The effect of oxidation on the Verwey transition in magnetite

TLDR

The Verwey transition (~110–120 K) changes magnetite’s crystal structure from monoclinic to cubic, and it was thought that remanence and susceptibility vary strongly in coarse grains but only slightly in fine (<1 µm) grains. The study aims to determine how oxidation degree affects the Verwey transition to provide a sensitive test for maghemitization in soils, sediments, and rocks. The authors examined submicron magnetite cubes (0.037–0.22 µm) that were initially non‑stoichiometric (z = 0.2–0.7) to study oxidation effects. Stoichiometric submicron magnetite shows a 50–80 % remanence drop at the Verwey transition, regardless of size, but surface oxidation suppresses the transition, with fine grains oxidizing more readily and masking the size effect; reducing oxidized surfaces restores the sharp transition, and even a 10^12 volume change has little impact, while z = 0.3 oxidation essentially eliminates it.

Abstract

At the Verwey transition (T v ≈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 T v in the case of coarse grains but only slightly or inappreciably in the case of fine (&lt;1 µm) grains. We find on the contrary that remanence changes at T v 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 T v but oxidation to z=0.3 essentially suppresses the transition. The effect of the degree of oxidation on T v provides a sensitive test for maghemitization in soils, sediments and rocks.