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1

Geck, Jochen. "Spins, charges, and orbitals in perovskite manganites : resonant and hard x-ray scattering studies /". Berlin : Mensch & Buch Verl, 2004. http://www.loc.gov/catdir/toc/fy0804/2007464041.html.

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2

Turner, Joshua J. "Probing dynamics of complex ordered phases in colossal magnetoresistive transition-metal oxides using coherent resonant soft x-ray scattering. /". Connect to title online (Scholar's Bank) Connect to title online (ProQuest), 2008. http://hdl.handle.net/1794/7506.

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Thesis (Ph. D.)--University of Oregon, 2008.
Typescript. Includes vita and abstract. Includes bibliographical references (leaves 200-207). Also available online in ProQuest, free to University of Oregon users.
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3

Johnstone, Graeme Eoin. "Neutron and X-ray scattering study of magnetic manganites". Thesis, University of Oxford, 2012. http://ora.ox.ac.uk/objects/uuid:a19f8d08-8468-489d-a959-1002af0c9dec.

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This thesis presents three investigations of the magnetic and electronic proper- ties of manganese oxide materials. The investigations are performed using a variety of neutron scattering and x-ray scattering techniques. The electronic ground-state of Pr(Sr0.1 Ca0.9)2 Mn2O7 an antiferromagnet with CE-type ordering, is determined using neutron spectroscopy, as opposed to the more usual approach of using diffraction. The Zener polaron model of the elec- tronic ground state of the CE-type magnetic phase is shown to be unsuitable for this material. The ground-state is shown to agree well with the electronic ground state proposed by Goodenough in the 1950’s, but without significant Mn3+/Mn4+ disproportionation. The distribution of the magnetisation density within the unit cell of the CE-type antiferromagnet La0.5Sr1.5MnO4 is determined from a polarised neutron diffraction experiment by analysing the results with the maximum entropy method. The majority of the magnetisation density is found to be located at the Mn site. The investigation shows tentative evidence of a small magnetic moment on the in-plane O site. However, a larger moment is observed at both the La/Sr site and the out-of-plane O site. The magnetic structure of the magnetoelectric multiferroic DyMn2O5 is inves- tigated using resonant magnetic x-ray scattering. The magnetic structure is shown to be similar to other members of the RMn2O5 series of multiferroics, but with the key difference that the magnetic moments are closely aligned parallel with the crystallographic b-axis, in contrast to the usual observation of the moments being close to parallel with the a-axis. This study also shows evidence that the electrical polarisation has a significant contribution from the valence electrons of the O ions, agreeing with previous work.
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4

Kötschau, Immo. "In situ x-ray study of orthorhombic lithium manganese oxide". Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1997. http://www.collectionscanada.ca/obj/s4/f2/dsk2/ftp04/mq24175.pdf.

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5

Mohameden, Ahmed O. "Mild chemical H-insertion into γ-manganese dioxides". Thesis, Middlesex University, 2001. http://eprints.mdx.ac.uk/13378/.

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About a hundred samples of y-manganese dioxide covering three materials coded SBP- A, Faradiser M and R2 have been reduced chemically by insertion of H through controlled additions of hydrazine hydrate solutions at about 1 °C. The H-inserted samples and the starting materials were subjected to chemical analysis for oxidation state, X-ray diffraction (XRD) for structure study and Fourier Transform Infrared (FTIR) spectroscopy to gain information on OH bonding. Additional techniques including FTIR spectroscopy at low temperature (~ -180 °C), electrode potential measurement and scanning electron microscopy (SEM) have also been applied. The intergrowth structure of the starting materials consisted of ramsdellite intercepted with pyrolusite layers, known as de Wolff faults, and quantified by the fraction of pyrolusite layers Pr. An additional structural parameter for these materials was the amount of micro twinning (Tw) across the 021/061 ramsdellite planes. This parameter, introduced by Pannetier, is given in percent. Values of (Pr , Tw) have been given as (0.41 , 17) for SBP-A, (0.70,10) for Faradiser M and (0.41, ~100) for R2. Upon H-insertion, the structure of the starting materials expanded homogeneously in a direction and to an extent which depended on the Pr and Tw parameters. Faradiser M, with high Pr and very low Tw, expanded homogeneously in the direction of the b lattice dimension up to an insertion level of 0.69 of s in MnOn/Hs. Above this level, the initial structure changed suddenly into the structure of the final product: the insertion then proceeded homogeneously in the new phase. The main changes were an expansion of the octahedra and a rotation leading to hinged tunnels. This is the first time that the existence of two solid solutions in the MnO2/H system has been noted. With SBP-A, the amount of microtwinning restricted the homogeneous expansion of SBP-A to s = 0.28, which occurred predominantly in the a direction. Further insertion broke the twinning boundary and formed a demicrotwinned phase of composition MnOn Ho.68 in which the tunnels were also hinged. Thereafter H-insertion proceeded heterogeneously from 0.28 to 0.68 in s. Above s = 0.68, the structure developed homogeneously towards that of the fully H-inserted product. The extensive microtwinning in R2 allowed for a homogeneous expansion, thought to be isotropic to maintain the microtwinned structure, up to s = 0.39. Higher insertion levels led to the expansion to proceed heterogeneously to a composition of MnOn Ho.63. Above s = 0.63, a new phase, the final product, was formed with fully demicrotwinned structure and fully hinged tunnels. R-insertion into y-manganese dioxide has never been reported to occur in three stages previously. The FTIR study at room temperature has shown absence of OH bond vibrations at insertion levels prior to the hinging of the tunnels, in contrast to their presence after the structure has rotated and the tunnels had hinged. This is seen as a strong indication of H mobility in the initial structure. The hinging is necessary for OH bonding as it brings the 02 and 01 oxygens closer allowing the proton to bond both covalently and by H-bonding. At low temperature, initially mobile hydrogen could be trapped and OR bonds formed only in H-inserted R2. This was linked to 061-microtwinning. The absence of OH bonds at low temperature in SBP-A and Faradiser M led to the conclusion that these materials have no 061 micro twinning faults. The absence of OH bonds at low temperature in the starting materials, particularly in R2, strongly questions the postulated OH groups in the structure of y-MnO2, according to the cation vacancy model. Electrode potential data supported the above conclusions in terms of the stages of the H-insertion. The battery activity of the materials seemed to be related to the extent at which the materials kept the initial structure with non-hinged tunnels. Comparison with previous works on the same materials suggested that the differences could be accounted for by the kinetics of the H-insertion. While protons in this work were released spontaneously on the surface of the MnO x , their diffusion into the bulk was slow due to the low temperature. In the compared literature, the reverse applies.
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6

