Thermal decomposition kinetics of potassium iodate

The rate and kinetics of the thermal decomposition of potassium iodate (KIO₃) has been studied as a function of particle size, in the range 63?C150???m, by isothermal thermogravimetry at different temperatures, 790, 795, 800 and 805?K in nitrogen atmosphere. The theoretical and experimental mass loss data are in good agreement for the thermal decomposition of all samples of KIO₃ at all temperatures studied. The isothermal decomposition of all samples of KIO₃ was subjected to both model-fitting and model-free (isoconversional) kinetic methods of analysis. It has been observed that the activation energy values are independent of the particle size. Isothermal model-fitting analysis shows that the thermal decomposition kinetics of all the samples of KIO₃ studied can be best described by the contracting cube equation.     

Thermal decomposition kinetics of potassium iodate

The thermal decomposition of potassium iodate (KIO₃) has been studied by both non-isothermal and isothermal thermogravimetry (TG). The non-isothermal simultaneous TG–differential thermal analysis (DTA) of the thermal decomposition of KIO₃ was carried out in nitrogen atmosphere at different heating rates. The isothermal decomposition of KIO₃ was studied using TG at different temperatures in the range 790–805 K in nitrogen atmosphere. The theoretical and experimental mass loss data are in good agreement for the thermal decomposition of KIO₃. The non-isothermal decomposition of KIO₃ was subjected to kinetic analyses by model-free approach, which is based on the isoconversional principle. The isothermal decomposition of KIO₃ was subjected to both conventional (model fitting) and model-free (isoconversional) methods. It has been observed that the activation energy values obtained from all these methods agree well. Isothermal model fitting analysis shows that the thermal decomposition kinetics of KIO₃ can be best described by the contracting cube equation.     

Kinetic studies on the thermal decomposition of phosphate-doped sodium oxalate

The thermal decomposition kinetics of sodium oxalate (Na₂C₂O₄) has been studied as a function of concentration of dopant, phosphate, at five different temperatures in the range 783–803 K under isothermal conditions by thermogravimetry (TG). The TG data were subjected to both model-fitting and model-free kinetic methods of analysis. The model-fitting analysis of the TG data of all the samples shows that no single kinetic model describes the whole α versus t curve with a single rate constant throughout the decomposition reaction. Separate kinetic analysis shows that Prout–Tompkins model best describes the acceleratory stage of the decomposition, while the decay region is best fitted with the contracting cylinder model. Activation energy values were evaluated by both model-fitting and model-free kinetic methods. The observed results favour a diffusion-controlled mechanism for the thermal decomposition of sodium oxalate.     

Kinetic analysis for non-isothermal decomposition of un-irradiated and gamma-irradiated potassium bromate

The thermal decomposition of un-irradiated and gamma-irradiated potassium bromate (KBrO₃) was performed under non-isothermal conditions at different heating rates (5, 10, 15 and 20 K min^?1). The data was analysed using isoconversional and non-isoconversional methods. The kinetic parameters of thermal decomposition process were obtained by three model-free isoconversional methods: Flynn–Wall–Ozawa, Kissinger–Akahira–Sunose and Friedman. Irradiation enhances the decomposition and the effect increases with the irradiation dose. The activation energy decreases on irradiation. Kinetic analysis of data in view of various solid-state reaction models showed that the decomposition of un-irradiated and irradiated anhydrous KBrO₃ is best described by the Avrami–Erofeev model equation, [?ln(l?α)]^1/2 = kt.     

Thermal decomposition of gamma-irradiated potassium bromate by dynamic thermogravimetry

The thermal decomposition of γ-irradiated KBrO₃studied by dynamic thermogravimetry. The reaction order, activation energy, frequency factor and entropy of activation were computed by means of the Coats-Redfern, Freeman-Carroll and modified Horowitz-Metzger methods and were compared with those for the unirradiated salt. Irradiation enhances the decomposition and the effect increases with the irradiation dose. The activation energy is decreased on irradiation. The mechanism for the decomposition of unirradiated and irradiated KBrO₃ follows the Avrami model equation, [1-(1-α)^1/3] = kt, and the rate-controlling process is a phase boundary reaction assuming spherical symmetry.     

