Crystallite size dependent cation distribution in nanostructured spinels studied by nmr, mössbauer spectroscopy and XPS

Owing to the structural flexibility of spinels, providing a wide range of physical and chemical behavior, these materials have been considered as a convenient model system for the investigation of the size dependent properties of complex ionic systems. In this work, quantitative formation is obtained on the crystallite size dependent ionic configuration in nanosized spinel oxides prepared by mechanochemical processing of the corresponding bulk materials. Experimentally determined values of the crystallite size and of the mean degree of inversion of nanostructured spinels are used to calculate the volume fraction of interfaces/surfaces and their thickness in the nanomaterials

The mechanically induced structural disorder in barium hexaferrite, BaFe12O19, and its impact on magnetism

The response of the structure of the M-type barium hexaferrite (BaFe12O19) to mechanical action through high-energy milling and its impact on the magnetic behaviour of the ferrite are investigated. Due to the ability of the Fe-57 Mossbauer spectroscopic technique to probe the environment of the Fe nuclei, a valuable insight on a local atomic scale into the mechanically induced changes in the hexagonal structure of the material is obtained. It is revealed that the milling of BaFe12O19 results in the deformation of its constituent polyhedra (FeO6 octahedra, FeO4 tetrahedra and FeO5 triangular bi-pyramids) as well as in the mechanically triggered transition of the Fe3+ cations from the regular 12k octahedral sites into the interstitial positions provided by the magnetoplumbite structure. The response of the hexaferrite to the mechanical treatment is found to be accompanied by the formation of a non-uniform nanostructure consisting of an ordered crystallite surrounded/separated by a structurally disordered surface shell/interface region. The distorted polyhedra and the non-equilibrium cation distribution are found to be confined to the amorphous near-surface layers of the ferrite nanoparticles with the thickness extending up to about 2 nm. The information on the mechanically induced short-range structural disorder in BaFe12O19 is complemented by an investigation of its magnetic behaviour on a macroscopic scale. It is demonstrated that the milled ferrite nanoparticles exhibit a pure superparamagnetism at room temperature. As a consequence of the far-from-equilibrium structural disorder in the surface shell of the nanoparticles, the mechanically treated BaFe12O19 exhibits a reduced magnetization and an enhanced coercivity.DFG/SPP/1415APVV/0528-11VEGA/2/0097/1

Magnesium Ferrite (MgFe2O4) Nanostructures Fabricated by Electrospinning

Magnesium ferrite (MgFe2O4) nanostructures were successfully fabricated by electrospinning method. X-ray diffraction, FT-IR, scanning electron microscopy, and transmission electron microscopy revealed that calcination of the as-spun MgFe2O4/poly(vinyl pyrrolidone) (PVP) composite nanofibers at 500–800 °C in air for 2 h resulted in well-developed spinel MgFe2O4nanostuctures. The crystal structure and morphology of the nanofibers were influenced by the calcination temperature. Crystallite size of the nanoparticles contained in nanofibers increased from 15 ± 4 to 24 ± 3 nm when calcination temperature was increased from 500 to 800 °C. Room temperature magnetization results showed a ferromagnetic behavior of the calcined MgFe2O4/PVP composite nanofibers, having their specific saturation magnetization (Ms) values of 17.0, 20.7, 25.7, and 31.1 emu/g at 10 Oe for the samples calcined at 500, 600, 700, and 800 °C, respectively. It is found that the increase in the tendency ofMsis consistent with the enhancement of crystallinity, and the values ofMsfor the MgFe2O4samples were observed to increase with increasing crystallite size

A simple and straightforward mechanochemical synthesis of the far-from-equilibrium zinc aluminate, ZnAl₂O₄, and its response to thermal treatment

Zinc aluminate (ZnAl2O4) nanoparticles with an average size of about 10 nm are synthesized via one-step mechanochemical processing of the ZnO : g-Al2O3 stoichiometric mixture at ambient temperature. The mechanochemically induced formation of the phase is followed by XRD and 27Al MAS NMR. Highresolution TEM studies reveal a non-uniform nanostructure of mechanosynthesized aluminate consisting of ordered grains surrounded or separated by disordered surface and interfacial regions. Due to the capability of 27Al MAS NMR to probe the local environment of the Al cations, valuable insights into the short-range structure of ZnAl2O4 on the °Angstr¨om length scale are provided. It is demonstrated that the as-prepared aluminate possesses a partly inverse spinel structure with a far-from equilibrium arrangement of cations and distorted polyhedra, which are spatially confined to the surface and interfacial regions with a volume fraction of ca. 50% and a thickness of ca. 1 nm. The response of the nanostructured ZnAl2O4 to subsequent thermal treatment is further investigated. It turned out that the thermally induced grain growth is accompanied by a release of microstrain, by a shrinkage of the lattice parameter, as well as by a variation in the oxygen parameter and metal–oxygen bond lengths. Evidence is given of the thermally induced redistribution of cations approaching their equilibrium positions. Upon heating above 1100 K, mechanosynthesized ZnAl2O4 relaxes towards a structural state that is similar to the bulk one

