CoFe(2)O(4) nanoparticles (D(NPD) ~6 nm), prepared by a thermal decomposition technique, have been investigated through the combined use of dc magnetization measurements, neutron diffraction, and (57)Fe Mössbauer spectrometry under high applied magnetic field. Despite the small particle size, the value of saturation magnetization at 300 K (M(s) ͠= 70 A m(2) kg(-1)) and at 5 K (M(s) ͠= 100 A m(2) kg(-1)) are rather close to the bulk values, making the samples prepared with this method attractive for biomedical applications. Neutron diffraction measurements indicate the typical ferrimagnetic structure of the ferrites, showing an inversion degree (γ(NPD) = 0.74) that is in very good agreement with cationic distribution established from low temperature (10 K) Mössbauer measurements in high magnetic field (γ(moss) = 0.76). In addition, the in-field Mössbauer spectrum shows the presence of a non-collinear spin structure in both A and B sublattices. The results allow us to explain the high value of saturation magnetization and provide a better insight into the complex interplay between cationic distribution and magnetic disorder in ferrimagnetic nanoparticles.

Remanence magnetization plots (e.g., Henkel or δM plots) have been extensively used as a straightforward way to determine the presence and intensity of dipolar and exchange interactions in assemblies of magnetic nanoparticles or single domain grains.Their evaluation is particularly important in functional materials whose performance is strongly affected by the intensity of interparticle interactions, such as patterned recording media and nanostructured permanent magnets, as well as in applications such as hyperthermia and magnetic resonance imaging. Here we demonstrate that δM plots may be misleading when the nanoparticles do not have a homogeneous internal magnetic configuration. Substantial dips in the δM plots of γ-Fe 2 O 3 nanoparticles isolated by thick SiO 2 shells indicate the presence of demagnetizing interactions, usually identified as dipolar interactions. Our results, however, demonstrate that it is the inhomogeneous spin structure of the nanoparticles, as most clearly evidenced by Mössbauer measurements, that has a pronounced effect on the δM plots, leading to features remarkably similar to those produced by dipolar interactions. X-ray diffraction results combined with magnetic characterization indicate that this inhomogeneity is due to the presence of surface structural (and spin) disorder. Monte Carlo simulations unambiguously corroborate the critical role of the internal magnetic structure in the δM plots. Our findings constitute a cautionary tale on the widespread use of remanence plots to assess interparticle interactions, as well as offer new perspectives in the use of Henkel-and δM-plots to quantify the rather elusive inhomogeneous magnetizations states in nanoparticles.Additional information on the δM and the in-field Mössbauer techniques, table with the complete results of the Mössbauer spectra fits, details of the Monte Carlo simulations, FC and ZFC magnetization curves of the VST series (Fig. S1a), Langevin scaling of M(H;T) data measured in VST45 (Fig. S1b), details on the estimate of the "magnetic size" from Langevin fits, δM plots of all the VST series and graphical analysis of the intraparticle and interparticle contributions to the dip (Fig. S2), example of hysteresis loops measured after ZFC and FC (for sample VST17, Fig. S3); X-ray diffraction patterns and lattice parameter across of the maghemite cores of different size (Fig. S4); complete results from Monte Carlo simulations showing the dependence of δM on core anisotropy (Fig. S5), surface anisotropy ( Fig. S6), exchange coupling constant ( Fig. S7) and disordered surface thickness (Fig. S8).