Thesis. 1977. M.S.--Massachusetts Institute of Technology. Dept. of Earth and Planetary Sciences. / Microfiche copy available in Archives and Science. / Vita. / Bibliography : leaves 77-79. / M.S.

Investigamos o fenômeno da segregação de fases em ligas ferro-níquel de estrutura cúbica de faces centradas, na região do invar (~35 a 50% Ni ). As amostras foram preparadas pela decomposição térmica de oxalatos mistos Fe1-x Ni xC2O4.2H20, a temperaturas selecionadas; este método de preparação assegura que o equilíbrio termodinâmico é atingido muito mais rapidamente que pelos métodos convencionais. As amostras foram examinadas por espectroscopia Mössbauer; evidências anteriores mostraram que as duas f ases resultantes da segregação diferem notavelmente em suas propriedades magnéticas, mas são idênticas do ponto de vista estrutural, o que impossibilita a sua distinção pelas técnicas usuais de raios X. Amostras foram preparadas com concentrações entre 36 e 50% Ni e a temperaturas entre 350 e 600°C. O aparecimento de uma linha central no espectro Mössbauer foi usado como critério para a ocorrência de segregação. Dessa forma, mapeamos a fronteira do \"gap\" de miscibilidade nessa região do diagrama de fases do Fe-Ni. / We have investigated the phenomenon of phase segregation in iron-nickel alloys with a face-centered cubic structure, in the invar region (~35 to 50% Ni ). The samples were prepared by thermal decomposition of mixed oxalates, Fe1-x Ni xC2O4.2H20, at selected temperatures. This method ensures that thermodynamic equilibrium is reached much more rapidly than by conventional methods. The samples were examined by means of Mössbauer spectroscopy; previous evidence has shown that the two phases resulting from segregation differ markedly in their magnetic properties but are structurally identical, which renders their distinction impossible by usual X-ray techniques. Samples were prepared at concentrations between 36 and 50% Ni and at temperatures ranging from 350 to 600°C. The appearance of a central line in the Mössbauer spectrum was taken as the criterion for segregation occurrence. We thus mapped the miscibility gap boundary in this region of the Fe-Ni phase diagram.

Investigamos os fenômenos de reorientação de spins em diversos compostos intermetálicos com a estrutura tipo ThMn IND. 12. Foram estudadas as ligas pseudoternárias (Dy IND. XGd IND. 1-x)Fe IND. 11Ti, (Dy IND. XEr IND. 1-x)Fe IND. 11Ti e (Tb IND. XGd IND. 1-X)Fe IND. 11Ti e o composto ternário DyFe IND. 10Si IND. 2. As técnicas utilizadas neste trabalho foram: suscetibilidade AC em campos baixos, dependência angular da magnetização em amostras orientadas, e espectroscopia Mössbauer. Todas as ligas sofrem uma reorientação de spins do tipo axial-cônico ao abaixar-se a temperatura. Além disto, (Dy IND. XGd IND. 1-x)Fe IND. 11Ti, (Dy IND. XEr IND. 1-x)Fe IND. 11Ti exibem uma reorientação cônico-planar a baixas temperaturas, mas somente para um intervalo limitado de concentrações de Gd ou Er, (Tb IND. XGd IND. 1-X)Fe IND. 11Ti, por outro lado, sofre uma transição axial-planar para x > 0,6, e nenhuma transição para x < 0,6. A partir de um modelo a um íon para as interações de troca e de campo cristalino, calculamos diagramas de fase magnéticos, que apresentaram boa concordância com os dados experimentais. Finalmente, estudamos a reorientação de spins em DyFe IND. 10Si IND. 2 por meio de uma análise detalhada da variação dos parâmetros hiperfinos do ANTPOT. 57 Fe com a temperatura. Dessa forma, determinamos com precisão o intervalo de temperaturas da transição axial-cônica e confinamos a ausência de uma transição cônica-planar neste composto. / We have investigated spin reorientation phenomena in various rare earth-iron intermetallic compounds with the ThMnl2 structure. Pseudoternary (DyxGdl-x)Fe11Ti, (DyEr1-x)Fe11Ti and (TbxGd1-x)Fe11Ti alloys and the ternary compound DyFe10Si2 were studied. The experimental techniques used in this work were: low-field AC susceptibility, oriented-powder magnetization angular dependence, and Mössbauer spectroscopy. All alloys studied undergo an axial-conical spin reorientation on cooling. In addition, (DyxGdl-x)Fe11Ti and(DyEr1-x)Fe11Ti exhibit a conical-planar reorientation at lower temperatures, but on1y for a small Gd or Er concentration range. (TbxGd1-x)Fe11Ti alloys, on the other hand, undergo a single axial-planar transition for x > 0.6, and no reorientation at all for x < 0.6. Theoretical magnetic phase diagrams were calculated with a single-ion model for exchange and crystal-field interactions, showing good agreement with the experimental data. Finally, the DyFe10Si2 reorientation was studied by means of a detailed analysis of the 57Fe hyperfine parameters temperature dependence; in this way the axial-conical transition temperature interval was accurately determined, and the absence of a further conical-planar transition for this compound was confirmed.

