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Hyperfine interactions in maghemite and magnetite particles
Křišťan, Petr
Thesis is aimed at studying of magnetic iron oxide particles of submicron and nanoscale dimensions by means of nuclear magnetic resonance (NMR). 57 Fe NMR inves- tigations were carried out in composite bentonite/maghemite with respect to tempera- ture of calcination (Tcalc) during the sample preparation and in magnetite submicron powders with respect to various range of the particles size. One of the main findings is that increasing Tcalc improves resolution in the NMR spectra, which is most likely connected with higher degree of atomic ordering in the spinel structure. Evaluating the integral intensities of NMR spectra allowed us to determine the relative content of maghemite phase in particular samples of the series: the content rapidly grows for Tcalc up to ∼420 deg. An approach to distinguish signal from tetrahedral and octahedral irons was developed and tested on pure maghemite sample. Analysis based on vacancy- distribution models was performed in the spinel structure and the results were compared to the experiment. 57 Fe NMR spectra in submicron magnetite samples were found to differ markedly from spectrum of a single crystal. It was concluded that the investigated powders possess high amount of defects in the crystal structure or contain additional phase (probably closely related to the maghemite phase).
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Influence of cationic substitution on hyperfine interactions in magnetite
Řezníček, Richard
The subject matter of the present work is a study of a series of single crystal samples of magnetite with substitutions of zinc and titanium by means of the NMR method. Ions of the zinc substitution Zn2+ replace a part of ferric ions at tetrahedral (A) sites, while the titanium ions Ti4+ occupy octahedral (B) sites replacing iron ions Fe2.5+ . Hyperfine interactions and local electronic structure are sensitive to the presence of substitution. The case when the valence of the substitution ion is different from that of the replaced ion is of a particular interest. Resonance frequencies of nuclei in the neighbourhood of the substitution are shifted due to the modified hyperfine field, thus satellite lines can be observed in NMR spectra. Temperature dependences of spectra above the Verwey transition were measured in a zero external magnetic field. Additionally, NMR spectra were also acquired at the temperature of 4.2 K. Temperature dependences of frequencies of main lines and satellite signals in the spectra above the Verwey transition were constructed and compared to the data for pure magnetite and magnetite with other substitutions and with cationic vacancies. Furthermore, variations of widths of A lines against the temperature above the Verwey transition were found and discussed.
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Hyperfine Interactions in Ferrites with Spinel Structure
Chlan, Vojtěch
Title: Hyperfine Interactions in Ferrites with Spinel Structure Author: Vojtěch Chlan Faculty of Mathematics and Physics, Charles University in Prague Supervisor: Prof. RNDr. Helena Štěpánková, CSc. Abstract: Ferrite systems with spinel structure, manganese ferrite, lithium ferrite and magnetite, are studied experimentally by nuclear magnetic resonance (NMR) spectroscopy and from the first principles by electron structure calculations based on density functional theory (DFT). Manganese ferrites with various degrees of manganese-iron inversion and with different manganese contents are investigated, with respect to magnetic structure and cationic arrangement. An approach for NMR spectra interpretation is elaborated on ordered lithium ferrite, consisting in matching the calculated hyperfine field anisotropy with experimental results. This method is then applied to low temperature structure of magnetite, showing a promising path towards solving its complicated structure, orbital and charge ordering. The switching of magnetic easy axis induced by external magnetic field is observed in magnetite and the accompanying structural changes are studied by means of magnetic and NMR measurements. Magnetite with cationic vacancies is investigated by analyzing satellite structure induced by the vacancies; it is shown that...
