Soma Salamon

Mössbauer Study of Temperature-Dependent Cycloidal Ordering in BiFeO3 Nanoparticles

To study the effects of different temperatures and particle sizes on the anharmonic cycloidal spin structure in BiFeO3 nanoparticles, Mössbauer spectroscopy was applied to three sets of particles with different mean diameters in the range of 54 nm to 1.6 μm at temperatures between 4.2 and 800 K. The paramagnetic transition showed a distinct broadening upon decreasing particle size with Néel temperatures decreasing from 652 to 631 K. The anharmonicity of the long-range cycloidal structure, calculated from experimental Mössbauer spectra, is revealed to decrease upon rising temperature, starting at 150-200 K and reaching the harmonic state at about 400 K.

A new (Ba, Ca) (Ti, Zr)O3 based multiferroic composite with large magnetoelectric effect

The lead-free ferroelectric 0.5Ba(Zr0.2Ti0.8)O3 − 0.5(Ba0.7Ca0.3)TiO3 (BCZT) is a promising component for multifunctional multiferroics due to its excellent room temperature piezoelectric properties. Having a composition close to the polymorphic phase boundary between the orthorhombic and tetragonal phases, it deserves a case study for analysis of its potential for modern electronics applications. To obtain magnetoelectric coupling, the piezoelectric phase needs to be combined with a suitable magnetostrictive phase. In the current article, we report on the synthesis, dielectric, magnetic, and magnetoelectric characterization of a new magnetoelectric multiferroic composite consisting of BCZT as a piezoelectric phase and CoFe2O4 (CFO) as the magnetostrictive phase. We found that this material is multiferroic at room temperature and manifests a magnetoelectric effect larger than that of BaTiO3 −CoFe2O4 bulk composites with similar content of the ferrite phase.

Multiferroic clusters: a new perspective for relaxor-type room-temperature multiferroics

Multiferroics are promising for sensor and memory applications, but despite all efforts invested in their research no single-phase material displaying both ferroelectricity and large magnetization at room-temperature has hitherto been reported. This situation has substantially been improved in the novel relaxor ferroelectric single-phase (BiFe0.9Co0.1O3)0.4-(Bi1/2K1/2TiO3)0.6, where polar nanoregions (PNR) transform into static-PNR (SPNR) as evidenced by piezoresponse force microscopy (PFM) and simultaneously enable congruent multiferroic clusters (MFC) to emerge from inherent strongly magnetic Bi(Fe,Co)O3 rich regions as verified by magnetic force microscopy (MFM) and secondary ion mass spectrometry (SIMS). The material’s exceptionally large Neel temperature TN = 670 ± 10 K, as found by neutron diffraction, is proposed to be a consequence of ferrimagnetic order in MFC. On these MFC, exceptionally large direct and converse magnetoelectric coupling coefficients, α ≈ 1.0 x 10-5 s/m at room-temperature, were measured by PFM and MFM respectively. We expect the non-ergodic relaxor properties which are governed by the Bi1/2K1/2TiO3 component to play a vital role in the strong ME coupling, by providing an electrically and mechanically flexible environment to MFC. This new class of non-ergodic relaxor multiferroics bears great potential for applications. Especially the prospect of a ME nanodot storage device seems appealing.

Open volume defects and magnetic phase transition in Fe60Al40 transition metal aluminide

Magnetic phase transition in the Fe60Al40 transition metal aluminide from the ferromagnetic disordered A2-phase to the paramagnetic ordered B2-phase as a function of annealing up to 1000 °C has been investigated by means of magneto-optical and spectroscopy techniques, i.e., Kerr effect, positron annihilation, and Mossbauer spectroscopy. The positron annihilation spectroscopy has been performed in-situ sequentially after each annealing step at the Apparatus for In-situ Defect Analysis that is a unique tool combining positron annihilation spectroscopy with temperature treatment, material evaporation, ion irradiation, and sheet resistance measurement techniques. The overall goal was to investigate the importance of the open volume defects onto the magnetic phase transition. No evidence of variation in the vacancy concentration in matching the magnetic phase transition temperature range (400–600 °C) has been found, whereas higher temperatures showed an increase in the vacancy concentration.