Investigamos os fenômenos de reorientação de spins em diversos compostos intermetálicos com a estrutura tipo ThMn IND. 12. Foram estudadas as ligas pseudoternárias (Dy IND. XGd IND. 1-x)Fe IND. 11Ti, (Dy IND. XEr IND. 1-x)Fe IND. 11Ti e (Tb IND. XGd IND. 1-X)Fe IND. 11Ti e o composto ternário DyFe IND. 10Si IND. 2. As técnicas utilizadas neste trabalho foram: suscetibilidade AC em campos baixos, dependência angular da magnetização em amostras orientadas, e espectroscopia Mössbauer. Todas as ligas sofrem uma reorientação de spins do tipo axial-cônico ao abaixar-se a temperatura. Além disto, (Dy IND. XGd IND. 1-x)Fe IND. 11Ti, (Dy IND. XEr IND. 1-x)Fe IND. 11Ti exibem uma reorientação cônico-planar a baixas temperaturas, mas somente para um intervalo limitado de concentrações de Gd ou Er, (Tb IND. XGd IND. 1-X)Fe IND. 11Ti, por outro lado, sofre uma transição axial-planar para x > 0,6, e nenhuma transição para x < 0,6. A partir de um modelo a um íon para as interações de troca e de campo cristalino, calculamos diagramas de fase magnéticos, que apresentaram boa concordância com os dados experimentais. Finalmente, estudamos a reorientação de spins em DyFe IND. 10Si IND. 2 por meio de uma análise detalhada da variação dos parâmetros hiperfinos do ANTPOT. 57 Fe com a temperatura. Dessa forma, determinamos com precisão o intervalo de temperaturas da transição axial-cônica e confinamos a ausência de uma transição cônica-planar neste composto. / We have investigated spin reorientation phenomena in various rare earth-iron intermetallic compounds with the ThMnl2 structure. Pseudoternary (DyxGdl-x)Fe11Ti, (DyEr1-x)Fe11Ti and (TbxGd1-x)Fe11Ti alloys and the ternary compound DyFe10Si2 were studied. The experimental techniques used in this work were: low-field AC susceptibility, oriented-powder magnetization angular dependence, and Mössbauer spectroscopy. All alloys studied undergo an axial-conical spin reorientation on cooling. In addition, (DyxGdl-x)Fe11Ti and(DyEr1-x)Fe11Ti exhibit a conical-planar reorientation at lower temperatures, but on1y for a small Gd or Er concentration range. (TbxGd1-x)Fe11Ti alloys, on the other hand, undergo a single axial-planar transition for x > 0.6, and no reorientation at all for x < 0.6. Theoretical magnetic phase diagrams were calculated with a single-ion model for exchange and crystal-field interactions, showing good agreement with the experimental data. Finally, the DyFe10Si2 reorientation was studied by means of a detailed analysis of the 57Fe hyperfine parameters temperature dependence; in this way the axial-conical transition temperature interval was accurately determined, and the absence of a further conical-planar transition for this compound was confirmed.