Isothermal decomposition of K2C2O4

The effect of semiconducting metal oxide (CuO and TiO₂) additives on the kinetics of thermal decomposition of potassium oxalate (K₂C₂O₄) to potassium carbonate has been studied at five different temperatures in the range 793–813 K under isothermal conditions by thermogravimetry (TG). The decomposition is enhanced by CuO (p-type) and suppressed by TiO₂ (n-type). The diverse behaviour of K₂C₂O₄ in the presence of different types of oxides in contrast with the like behaviour of K₂C₂O₄ suggests the involvement of different rate determining steps in the decomposition of these solids. The TG data of 2 mass% oxide mixed samples of K₂C₂O₄ were subjected to both model fitting and model-free (isoconversional) kinetic methods of analysis. The model fitting method of analysis shows that the rate law for the decomposition of K₂C₂O₄ (Prout–Tompkins and contracting cylinder models, respectively, for the acceleratory and decay stages) remained unaffected by the additives.     

Effects of ball milling and thermal annealing on size and strain of ASnO3 (A = Ba,Sr) ceramics

An investigation of the impact of ball milling and consequent thermal annealing on particle size and crystallite strain of ASnO₃ (A = Ba, Sr) ceramics is presented. Whole Powder Pattern Modeling (WPPM) algorithms were used in the analysis of these nanoparticle stannates. Samples of BaSnO₃ and SrSnO₃ showed an increase in strain coupled with a decrease in particle size when milled for longer periods of time. Interestingly, thermal annealing at controlled temperatures led to a slight increase in particle size with a large decrease in strain. Samples of ASnO₃ with particle sizes ranging from 15 nm to 60 nm were reproducibly synthesized. These findings allow for the facile preparation of nanoparticles with predetermined particle size and strain for optimal performance in applications including dye-sensitized solar cells (DSSCs), thermoelectric devices, and fuel cells.     

Effect of Divalent ion Dopants on the Kinetics of Thermal Decomposition of Potassium Bromate

Isothermal decomposition of KBrO₃ has been studied as a function of concentration of the dopants, SO₄ ^2- and Ba²⁺ by isothermal thermogravimetry in the temperature range 668 - 683 K. The rate law and the activation energies remained unaltered by doping. The results suggest a diffusion-controlled mechanism, the diffusing species being both K⁺ and BrO₃ ^-.     

Studies on kinetics and mechanism of initial thermal decomposition of nitrocellulose

The thermal decomposition of nitrocellulose (NC) 12.1% N, has been studied with regard to kinetics, mechanism, morphology and the gaseous products thereof, using thermogravimetry (TG), differential thermal analysis (DTA), IR spectroscopy, differential scanning calorimetry (DSC) and hot stage microscopy. The kinetics of the initial stage of thermolysis ofNC in condensed state has been investigated by isothermal high temperature infrared spectroscopy (IR). The decomposition ofNC in KBr matrix in the temperature range of 142–151°C shows rapid decrease in O?NO₂ band intensity, suggesting that the decomposition of NC occurs by the rupture of O?NO₂ bond. The energy of activation for this process has been determined with the help of Avrami-Erofe'ev equation (n=1) and is ≈188.35 kJ·mol^?1. Further, the IR spectra of the decomposition products in the initial stage of thermal decomposition ofNC, indicates the presence of mainly NO₂ gas and aldehyde.     

Preparation and characterization of a new series of solid solutions of Bi1−xYxFeO3 (0 < x < 1) from the thermal decomposition of hexacyanoferrates doped with yttrium

Solid solutions of Bi_1?xY_x[Fe(CN)₆]·4H₂O (0?<?x?<?1) complexes were synthesized and characterized. The crystal structures were refined by Rietveld analysis using X-ray powder diffraction data. The complexes of the series crystallized in the orthorhombic system, space group Cmcm. The gradual decrease in cell volume indicates that the substitution of Bi³⁺ by Y³⁺ was appropriately materialized. The thermal behavior was studied by thermogravimetric and differential thermal analysis. A single phase of perovskite-type Bi_1?xY_xFeO₃ powders was obtained by thermal decomposition of the complexes at about 600 °C. The obtained products were identified and characterized by energy-dispersive spectroscopy, Raman and Fourier transform infrared spectroscopy and powder X-ray diffraction. The size and morphology of the complexes and their thermal decomposition products were evaluated by scanning electron microscopy. Thermal analysis showed that the complexes were good intermediaries for the synthesis of high-purity mixed oxides with a uniform particle size of the order of nanometers. To evaluate the effect of doping with yttrium, electrical transport measurements were performed.

