Rehydroxylation of fired clays: Is the time to the quarter (TTTQ) model correct?

Kuligiewicz, Artur; Derkowski, Arkadiusz

doi:10.1016/j.jas.2020.105301

Cited by 7 publications

(12 citation statements)

References 33 publications

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“…By introducing the time offset in the model, one obtains a curve with a concave‐up curvature in the mass gain data, which is very similar to a combination of t 1/4 and t 1/2 transport processes as obtained in the measurements of Gallet and Le Goff 21‐22 . However, introducing such time offsets into the fitting procedure has been proven most recently to result in highly inaccurate E a values and provide misleading results albeit a good fit 40 . The time offset should thus be used with caution only if its physical meaning is independently proven.…”

Section: Rehydroxylation (Rhx) Dating Of Archeological Artifactsmentioning

confidence: 58%

“…[21][22] However, introducing such time offsets into the fitting procedure has been proven most recently to result in highly inaccurate Ea values and provide misleading results albeit a good fit. 40 The time offset should thus be used with caution only if its physical meaning is independently proven. We also note that an important effect here is the cooling rate.…”

Section: Assumptions Of the Rhx Dating Methods By Gravimetrymentioning

confidence: 99%

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Searching for the fundamentals of rehydroxylation dating of archaeological ceramics via NMR and IR microscopy

et al. 2021

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Chronology assumes a central role in the process of historical and archaeological reconstruction by allowing us to time the change and development of human societies. Dating provides a framework for linking individual events together. It is the backbone for historical narratives, and connections between environmental and archaeological records on a global scale. However, until today, establishing a reliable chronology for ancient human societies and civilizations using pottery has remained one of the most contested topics of scientific discourse. Although the field of chronology has been revolutionized by modern historical and archaeological critical methods, through assessing historical sources and material

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Section: Rehydroxylation (Rhx) Dating Of Archeological Artifactsmentioning

confidence: 58%

Section: Assumptions Of the Rhx Dating Methods By Gravimetrymentioning

confidence: 99%

Searching for the fundamentals of rehydroxylation dating of archaeological ceramics via NMR and IR microscopy

et al. 2021

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“…Explained as corresponding to restricted, single-file diffusion in fired clay minerals, the TTTQ model has been applied to clay-based traditional ceramics and used to predict the time elapsed since firing, hence for archeological dating (Hare et al, 2016;Wilson et al, 2009). Both the root coefficient of the TTTQ (Barret, 2017) and the overall validity of TTTQ model for kinetic calculations have been criticized strongly (Kuligiewicz & Derkowski, 2021).…”

Section: Rehydration and Rehydroxylationmentioning

confidence: 99%

“…Studies of E a of smectite rehydroxylation are still rare and the E a values calculated based on the TTTQ model remain within an unexpectedly broad range, between 19 and 173 kJ/mol for experiments performed at 110-400°C Stevenson & Gurnick, 2016). However, Kuligiewicz and Derkowski (2021) recently proved that the TTTQ model describes well the progress of various reactions governed by unexpectedly different mechanisms. E a obtained with the TTTQ model for those reactions was grossly incorrect despite an apparent agreement with simulated data, making the TTTQ model unreliable.…”

Section: Rehydration and Rehydroxylationmentioning

confidence: 99%

Thermal Analysis and Thermal Reactions of Smectites: a Review of Methodology, Mechanisms, and Kinetics

Derkowski

Kuligiewicz

2022

Clays and clay miner.

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Smectites are a group of minerals traditionally analyzed by thermal methods due to their exceptionally large adsorbed-water contents and the presence of OH groups, which makes them unique among all common soil- and rock-forming minerals. The dehydration reaction of smectite is a low-temperature endothermic effect that ends typically below 200°C. Although the removal of bulk interlayer water requires activation energy (Ea) of just above 30 kJ/mol, the removal of the last few H2O molecules attached strongly to interlayer cations requires Ea > 100 kJ/mol. Dehydroxylation is the loss of structural OH groups that proceeds as evolution of H2O molecules out of the smectite structure and occurs in the 300–900°C range. In trioctahedral species, dehydroxylation is combined with recrystallization and proceeds usually at > 700°C. In dioctahedral species, the temperature of dehydroxylation is controlled by the type of octahedral vacancy, having trans-vacant and cis-vacant distinguished by the boundary at ~ 600°C, and by the octahedral cation–OH bond strength, following the order Mg > Al > Fe. The Ea of dehydroxylation correlates linearly with the temperature of maximum dehydroxylation; from > 170 kJ/mol for Cs+-exchanged beidellite and nontronite, through ~ 300 kJ/mol in Mg-rich montmorillonite, to > 500 kJ/mol in trioctahedral saponite. Dehydration and dehydroxylation of smectites can be accompanied by a number of other phenomena, such as dehydrogenation or defluorination. At high temperatures, smectite amorphization and recrystallization occurs. Unless amorphized and/or recrystallized, smectites can undergo rehydration and rehydroxylation, which are opposite reactions to dehydration and dehydroxylation, respectively. This review discusses the details of the above-mentioned thermal reactions of smectites, focusing on thermogravimetric methods, evolved gas analysis, and structural alterations. Factors affecting the accuracy and precision of thermal analysis of smectite are discussed along with examples of best laboratory practices. The paper also provides the most recent description and critical evaluation of smectite reaction kinetics.

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“…However, following studies [6] showed that experimental data can be fit parametrizing N with values between 2 and 6. The value of N is linked to the diffusion mechanism in the ceramic lattice, which is not yet fully clear, and it is still being studied [7]. A better knowledge of the diffusion mechanisms involved in the different rehydroxylation stages would improve the reliability and the precision of the technique.…”

Section: 3mentioning

confidence: 99%

Rehydroxylation: a promising technique for ceramic dating

Maspero

Galli

Panzeri

et al. 2022

J. Phys.: Conf. Ser.

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The kinetics of expansion in ceramic materials due to rehydration and rehydroxylation was investigated since the early XX century as a cause of crazing in glazed ceramics. Since then, the study of expansion and mass gain of ceramic has been studied extending the monitored times and modeling the involved processes. In the last 20 years, the interest in this process grew due to its possible application in the dating field, supporting well-established techniques such as thermoluminescence and optically stimulated luminescence. The principle of the dating technique is based on the fact that after the firing all water and hydroxyl molecules are desorbed from the ceramic structure, and after cooling are slowly adsorbed following a mathematical law. Nowadays, the correlation between time and mass gain is well established, but there is still no agreement on the mathematical model of the rehydroxylation process, and on a reliable protocol to date the materials. However, promising results have been reached, and more efforts must be put into the study of the role of involved parameters (storage temperature, activation energy, experimental setup…). Considerations on the last point will be shown, together with experimental evidence collected at Lambda (Laboratory of Milano Bicocca university for Dating and Archaeometry).

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Rehydroxylation of fired clays: Is the time to the quarter (TTTQ) model correct?

Cited by 7 publications

References 33 publications

Searching for the fundamentals of rehydroxylation dating of archaeological ceramics via NMR and IR microscopy

Searching for the fundamentals of rehydroxylation dating of archaeological ceramics via NMR and IR microscopy

Thermal Analysis and Thermal Reactions of Smectites: a Review of Methodology, Mechanisms, and Kinetics

Rehydroxylation: a promising technique for ceramic dating

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