Investigamos o fenômeno da segregação de fases em ligas ferro-níquel de estrutura cúbica de faces centradas, na região do invar (~35 a 50% Ni ). As amostras foram preparadas pela decomposição térmica de oxalatos mistos Fe1-x Ni xC2O4.2H20, a temperaturas selecionadas; este método de preparação assegura que o equilíbrio termodinâmico é atingido muito mais rapidamente que pelos métodos convencionais. As amostras foram examinadas por espectroscopia Mössbauer; evidências anteriores mostraram que as duas f ases resultantes da segregação diferem notavelmente em suas propriedades magnéticas, mas são idênticas do ponto de vista estrutural, o que impossibilita a sua distinção pelas técnicas usuais de raios X. Amostras foram preparadas com concentrações entre 36 e 50% Ni e a temperaturas entre 350 e 600°C. O aparecimento de uma linha central no espectro Mössbauer foi usado como critério para a ocorrência de segregação. Dessa forma, mapeamos a fronteira do \"gap\" de miscibilidade nessa região do diagrama de fases do Fe-Ni. / We have investigated the phenomenon of phase segregation in iron-nickel alloys with a face-centered cubic structure, in the invar region (~35 to 50% Ni ). The samples were prepared by thermal decomposition of mixed oxalates, Fe1-x Ni xC2O4.2H20, at selected temperatures. This method ensures that thermodynamic equilibrium is reached much more rapidly than by conventional methods. The samples were examined by means of Mössbauer spectroscopy; previous evidence has shown that the two phases resulting from segregation differ markedly in their magnetic properties but are structurally identical, which renders their distinction impossible by usual X-ray techniques. Samples were prepared at concentrations between 36 and 50% Ni and at temperatures ranging from 350 to 600°C. The appearance of a central line in the Mössbauer spectrum was taken as the criterion for segregation occurrence. We thus mapped the miscibility gap boundary in this region of the Fe-Ni phase diagram.

An intriguing mystery about tryptophan 2, 3-dioxygenase is its hydrogen peroxide-triggered enzyme reactivation from the resting ferric oxidation state to the catalytically active ferrous form. In this study, we found that such an odd Fe(III) reduction by an oxidant depends on the presence of L-Trp, which ultimately serves as the reductant for the enzyme. In the peroxide reaction with tryptophan 2, 3-dioxygenase, a previously unknown catalase-like activity was detected. A ferryl species (δ = 0.055 mm/s and ΔEQ = 1.755 mm/s) and a protein-based free radical (g = 2.0028 and 1.72 millitesla linewidth) were characterized by Mössbauer and EPR spectroscopy, respectively. This is the first compound ES-type of ferryl intermediate from a heme-based dioxygenase characterized by EPR and Mössbauer spectroscopy. Density functional theory calculations revealed the contribution of secondary ligand sphere to the spectroscopic properties of the ferryl species. A Trp-Trp dimer and a monooxygenated L-Trp were both observed as the enzyme reactivation by-products by mass spectrometry. Together, these results lead to the unraveling of an over 60-year old mystery of peroxide reactivation mechanism.