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Measuring magnetic properties of environmental samples
Zárubová, Alžběta ; Petrovský, Eduard (advisor) ; Kapička, Aleš (referee)
A. Zárubová: Měření magnetických vlastností environmentálních vzorků 1 ENGLISH ABSTRACT This bachelor's thesis presents briefly principles and examples of applications of magnetic measurements in environmental studies. Environmental magnetism is based on determination of iron oxides, their content, concentration and grain size. This information can be interpreted in terms of particle origin, transport or diagenesis. The results can provide information on, e.g., climatic changes in the past, short-term events influencing our environment (e.g., volcanic eruptions) or about contemporary problems associated with human activity (environmental pollution). In the last case, environmental magnetism does not intend to replace geochemical methods, but the main aim is to provide fast and easily available additional information, which helps us to be more effective in mapping contaminated areas, monitoring progression of pollution or modeling transport processes of contaminants. Magnetometry is currently intensively used for mapping contamination of atmosphere, soils and sediments; it can be used in defining long-term levels of contamination, individual pollution sources and their contribution to the overall pollution. This thesis provides a brief overview of the physical basics of environmental magnetism and examples...
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Low-field excitations in magnetite
Švindrych, Zdeněk ; Janů, Zdeněk (advisor) ; Novák, Pavel (referee) ; Svoboda, Pavel (referee)
We have performed detailed measurements of magnetic and dielectric properties of high quality magnetite (Fe3O4) single crystals in weak magnetic and electric fields. These measurements can reveal details of phase transitions and other features that are not yet fully understood. We focused not only at the Verwey transition - a well known phase transition taking place at about 120 K in stoichiometric samples - but we also explored and described new relaxation effects in magnetite at low temperatures. The low-temperature properties were also found to be exceptionally sensitive to sample quality, stoichiometry and homogeneity. The results presented in this thesis were acquired on sensitive non-commercial SQUID magnetometer complemented by four-probe dielectric spectroscopy and dc conductivity measurements.
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Study of hyperfine interactions in nanoparticles present in biological systems
Kubániová, Denisa ; Kohout, Jaroslav (advisor) ; Závěta, Karel (referee)
In the submitted bachelor thesis we studied iron oxides by zero-field and in-field Mössbauer spectroscopy at room and liquid helium temperature. The relative composition in synthe- tically prepared nanoparticles of ferric oxide in SiO2 matrix is investigated in dependence on ferric oxide concentration and heating temperature and further the phase composi- tion and structure of biological nanoparticles produced by Geoalkalibacter ferrihydriticus bacteries in dependence on concentration of quinone in the cultivating solution. By data analysis the chemical and phase composition of the samples and hyperfine parametres of 57 Fe cations in nonequivalent crystallographic positions are determined. 1
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Hyperfine interactions in maghemite and magnetite particles
Křišťan, Petr ; Štěpánková, Helena (advisor) ; Procházka, Ivan (referee)
Thesis is aimed at studying of magnetic iron oxide particles of submicron and nanoscale dimensions by means of nuclear magnetic resonance (NMR). 57 Fe NMR inves- tigations were carried out in composite bentonite/maghemite with respect to tempera- ture of calcination (Tcalc) during the sample preparation and in magnetite submicron powders with respect to various range of the particles size. One of the main findings is that increasing Tcalc improves resolution in the NMR spectra, which is most likely connected with higher degree of atomic ordering in the spinel structure. Evaluating the integral intensities of NMR spectra allowed us to determine the relative content of maghemite phase in particular samples of the series: the content rapidly grows for Tcalc up to ∼420 deg. An approach to distinguish signal from tetrahedral and octahedral irons was developed and tested on pure maghemite sample. Analysis based on vacancy- distribution models was performed in the spinel structure and the results were compared to the experiment. 57 Fe NMR spectra in submicron magnetite samples were found to differ markedly from spectrum of a single crystal. It was concluded that the investigated powders possess high amount of defects in the crystal structure or contain additional phase (probably closely related to the maghemite phase).
