Superparamagnetism of Baked Clays Containing Polymorphs of Iron Oxides: Experimental Study and Theoretical Modeling

A comprehensive study of the magnetic properties of baked clays containing ferrimagnetic particles in various magnetic states, including superparamagnetic, has been carried out in this work. The phase composition of the magnetic fraction of laboratory and industrial samples made from the same clay is mainly represented by iron (III) oxide polymorphs and possibly non-stoichiometric magnetite. Experimental methods included magnetic granulometry, Mössbauer spectroscopy, scanning electron microscopy, X-ray phase analysis, and pulsed electromagnetic measurements. A theoretical model of magnetostatically interacting particles with a lognormal volume distribution was used to interpret the experimental data, allowing the contribution of superparamagnetic grains to be taken into consideration. It is shown that the firing mode significantly affects the composition of iron oxide phases and their magnetic characteristics. Laboratory samples are characterized by approximately twice the proportion of superparamagnetic particles. At sufficiently low concentrations of ferrimagnet in samples <0.1%, the concentration of superparamagnetic particles is even two orders of magnitude lower. It is the use of pulse methods that provides a more reliable diagnosis of their presence. The complex application of experimental methods with theoretical modeling makes it possible to reveal and quantitatively describe the microheterogeneous nature of the magnetic state of baked clays, which is applicable to a wide range of magnetic materials, and to analyze more deeply the thermal and phase history of archaeological and geological objects.