Ehrke, Henri P. "Dynamics of electronic order in magnetoresistive manganites studied with time-resolved X-ray scattering". Thesis, University of Oxford, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.540134.

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7

Kose, Muhammet. "Manganese complexes as catalase and superoxide dismutase mimics : structure and reactivity relationships". Thesis, Loughborough University, 2012. https://dspace.lboro.ac.uk/2134/10801.

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Macrocycle (H2L1) was prepared by a Schiff base condensation reaction of 2,6-diformylpyridine and 1,3-diamino-2-propanol in the presence of Ba(II) as template ion. Seven-coordinate Mn(II) complexes were prepared by transmetallation reactions of the initial [Ba(H2L1)(μ1,2-ClO4)]2(ClO4)2 complex. Two mononuclear, ring-contracted complexes were obtained when methanol or ethanol were used as solvents in transmetallation reactions. For both complexes, X-ray analysis showed that the H2L1 macrocycle undergoes a ring-contraction via addition of methanol or ethanol across one imine bond, followed by a nucleophilic addition of the secondary amine across an adjacent imine bond resulting in a six-membered, hexahydropyrimidine ring sitting in a chair conformation. The ring-contraction process reduces the size of the cavity in the macrocycle to accommodate one Mn(II) ion in the macrocycle. The macrocyclic tetraimine ligand (H2L1) gave access to the polynuclear, ring-expanded assemblies, [Mn4(H2L*)Cl4][MnCl4] and [Mn4(H2L*)(N3)4](ClO4)2, when acetonitrile was used as a solvent. The macrocycle (H2L1) undergoes rearrangement from a 20-membered to a 40-membered tetranuclear Mn(II) complex. Manganese complexes of acyclic ligands, derived from 2,6-diformylpyridine and several aminoalcohols and aminophenols, were prepared and structurally characterised by X-ray crystallography. Most of the complexes are seven-coordinate with approximate pentagonal bipyramidal geometry, however, some five, six and seven-coordinate complexes were identified. Asymmetric and symmetric tripodal Schiff base ligands and their manganese complexes were also prepared and characterised. Additionally, N-alkylated benzimidazole 2,6-bis(1-butyl-1H-benzo[d]imidazol-2-yl)pyridine and its Mn(II) complexes were prepared and characterised. The potential application of the complexes has been tested in two main areas: (a) as new catalase mimics and (b) as new superoxide dismutase (SOD) mimics. The trinuclear, acyclic complex, [Mn3(L9)2(OAc)2(MeOH)2] 2MeOH, derived from 2,6-diformylpyridine and 2-aminophenol, was found to be the most efficient catalase mimic of the tested complexes with approximately 500 molecules of H2O2 broken down per second for each complex during the fastest rate of activity. Catalase testing showed that an increase of the arm size of the tripodal complexes produced an increase in activity overall for the complexes. Most of the complexes tested for catalase activity showed an induction period prior to the activity being observed. This may be due to a rearrangement occurring before catalase activity is observed. The tripodal complex, [Mn(L18)](ClO4)2 is the only complex to show a catalase activity without added base, but with a long induction period. The results that are presented indicate that the axial ligands have an effect on both the rate of catalase activity and the observed induction period. The SOD results indicated that the complex, [Mn(H2L6)Cl(H2O)]Cl H2O, derived from 2,6-diformylpyridine and 1 aminopropan-2-ol, shows the highest SOD activity amongst the complexes prepared, with a rate of 2.05x106 M-1s-1 and the IC50 value of 0.78 μM. Most of the complexes showed SOD activity with a rate around 105-106 M-1s-1. The SOD results showed that the axial ligands have an effect on SOD activity; strongly bound ligands such as thiocyanate and azide generally result in lower SOD activity. Most of the complexes showed both SOD and catalase activity. Ring-contracted complexes, [Mn(H3L2)(NCS)2] and [Mn(H3L3)(NCS)2], show high rates of superoxide dismutase activity but possess limited catalase activity.
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8

