Heating rate effect on the thermal behavior of ammonium nitrate and its blends with limestone and dolomite

The effect of heating rate on the thermal behavior of ammonium nitrate (AN) and on the kinetic parameters of decomposition of AN and its blends with limestone and dolomite was studied on the basis of commercial fertilizer-grade AN and several Estonian limestone and dolomite samples. Experiments were carried out under dynamic heating conditions up to 900 °C at heating rates of 2, 5, 10 and 20 °C min⁻¹ in a stream of dry air using Setaram Labsys 2000 equipment. For calculation of kinetic parameters, the TG data were processed by differential isoconversional method of Friedman. The variation of the value of activation energy E along the reaction progress α showed a complex character of decomposition of AN—interaction of AN with limestone and dolomite additives with the formation of nitrates as well as decomposition of these nitrates at higher temperatures.     

Thermal study on electrospun polyvinylpyrrolidone/ammonium metatungstate nanofibers: optimising the annealing conditions for obtaining WO<Subscript>3</Subscript> nanofibers

This article demonstrates how important it is to find the optimal heating conditions when electrospun organic/inorganic composite fibers are annealed to get ceramic nanofibers in appropriate quality (crystal structure, composition, and morphology) and to avoid their disintegration. Polyvinylpyrrolidone [PVP, (C₆H₉NO) _n ] and ammonium metatungstate [AMT, (NH₄)₆[H₂W₁₂O₄₀]·nH₂O] nanofibers were prepared by electrospinning aqueous solutions of PVP and AMT. The as-spun fibers and their annealing were characterized by TG/DTA-MS, XRD, SEM, Raman, and FTIR measurements. The 400–600 nm thick and tens of micrometer long PVP/AMT fibers decomposed thermally in air in four steps, and pure monoclinic WO₃ nanofibers formed between 500 and 600 °C. When a too high heating rate and heating temperature (10 °C min⁻¹, 600 °C) were used, the WO₃ nanofibers completely disintegrated. At lower heating rate but too high temperature (1 °C min⁻¹, 600 °C), the fibers broke into rods. If the heating rate was adequate, but the annealing temperature was too low (1 °C min⁻¹, 500 °C), the nanofiber morphology was excellent, but the sample was less crystalline. When the optimal heating rate and temperature (1 °C min⁻¹, 550 °C) were applied, WO₃ nanofibers with excellent morphology (250 nm thick and tens of micrometer long nanofibers, which consisted of 20–80 nm particles) and crystallinity (monoclinic WO₃) were obtained. The FTIR and Raman measurements confirmed that with these heating parameters the organic matter was effectively removed from the nanofibers and monoclinic WO₃ was present in a highly crystalline and ordered form.     

Kinetic study of wood chips decomposition by TGA

Pyrolysis of a wood chips mixture and main wood compounds such as hemicellulose, cellulose and lignin was investigated by thermogravimetry. The investigation was carried out in inert nitrogen atmosphere with temperatures ranging from 20°C to 900°C for four heating rates: 2 K min⁻¹, 5 K min⁻¹, 10 K min⁻¹, and 15 K min⁻¹. Hemicellulose, cellulose, and lignin were used as the main compounds of biomass. TGA and DTG temperature dependencies were evaluated. Decomposition processes proceed in three main stages: water evaporation, and active and passive pyrolysis. The decomposition of hemicellulose and cellulose takes place in the temperature range of 200–380°C and 250–380°C, while lignin decomposition seems to be ranging from 180°C up to 900°C. The isoconversional method was used to determine kinetic parameters such as activation energy and pre-exponential factor mainly in the stage of active pyrolysis and partially in the passive stage. It was found that, at the end of the decomposition process, the value of activation energy decreases. Reaction order does not have a significant influence on the process because of the high value of the pre-exponential factor. Obtained kinetic parameters were used to calculate simulated decompositions at different heating rates. Experimental data compared with the simulation ones were in good accordance at all heating rates. From the pyrolysis of hemicellulose, cellulose, and lignin it is clear that the decomposition process of wood is dependent on the composition and concentration of the main compounds.     

Non-isothermal kinetic of oxidation of tungsten carbide

Tungsten carbide, WC, has shown dissimilar thermal behavior when it is heated on changeable heating rate and flow of oxidant atmosphere. The oxidation of WC to WO₃ tends to be in a single and slow kinetic step on slow heating rate and/or low flux of air. Kinetic parameters, on non-isothermal condition, could be evaluated to the oxidation of WC to heating rate below 15°C min⁻¹ or low flow of air (10 mL min⁻¹). The reaction is governed by nucleation and growth at 5 to 10°C min⁻¹ then the tendency is to be autocatalytic, JMA and SB, respectively.     

