Magnetic spinel ferrite MFe2O4 (M = Mn, Co, Ni, Zn) nanoparticles have been prepared via simple, green and scalable hydrothermal synthesis pathways utilizing sub- and supercritical conditions to attain specific product characteristics. The crystal-, magnetic- and micro-structures of the prepared crystallites have been elucidated through meticulous characterization employing several complementary techniques. Analysis of energy dispersive X-ray spectroscopy (EDS) and X-ray absorption near edge structure (XANES) data verifies the desired stoichiometries with divalent M and trivalent Fe ions. Robust structural characterization is carried out by simultaneous Rietveld refinement of a constrained structural model to powder X-ray diffraction (PXRD) and high-resolution neutron powder diffraction (NPD) data. The structural modeling reveals different affinities of the 3d transition metal ions for the specific crystallographic sites in the nanocrystallites, characterized by the spinel inversion degree, x, [M2+1-xFe3+x]tet[M2+xFe3+2-x]octO4, compared to the well-established bulk structures. The MnFe2O4 and CoFe2O4 nanocrystallites exhibit random disordered spinel structures (x = 0.643(3) and 0.660(6)), while NiFe2O4 is a completely inverse spinel (x = 1.00) and ZnFe2O4 is close to a normal spinel (x = 0.166(10)). Furthermore, the size, size distribution and morphology of the nanoparticles have been assessed by peak profile analysis of the diffraction data, transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). The differences in nanostructure, spinel inversion and distinct magnetic nature of the M2+ ions directly alter the magnetic structures of the crystallites at the atomic-scale and consequently the macroscopic magnetic properties of the materials. The present study serves as an important structural benchmark for the rapidly expanding field of spinel ferrite nanoparticle research.

The influence of synthesis and compaction parameters is investigated with regards to formation of high performance SrFe12O19 bulk magnets. The produced magnets consist of highly aligned, single-magnetic domain nanoplatelets of SrFe12O19. The relationship between the magnetic performance of the samples and their structural features is established through systematic characterization by Vibrating Sample Magnetometry (VSM) and Rietveld refinement of powder X-ray diffraction data (PXRD). The analysis is supported by complementary techniques including Transmission Electron Microscopy (TEM), Atomic Force Microscopy (AFM) and X-ray pole figure measurements. SrFe12O19 hexagonal nanoplatelets with various sizes are synthesized by a supercritical hydrothermal flow method. The crystallite sizes are tuned by varying the Fe/Sr ratio in the precursor solution. Compaction of SrFe12O19 nanoplatelets into bulk magnets is performed by Spark Plasma Sintering (SPS). Rietveld refinement of the pressed pellets and texture analysis of pole figure measurements reveal that SPS pressing produces a high degree of alignment of the nanoplatelets, achieved without applying any magnetic field prior or during compaction. The highly aligned nanocrystallites combined with crystal growth during SPS give rise to an enormous enhancement of the magnetic properties compared to the as-synthesized powders, leading to high performance bulk magnets with energy products of 26 kJ m(-3).

Magnetic materials are ubiquitous in electric devices and motors making them indispensable for modern-day society. The hexaferrites currently constitute the most widely used permanent magnets (PMs), accounting for 85% (by weight) of the global sales of PMs. This work presents a complete bottom-up nanostructuring protocol for preparation of magnetically aligned, high-performance hexaferrite PMs with a record-high (BH)max for dry-processed ferrites. The procedure includes the supercritical hydrothermal flow synthesis of anisotropic magnetic-single-domain strontium hexaferrite (SrFe12O19) nanocrystallites of various sizes, and their subsequent compaction into bulk magnets by spark plasma sintering (SPS). Interestingly, Rietveld modeling of neutron powder diffraction data reveals a significant difference between the magnetic structure of the thinnest nanoplatelets and the bulk compound, indicating the Sr-containing atomic layer to be the termination layer. Subsequently, high-density SrFe12O19 magnets (>95% of the theoretical density) are produced by SPS of the flow-synthesized nanoplatelets. Texture analysis by X-ray pole figure measurements demonstrates how the anisotropic shape of the nanoplatelets causes a self-induced alignment during SPS, without application of an external magnetic field. The self-induced texture is accompanied by crystallite growth along the magnetic easy-axis, i.e., the thickness of the platelets, resulting in high-performance PMs with square hysteresis curves and (BH)max of 30 kJ/m3. The (BH)max is further enhanced by annealing, reaching 36 kJ/m3 after 4 h at 850 °C, which exceeds the (BH)max of the highest grade of dry-processed commercial ferrites worldwide.

Nanocrystallites of the permanent magnetic material SrFe12O19 were synthesised using a conventional sol-gel (CSG) and a modified sol-gel (MSG) synthesis route. In the MSG synthesis, crystallite growth takes place in a solid NaCl matrix, resulting in freestanding nanocrystallites, as opposed to the CSG synthesis, where the produced nanocrystals are strongly intergrown. The resulting nanocrystallites from both methods exhibit similar intrinsic magnetic properties, but significantly different morphology and degree of aggregation. The nanocrystallites were compacted into dense pellets using a Spark Plasma Sintering (SPS) press, this allows investigating the influence of crystallite morphology and the alignment of the nanocrystallites on the magnetic performance. A remarkable correlation was observed between the crystallites morphology and their ability to align in the compaction process. Consequently, a significant enhancement of the maximum energy product was obtained after SPS for the MSG prepared sample (22.0 kJ/m3), compared to CSG sample, which achieved an energy product of 11.6 kJ/m3.