Xi, Yan. "Ozone Decomposition and Acetone Oxidation on Manganese Oxide Catalysts". Thesis, Virginia Tech, 2005. http://hdl.handle.net/10919/33112.

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This thesis describes the preparation and characterization of manganese oxide catalysts and their application in the oxidation of acetone, a typical volatile organic compound (VOC), and ozone decomposition. This topic is of great value because of environmental concerns of the elimination of the harmful VOCs and ozone. Manganese oxide was chosen because it is a well-known complete oxidation catalyst for VOCs and also an active catalyst for ozone decomposition. Two cases of studies were carried out in this work. The first study involved the oxidation of acetone using ozone on silica- and alumina-supported manganese oxide catalysts deposited on aluminum oxide foam substrates. The characteristics of the catalysts were determined through various techniques, including x-ray diffraction (XRD), x-ray absorption spectroscopy (XAS), Brunauer-Emmett-Teller (BET) surface area analysis, temperature-programmed reduction (TPR), and oxygen chemisorption. The use of these techniques allowed better understanding of the nature of the catalysts. Activity tests were carried out in the acetone oxidation reaction and it was found that the usage of ozone substantially reduced the oxidation temperature. Steady-state in situ Raman spectroscopy was also carried out to better understand the mechanism of the acetone oxidation reaction using ozone. The second study involved an investigation of structural and electronic properties of manganese centers of the MnOx/SiO2 and MnOx/Al2O3 catalysts during the ozone decomposition reaction using in situ x-ray absorption spectroscopy (XAS). The number of surface active sites was again determined through TPR and oxygen chemisorption measurements. The performance of the catalysts with different loadings and supports were also compared.
Master of Science
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9

Bodiba, A. L. "X-ray spectroscopic method development for quantitative analysis of manganese ore in the Kalahari basin". Thesis, Vaal University of Technology, 2016. http://hdl.handle.net/10352/386.

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Manganese is a crucial element in the manufacturing of steel, which in turn is an essential material in many industries including construction and transportation. Its use in the steel making process results in increased strength and resistance. Manganese samples are analyzed quantitatively by volumetric titration techniques. These wet chemistry methods are simple, accurate, and are sufficiently detailed for ordinary personnel to follow with ease. The research method used included the investigation of using secondary standard created from the current mining activities to match the matrix and mineralogy. The matrix matching standard has shown that the mineralogical effect and matrix effect can be controlled by creating the ore specific program. The matrix and mineralogical effect are the main sources of errors in wavelength dispersive X-ray fluorescence analysis with pressed powder pellets. No fundamental parameters corrections and empirical coefficient correction were made on the press pellets calibration lines. The fusion method was investigated as a universal method that can produce fused beads retaining all the elements of interest. The calibration lines were developed from certified reference material and the results were accurate, substantiating that the fusion method elimination the mineralogical effect, matrix effect and particle size effects. Fusion and press pellet methods were compared with the traditional wet chemical method and the results shows no significant difference between the methods. The new methods were tested against three proficiency schemes for manganese and the results were satisfactory, the z-score was below ±3 for all the elements. The participants used different methods including traditional wet chemical analysis and Inductive coupled plasma (ICP). The press pellets method has shown a good correlation with a fusion method were certified reference material was used for calibrations. The new methods were validated using different statistical methods. All the validation criteria were satisfactory. The calibration range for all the lines were satisfactory. The Limit of quantification (LOQ) values for Mn, Fe, CaO, SiO2, MgO, Al2O3, and P were very low. The new methods for the analysis are therefore sensitive enough to give good results for the expected concentration ranges of each element. The statistical analysis performed between fusion and press pellets methods has proven that there was no significant difference between the methods. The conclusion made after the validation procedures was that the methods Page | iv developed for the analysis of manganese ore was fit for purpose of the analysis of the elements of interest for the Kalahari manganese ore. The study confirmed that the newly developed press pellets methods can be used to analyse routine production samples based on the ore type or the area. Borates fusion method can be used for geological explorations, consignment and trade samples. The proposed XRF methods can replace the traditional wet chemical analysis which is time-consuming, toxic and labourintensive.
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10

Turner, Joshua J. 1979. "Probing dynamics of complex ordered phases in colossal magnetoresistive transition-metal oxides using coherent resonant soft x-ray scattering". Thesis, University of Oregon, 2008. http://hdl.handle.net/1794/7506.