The Thermal Expansion of Wood Cellulose Crystals

We have investigated tension wood cellulose obtained from Populus maximowiczii using X-ray diffraction at temperatures from room temperature to 250 °C. Three equatorial and one meridional d-spacings showed a gradual linear increase with increasing temperature. For temperatures above 180 °C, however, the equatorial d-spacing increased dramatically. Thus, the linear and volume thermal expansion coefficients (TECs) below 180 °C were determined from the d-spacings. The linear TECs of the a-, b-, and c-axes were: α _a = 13.6 × 10⁻⁵ °C⁻¹, α _b = −3.0× 10⁻⁵ °C⁻¹, and α _c =0.6× 10⁻⁵ °C⁻¹, respectively, and the volume TEC was β = 11.1× 10⁻⁵ °C⁻¹. The anisotropic thermal expansion in the three coordinate directions was closely related to the crystal structure of the wood cellulose, and it governed the macroscopic thermal behavior of solid wood.     

Thermal decomposition of methylxanthines

The thermal decomposition of theophylline, theobromine, caffeine, diprophylline and aminophylline were evaluated by calorimetrical, thermoanalytical and computational methods. Calorimetrical studies have been performed with aid of a heat flux Mettler Toledo DSC system. 10 mg samples were encapsulated in a 40 μL flat-bottomed aluminium pans. Measurements in the temperature range form 20 to 400°C were carried out at a heating rate of 10 and 20°C min⁻¹ under an air stream. It has been established that the values of melting points, heat of transitions and enthalpy for methylxanthines under study varied with the increasing of heating rate. Thermoanalytical studies have been followed by using of a derivatograph. 50, 100 and 200 mg samples of the studied compounds were heated in a static air atmosphere at a heating rate of 3, 5, 10 and 15°C min⁻¹ up to the final temperature of 800°C. By DTA, TG and DTG methods the influence of heating rate and sample size on thermal destruction of the studied methylxanthines has been determined. For chemometric evaluation of thermoanalytical results the principal component analysis (PCA) was applied. This method revealed that first of all the heating rate influences on the results of thermal decomposition. The most advantageous results can be obtained taking into account sample masses and heating rates located in the central part of the two-dimensional PCA graph. As a result, similar data could be obtained for 100 mg samples heated at 10°C·min⁻¹ and for 200 mg samples heated at 5°C min⁻¹.     

Investigation of thermal behavior of nicotinic acid

The thermal behavior of nicotinic acid under inert conditions was investigated by TG, FTIR and TG/DSC-FTIR. The results of TG/DSC-FTIR and FTIR indicated that the thermal behavior of nicotinic acid can be divided into four stages: a solid-solid phase transition (176–198°C), the process of sublimation (198–232°C), melting (232–263°C) and evaporation (263–325°C) when experiment was performed at the heating rate of 20 K min⁻¹. The thermal analysis kinetic calculation of the second stage (sublimation) and the fourth stage (evaporation) were carried out respectively. Heating rates of 1, 1.5, 2 and 3 K min⁻¹ were used to determine the sublimation kinetics. The apparent activation energy, pre-exponential factor and the most probable model function were obtained by using the master plots method. The results indicated that sublimation process can be described by one-dimensional phase boundary reaction, g(α)=α. And the ‘kinetic triplet’ of evaporation process was also given at higher heating rates of 15, 20, 25, 30 and 35 K min⁻¹. Evaporation process can be described by model of nucleation and nucleus growing, .     

Kinetic parameters for thermal decomposition of supramolecular polymers derived from flunixin-meglumine adducts

Meglumine, (2R,3R,4R,5S)-6-methylaminohexane-1,2,3,4,5-pentol, is a carbohydrate derived from sorbitol in which the hydroxyl group in position one is replaced by a methylamine group. It forms binary adducts with substances having carboxyl groups, which have in common the presence of hydrogen bonding as the main force in the stabilization of these species. During melting, adducts of meglumine with flunixin (2-[[2-methyl-3-(trifluoromethyl)phenyl]amino]pyridine-3-carboxylic acid) polymerize or self-assemble in amorphous supramolecular structures with molecular weights around 2.0 × 10⁵ kDa. DSC curves, in a first heating, show isomorphic transitions where the last one at 137 °C for the flunixin-meglumine adduct originated the supramolecular amorphous polymers with glass transition around 49.5 °C. The kinetic parameters for the thermal decomposition step of the polymers were determined by the Capela-Ribeiro non-linear isoconversional method. From data for the TG curves in nitrogen atmosphere and heating rates of 5, 10, 15, and 20 °C min⁻¹, the E _α and B _α terms could be determined and, consequently, the pre-exponential factor, A_α, as well as the kinetic model, g(α).     

