The effect of oxidation on the Verwey transition in magnetite

Abstract

At the Verwey transition (Tv≈110–120 K), magnetite transforms from monoclinic to cubic spinel structure. It has long been believed that magnetic remanence and susceptibility would change markedly at Tv in the case of coarse grains but only slightly or inappreciably in the case of fine (<1 µm) grains. We find on the contrary that remanence changes at Tv by 50–80% in both large and small crystals, if they are stoichiometric. However, minor surface oxidation suppresses the transition, and the fact that fine grains oxidize more readily leads to an apparent size dependence. Our experiments used submicron magnetite cubes with mean sizes of 0.037, 0.076, 0.10 and 0.22 µm which were initially non-stoichiometric (oxidation parameter z from 0.2–0.7). A saturation isothermal remanent magnetization (SIRM) given in a 2.5 T field at 5 K decreased steadily during zero-field warming to 300 K with little or no indication of the Verwey transition. After the oxidized surface of each crystal was reduced to stoichiometric magnetite, the SIRM decreased sharply during warming by 50–80% around 110 K. The change in SIRM for the 0.22 µm grains was almost identical to that measured for a 1.5 mm natural magnetite crystal. Thus a 10^12 change in particle volume does not materially affect the remanence transition at Tv but oxidation to z=0.3 essentially suppresses the transition. The effect of the degree of oxidation on Tv provides a sensitive test for maghemitization in soils, sediments and rocks.