     

Porosity development in chars from thermal decomposition of poly(p-phenylene terephthalamide)

The main objective of this work was to investigate the development of porosity in solid residues from the thermal decomposition of the polymer, poly(p-phenylene terephthalamide) (PPTA). PPTA chars were prepared at different temperatures and characterized by X-ray diffraction and physical adsorption of CO₂ at 0 °C. The carbonization temperatures were selected on the basis of thermogravimetric analysis results. The effect of introducing an isothermal treatment at 500 °C on the characteristics of the resulting chars was also studied. It was found that this pre-treatment lowers the decomposition temperature of PPTA and yields a somewhat less ordered material than in the case of pyrolysis under a constant heating rate. The micropore volume increases with increasing heat treatment temperature for both series of samples. The mean micropore size decreases for the two series of chars until the 700-800 °C interval; above these temperatures, this evolution is reversed. The micropore volume of the samples submitted to the isothermal treatment is higher than when PPTA is treated under a constant heating rate. Likewise, the pore size distribution is more heterogeneous when the intermediate isothermal treatment at 500 °C is introduced during PPTA pyrolysis. Some differences between porosity development in chars from PPTA and other high thermal stability polymers were explained on the basis of different mechanistic features in polymer pyrolysis.     

Study of size-dependent glass transition and Kauzmann temperatures of tin dioxide nanoparticles

The size and shape effects on melting, glass transition, and Kauzmann temperatures of SnO₂ nanoparticles using Lindemann??s criterion have been studied. The melting temperature of SnO₂ nanoparticles decreases as the size of the particle decreases. As the particle size increases, melting temperature increases and approaches to the melting temperature 1,903?K of bulk irrespective of the shape. The glass transition and Kauzmann temperatures are analyzed through the size effect on the melting temperature. The glass transition and Kauzmann temperatures decrease with the decrease in size of SnO₂ nanoparticles.     

Thermal behaviour of mechanically amorphized colemanite

The effect of mechanical treatment on the thermal decomposition of calcium borate, colemanite — Ca₂B₆O₈(OH)₆·2H₂O was studied by means of XRD, FTIR, SEM and thermal analysis methods. Grinding of colemanite causes the solid-state amorphization of this mineral, as a result of the destruction of its structure along the cleavage plane. The decrease in the particle size of the original material and the increase in its internal structural disorder affect the temperatures and the magnitudes of the thermal effects accompanying the processes of dehydration and dehydroxylation. The diminishing values of the enthalpies of these processes may be a quantitative measure of the degree of amorphization of colemanite.Dedicated to Dr. Robert Mackenzie on the occasion of his 75th birthdayThe author is grateful to Professor L. Stoch for helpful discussions.Support for this work was provided by the Polish Committee for Scientific Research (KBN) — Grant No. 3 P407 034 06.     

Time‐Resolved Phase Transitions of the Nanocrystalline Cubic to Submicron Monoclinic Phase in Mn2O3‐ZrO2

The nanocrystalline cubic phase of zirconia was found to be thermally stabilized by the addition of 3 to 40 mol % manganese. The nanocrystalline cubic, tetragonal and monoclinic phases of zirconia stabilized with manganese (III)oxide (Mn‐Stabilized Zirconia) were prepared by thermal decomposition of carbonate and hydroxide precursors. Both the crystallization and isothermal phase transitions associated with Mn‐SZ were studied using high temperature x‐ray diffraction and x‐ray diffraction of quenched samples. Cubic Mn‐SZ initially crystallized and progressively transformed to tetragonal, and monoclinic structures above 700°C. The nanocrystalline cubic Mn‐SZ containing 25 mol % Mn was found to have the greatest thermal stability, retaining its cubic form at temperatures as high as 800°C for periods up to 25 hours. Higher than 40 mol %, cubic Mn₂O₃ was found to coexist with cubic Mn‐SZ. The crystallite sizes observed for the cubic, tetragonal and monoclinic Mn‐SZ phases ranged from 50 to 137, 130 to 220, and 195 to 450 Å respectively, indicating, for ZrO₂, that particle size was a primary factor in determining its polymorphs. The classical Avrami equation for nucleation and growth was applied to the observed phase transformations.     