Analysis of Spectinomycin by HPLC with Evaporative Light-Scattering Detection

A high-performance liquid chromatographic method with evaporative light-scattering detection (ELSD) has been developed for analysis of spectinomycin and related impurities. Separation of spectinomycin from structurally related impurities was achieved on a C₁₈ column. The optimized mobile phase was 25 mmol L⁻¹ ammonium acetate (pH 7.5)-methanol, 90:10 (v/v), at a flow rate of 0.6 mL min⁻¹. The temperature of the drift tube of the ELSD was 95°C and the flow rate of carrier gas was 2.2 L min⁻¹. The accuracy, specificity, precision, linearity, sensitivity, and robustness of the method were validated in accordance with ICH guidelines. In addition to determination of spectinomycin and related impurities, the method is also ideal for determination of the salts spectinomycin hydrochloride and spectinomycin sulfate.     

The use of sulfated tin oxide as solid superacid catalyst for heterogeneous transesterification of <Emphasis Type="Italic">Jatropha curcas</Emphasis> oil

This work presents the use of sulfated tin oxide enhanced with SiO₂ (SO₄²⁻/SnO₂-SiO₂) as a superacid solid catalyst to produce methyl esters from Jatropha curcas oil. The study was conducted using the design of experiment (DoE), specifically a response surface methodology based on a threevariable central composite design (CCD) with α = 2. The reaction parameters in the parametric study were: reaction temperature (60°C to 180°C), reaction period (1 h to 3 h), and methanol to oil mole ratio (1: 6 to 1: 24). Production of the esters was conducted using an autoclave nitrogen pressurized reactor equipped with a thermocouple and a magnetic stirrer. The maximum methyl esters yield of 97 mass % was obtained at the reaction conditions: temperature of 180°C, reaction period of 2 h, and methanol to oil mole ratio of 1: 15. The catalyst amount and agitation speed were fixed to 3 mass % and 350–360 min⁻¹, respectively. Properties of the methyl esters obtained fell within the recommended biodiesel standards such as ASTM D6751 (ASTM, 2003).     

Thermal behaviour of cephalexin in different mixtures

The thermoanalytical curves (TA), i.e. TG, DTG and DTA for pure cephalexin and its mixtures with talc, magnesium stearate, starch and microcrystalline cellulose, respectively, were drawn up in air and nitrogen at a heating rate of 10 °C min⁻¹. The thermal degradation was discussed on the basis of EGA data obtained for a heating rate of 20 °C min⁻¹. Until 250 °C, the TA curves are similar for all mixtures, up this some peculiarities depending on the additive appears. These certify that between the pure cephalosporin and the excipients do not exists any interaction until 250 °C. A kinetic analysis was performed using the TG/DTG data in air for the first step of cephalexin decomposition at four heating rates: 5, 7, 10 and 12 °C min⁻¹. The data processing strategy was based on a differential method (Friedman), an integral method (Flynn–Wall–Ozawa) and a nonparametric kinetic method (NPK). This last one allowed an intrinsic separation of the temperature, respective conversion dependence on the reaction rate and less speculative discussions on the kinetic model. All there methods had furnished very near values of the activation energy, this being an argument for a single thermooxidative degradation at the beginning (192–200 °C).     

Sintering of a nano-crystalline metastable alumina

The influence of the heating rate on phase transformation and microstructural evolution during sintering of a de-agglomerated nanocrystalline, transition alumina was investigated. A low heating rate treatment allowed to decrease the α-Al₂O₃ crystallization temperature as well as to displace densification at lower temperatures, also implying a refinement of the fired microstructures. In addition, the set-up of sintering cycles in which the heating rate changed in the range 0.5–20°C min⁻¹ starting from intermediate, selected temperatures resulted in a further retention of a very fine and homogeneous grain size in final materials.     