The synthesis, structure and physical properties of a series of Mnx(Co, Mg)₁ˍxFe₂O₄, (Mg, Sr)₀.₂ Mn₀.₁Co₀.₇Fe₂O₄ and Mg₀.₅Mn₀.₅(RE)₀.₁Fe₁.₉O₄ (where RE are rare earth elements) nanoferrites have been studied. These compounds were synthesized at low reaction temperature of about 200 ⁰C using the glycol-thermal method. The starting materials were high-purity metal chlorides or nitrates which were precipitated by NH₄OH and KOH respectively. In addition, MnxCo₁₋xFe₂O₄ (x = 0, 0.5 and 1) samples were produced directly from high-purity metal oxides by high-energy ball milling technique. Single-phase cubic spinel structure and nanoparticle structure of the synthesized samples were confirmed by X-ray diffraction (XRD) and transmission electron microscope (TEM). The results show that the produced powders of the asprepared samples have average grain sizes ranging from 7 to 16 nm. Filtering the precipitates by Whatman glass microfiber filters (GF/F) appears to be important in obtaining the small particle sizes. We suspect higher stability of the MnxCo₁₋xFe₂O₄ at x = 0 and 0.5 where complete symmetry in the proportion of the atoms on tetrahedral (A) and octahedral (B) sites would tend to favour larger nanoparticles. The evolutions of the magnetic properties as a function of composition, annealing temperature under air and argon atmospheres or measuring temperature have been investigated by ⁵⁷Fe Mössbauer spectroscopy, vibration sample magnetometer (VSM) and superconducting quantum interference device (SQUID). Significant changes in magnetic properties are observed across the composition ranges studied. The Mössbauer spectra indicate ferrimagnetic, superparamagnetic and paramagnetic behaviours of the compounds. The results show evidence of transformation from single-domain to multi-domain structure with thermal annealing in our samples. Temperature dependence of magnetization shows differences between field cooling (FC) and zero field cooling (ZFC) which we attribute to spin-freezing and thermal relaxation for typical nanoparticles. Significant increase in coercive field with reduction in measuring temperature is obtained in Co- based compounds. Mn₀.₅Co₀.₅Fe₂O₄, Sr₀.₂Mn₀.₁Co₀.₇Fe₂O₄ and Mg₀.₂Mn₀.₁Co₀.₇Fe₂O₄ have large coercive fields of 1.45, 3.02 and 10.70 kOe at 4 K compared to 0.17, 0.05 and 0.05 kOe at room temperature respectively. Variation of coercive fields (Hc) with measuri ing temperature for MnxCo₁₋xFe₂O₄ (x = 0.1 and 0.05), (Mg, Sr)₀.₂Mn₀.₁Co₀.₇Fe₂O₄ nanoferrites follow the Kneller's law for uniaxial non-interacting single domain particles of the form Hc(T) = Hc(0)[1-( T/Tβ)α]. The observed temperature dependences are consistent with α = 1/2. We also find evidence of the departure from this law at lower temperature. The temperature dependence of the saturation magnetizations were observed to vary with temperature according to the modified Bloch's law Ms(T) = Ms(0)[1 - ( T/T₀)ᵝ] where β is at least 1.5. This is attributed to the confinement effects of the spin-wave spectrum for magnetic clusters. The equation appears to fit the saturation magnetization data over the entire temperature range with values of β from 2.1 to 2.4 for the samples studied. These results are consistent with the nanoparticle nature of the compounds. In Mg₀.₅Mn₀.₅(RE)₀.₁Fe₁.₉O₄ nanoferrites, the grain sizes, lattice parameters and saturation magnetizations increase with RE substitution which we attribute to larger RE ions substituting smaller Fe ions. The results show evidence of superparamagnetic behaviour of the nanoparticles. The highest grain size and magnetizations are obtained for the Gd substituted sample. We find strong correlation between the saturation magnetizations, grain sizes and microstrains with de Gennes factor G. The correlation with grain sizes and microstrains appear to be unique and characteristic of the nanoparticle nature of the compounds. Bulk samples in the form of pellets were also produced from the as-prepared samples of MnxCo₁₋xFe₂O₄ for resistivity measurements. The temperature dependence of the electrical resistivity for samples sintered from 600 - 1100 ⁰C under argon atmosphere were studied using the four-probe method from room temperature to about 110 ⁰C. Two possible mechanisms for resistivity involving Tˉ¹ and Tˉ¹/² dependences were investigated which we associated with semiconducting and inter-grain conductivity respectively. The Tˉ¹/² dependence is found to fit the data better and predicts higher activation energies. The resistivity was observed to be sensitive to the surface of the pellet being probed and the annealing temperature. / Thesis (Ph.D.)-University of KwaZulu-Natal, Durban, 2012.