Role of Composition and Size of Cobalt Ferrite Nanocrystals in the Oxygen Evolution Reaction

Sub‐10 nm CoFe2O4 nanoparticles with different sizes and various compositions obtained by (partial) substitution of Co with Ni cations have been synthesized by using a one‐pot method from organic solutions by the decomposition of metal acetylacetonates in the presence of oleylamine. The electrocatalytic activity of CoFe2O4 towards the oxygen evolution reaction (OER) is clearly enhanced with a smaller size (3.1 nm) of the CoFe2O4 nanoparticles (compared with 4.5 and 5.9 nm). In addition, the catalytic activity is improved by partial substitution of Co with Ni, which also leads to a higher degree of inversion of the spinel structure. Theoretical calculations attribute the positive catalytic effect of Ni owing to the lower binding energy differences between adsorbed O and OH compared with pure cobalt or nickel ferrites, resulting in higher OER activity. Co0.5Ni0.5Fe2O4 exhibited a low overpotential of approximately 340 mV at 10 mA cm−2, a smaller Tafel slope of 51 mV dec−1, and stability over 30 h. The unique tunability of these CoFe2O4 nanocrystals provides great potential for their application as an efficient and competitive anode material in the field of electrochemical water splitting as well as for systematic fundamental studies aiming at understanding the correlation of composition and structure with performance in electrocatalysis.

Simultaneous Study of Brownian and Neel Relaxation Phenomena in Ferrofluids by Mossbauer Spectroscopy.

We demonstrate the ability of Mössbauer spectroscopy to simultaneously investigate Brownian motion and Néel relaxation in ferrofluidic samples. For this purpose, Mössbauer spectra of coated iron oxide nanoparticles with core diameters of 6.0-26.4 nm dissolved in 70 vol % glycerol solution were recorded in the temperature range of 234-287 K and compared to low-temperature spectra without Brownian motion. By comparison to theory, we were able to determine the particle coating thickness and the dynamic viscosity of the fluid from the broadening of the absorption lines (Brownian motion), as well as the state of Néel relaxation. Results from Mössbauer spectroscopy were crosschecked by AC-susceptometry at several temperatures for Brownian motion and in the high-frequency regime (100 Hz-1 MHz) for Néel relaxation.

Moment-Volume Coupling in La(Fe1−x Si x )13

We investigate the origin of the volume change and magnetoelastic interaction observed at the magnetic first-order transition in the magnetocaloric system La(Fe1-xSix)(13) by means of first-principles calculations combined with the fixed-spin moment approach. We find that the volume of the system varies with the square of the average local Fe moment, which is significantly smaller in the spin disordered configurations compared to the ferromagnetic ground state. The vibrational density of states obtained for a hypothetical ferromagnetic state with artificially reduced spin-moments compared to a nuclear inelastic X-ray scattering measurement directly above the phase transition reveals that the anomalous softening at the transition essentially depends on the same moment-volume coupling mechanism. In the same spirit, the dependence of the average local Fe moment on the Si content can account for the occurence of first- and second-order transitions in the system.