Kinetic study of pyrolysis of waste water treatment plant sludge

Activated sewage sludge samples obtained from two different waste water treatment plants were investigated by thermogravimetric analysis. Due to a very high content of water in the sludge samples, these had to be dried at 160°C in an electrical oven in order to remove all adsorbed water. To ensure pyrolysis conditions, nitrogen atmosphere was applied. The pyrolysis decomposition process was carried out in the temperature range from ambient temperature to 900°C at three different heating rates: 2 K min⁻¹, 5 K min⁻¹, 10 K min⁻¹. TGA and DTG curves of the decomposition processes were obtained. Temperature of onset decomposition, final temperature of decomposition, maximum decomposition rate, and decomposition temperature were determined by thermogravimetric analysis for both sludge samples used. The main decomposition process takes place at temperatures in the range from 230°C to 500°C. Above this temperature, there are only small changes in the mass loss which are often attributed to the decomposition of carbonates present in the sewage sludge samples. To determine the apparent kinetic parameters such as the activation energy and the preexponential factor, the so called Friedman isoconversional method was used. Because of the requirements of this method, initial and final parts of the decomposition process, where crossings of the decomposition lines occurred, were cut off. Obtained dependencies of the apparent activation energies and preexponential factors as a function of conversion were used backwards to calculate the modeled decomposition process of sewage sludge and the experimental data were in good accordance with the data obtained by simulation.     

The simulation of the thermal behavior of energetic materials based on DSC and HFC signals

Two small calibre and four medium calibre types of propellants were investigated non-isothermally (0.25–4K min⁻¹) by differential scanning calorimetry (DSC) in the range of RT-260°C and isothermally (60–100°C) by heat flow calorimetry (HFC). The data obtained from both techniques were used for the calculation and comparison of the kinetic parameters of the decomposition process. The application of HFC allowed to determine the kinetic parameters of the very early stage of the reaction (reaction progress α below 0.02) what, in turn, made possible the precise prediction of the reaction progress under temperature mode corresponding to real atmospheric changes according to STANAG 2895. In addition, the kinetic parameters obtained from DSC data enabled determination of self-accelerating decomposition temperature (SADT) and comparison of the predicted ignition temperature during slow cook-off with the experimental results. The study contains also the results of the calculation of the time to maximum rate (TMR_ad) of the propellants under adiabatic conditions.     

Kinetics of the exothermic decomposition of 1-nitro-3-(β,β,β-trinitroethyl)-4,5-dinitroiminoimidazolidine-2-one

The kinetic parameters of the exothermic decomposition of the title compound in a temperatureprogrammed mode have been studied by means of DSC. The DSC data obtained are fitted to the integral, differential, and exothermic rate equations by the linear least-squares, iterative, combined dichotomous, and least-squares methods, respectively. After establishing the most probable general expression of differential and integral mechanism functions by the logical choice method, the corresponding values of the apparent activation energy (E _a), preexponential factor (A), and reaction order (n) are obtained by the exothermic rate equation. The results show that the empirical kinetic model function in differential form and the values of E _a and A of this reaction are (1 − α)^−4.08, 149.95 kJ mol⁻¹, and 10^14.06 s⁻¹, respectively. With the help of the heating rate and kinetic parameters obtained, the kinetic equation of the exothermic decomposition of the title compound is proposed. The critical temperature of thermal explosion of the compound is 155.71°C. The above-mentioned kinetic parameters are quite useful for analyzing and evaluating the stability and thermal explosion rule of the title compound. The text was submitted by the authors in English.     

Synthesis,molecular structure,non-isothermal decomposition kinetics and adiabatic time to explosion of 3,3-dinitroazetidinium 3,5-dinitrosalicylate

The title compound 3,3-dinitroazetidinium (DNAZ) 3,5-dinitrosalicylate (3,5-DNSA) was prepared and the crystal structure has been determined by a four-circle X-ray diffractometer. The thermal behavior of the title compound was studied under a non-isothermal condition by DSC and TG/DTG techniques. The kinetic parameters were obtained from analysis of the TG curves by Kissinger method, Ozawa method, the differential method and the integral method. The kinetic model function in differential form and the value of E _a and A of the decomposition reaction of the title compound are f(α)=4α^3/4, 130.83 kJ mol⁻¹ and 10_13.80s⁻¹, respectively. The critical temperature of thermal explosion of the title compound is 147.55 °C. The values of ΔS ^≠, ΔH ^≠ and ΔG ^≠ of this reaction are −1.35 J mol⁻¹ K₋₁, 122.42 and 122.97 kJ mol⁻¹, respectively. The specific heat capacity of the title compound was determined with a continuous C _p mode of mircocalorimeter. Using the relationship between C _p and T and the thermal decomposition parameters, the time of the thermal decomposition from initiation to thermal explosion (adiabatic time-to-explosion) was obtained.     

