Possibilities of two non-isothermal procedures (temperature- or rate-controlled) for kinetical studies

The applicability of both conventional Thermal Analysis (TA) and Controlled Rate Thermal Analysis (CRTA) for kinetic analysis is discussed. It is shown that TA method can give a reliable kinetic information and meaningful kinetic parameters especially for solid state transformation. On the other hand the CRTA method is more suitable for decomposition process where one or more gasses are evolved. A consistent and reliable method of kinetic analysis is proposed for both techniques. This method is illustrated to analyze the crystallization process of chalcogenide glass and the decomposition of dolomite.     

RCTA Techniques Used in Studies of Solid State Reactions in Inorganic Compounds

The Reaction Controlled Thermal Analysis techniques, RCTA, are very useful both in thermogravimetric and dilatometric studies. In the present paper this big family of techniques is divided into three main classes: Quasi-Isothermal techniques (QIA); Controlled Reaction Rate Thermal Analysis (CRTA) and Reaction (Event) Controlled Heating Rate Adaption. After a short presentation of these techniques and the general advantages of RCTA, two examples of kinetic studies on thermal decomposition of Ba- and Ce oxalates by using Stepwise Isothermal Analysis, SIA, introduced by the author is presented and discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal behavior and thermokinetic of double-base propellant catalyzed with magnesium oxide nanoparticles

Journal of Thermal Analysis and Calorimetry - Catalytic effect of magnesium oxide nanoparticles (nano-MgO) on the thermal behavior and decomposition reaction kinetic of the double-base propellant...     

由热重数据计算动力学参数

热重法(TG)是一种动态测量技术,可在程序升温或降温情况下对给定物质或体系提供一个连续的,以温度或时间为函数的重量变化曲线,所以由它跟踪反应能给出反应动力学的有关信息。这种非等温法与早期使用的等温法相比,有快速、连续和需要较少实验数据等优点,近年来在动力学研究方面得到广泛应用,但还只限于研究下列几种类型的简单     

Reaction mechanism and kinetic analysis of citrate gel-combustion synthesis of nanocrystalline urania

Journal of Thermal Analysis and Calorimetry - The reaction mechanism and the determination of kinetic parameters of the citrate gel combustion synthesis of nanocrystalline urania (U3O8) are being...     

Simultaneous use of isothermal,nonisothermal, and constant rate thermal analysis (CRTA) for discerning the kinetics of the thermal dissociation of smithsonite

The mechanism of the thermal decomposition of smithsonite has been determined from a comparison of the results obtained from isothermal, linear heating rate (TG), and Constant Rate Thermal Analysis (CRTA) experiments. Two important precautions have been taken in this work. Firstly, the chemical composition of the sample has been checked in order to be sure that pure anhydrous zinc carbonate has been used. Secondly, the experimental conditions have been selected in such a way to avoid the influence of heat and mass transfer phenomena on the forward reaction. It has been shown that the mechanism for the thermal decomposition of smithsonite depends upon temperature. Thus, at temperatures lower than 650 K, approximately, an A_0.5 kinetic model describes the reaction, whereas, at temperatures roughly higher than 690 K the above reaction obeys a F₁ kinetic law. An interpretation of this behavior is given. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 647–655, 1998     

Homogenization heat treatment and segregation analysis of equiaxed CMSX-4 superalloy for gas turbine components

Journal of Thermal Analysis and Calorimetry - Two new zinc(II) coordination compounds have been synthesized by the reaction of diazine-ring containing Schiff bases di(2-pyridyl) ketone...     

Thermal analysis applied to the characterization of degradation in soil of polylactide: I. Calorimetric and viscoelastic analyses

An accelerated soil burial test has been performed on a commercial polylactide (PLA) for simulating non-controlled disposal. Degradation in soil promotes physical and chemical changes in polylactide properties, which can be characterized by Thermal Analysis techniques. Physical changes occurred in polylactide due to the degradation in soil were evaluated by correlating their calorimetric and viscoelastic properties. It is highly remarkable that each calorimetric scan offers specific and enlightening information. Degradation in soil affects the polylactide chains reorganization. A multimodal melting behavior is observed for buried PLA, degradation in soil also promotes the enlarging the lamellar thickness distribution of the population with bigger average size. Morphological changes due to degradation in soil lead to an increase in the free volume of the polylactide chains in the amorphous phase that highly affected the bulk properties. Thermal Analysis techniques provide reliable indicators of the degradation stage of polylactide induced by degradation in soil, as corroborated by molecular weight analysis.     

Effect of mechanical grinding on the reaction pathway and kinetics of the thermal decomposition of hydromagnesite

Effect of mechanical grinding of hydromagnesite on the reaction pathway and kinetic behaviors of the thermal decomposition process was investigated by means of thermoanalytical techniques, together with crystallographic and morphological measurements. A crystalline hydromagnesite, the as-received sample, was decomposed in two distinguished mass loss steps of overlapped dehydration-dehydroxylation and dehydroxylation-decarbonation via an amorphous intermediate of carbonate compound. Thermal decomposition of an amorphous hydromagnesite, obtained by mechanical grinding of the as-received sample, was characterized by three well-separated decomposition processes of dehydration, dehydroxylation and decarbonation. The kinetic behaviors of the respective decomposition steps were estimated separately using a mathematical deconvolution of the partially overlapped reaction steps. From the formal kinetic analyses of the respective reaction processes, it was revealed that the dehydration and dehydroxylation processes indicate the decelerate rate behaviors controlled by diffusion, while the rate behavior of nucleation limited type is predominant for the decarbonation process.     

