“Model-free” kinetic analysis?

Sewry, Joyce D.; Brown, Michael E.

doi:10.1016/s0040-6031(02)00083-7

Cited by 96 publications

(60 citation statements)

References 29 publications

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“…The expressions are generally complex and non-linear; and solutions can be obtained using computer algorithms, some of which are available in commercial software. The "model free" non-parametric kinetics (NPK) method derived by Serra and coworkers [47,48] is considered to be accurate, but, due to its mathematical complexity, has been applied very little [1]. (It was shown that for one particular reaction occurring at about y=30, the method obtained an activation energy 0.6% higher than the KAS method.…”

Section: Other Activation Energy Analysis Methodsmentioning

confidence: 99%

“…A general objective of the modelling of thermally activated reactions is the derivation of a complete description of the progress of a reaction that is valid for any thermal treatment, be it isothermal, by linear heating or any other non-isothermal treatment [1,2]. For many reactions this objective is a daunting one as any given reaction might progress through a range of mechanisms and intermediate stages, all of which can have a different temperature-dependency, and this is especially so for solidstate reactions.…”

Section: Introductionmentioning

confidence: 99%

“…[1]). A deviation in the determination of any of the three will cause a deviation in the other parameters of the triplet.…”

Section: Introductionmentioning

confidence: 99%

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The determination of activation energy from linear heating rate experiments: a comparison of the accuracy of isoconversion methods

2003

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Model-free isoconversion methods are the most reliable methods for the calculation of activation energies of thermally activated reactions. A large number of these isoconversion methods have been proposed in the literature. A classification of these methods is proposed. Type A methods such as Friedman methods make no mathematical approximations, and Type B methods, such as the generalised Kissinger equation, apply a range of approximations for the temperature integral. The accuracy of these methods is investigated, by deriving expressions for the main sources of error which includes the inaccuracy in reaction rate measurement, approximations for the temperature integral and inaccuracies in determination of temperature for equivalent fraction transformed. Both highly inaccurate and highly accurate Type B methods are identified. In cases where some uncertainty over baselines of the thermal analysis data exists or where accuracy of determination of transformation rates is limited, type B methods will often be more accurate than type A methods.

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Section: Other Activation Energy Analysis Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The determination of activation energy from linear heating rate experiments: a comparison of the accuracy of isoconversion methods

2003

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“…As the determination of g(), E and K 0 (the so-called kinetic triplet) is an interlinked problem in non-isothermal experiments [54,60], a deviation in the determination of any of the three will cause a deviation in the other parameters of the triplet. Thus, it is important to start the analysis of a non-isothermal experiment by determining one element of the triplet with high accuracy.…”

Section: Introductionmentioning

confidence: 99%

Comments About the Strengthening Mechanisms in Commercial Microalloyed Steels and Reaction Kinetics on Tempering in Low-Alloy Steels

Morales¹

2011

Alloy Steel - Properties and Use

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“…For nonisothermal experiments, the reaction rate at all times depends on both f(α) and k(T), and the determination of f(α), k o and E (the so-called kinetic triplet) is an interlinked problem (see e.g. [8]). A deviation in the determination of any of the three will cause a deviation in the other parameters of the triplet.…”

Section: Introductionmentioning

confidence: 99%

Activation energy determination for linear heating experiments: deviations due to neglecting the low temperature end of the temperature integral

Starink

2006

J Mater Sci

127

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Model-free isoconversion methods which use approximations of the temperature integral are generally reliable methods for the calculation of activation energies of thermally activated reactions studied during linear heating. These methods generally neglect the temperature integral at the start of the linear heating, I (T o ). An analytical equation is derived which describes the deviations introduced by this approximation.It is shown that for most reactions encountered this assumption does not have a significant influence on the accuracy of the method. However, in cases where T o is within about 50 to 70K of the reaction stage to be investigated and activation energies are relatively low, significant deviations are introduced. It is shown that some of the published thermal analysis work on activation energy analysis of reactions occurring at relatively low temperatures is affected by these deviations. Examples are specific cases of dehydration reactions, cure reactions and cluster formation in Al alloys.

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“Model-free” kinetic analysis?

Cited by 96 publications

References 29 publications

The determination of activation energy from linear heating rate experiments: a comparison of the accuracy of isoconversion methods

The determination of activation energy from linear heating rate experiments: a comparison of the accuracy of isoconversion methods

Comments About the Strengthening Mechanisms in Commercial Microalloyed Steels and Reaction Kinetics on Tempering in Low-Alloy Steels

Activation energy determination for linear heating experiments: deviations due to neglecting the low temperature end of the temperature integral

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