Kinetic Aspect of Thermal Decomposition of Natural Phosphate and its Kerogen. Influence of heating rate and mineral matter

The natural phosphate and its demineralization products from Moroccan deposit were pyrolysed in a thermogravimetric analyser (TG) to examine the influence of the heating rate and mineral matter on their thermal decomposition. The heating rates investigated in the TG were 5–100°C min⁻¹ to final temperature of 1200°C. The integral method was used in the analysis of the TG to determine the kinetic parameters. It has been found that for the natural phosphate and corresponding kerogen analysed in the TG, the increase of the heating rate shifts the maximum rate loss to higher temperature. A first order reaction was found to be adequate for pyrolysis in the range 150–600°C which was attributed to kerogen decomposition. In addition, the results indicate that the removal of mineral matter affected the kinetic parameters found for kerogen in the natural phosphate. This revised version was published online in August 2006 with corrections to the Cover Date.     

Non-isothermal kinetic analysis and feasibilty study of medium grade crude oil field

In this research, non-isothermal kinetics and feasibility study of medium grade crude oil is studied in the presence of a limestone matrix. Experiments were performed at a heating rate of 10°C min⁻¹, whereas the air flow rate was kept constant at 50 mL min⁻¹ in the temperature range of 20 to 600°C (DSC) and 20 to 900°C (TG). In combustion with air, three distinct reaction regions were identified in all crude oil/limestone mixtures, known as low temperature oxidation (LTO), fuel deposition (FD) and high temperature oxidation (HTO). The activation energy values were in the order of 5–9 kJ mol⁻¹ in LTO region and 189–229 kJ mol⁻¹ in HTO region. It was concluded that the medium grade crude oil field was not feasible for a self-sustained combustion process.     

Evolved gas analysis at thermal treatment of some solid fossil fuels

Coupled TG-FTIR technique was used for identification of gaseous compounds evolved at thermal treatment of six coal samples from different deposits (Bulgaria, Russia, Ukraine). The experiments were carried out under dynamic heating conditions up to 900°C at heating rates of 5, 10 or 50 K min^–1 in a stream of dry air. The emission of CO₂, H₂O, CO, SO₂, COS, methane, methanol, formic acid, formaldehyde, acetaldehyde, chlorobenzene was clearly identified in FTIR spectra of the samples studied. The formation of ethanol, ethane, ethylene and p-xylene, at least on the level of traces, was also identified. At the heating rate of 5°C min^–1 the temperature of maximum intensities of the characteristic peaks of COS was 270°C, of formaldehyde, formic acid, ethane and methanol 330°C, of SO₂, CO, acetic acid, ethylene and p-xylene 400°C and of chlorobenzene 500°C. At 10°C min^–1 and 50°C min^–1 these temperatures were shifted, respectively, by 70–300°C and 150–450°C towards higher temperatures and the respective absorption bands in FTIR spectra were, as a rule, more intensive.     

Thermal behavior and thermal safety on 3,3-dinitroazetidinium salt of perchloric acid

3,3-Dinitroazetidinium (DNAZ) salt of perchloric acid (DNAZ·HClO₄) was prepared, it was characterized by the elemental analysis, IR, NMR, and a X-ray diffractometer. The thermal behavior and decomposition reaction kinetics of DNAZ·HClO₄ were investigated under a non-isothermal condition by DSC and TG/DTG techniques. The results show that the thermal decomposition process of DNAZ·HClO₄ has two mass loss stages. The kinetic model function in differential form, the value of apparent activation energy (E _a) and pre-exponential factor (A) of the exothermic decomposition reaction of DNAZ·HClO₄ are f(α) = (1 − α)⁻¹/2, 156.47 kJ mol⁻¹, and 10^15.12 s⁻¹, respectively. The critical temperature of thermal explosion is 188.5 °C. The values of ΔS ^≠, ΔH ^≠, and ΔG ^≠of this reaction are 42.26 J mol⁻¹ K⁻¹, 154.44 kJ mol⁻¹, and 135.42 kJ mol⁻¹, respectively. The specific heat capacity of DNAZ·HClO₄ was determined with a continuous C _p mode of microcalorimeter. Using the relationship between C _p and T and the thermal decomposition parameters, the time of the thermal decomposition from initiation to thermal explosion (adiabatic time-to-explosion) was evaluated as 14.2 s.