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xxv, 207 p. ; ill. (some col.) A print copy of this title is available from the UO Libraries, under the call number: SCIENCE QD172.T6 T87 2008
A growing interest in the physics of complex systems such as in the transition-metal oxide family has exploded recently, especially in the last 20 years or so. One notable effect is the change in electrical resistivity of a system by orders of magnitude in an applied magnetic field, coined the "colossal magnetoresistance effect". In efforts to understand these types of effects, there has been an unveiling of a rich variety of phenomena in the field of strongly correlated electron physics that has come to dominate the current scientific times. Most notable is the competition of myriad types of order: magnetic, lattice, charge and orbital all self-organize to display a fascinating array of phases on a variety of length scales. Furthermore, it has become apparent that new probes are needed to grasp some of this physics that transcends current condensed matter theory, where much of the behavior of these types of systems has remained unexplored. We have developed a new technique to gain more information about the system than with conventional x-ray diffraction. By scattering highly coherent, low energy x-rays, we can measure manganite speckle: a "fingerprint' of the microscopic structure in the bulk. The coherence of the x-rays can further be used to elucidate new insight into the dynamics of these phases. We describe here a number of novel effects near the orbital order phase transition in a half-doped manganite. We observe a small fluctuating component in the scattered signal that is correlated with three effects: both a rapidly decreasing total signal and orbital domain size, as well as an abrupt onset of a broad background intensity that we attribute to the thermal production of correlated polarons. Our results suggest that the transition is characterized by a competition between a pinned orbital domain topology that remains static, and mobile domain boundaries that exhibit slow, spatiotemporal fluctuations. This study opens up a new chapter to the study of manganite physics as coherent x-ray scattering offers a new direction to understand the strange and exotic behavior demonstrated in the multifaceted manganites.
Adviser: Stephen Kevan
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11

Kruth, Angela. "Synthesis and characterisation of a novel oxygen- deficient manganese-based perovskite series". Thesis, University of Aberdeen, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.310732.

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A family of oxygen-deficient perovskite phases with compositions, Ca2Mn2-xNbxOγ has been synthesised and characterised using X-ray Powder Diffraction and Thermogravimetry. Property characterisation has included the study of electrical properties by Impedance Spectroscopy and the investigation of magnetic properties for one composition, x = 1.0. Some compositions were tested for possible application as electrode materials in gas sensors. The Ca2Mn2-xNbxOγ system 0 ≤ x ≤ 1.2, with variable oxygen content, γ, can accommodate up to 20% vacancies at oxygen sites and Mn occurs in valence states ranging from +2 to +4. Depending on the B-cation ratio and oxygen content, two solid solution form: an extensive GdFeO3-type solid solution over the entire range of cation content, 0 ≤ x ≤ 1.2, with zero or small oxygen deficiencies and a closely-related, grossly oxygen-deficient solid solution over the range 0.3 ≤ x ≤ 0.8 with a simple cubic perovskite structure. Unit cell volume and orthorhombic GdFeO3-type distortion vary greatly with Mn valency, oxygen content and B-cation content. The orthorhombic GdFeO3-type structure of composition x = 1.0 was refined by the Rietveld method. Mn and Nb are disordered over the B-sites. Jahn-Teller activity of Mn3+ does not result in cooperative distortions of (Mn,Nb)O6 octahedra, but it was observed to effect the oxygen stoichiometry. The Nb-rich composition, x = 1.0, can accommodate large amounts of Ca-vacancies (up to 10%). Electrical conductivity varies greatly with the composition. Results suggest that t2g electrons are responsible for a variation of conductivity and activation energy rather than eg electrons. Conductivities are believed to depend mainly on the degree of π-orbital overlap between Mn and oxygen and hence, on interatomic distances. At low temperatures, the material exhibits spin glass-like behaviour.
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12

Jabua, Malkhaz [Verfasser] y Detlev [Gutachter] Gotta. "Ultimate Resolution X-ray Spectroscopy of Chemical-Effects in Manganese Compounds / Malkhaz Jabua. Gutachter: Detlev Gotta". Köln : Universitäts- und Stadtbibliothek Köln, 2016. http://d-nb.info/1112652132/34.

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13

Lesturgez, Stephanie. "Propriétés redox de manganites à valence modulée de structure bi ou tridimensionnelle". Thesis, Bordeaux, 2015. http://www.theses.fr/2015BORD0303/document.

