title: Electron paramagnetic resonance, scanning electron microscopy with energy dispersion X-ray spectrometry, X-ray powder diffraction, and NMR characterization of iron-rich fired clays.
abstract: The aim of this study is to clarify the structure of an iron-rich clay and the structural changes involved in the firing process as a preliminary step to get information on ancient ceramic technology. To this purpose, illite-rich clay samples fired at different temperatures were characterized using a multitechnique approach, i.e., by electron paramagnetic resonance, scanning electron microscopy with electron dispersion X-ray spectrometry, X-ray powder diffraction, magic angle spinning and multiple quantum magic angle spinning NMR. During firing, four main reaction processes occur: dehydration, dehydroxylation, structural breakdown, and recrystallization. When the results are combined from all characterization methods, the following conclusions could be obtained. Interlayer H2O is located close to aluminum in octahedral sites and is driven off at temperatures lower than 600 degrees C. Between 600 and 700 degrees C dehydroxylation occurs whereas, between 800 and 900 degrees C, the aluminum in octahedral sites disappears, due to the breakdown of the illite structure, and all iron present is oxidized to Fe3+. In samples fired at 1000 and 1100 degrees C iron clustering was observed as well as large single crystals of iron with the occurrence of ferro- or ferrimagnetic effects. Below 900 degrees C the aluminum in octahedral sites presents a continuous distribution of chemical shift, suggesting the presence of slightly distorted sites. Finally, over the whole temperature range, the presence of at least two tetrahedral aluminum sites was revealed, characterized by different values of the quadrupolar coupling constant.
authors.affiliation: Chemistry Department and Center SMAArt, University of Perugia, Via Elce di Sotto 8, 06123 Perugia, Italy.
authors.forename: Federica
authors.initials: F
authors.lastname: Presciutti
authors.forename: Donatella
authors.initials: D
authors.lastname: Capitani
authors.forename: Antonio
authors.initials: A
authors.lastname: Sgamellotti
authors.forename: Brunetto Giovanni
authors.initials: BG
authors.lastname: Brunetti
authors.forename: Ferdinando
authors.initials: F
authors.lastname: Costantino
authors.forename: Stéphane
authors.initials: S
authors.lastname: Viel
authors.forename: Annalaura
authors.initials: A
authors.lastname: Segre
mesh_terms: D000538:Aluminum Silicates / Q000737:chemistry*; D000077215:Clay; D004578:Electron Spin Resonance Spectroscopy / Q000379:methods; D007501:Iron / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008855:Microscopy, Electron, Scanning / Q000379:methods; D010316:Particle Size; D033362:Powder Diffraction; D012680:Sensitivity and Specificity; D013053:Spectrophotometry; D014965:X-Rays
chemical_list: D000538:Aluminum Silicates; D007501:Iron; D000077215:Clay