Separating the contributions of the magnetic subsystems in antiferromagnetic ferrihydrite nanoparticles by analyzing the magnetization in fields of up to 250 kOe

https://doi.org/10.1016/j.jmmm.2024.171781

Contributions of different magnetic subsystems formed in the systems of synthetic ferrihydrite nanoparticles (characterized previously) with an average size of < d> ≈ 2.7 nm coated with polysaccharide arabinogalactan in different degrees have been separated by measuring the dependences of their magnetization M on magnetic field H of up to 250 kOe on vibrating sample and pulsed magnetometers. The use of a wide measuring magnetic field range has been dictated by the ambiguity in identifying a linear M(H) portion for such antiferromagnetic nanoparticle systems within the conventional field range of 60–90 kOe. The thorough analysis of the magnetization curves in the temperature range of 100–250 K has allowed the verification of the contributions of (i) uncompensated magnetic moments µ_un in the superparamagnetic subsystem, (ii) the subsystem of surface spins with the paramagnetic behavior, and (iii) the antiferromagnetic susceptibility of the antiferromagnetically ordered ferrihydrite particle core. As a result, a model of the magnetic state of ferrihydrite nanoparticles has been proposed and the numbers of spins corresponding to magnetic subsystems (i)–(iii) have been estimated. An average magnetic moment μ_un of ∼ 145 μ_B (μ_B is the Bohr magneton) per particle corresponds approximately to 30 decompensated spins of iron atoms in a particle (about 3 % of all iron atoms), which, according to the Néel’s hypothesis μ_un ∼ <d>^3/2, are localized both on the surface and in the bulk of an antiferromagnetically ordered particle. The fraction of free (paramagnetic) spins is minimal in the sample without arabinogalactan coating of the nanoparticle surface (7 %) and is attained 20 % of all iron atoms in the sample with the highest degree of spatial separation of particles. According to this estimation, paramagnetic spins are located mainly on the edges and protruding areas of particles. Most magnetic moments of iron atoms are ordered antiferromagnetically and the corresponding magnetic susceptibility of this subsystem behaves as in an antiferromagnet with the randomly distributed crystallographic axes, i.e., increases with temperature.