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Ce travail porte sur la synthèse et la caractérisation d’oxydes de manganèse de formule généraleCaxMnyOz avec y/x > 1. Par une approche de chimie du solide, les propriétés redox de ces matériauxseront corrélées à leur composition chimique et leur structure cristalline ce qui constitue une étude enamont de l’application pour ces systèmes pouvant jouer le rôle de tampon à oxygène dans desprocessus catalytiques. Les composés ont été synthétisés par autocombustion en voie aqueuse etcaractérisés d’un point de vue structural. Les propriétés redox ont été évaluées par ATG et lespropriétés de réductibilité par H2-TPR pour certains composés. Quelles que soient la structure, ladimensionnalité ou la valence du manganèse dans les composés oxydés (Mn4+/Mn3+), le manganèsese réduit totalement en Mn2+ sous atmosphère réductrice (Ar/H2). Les composés réduits cristallisentdans une solution solide de type NaCl de formule Ca1-xMnxO. Les mécanismes de réduction dumanganèse au sein de ces structures ont été appréhendés sur la base des analysesthermogravimétriques. Afin de faire varier les températures de réduction, l’iono-covalence de la liaisonMn-O a été modifiée via des substitutions cationiques (i) sur les sites du calcium principalement ausein de réseaux 2D ou (ii) sur les sites du manganèse essentiellement dans les réseaux 3D avec laprésence d’Al3+ ou de Fe3+ de rayons ioniques comparables respectivement à Mn4+ et Mn3+. Lessolutions solides ont été caractérisées d’un point de vue structural mais aussi pour leurs propriétésredox. Il convient de souligner que les phases substituées au Fer présentent des propriétés redox toutà fait remarquables dans la mesure où les ions Fe3+ tout comme Mn4+/3+ se réduisent d’abord en Fe2+puis en Fe° qui est dès lors expulsé hors de la matrice oxyde. Lors de la réoxydation, le fer réintègrele réseau 3D et les matériaux sont cyclables dans des conditions réductrices puis oxydantes à l’air àdes températures inférieures à 1000°C
This work deals with the synthesis and characterization of manganese oxides with CaxMnyOz formulaand y/x >1. According to a solid state chemistry scope, the redox properties of these materials will becorrelated to their chemical composition and crystallographic structure which constitutes a forehandexploratory study of compounds that are intended to be used for the automotive catalysis exhaustbased on the three-way catalysis principle. The materials were synthesized by aqueous selfcombustionroute and structurally characterized. Redox properties and reducibility properties wereevaluated by TGA and H2-TPR, respectively. Whatever the structure, the dimensionality of the networkor the manganese valence in the starting oxidized material, all of the manganese ions are completelyreduced (Mn2+) in a Ar/H2 atmosphere. The reduced compounds crystallize in a rock-salt type solidsolution with the formula Ca1-xMnxO. The mechanisms of manganese reduction within these structureswere explored on the basis of TGA analysis. In order to tune the reduction temperatures, the ionocovalenceof the Mn-O bond has been modified by either cationic substitution of calcium in the 2Dnetworks or either substitution of manganese in the 3D networks. In this last case, Substituting ionswere Al3+ and Fe3+ which ionic radii comparable to Mn4+ and Mn3+, respectively. Solid solutions havebeen characterized from a structural point of view but also for their redox properties. One shouldnotice that iron substituted compounds exhibit remarkable redox properties because Fe3+ ions firstreduce in Fe2+ iron before a final reduction in Fe° that is consequently expulsed from the matrix. Atreoxidation, iron returns into the 3D network and cycling can be observed when reducing and oxidizingat temperatures lower than 1000°C
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14

Felker, Daniel L. "Studies of oxide-free phosphates film surfaces on magnesium, zinc, and manganese by X-ray photoelectron spectroscopy /". Search for this dissertation online, 2005. http://wwwlib.umi.com/cr/ksu/main.

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ITEPAN, NATANAEL M. "Aplicacao da tecnica de fluorescencia de raios X na marcacao com Mn, Sr e Cu, do parasitoide e do hospedeiro: Muscidifurax uniraptor Kogan e Legner, 1970 (Hymenoptera: Pteromalidae) e Musca domestica L., 1758 (Diptera: Muscidae)". reponame:Repositório Institucional do IPEN, 2003. http://repositorio.ipen.br:8080/xmlui/handle/123456789/11144.

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IPEN/T
Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP
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Santos, Cássio Morilla dos [UNESP]. "Síntese e caracterização de compostos HoMn1-x(Ni,Co)xO3". Universidade Estadual Paulista (UNESP), 2011. http://hdl.handle.net/11449/106644.

