Studies of anisotropy mechanisms in polyphosphate-treated magnetic iron oxide particles

The coercive force of small, acicular ( 2000 Å length, 8:1 length-to-diameter ratio) spinel-type iron oxide particles increases substantially following surface treatment with sodium polyphosphate. Regardless of Fe²⁺/Fe³⁺ cation ratio, H_c always attains a peak value when the polyphosphate/iron oxide weight ratio P/Fe is in the range 0.5–0.6, denoted (P/Fe)_max. The maximum change in H_c is observed when Fe²⁺/Fe³⁺ ≈ 0.10–0.15. When P/Fe0.5–0.6, however, both magnitude and sign of the change in coercive force show strong dependence on the Fe²⁺ content of the oxide, suggesting that the H_c changes are caused by a magnetostrictive mechanism at these high treatment ratios. Calculated anisotropy field distributions of treated specimens show that both the mean anisotropy field δH_kδ_G and predicted H_c reach a peak when particles are treated at (P/Fe)_max, where the distribution becomes very broad. At high treatment ratios both δH_kδ_G and predicted H_c decrease to values below that of the untreated oxide. Mössbauer studies of treated and untreated particles show no significant change in the environment of surface iron ions following treatement at P/FE = 0.5, but indicate a small increase in the Fe³⁺ concentration of the particle core. When P/Fe = 2.5, however, the Fe²⁺ concentration of the core increases markedly.