Influence of atmospheric CO2 on the thermal decomposition of perlite concrete

Journal of Thermal Analysis and Calorimetry - The thermal behavior of perlite concrete, which is used in sodium-cooled fast reactor plants, was subjected to kinetic modeling to gather the...     

Thermal analysis applied to the characterization of degradation in soil of polylactide: II. On the thermal stability and thermal decomposition kinetics

The disposal stage of polylactide (PLA) was assessed by burying it in active soil following an international standard. Degradation in soil promotes physical and chemical changes in the polylactide properties. The characterization of the extent of degradation underwent by PLA was carried out by using Thermal Analysis techniques. In this paper, studies on the thermal stability and the thermal decomposition kinetics were performed in order to assess the degradation process of a commercial PLA submitted to an accelerated soil burial test by means of multi-linear-non-isothermal thermogravimetric analyses. Results have been correlated to changes in molecular weight, showing the same evolution as that described by the parameters of thermal stability temperatures and apparent activation energies. The decomposition reactions can be described by two competitive different mechanisms: Nucleation model (A2) and Reaction Contracting Volume model (R3). The changes in the kinetic parameters and kinetic models are in agreement with the calorimetric and dynamic-mechanical-thermal results, presented in the Part I of the study [1].     

Some recent studies of the mechanisms of dehydration reactions of solids

Thermal Analysis, the central topic of this conference, is a technique that is widely used for the measurement of reaction rates and from which deductions can be made concerning the identity of the bond redistribution steps contributing to the chemical change being investigated. The mechanistic insights obtained from such studies enable us to identify the factors that determine reactivity and to understand theoretically the controls operating in chemical reactions. The present article points out, however, that kinetic data alone do not usually provide sufficient information to enable detailed identification of the sequence of steps through which reactants are converted into products.This review discusses recent research concerned with characterizing mechanisms within a group of solid state processes that has been the subject of extensive kinetic investigations (including thermal analyses): the dehydrations of crystalline hydrates. Conclusions from previous studies of reactions of this type have contributed extensively to the more general understanding of solid-state reactions. Here we discuss some mechanistic conclusions from a number of recent studies in the field and emphasize the value of complementing rate measurements with other relevant observations, including microscopic examinations of the textural modifications that accompany chemical changes.The sincere thanks of the author to all his collaborators cited in the reference list and to M. E. Brady for his helpful contributions during the preparation of this review.     

Effects of solvents and solutes on glass-transition thermodynamics and kinetic fragility for amine and alcohol solutions of inorganic salts

Journal of Thermal Analysis and Calorimetry - We have used differential scanning calorimetry (DSC) to investigate the thermodynamic and kinetic properties of the glass transition of simple amine...     

Obtaining more,and better,information from simple ramped temperature screening tests

Thermal screening of materials is a vital part of hazard assessment in the chemical industry. There is the need to identify the worst potential hazards and to further investigate these scenarios. Several screening methods are presented, and the subject of ramped temperature screening tests is studied in detail. Methods for the detection of exothermic reaction 'onset' temperatures are given. It is shown that, under some circumstances, the temperature data obtained during a simple controlled ramp heating experiment can be used to estimate the expected temperature rise that would occur under adiabatic conditions and the heat of reaction. The use of the data to obtain n^th order kinetic parameters is also demonstrated. Data obtained using the Thermal Screening Unit (TS^U) are compared to those obtained using other forms of apparatus. Heats of reaction and kinetic data have also been calculated and compare very well with data obtained using much more sophisticated adiabatic calorimeters. This revised version was published online in July 2006 with corrections to the Cover Date.     

热分析动力学研究方法的新进展

"非等温动力学"作为热分析动力学研究的核心,已经被广泛应用于化学、化工、冶金、地质、药物和环保等重要领域。热分析动力学研究的主要任务是确定机理函数、活化能和指前因子等动力学参数。在众多的热分析动力学研究方法中,"等转化率法"由于其可以在不涉及动力学模式函数的前提下,获得较为可靠的活化能值,因此被国际热分析与量热学协会(ICTAC)推荐使用。本文简要介绍了近十年来提出的热分析动力学研究方法,特别是等转化率方法的研究进展情况,评述了各种方法的特点与局限。同时,展望了热分析动力学研究方法未来的发展趋势。     

The generalisation of a multi-reaction model for polynomial ramping of temperature

Journal of Thermal Analysis and Calorimetry - This paper deals with the numerical solution of a multi-reaction model for the complex thermal history. The effect of thermal and kinetic parameters is...     

Studies on the thermal stability and kinetic parameters of naturally aged Octol formulation

Journal of Thermal Analysis and Calorimetry - A study on the thermal stability and kinetic parameters of an Octol formulation stockpiled for prolonged period a 20 year under natural...     

Differential thermometric kinetic analysis. a new general technique of interpreting the data obtained in kinetic analyses

The concentration-time data obtained in kinetic analyses may be easily and conveniently interpreted by multiparametric curve-fitting. A new technique of kinetic analysis, in which the overall extent of reaction is monitored by following the variation with time of the difference between the temperature of a reaction mixture and that of a reference solution, is described. Both these techniques are illustrated with-data obtained in oximations of mixtures of propanal-and cyclohexanone. The results confirm the existence of the synergic effect reported by Siggia and Hanna.     

Correlation between sample geometry and kinetics

Journal of Thermal Analysis and Calorimetry - The influence of the specimen shape on the form of the kinetic equation for thermal reactions was demonstrated by means of the spectral function theory.     

Calorimetric examination of suitability of calcium,cobalt and nickel nitrate hydrates for thermal energy storage

Journal of Thermal Analysis and Calorimetry - The influence of composition and neodymium doping on the crystallization kinetic of calcium aluminosilicate glasses, melted under vacuum atmosphere,...