The lepidocrocite-maghemite-haematite reaction chain-I. Acquisition of chemical remanent magnetization by maghemite, its magnetic properties and thermal stability

Abstract

SUMMARY We report on the magnetic properties and the acquisition of a chemical remanent magnetization (CRM) in a field of 100 μT as a function of temperature and time during the lepidocrocite–maghemite–haematite reaction chain. The development of CRM was monitored at a series of 13 temperatures ranging from 175 to 550 °C; data acquisition was done at the specific formation temperatures for durations of up to 500 hr. Up to acquisition temperatures of 200 °C it takes a considerable time (up to 7 hr) before the CRM is measurable. This time decreases with increasing temperature, reflecting the activation energy of the reaction to form the first maghemite. During the lepidocrocite conversion, formation of two types of maghemite is suggested by two peaks in the CRM versus time curves. Magnetic properties were analysed after various stages in the reaction. They indicate a mixture of superparamagnetic and single-domain maghemite. The first reaction product (obtained after annealing at 200 °C) is a fine-grained yet crystalline maghemite (labelled type A). Before massive maghemite formation occurs, the coercive and remanent coercive forces go through a minimum at intermediate temperatures of 250–300 °C (annealing for 2.5 hr). This minimum lowers to 200–250 °C with increasing annealing time (500 hr). This is probably the result of two processes acting simultaneously—formation of superparamagnetic maghemite particles of a second less crystalline maghemite type (labelled type B) and removal of stacking faults in type A maghemite. The second process is suggested by analogy to the behaviour of natural magnetite/maghemite systems on annealing. Removal of stacking faults is reported to result in a magnetic softening of the grain assemblage. Annealing at 300–350 °C removes most of the lepidocrocite and the second maghemite type, type B, becomes prominent. Haematite formation sets in at slightly higher temperatures, yet the type B maghemite is in part thermally stable up to 600 °C enabling Thellier–Thellier experiments. This stability is also inferred from Arrhenius fitting that shows a comparatively high activation energy for the maghemite to haematite reaction. In Thellier–Thellier experiments the CRM showed a markedly downward convex Arai–Nagata plot while a second thermoremanent magnetization (TRM) showed perfect linear behaviour as expected. This feature may be used to recognize CRM in natural rocks.