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The use of (nano)oxides for metal and metalloid stabilization in contaminated soils
Michálková, Zuzana ; Komárek, Michael (advisor) ; Luke, Luke (referee)
The main objective of the thesis was to evaluate the potential of selected Mn and Fe (nano)oxides for the stabilization of metals and metalloids in contaminated soils. The research was focused basically on three materials - commercial nanomaghemite (Fe III), nanomagnetite (Fe II,III) and a synthetic amorphous Mn oxide (AMO). The main aim of the work was to provide a complex view on the chosen stabilizing amendments regarding not just their direct influence on contaminants mobility and stabilization mechanisms, but also their stability and alterations in soil conditions together with influence on soil microorganisms and higher plants. Firstly, adsorption properties of the tested materials towards Cd, Cu, Pb and As were investigated. In this context, the most effective material showed to be the AMO reaching one to two orders of magnitude higher adsorption capacities than Fe III and Fe II,III under given experimental conditions. Interestingly, the rate of As(V) adsorption onto AMO was increasing with increasing pH as a result of high pHzpc of the AMO (8.1) and significant dissolution of this phase at lower pH values. As a next step, the influence of (nano)oxides on metal(loid)s mobility and other physico-chemical soil characteristics after application to contaminated soil was examined. Again, the AMO proved to be the most efficient in reducing mobile pools of Cd, Cu, Pb, Zn and As. On the other hand, Fe III and Fe II,III addition had generally less significant effects on contaminants mobility. AMO application further resulted in an increase of soil pH connected with AMO dissolution and unwanted decomposition of soil organic matter. When (nano)oxides alterations in soil conditions were observed, MnCO3 coatings were identified on AMO surface while no significant changes were recorded for Fe III and Fe II,III. As the MnCO3 formation was connected with increased AMO stability, AMO particles synthetically covered with MnCO3 coating (denoted as SM AMO) were prepared. Although the SM-AMO had a lower mass loss in soil than pure AMO, the stabilizing efficiency was almost the same for both materials. The differences in surface composition of both materials were decreasing with time as MnCO3 naturally precipitated on the AMO surface in soils while the SM AMO coating was gradually dissolving. When investigating the effect on soil microbiota, AMO efficiently promoted soil microbial activity while no significant changes were observed in the case of Fe III and Fe II,III. The AMO was also able to reduce the uptake of Cd, Pb and Zn by sunflower (Helianthus annuus L.), eliminate Zn phytotoxicity symptoms and increase biomass yield. On the other hand, toxic levels of Mn released from the AMO in an acidic soil were found in sunflower tissues. AMO application is thus recommended for contaminated neutral or slightly alkaline pH with a higher cation exchange capacity in order to avoid unwanted release of Mn. Finally, various types of AMO-biochar composite sorbents were recently prepared and field experiment focused on stabilization of Cd, Pb, Zn and As using studied materials is currently under preparation. The combined results from the thesis highlight the importance of a complex experimental approach dealing with all parts of the contaminated soil environment in order to obtain complete information about the efficiency and usefulness of any newly developed stabilizing amendment.
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Single Atomic Catalysts
Závodný, Adam ; Švec,, Martin (referee) ; Čechal, Jan (advisor)
Single atom catalysts are prospective class of materials, which holds promises to reach the ultimate limit of improvement in catalyst performance, selectivity, lifetime and cost reduction. The ability to efficiently capture the adsorbates at the active sites is the key prerequisite for catalytic transformation to the products. In this respect, our experimental study aims to describe the interaction of gas molecules (H2O, CO, O2 and NO) with single metal atoms (Rh, Ir, Cu) on the magnetite surface employing scanning tunneling microscopy.
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Magnetic modification of microbial cells
BALDÍKOVÁ, Eva
Baker´s yeast (Saccharomyces cerevisiae) were magnetically modified by three different methods, namely, surface modification by magnetic fluid, entrapment of cells into alginate and covalent immobilization on particles of magnetic chitosan. The ability of H2O2 decomposition was tested for all types of modification. It is apparent that the most amount of hydrogen peroxid was degraded by magnetic fluid - modified cells (84-95%), while the efficiency of cell which were modified by other methods was much lower (40-60%). Thanks to immobilization on particles of magnetic chitosan, we made completely new type of magnetic material, which was tested for adsorption of Crystal violet and Safranin O. It was founded that magnetic chitosan adsorbs no dyes, so all adsorption belongs to immobilized yeast. The maximum adsorption capacities were determined using Langmuire isotherm at 69,4 mg/g for Crystal violet and 99,0 mg/g for Safranin O.
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