data reduction: Automated feature identification and extraction

Imaging MS now enables the parallel analysis of hundreds of biomolecules, spanning multiple molecular classes, which allows tissues to be described by their molecular content and distribution. When combined with advanced data analysis routines, tissues can be analyzed and classified based solely on their molecular content. Such molecular histology techniques have been used to distinguish regions with differential molecular signatures that could not be distinguished using established histologic tools. However, its potential to provide an independent, complementary analysis of clinical tissues has been limited by the very large file sizes and large number of discrete variables associated with imaging MS experiments. Here we demonstrate data reduction tools, based on automated feature identification and extraction, for peptide, protein, and lipid imaging MS, using multiple imaging MS technologies, that reduce data loads and the number of variables by >100×, and that highlight highly-localized features that can be missed using standard data analysis strategies. It is then demonstrated how these capabilities enable multivariate analysis on large imaging MS datasets spanning multiple tissues.     

Structure and features of thermal oxidation of carbon nanostructured materials

The process of the thermal oxidation in air of various carbon materials used as a catalyst support and a component of fuel cell catalytic layers was studied by differential thermal analysis. The structural characteristics of carbon materials of various classes were compared using data of the adsorption-structure and differential thermal analyses.     

Thermal stability of cellulose acetate urethanes

The thermal degradation of isocyanate modified cellulose acetate has been studied by dynamic thermogravimetric analysis in air. The activation energy of decomposition of these modified polymers has also been determined from differential thermal analysis thermograms. The data indicate that the cellulose acetate urethane polymers are thermally stable.