Local electronic and magnetic properties of pure and Mn-containing magnetocaloric LaFe13-xSix compounds inferred from Mossbauer spectroscopy and magnetometry

Manganese containing La–Fe–Si alloys are important magnetocaloric compounds, since Mn atoms prevent segregation of hydrogen in partially hydrogenated La–Fe–Mn–Si alloys when their Curie temperature is tuned to room temperature by hydrogen. The effect of Mn alloying on the Fe atomic magnetic moment μ Fe is still rather unexplored. Therefore, we investigated the (local) magnetic and electric hyperfine interactions in the strongly magnetocaloric compound LaFe11.3Mn0.3Si1.4 and, for comparison, LaFe11.6Si1.4 by 57Fe Mossbauer spectroscopy, and the global magnetic properties by vibrating sample magnetometry. The NaZn13 structure was confirmed by x-ray diffraction. Two non-equivalent Fe lattice sites are known to exist in this material: the (96i) sites (FeII) of low local symmetry, and the highly symmetrical (8b) sites (FeI). At room temperature in the paramagnetic state, the electric hyperfine parameters of Fe atoms on both sites were obtained. At low temperatures (4.8 K), the observed magnetically split nuclear Zeeman sextets with broad apparent lines were analyzed in terms of a distribution P(B hf) of hyperfine magnetic fields B hf. The average hyperfine field 〈B hf〉, originating predominantly from FeII sites, was found to be rather high (30.7(1) T at 4.8 K) for LaFe11.6Si1.4, and the approximate relation 〈B hf〉 = Aμ Fe is confirmed for FeII sites, with A = 14.2 T/μ B. 〈B hf〉 is significantly reduced (to 27.7(1) T at 4.8 K) for the Mn-containing sample LaFe11.3Mn0.3Si1.4, providing evidence for a reduction by 9.7% of the average Fe atomic moment μFe from ~2.16 μ B to a value of ~1.95 μ B by Mn substitution of Fe. Our Mossbauer results are in good agreement with magnetometry, which reveals a reduction of the saturation magnetization of M s = 163.1(1) Am2 kg−1 of LaFe11.6Si1.4 by 10.5% due to Mn substitution.

Adjusting the catalytic properties of cobalt ferrite nanoparticles by pulsed laser fragmentation in water with defined energy dose

Highly active, structurally disordered CoFe2O4/CoO electrocatalysts are synthesized by pulsed laser fragmentation in liquid (PLFL) of a commercial CoFe2O4 powder dispersed in water. A partial transformation of the CoFe2O4 educt to CoO is observed and proposed to be a thermal decomposition process induced by the picosecond pulsed laser irradiation. The overpotential in the OER in aqueous alkaline media at 10 mA cm−2 is reduced by 23% compared to the educt down to 0.32 V with a Tafel slope of 71 mV dec−1. Importantly, the catalytic activity is systematically adjustable by the number of PLFL treatment cycles. The occurrence of thermal melting and decomposition during one PLFL cycle is verified by modelling the laser beam energy distribution within the irradiated colloid volume and comparing the by single particles absorbed part to threshold energies. Thermal decomposition leads to a massive reduction in particle size and crystal transformations towards crystalline CoO and amorphous CoFe2O4. Subsequently, thermal melting forms multi-phase spherical and network-like particles. Additionally, Fe-based layered double hydroxides at higher process cycle repetitions emerge as a byproduct. The results show that PLFL is a promising method that allows modification of the structural order in oxides and thus access to catalytically interesting materials.

Molecular Design for Tailoring a Single-Source Precursor for Bismuth Ferrite

Nearly phase-pure bismuth ferrite particles were formed by thermolysis of the single-source precursor [Cp(CO)2FeBi(OAc)2] (1) in octadecene at 245 °C, followed by subsequent calcination at 600 °C for 3 h. In contrast, the slightly modified compound [Cp(CO)2FeBi(O2C(t)Bu)2] (2) yielded only mixtures of different bismuth oxide phases, revealing the distinctive influence of molecular design in material synthesis. The chemical composition, morphology, and crystallinity of the resulting materials were investigated by X-ray diffraction, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. In addition, the optical properties were investigated by Fourier transform infrared and UV-vis spectroscopies, showing a strong band gap absorption in the visible range at 590 nm (2.2 eV). The magnetic behavior was probed by vibrating-sample and superconducting quantum interference device magnetometry, as well as (57)Fe Mössbauer spectroscopy.