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Nesse trabalho foi realizado o processo de síntese, e a caracterização estrutural e magnética de compostos HoMn1-x(Ni, Co)xO3 de estrutura perovskita. As sínteses das amostras foram realizadas por meio do método dos precursores poliméricos modificado. Após a síntese e a remoção do solvente, a resina polimérica formada foi tratada em 350ºC/4h para a remoção dos constituintes orgânicos, seguida de tratamentos térmicos em 500ºC/4h e 900ºC/20h para obtenção da fase cristalina. Para a caracterização estrutural foi utilizada a linha D10B-XPD do Laboratório Naiconal de Luz Síncrotron (LNLS), onde comprimentos de onda de raios X abaixo da borda de absorção do cobalto, do maganês e do níquel, foram utilizados. A formação das fases HoNi0.50Mn0.50O3, HoCo0.50O3 e HoNi0.25Co0.25Mn0.50O3, foram observadas pelas técnica da difração de raios X. Com o método de refinamento Reitveld para a amostra HoNi0.25Co0.25Mn0.50O3, foi determinado que o cobalto e o níquel apresentaram ocupações similares, no topo e na base da cela unitária, enquanto que o manganês ocupou preferencialmente o plano 002. A resposta magnética das amostras foi estudada através de curvas de magnetização em função da temperatura, e do campo magnético aplicado. As curvas ZFC demonstraram uma resposta paramagnética associada ao momento magnético do hólmio, além da coexistência de ferromagnetismo, antiferromagnetismos e ferrimagnetismo, devido às sub-redes formadas pelos metais de transição. As curvas FC evidenciaram o fenômeno da inversão de spin, associado à interação entre as sub-redes formadas pelos metais de transição com a sub-rede formada pela terra-rara, considerando um mecanismo de interação de troca antiferromagnética
In this work was accomplished the syntheis process and structural and magnetic characterization of HoMn1-x(NiCo)xO3 compounds of pervskites structure. The sample synthesis were performed through modified polymeric precursos method. After synthesis and solvent removal, the polymer resin formed was treated at 350ºC/4h for organic constituents removal, followed by heating treatment at 500ºC/4h and 900ºC/20h to obtain the crystalline phase. For structural characterization, it was used D10B-XPD beam line of Laboratório Nacional de Luz Síncrotron (LNLS), where X-rays wavelengths below cobalt, manganeses and nickel absorption edge, were used. The formation of HoNi0.50Mn0.50O3, HoCo0.50O3 e HoNi0.25Co0.25Mn0.50O3 phases were observed by X-ray diffraction technique. By Rietveld refinement method for sample HoNi0.25Co0.25Mn0.50O3, it was determined that cobalt and nickel had similar occupations at the top and bottom of unit cell, while the manganeses preferentially occupied plan 002. The magnetic response of samples was studied through magnetization curves according to the temperature function and the applied magnetic field. The ZFC curves showed a paramagnetic response associated to holmium magnetic moment, and ferromagnetism, antiferromagnetism and ferrimagnetism coexistence, due to sublattices formed by transition metals. The FC curves evidenced the spin reversal phenomenon, associated to the interaction between the sublattice formed bu transition metals with sublattices formed by rare-earth, considering a mechanism of antiferromagnetic exchange interaction
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17

Grundmeier, Alexander Peter [Verfasser]. "The water-oxidizing manganese complex of oxygenic photosynthesis : structural models based on X-ray absorption spectroscopy / Alexander Peter Grundmeier". Berlin : Freie Universität Berlin, 2012. http://d-nb.info/1026883717/34.

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18

Nugent, Ayres Michelle V. "Spatial and Geochemical Techniques to Improve Exposure Assessment of Manganese in Windsor, Ontario". Thèse, Université d'Ottawa / University of Ottawa, 2011. http://hdl.handle.net/10393/20276.

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This study was conducted to investigate the urban geochemistry of the city of Windsor (Ontario) and to provide added source apportionment information to work being carried out by the Canadian government. The goal of this study was to investigate the distribution, spatial variation and sources of manganese in urban Windsor soil. The literature indicates that human exposure to high levels of manganese, via inhalation, can cause respiratory and/or neurological effects. At the outset of the present study it was first hypothesized that vehicular traffic was the dominant source of anthropogenic manganese. An alternative hypothesis was that there were multiple anthropogenic sources of manganese in Windsor. The sample collection scheme was designed to determine (1) the current and background soil concentrations of manganese in Windsor, (2) the spatial distribution of manganese in order to reveal sources of manganese, and (3) the manganese content of moss-sequestered airborne particles, which can potentially deposit onto the soil surface, using low-technology biomonitoring. The first phase of the study consisted of a preliminary soil survey which identified elevated areas of soil manganese concentrations. During this survey, the field efficiency of a field portable X-ray fluorescence (FPXRF) instrument, as well as sample preparation methods were evaluated. Efficiency of the FPXRF was determined by comparison to ICP-MS, a traditional trace element analysis method. The preliminary soil survey identified several areas of elevated (ranging from 884 to 2390 ppm) soil manganese which were further investigated during the second, more complete, soil survey. The moss biomonitoring technique of using moss bags was used to collect airborne particles for semi-quantitative analysis. Analysis of soil samples included total manganese and other trace elements, pH, moisture and carbon content, and manganese speciation. Urban Windsor soil manganese distribution revealed both natural and anthropogenic sources of soil manganese and three distinct soil sample types, transect, baseline and natural. In general, manganese in Windsor had a west-to-east trend of decreasing levels in soil and moss-sequestered airborne particles. The latter showed a modern-day elemental signature while the former (collocated soil) a legacy elemental signature. It was concluded that both the FPXRF instrument and the moss biomonitoring technique can be useful screening tools in studies of urban environments.
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19

