Magnetic phase transitions in nanostructures induced by shear stress under high pressure

Magnetic phase transitions of the first and second order were revealed by Mössbauer spectroscopy in nanosystems of - and -ferric oxides and metallic europium subjected to shear stress (240°) under high pressure (20 kbar). For - and -ferric oxide nanoclusters, the Curie (Neel) points decreased to 300 K, whereas for nanostructured europium the Neel point increased from 90 to 100 K. The thermodynamic model of magnetic phase transitions predicting a change in the character of magnetic phase transitions and a decrease (increase) in the critical Neel (Curie) points in nanoclusters was developed. The type of magnetic phase transitions and the change in the critical points were caused by defects in nanoclusters, whose maximum concentration was observed for the clusters with the 20—50 nm size range.     

Effectiveness of linearization of calibration curves in Zeeman graphite furnace atomic absorption spectrometry

A theoretical analysis is made of the effect of analytical line broadening and of non-absorbable radiation in the light source on the shape of concentration curves in Zeeman graphite furnace atomic absorption spectrometry. These results have been used in a systematic study of the effect of spectrometer slit width and hollow-cathode lamp (HCL) current on linearization of calibration graphs for 11 elements: Ag, Au, Bi, Cd, Co, Cu, Fe, Mn, Ni, Pb, and Sb. The effectiveness of linearization throughout the analytical range covered was estimated experimentally on series of 25–30 solutions. Three solutions in each series were used as standards for constructing the calibration graph, the others serving to evaluate the linearization effectiveness. Increasing the slit width and decreasing the HCL current compared to the standard measurement conditions have permitted us to reach a sufficiently high effectiveness of linearization for all the elements studied, with the exception of Ni. The maximum deviation of experimental points from the linear graph under optimum conditions does not exceed 6%. The effect of the Δ parameter used in the computational algorithm on linearization effectiveness is investigated.     

Structural Transformation of a (1 – x)Fe2O3–xRuO2 Nanosystem at Different Reduction Temperatures

Technical Physics - The phase composition and structure of oxide and hydrogen-reduced iron–ruthenium systems are studied using conversion and adsorption Mössbauer spectroscopy, as well...     

Precision and detection limits in Zeeman graphite furnace atomic absorption spectrometry

This is the first theoretical study of photometric errors in Zeeman graphite furnace atomic absorption spectrometry with evaluation of their effect on the precision in the traditional method of peak area determination and the pulse restoration method proposed earlier for linearization and expansion of calibration curves. Besides the fraction of non-absorbed radiation, α, and Zeeman sensitivity ratio, R, the theoretical calculations make use of three more parameters, namely the “energy” value, E, the baseline offset compensation time, t_toc, and the integration time, t_int. The theoretical calculations are supported by experimental data on detection limits for a number of elements and on the RSD obtained in Ag and Cd determinations. A comparison of the precision in the case of pulses with dips has shown the pulse restoration method to be superior over the traditional technique. The theoretical results can be used to improve the measurement precision and the detection limits by proper modification of the spectrophotometer and optimization of experimental conditions.     

Magnetic Phase Transitions in Nanosystems: Role of Size Effects,Intercluster Interactions and Defects

Shear stress under high pressure loaded nanoclusters of α, γ-ferric oxides and metallic europium showed first- and second-order magnetic phase transitions. For nanoclusters of α, γ-ferric oxides and metallic europium 57Fe and 151Eu, Mossbauer spectroscopy revealed a considerable change in the Curie (Neel) points. The thermodynamic model predicts first-to-second-order (Eu) and second-to-first-order (Fe oxides) changes in the character of magnetic phase transitions and a decrease or increase of critical Curie (Neel) points. The model defines the critical cluster size and concentration of defects in nanosystems responsible for the change in magnetic properties. For nanoclusters of Fe oxides and metallic Eu, the critical (and maximum) concentration of defects corresponds to a cluster size 20–50nm.     

Mössbauer spectroscopy and proton relaxometry study of magnetite nanoparticles designed for preparing diagnostic contrast media

Mössbauer spectroscopy, proton relaxometry, and transmission electron microscopy are used to study magnetite nanoparticles designed for creating diagnostic contrast media. Superparamagnetic magnetite nanoparticles with a size of 5–7 nm and blocking temperature of T _b = 50 K are examined as a component of diagnostic contrast media with relaxation times T ₁ and T ₂ capable of circulating in the bloodstream for a long time. Larger ferrimagnetic nanoparticles (30–40 nm) can be concentrated in pathological tissues by applying an external magnetic field, thereby providing a means for hyperthermia.     

The formation of magnetic iron clusters on activated carbon

A series of carbon-supported iron samples for medical usage has been studied by means of Mössbauer spectroscopy. The spectra obtained at 300 K and 80 K show the coexistence of α-Fe and iron oxides particles. The influence of reduction temperature, pore size distribution and surface properties of active carbon on the state of iron are derived.     

Magnetic properties of ultrafine ferrihydrite clusters studied by Mossbauer spectroscopy and by thermodynamical analysis

Magnetic properties of ultrafine clusters of Fe₅HO₈·₄H₂O (ferrihydrite, FH), isolated in pores of polysorb, were studied by Mossbauer spectroscopy and by thermodynamical analysis. Thermodynamical analysis allowed the conclusion that magnetic properties of ultrafine clusters cannot be interpreted in terms of a secondorder magnetic phase transition or of superparamagnetic behavior alone but require the consideration of a jumplike first order magnetic phase transition (JMT). The critical radius R _cr below which the JMT is to be expected in clusters was derived from thermodynamic criteria. It was determined as R _cr = 2 α β η/(1 - T _cc/T ₀), where α, β and η are constants derived from surface energy, magnetostriction, compressibility and T _cc = 3/2 Nκ _B T _o ² ηβ ² (N is the number of iron atoms, κ _B is the Boltzmann constant, T _o is the Curie temperature of the clusters). For the smallest FH clusters isolated in pores of polysorb, the critical radius and the JMT temperature were estimated by Mossbauer spectroscopy to be R _cr ～ 1.5–2.0 nm and T _JMT ～ 4.2–6 K, respectively. Satisfactory agreement between the value R _cr, estimated from the experimental data and the one derived by thermodynamical analysis was achieved. Interfacial (cluster-surface) and intercluster interactions were found to destroy the JMT effect and to give rise to a second-order magnetic phase transition.