Effect of MnC2O4 nanoparticles on the thermal decomposition of TEGDN/NC propellant

The effect of MnC₂O₄ nanoparticles on the thermal decomposition of double-base propellant composed of nitrocellulose (NC) and triethylene glycol dinitrate (TEGDN) has been investigated by TG/DSC?CMS?CFTIR coupling technique. The results show that the decomposition of TEGDN/NC propellant has two stages, the first stage is the volatility and decomposition of TEGDN, the second is the decomposition of NC. The addition of MnC₂O₄ nanoparticles gets the onset temperature of first stage higher, and makes the activation energy of decomposition of TEGDN grow by about 20?C30?kJ/mol. The catalytic also accelerates the total weight loss, and makes the peak temperatures of DSC curves higher. The activation energy of the second stage has a decrease of 20?C40?kJ/mol. MS and FTIR analysis show that the catalyst gets the gas products of macromolecular significantly reduce, while small molecules increase significantly. It also results in the decrease of H₂O, N₂O, and NO₂, and the increase of NO and HCN. Above all, the catalytic improves the thermal stability of TEGDN/NC propellant, make it more safety in storage, and make the decomposition easier and more thorough in main reaction zone.     

Thermochemical and morphological aspects of the thermal decomposition of lead dioxide

The thermal decomposition of a range of PbO₂ samples prepared by different techniques has been studied using thermogravimetric analysis, differential thermal analysis. X-ray diffraction and scanning electron microscopy. The effects of preparation technique, material crystallinity, particle size and morphology, gas atmosphere and heating rate were studied.A range of decomposition sequences were found from which it was concluded that no definite decomposition sequences exist for either α-PbO₂ or β-PbO₂.Morphologically it was not found possible to study the nucleation and growth of the intermediate oxides formed.     

Influence of particle size and pyrolysis conditions on yield,density and some textural parameters of chars prepared from holm-oak wood

Chars were prepared from holm-oak wood (Quercus ilex) using sawdust, cubes (20 × 20 × 20 mm) and octagonal prisms (20 × 20 × 80 mm) by heating in nitrogen under dynamic (sawdust and cubes) and isothermal (sawdust and prisms) conditions to different final temperatures. The yield of char production depends on the wood particle size, heating rate and final temperature. The density of the chars as measured by helium displacement, ϱ_He (g/cm³), is influenced by the wood particle size and heating conditions. Chars prepared from holm-oak wood are essentially microporous solids. The apparent surface area and the micropore volume increase only slightly up to the treatment temperature of 500°C, increase greatly up to 800°C and decrease at higher temperatures.     

Particle size effects on the thermal behavior of hematite

Hematite with different particle sizes was obtained through isothermal annealing and mechanochemical ball-milling methods. The hematite phase is very stable under air atmosphere. The thermal stabilities of hematite under argon atmosphere were characterized by thermal analysis studies up to 800 °C using a simultaneous DSC–TG technique. The lattice parameters a and c of hematite with different particle sizes were extracted from the Rietveld structural refinement of powder X-ray diffraction patterns. Decomposition of hematite into a lower oxidation state in inert argon atmosphere was studied by the TG experiments for the first time and the enthalpy associated with the decomposition reaction was determined from the DSC studies. Particle size has a strong effect on the thermal behavior of hematite samples. Ball-milled hematite samples with smaller particle size showed that the phase transformation was extended to higher temperature range with larger enthalpy. Hematite with larger average particle size showed higher stability under argon atmosphere.     

Thermal decomposition of cerium(III) perchlorate

Thermal decomposition of Ce(ClO₄)₃ ? 9H₂O and Ce(ClO₄)₃ to give cerium(IV) dioxide in the temperature range 240–460°C was studied by DSC–TGA, X-ray powder diffraction, IR and mass spectroscopy. The thermolysis of these salts was shown to proceed through the stage of formation of intermediate product supposedly cerium oxoperchlorate. The thermal decomposition of cerium(III) perchlorate hydrate at 460°C leads to formation of nanocrystalline cerium dioxide with particle size of 13 nm.     

Thermal study of boehmite nanofibers with controlled particle size

Boehmite nanofiber materials with controlled particle size were synthesized without any surfactant by careful tuning of the hydrothermal temperatures, and followed by a series of characterizations. It was found that the boehmite nanofibers became shorter and coarser with the increase of temperature, and resulted in a gradual decrease of their specific surface areas. Moreover, the thermal stability of the boehmite nanofibers was studied by in situ HT X-ray diffraction and thermogravimetry–differential scanning calorimetry. All materials showed the phase transition from γ-Al₂O₃ to other forms. Yet the transition temperature was increased with the increase of hydrothermal temperature. The boehmite nanofibers with the largest diameter showed the best thermal stability.