RODRIGUES, RANIERI A. "Estudo da formação de fases secundárias no compósito LSM/YSZ". reponame:Repositório Institucional do IPEN, 2007. http://repositorio.ipen.br:8080/xmlui/handle/123456789/11563.

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Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP
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20

Mierwaldt, Daniel Joachim [Verfasser], Christian [Akademischer Betreuer] Jooß, Christian [Gutachter] Jooß y Simone [Gutachter] Techert. "In Situ X-ray Spectroscopy and Environmental TEM Study on Manganite Water Oxidation Catalysts / Daniel Joachim Mierwaldt ; Gutachter: Christian Jooß, Simone Techert ; Betreuer: Christian Jooß". Göttingen : Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2017. http://d-nb.info/1149959045/34.

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21

Radhakrishnan, Rakesh. "Structure and Ozone Decomposition Reactivity of Supported Manganese Oxide Catalysts". Diss., Virginia Tech, 2001. http://hdl.handle.net/10919/26033.

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Manganese oxide catalysts supported on Al2O3, ZrO2, TiO2 and SiO2 supports were used to study the effect of support on ozone decomposition kinetics. X-ray diffraction (XRD), in-situ laser Raman spectroscopy, temperature programmed oxygen desorption, surface area measurements, extended and near edge x-ray absorption fine structure (EXAFS and NEXAFS) showed that the manganese oxide was highly dispersed on the surface of the supports. EXAFS spectra suggest that the manganese active centers on all of the surfaces were surrounded by five oxygen atoms. These metal centers were of a mononuclear type for the Al2O3 supported catalyst and multinuclear for the other supports. NEXAFS spectra for the catalysts showed a chemical shift to lower energy and an intensity change in the L-edge features which followed the trend Al2O3 > ZrO2 > TiO2 > SiO2. The trends provided insights into the positive role of available empty electronic states required in the reduction step of a redox reaction. The catalysts were tested for their ozone decomposition reactivity and reaction rates had a fractional order dependency (n < 1) with ozone partial pressure. The apparent activation energies for the reaction was low (3-15 kJ/mol). The support influenced the desorption step (a reduction step) and this effect manifested itself in the pre-exponential factor of the rate constant for desorption. Trends for this pre-exponential factor correlated with trends in NEXAFS features and reflected the ease of electron donation from the adsorbed species to the active center.
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22

Ndipingwi, Miranda Mengwi. "Designing next generation high energy density lithium-ion battery with manganese orthosilicate-capped alumina nanofilm". University of the Western Cape, 2015. http://hdl.handle.net/11394/5136.

