The possibility to finely control nanostructured cubic ferrites (M^IIFe₂O₄) paves the way to design materials with the desired magnetic properties for specific applications. However, the strict and complex interrelation among the chemical composition, size, polydispersity, shape and surface coating renders their correlation with the magnetic properties not trivial to predict. In this context, this work aims to discuss the magnetic properties and the heating abilities of Zn-substituted cobalt ferrite nanoparticles with different zinc contents (Zn_xCo_1−xFe₂O₄ with 0 < x < 0.6), specifically prepared with similar particle sizes (∼7 nm) and size distributions having the crystallite size (∼6 nm) and capping agent amount of 15%. All samples have high saturation magnetisation (M_s) values at 5 K (>100 emu g⁻¹). The increase in the zinc content up to x = 0.46 in the structure has resulted in an increase of the saturation magnetisation (M_s) at 5 K. High M_s values have also been revealed at room temperature (∼90 emu g⁻¹) for both CoFe₂O₄ and Zn_0.30Co_0.70Fe₂O₄ samples and their heating ability has been tested. Despite a similar saturation magnetisation, the specific absorption rate value for the cobalt ferrite is three times higher than the Zn-substituted one. DC magnetometry results were not sufficient to justify these data, the experimental conditions of SAR and static measurements being quite different. The synergic combination of DC with AC magnetometry and ⁵⁷Fe Mössbauer spectroscopy represents a powerful tool to get new insights into the design of suitable heat mediators for magnetic fluid hyperthermia.

The magnetic properties of ultra-small (3 nm) CoFe(2)O(4) nanoparticles have been investigated by DC magnetization measurements as a function of temperature and magnetic field. The main features of the magnetic behaviour are blocking of non-interacting particle moments (zero-field-cooled magnetization T(max) approximately 40 K), a rapid increase of saturation magnetization (up to values higher than for the bulk material) at low T and an increase in anisotropy below 30 K due to the appearance of exchange bias. The low temperature behaviour is determined by a random freezing of surface spins. Localized spin-canting and cation distribution between the two sublattices of the spinel structure account quantitatively for the observed increase in saturation magnetization.

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.