Modification of TiO2 and ZnO Particles Under Mechanical Stress with Polypropylene

Solid-state process of introducing oxygen vacancies into the structure of TiO2 and ZnO particles was studied. The phase transformations of metal oxides throughout the process were examined by X-ray diffraction (XRD). The influence of the loaded mechanical stress on the band gap was studied by diffuse reflectance spectroscopy (DRS). Mechanism of elimination of oxygen atoms from the surface of the oxides by co-milling with polyolefins, which can lead to creation of more effective materials for waste water treatment, was proposed.This is the peer-reviewed version of the paper: Skurikhina, O., Tothova, E., Markovic, S., Senna, M., 2020. Modification of TiO2 and ZnO Particles Under Mechanical Stress with Polypropylene, in: Petkov, P., Achour, M.E., Popov, C. (Eds.), Nanoscience and Nanotechnology in Security and Protection against CBRN Threats, NATO Science for Peace and Security Series B: Physics and Biophysics. Springer Netherlands, Dordrecht, pp. 209–213. [https://doi.org/10.1007/978-94-024-2018-0_16

Magnetic enhancement of Co0.2_{0.2}Zn0.8_{0.8}Fe2_2O4_4 spinel oxide by mechanical milling

We report the magnetic properties of mechanically milled Co$_{0.2}$Zn$_{0.8}$Fe$_2$O$_4$ spinel oxide. After 24 hours milling of the bulk sample, the XRD spectra show nanostructure with average particle size $\approx$ 20 nm. The as milled sample shows an enhancement in magnetization and ordering temperature compared to the bulk sample. If the as milled sample is annealed at different temperatures for the same duration, recrystallization process occurs and approaches to the bulk structure on increasing the annealing temperatures. The magnetization of the annealed samples first increases and then decreases. At higher annealing temperature ($\sim$ 1000$^{0}$C) the system shows two coexisting magnetic phases {\it i.e.}, spin glass state and ferrimagnetic state, similar to the as prepared bulk sample. The room temperature M\"{o}ssbauer spectra of the as milled sample, annealed at 300$^{0}$C for different durations (upto 575 hours), suggest that the observed change in magnetic behaviour is strongly related with cations redistribution between tetrahedral (A) and octahedral (O) sites in the spinel structure. Apart from the cation redistribution, we suggest that the enhancement of magnetization and ordering temperature is related with the reduction of B site spin canting and increase of strain induced anisotropic energy during mechanical milling.Comment: 14 pages LaTeX, 10 ps figure

Synthesis, Magnetic Anisotropy and Optical Properties of Preferred Oriented Zinc Ferrite Nanowire Arrays

Preferred oriented ZnFe2O4 nanowire arrays with an average diameter of 16 nm were fabricated by post-annealing of ZnFe2 nanowires within anodic aluminum oxide templates in atmosphere. Selected area electron diffraction and X-ray diffraction exhibit that the nanowires are in cubic spinel-type structure with a [110] preferred crystallite orientation. Magnetic measurement indicates that the as-prepared ZnFe2O4 nanowire arrays reveal uniaxial magnetic anisotropy, and the easy magnetization direction is parallel to the axis of nanowire. The optical properties show the ZnFe2O4 nanowire arrays give out 370–520 nm blue-violet light, and their UV absorption edge is around 700 nm. The estimated values of direct and indirect band gaps for the nanowires are 2.23 and 1.73 eV, respectively

A Mössbauer effect study, as the main key to the investigation of anomalous magnetic properties of MnZn nanoferrite

  In this research, a low temperature in-field 57Fe Mössbauer spectroscopy is used for investigation of anomalous magnetic properties of MnZn nanoferrite. Based on Mössbauer spectroscopy results, the reduced saturation magnetization of MnZn nanoferrite in respect to that of bulk sample is due to nonequilibrium cation distribution and spin disorder. The enhanced Curie temperature of MnZn nanoferrite in respect to that of bulk sample can be attributed to the strengthening of the (A)-O-[B] superexchange interactions due to an increase of the magnetic ion concentration in the (A) site