Iron is essential in nearly all organisms. It is a cofactor in many proteins and enzymes. This transition metal can also be toxic because it participates in reactions which produce reactive oxygen species. To avoid these toxic effects while still being used for essential processes, the cell must regulate tightly iron import, metabolism, trafficking, and homeostasis. These processes were studied using biophysical methods centered on Mossbauer spectroscopy supplemented by electron paramagnetic resonance, electronic absorption spectroscopy, and inductively coupled plasma mass spectrometry. This integrated biophysical approach was applied to yeast cells, isolated yeast mitochondria, and mouse brains. We determined the concentration of Fe, and the proportion of that Fe present as iron-sulfur clusters, heme centers, mononuclear nonheme centers, and as Fe3+ oxyhydroxide (phosphate) nanoparticles for each system. In yeast, the dependence of metabolic mode of growth and iron in the growth medium on this distribution was studied. Approximately three-quarters of the iron in fermenting cells was located in vacuoles, where it was present as high-spin mononuclear Fe3+ species with rhombic symmetry. The remaining quarter was present in the mitochondria. In fermenting mitochondria 4 distinct species of iron were observed, including [Fe4S4]2+ clusters and low-spin Fe2+ hemes arising from respiratory complexes, non-heme high spin (NHHS) Fe2+ species, high spin nonheme Fe3+ species, and nanoparticles. These distributions (in both the cells and mitochondria) change when the cells are grown on iron deficient medium but remained relatively unaltered as iron in the growth medium was increased. Respiring cells had less Fe associated with vacuoles, and more Fe present as HS Fe2+. Respiring mitochondria contain more [Fe4S4]2+ clusters and low-spin Fe2+ hemes, more S = 1/2 [Fe2S2]1+ clusters, and less NHHS Fe2+, HS Fe3+ species and Fe3+ nanoparticles. These changes were rationalized by assuming that the NHHS Fe2+ and Fe3+ species, and the nanoparticles were in equilibrium within the matrix of the mitochondria, and that the Fe2+ species served as feedstock for the synthesis of iron-sulfur clusters and heme centers. The iron in the mouse brain consisted mostly of [Fe4S4]2+ clusters and Fe2+ hemes from mitochondria respiratory complexes, and of ferritin, an Fe storage protein complex. NHHS Fe2+ and Fe3+ species were also observed. The ratio of stored Fe to mitochondrial Fe was sensitive to age. The brains of prenatal animals were dominated by ferritin. Following birth up to the first 4 weeks of life, there was an increase in mitochondrial Fe and a decline of ferritin Fe. Beyond 4 weeks up to 58 weeks, levels of ferritin increased and mitochondrial Fe remained constant. The brains of mice fed an Fe-deficient diet were also studied; most of the Fe in these brains was present as mitochondrial Fe, with little stored as ferritin. A model was developed to explain these changes.

M.Sc. (Physics) / Please refer to full text to view abstract

Multiferroic materials, in which spontaneous orderings (especially magnetic and electrical, in some cases elastic) jointly exist and may mutually interact, are currently in the center of attention in many fields of research due to their high application potential. They are already used in many applications, as in various sensors, microwave filters or electro / magneto- mechanical manipulators and actuators. Nevertheless, many features of microstructure and moment arrangements are not yet fully explained and understood. The presented work is mostly experimental and focuses on the investigation of several promising multiferroic materials: Pb1 − xBax(Fe0.5Nb0.5)O3 (x = 0 - 1) and Pb(Fe0.5Sb0.5)O3 with a perovskite structure and labeled as multiferroics of the I. type according to the Khomsky classification, BaYFeO4, which belongs to the multiferroics of the II. Khomsky class, and LiFePO4, which is a potentially multiferroic substance containing Fe2+ and are used in electric accumulators at present. Mössbauer spectroscopy of the 57 Fe isotope was used as a key experimental method, which can provide new information about the local arrangement in the vicinity of resonantly absorbing nuclei in the investigated substances. Data evaluation and interpretation would not be possible without the using results...