High-performance hexaferrite magnets tailored through alignment of shape-controlled nanocomposites.

Nanoparticles of strontium hexaferrite, SrFe12O19, were prepared by two different synthesis methods: hydrothermal (autoclave) and sol-gel autocombustion (solid-salt-matrix). The two synthesis pathways yield nanoparticles with different morphologies and correspondingly different magnetic characteristics. The autoclave synthesis results in large plate-like crystallites, which spontaneously align with a preferred crystallographic orientation when applying a uniaxial pressure, but exhibit a relatively poor coercivity. Meanwhile, the solid-salt-matrix synthesis method results in smaller less anisotropic crystallites with enhanced coercivity, but with a relatively limited ability to align under a uniaxial applied pressure. The obtained nanocrystalline powders were dry or wet mixed in different ratios followed by Spark Plasma Sintering (SPS) into dense pellets. A clear correlation between mixing ratio, the level of alignment and resulting coercivity was observed for the dry mixed samples, i.e. as more solid-salt-matrix powder is added, the texture of the pellets decreases and the coercivity increases. The best performing pellet in terms of maximum energy product (BHmax = 32.1(6) kJ m-3) was obtained by dry-mixing of 75 wt% autoclave prepared powder and 25 wt% solid-salt-matrix powder. The results presented here illustrate the potential of mixing magnetic nanoparticle powders with different shape characteristics to gain improved magnetic performance.

Elucidating the relationship between nanoparticle morphology, nuclear/magnetic texture and magnetic performance of sintered SrFe12O19 magnets.

Several M-type SrFe12O19 nanoparticle samples with different morphologies have been synthesized by different hydrothermal and sol-gel synthesis methods. Combined Rietveld refinements of neutron and X-ray powder diffraction data with a constrained structural model reveal a clear correlation between crystallite size and long-range magnetic order, which influences the macroscopic magnetic properties of the sample. The tailor-made powder samples were compacted into dense bulk magnets (>90% of the theoretical density) by spark plasma sintering (SPS). Powder diffraction as well as X-ray and neutron pole figure measurements and analyses have been carried out on the compacted specimens in order to characterize the nuclear (structural) and magnetic alignment of the crystallites within the dense magnets. The obtained results, combined with macroscopic magnetic measurements, reveal a direct influence of the nanoparticle morphology on the self-induced texture, crystallite growth during compaction and macroscopic magnetic performance. An increasing diameter-to-thickness aspect ratio of the platelet-like nanoparticles leads to increasing degree of crystallite alignment achieved by SPS. Consequently, magnetically aligned, highly dense magnets with excellent magnetic performance (30(3) kJ m-3) are obtained solely by nanostructuring means, without application of an external magnetic field before or during compaction. The demonstrated control over nanoparticle morphology and, in turn, crystal and magnetic texture is a key step on the way to designing nanostructured hexaferrite magnets with optimized performance.

Exploring the direct synthesis of exchange-spring nanocomposites by reduction of CoFe2O4 spinel nanoparticles using in situ neutron diffraction.

In situ neutron powder diffraction (NPD) was employed for investigating gram-scale reduction of hard magnetic CoFe2O4 (spinel) nanoparticles into CoFe2O4/CoFe2 exchange-spring nanocomposites via H2 partial reduction. Time-resolved structural information was extracted from Rietveld refinements of the NPD data, revealing significant changes in the reduction kinetics based on the applied temperature and H2 available. The nanocomposite formation was found to take place via the following two-step reduction process: CoxFe3-xO4 → CoyFe1-yO → CozFe2-z. The refined lattice parameters and site occupation fractions indicate that the reduced phases, i.e. CoyFe1-yO and CozFe2-z, initially form as Co-rich compounds (i.e. y > 0.33 and z > 1), which gradually incorporate more Fe as the reduction proceeds. The reduction depletes the Co-content in the parent spinel, which may end up becoming magnetically soft Fe3O4 at high temperature (T = 542 °C), while at lower temperatures there may be a co-existence of Fe3O4 and γ-Fe2O3 or CoxFe3-xO4. The macroscopic magnetic properties of the products were measured by vibrating sample magnetometry (VSM) and revealed the hard and soft magnetic domains in the nanocomposites to be effectively exchange-coupled. An increase of approximately 70% in specific saturation magnetisation, remanence magnetisation, and coercivity compared to the parent CoFe2O4 material was achieved for the best sample.

Electrochemically activated solid synthesis: an alternative solid-state synthetic method.

Solid-state synthesis is one of the most common synthetic methods in chemistry and is extensively used in lab-scale syntheses of advanced functional materials to ton-scale production of chemical compounds. It generally requires at least one or several high temperature and/or high-pressure steps, which makes production of compounds via solid-state methods very energy and time intensive. Consequently, there is a persistent economic and environmental incentive to identify less energy and time consuming synthetic pathways. Here, we present an alternative solid-state synthetic method, which utilizes structural changes, induced by an electrochemical "activation" step followed by a thermal treatment step. The method has been used to synthesize a Sc0.67WO4-type phase where Sc0.67WO4 has previously only been obtained at 1400 °C and 4 GPa for 1 h. Through our method the Sc0.67WO4-type phase has been prepared at only 600 °C and ambient pressure. Experimental factors that influence phase formation from the electrochemical perspective are detailed. Overall, the method presented in this work appears to be able to generate the conditions for unusual and new phases to form and thus becomes another tool for synthetic solid-state chemists. This in turn permits the exploration of a larger synthetic parameter space.

Crystalline and magnetic structure-property relationship in spinel ferrite nanoparticles.

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.