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>Magister Scientiae - MSc
In the wide search for advanced materials for next generation lithium-ion batteries, lithium manganese orthosilicate, Li₂MnSiO₄ is increasingly gaining attention as a potential cathode material by virtue of its ability to facilitate the extraction of two lithium ions per formula unit, resulting in a two-electron redox process involving Mn²⁺/Mn³⁺ and Mn³⁺/Mn⁴⁺ redox couples. This property confers on it, a higher theoretical specific capacity of 333 mAhg⁻¹ which is superior to the conventional layered LiCoO₂ at 274 mAhg⁻¹ and the commercially available olivine LiFePO₄ at 170 mAhg⁻¹. Its iron analogue, Li₂FeSiO₄ has only 166 mAhg⁻¹ capacity as the Fe⁴⁺ oxidation state is difficult to access. However, the capacity of Li₂MnSiO₄ is not fully exploited in practical galvanostatic charge-discharge tests due to the instability of the delithiated material which causes excessive polarization during cycling and its low intrinsic electronic conductivity. By reducing the particle size, the electrochemical performance of this material can be enhanced since it increases the surface contact between the electrode and electrolyte and further reduces the diffusion pathway of lithium ions. In this study, a versatile hydrothermal synthetic pathway was employed to produce nanoparticles of Li₂MnSiO₄, by carefully tuning the reaction temperature and the concentration of the metal precursors. The nanostructured cathode material was further coated with a thin film of aluminium oxide in order to modify its structural and electronic properties. The synthesized materials were characterized by microscopic (HRSEM and HRTEM), spectroscopic (FTIR, XRD, SS-NMR, XPS) and electrochemical techniques (CV, SWV and EIS). Microscopic techniques revealed spherical morphologies with particle sizes in the range of 21-90 nm. Elemental distribution maps obtained from HRSEM for the novel cathode material showed an even distribution of elements which will facilitate the removal/insertion of Li-ions and electrons out/into the cathode material. Spectroscopic results (FTIR) revealed the vibration of the Si-Mn-O linkage, ascertaining the complete insertion of Mn ions into the SiO₄⁴⁻ tetrahedra. XRD and ⁷Li MAS NMR studies confirmed a Pmn21 orthorhombic crystal pattern for the pristine Li₂MnSiO₄ and novel Li₂MnSiO₄/Al₂O₃ which is reported to provide the simplest migratory pathway for Li-ions due to the high symmetrical equivalence of all Li sites in the unit cell, thus leading to high electrochemical reversibility and an enhancement in the overall performance of the cathode materials. The divalent state of manganese present in Li₂Mn²⁺SiO₄ was confirmed by XPS surface analysis. Scan rate studies performed on the novel cathode material showed a quasi-reversible electron transfer process. The novel cathode material demonstrated superior electrochemical performance over the pristine material. Charge/discharge capacity values calculated from the cyclic voltammograms of the novel and pristine cathode materials showed a higher charge and discharge capacity of 209 mAh/g and 107 mAh/g for the novel cathode material compared to 159 mAh/g and 68 mAh/g for the pristine material. The diffusion coefficient was one order of magnitude higher for the novel cathode material (3.06 x10⁻⁶ cm2s⁻¹) than that of the pristine material (6.79 x 10⁻⁷ cm2s⁻¹), with a charge transfer resistance of 1389 Ω and time constant (τ) of 1414.4 s rad⁻¹ for the novel cathode material compared to 1549 Ω and 1584.4 s rad-1 for the pristine material. The higher electrochemical performance of the novel Li₂MnSiO₄/All₂O₃ cathode material over the pristine Li₂MnSiO₄ material can be attributed to the alumina nanoparticle surface coating which considerably reduced the structural instability intrinsic to the pristine Li₂MnSiO₄ cathode material and improved the charge transfer kinetics.
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23

Menendez-Alonso, Elena. "Trace metal and speciation analysis using ion-exchange and energy dispersive X-ray fluorescence spectrometry". Thesis, University of Plymouth, 2000. http://hdl.handle.net/10026.1/896.

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Studies have been carried out on specific ion-exchange (Dowex 50W-X8 and Dowex 1-X8) and chelation (Chelex-100) resins, in order to determine their physical and chemical characteristics, to understand and explain their limits of function and to optimise their use as substrates in trace metal and speciation measurement by EDXRF. Structural information was obtained by scanning electron microscopy and x-ray microanalysis showing a homogeneous distribution of functional groups and retained ions on both sectioned and whole resins. Particle size experiments performed on Dowex 50W-X8 (38 - 840 µm) showed that this parameter has no effect on the relationship between intensity of fluorescence and concentration or mass of resin. Inter-element effects were not observed in the analysis of multielemental specimens prepared on ion-exchange / chelation media by EDXRF. This indicates that the proposed method has a significant advantage when compared with other methodologies. A theoretical ‘model’, based on the formation of thin films on the surface of the resin beads, has been proposed in order to link and explain the effects observed in these experiments. The use of a batch retention system has shown distinct advantages over using columns in terms of linearity, accuracy, precision, rapidity and simplicity. Parameters such as pH and ionic strength of the solution, concentration of competing ions and volume of the sample have been proven to be critical. The maximum retention capacity has been determined as 3.2, 1.1 and 0.67 mEq/g for Dowex 50W-X8, Dowex 1-X8 and Chelex-100 respectively. The optimum mass of resin for XRF analysis was found to be 0.5 g, for all resins tested. The linear range covered 4 to 5 orders of magnitude. These findings show the potential of the investigated media to overcome instrumental and sample limitations. Based on the physico-chemical information found, methodologies for three different applications of the resins to EDXRF determinations have been developed and their analytical possibilities explored. The multi-elemental determination of metals in sewage sludge digests was achieved by retaining the metals on Dowex 50W-X8 at pH 2 and Chelex-100 at pH 4. Chelex-100 allows quantitative recoveries for Cu and Zn. A wider range of elements was determined on Dowex 50W-X8, although with poorer recoveries (60 - 90%). The limits of detection were 10 - 21 µg when Dowex 50W-X8 was used and 8 - 49 µg for Chelex-100. The method was validated by the analysis of a certified material. The determination of Kβ/Kα intensity ratios for Cr and Mn species and its potential as a tool for direct elemental speciation has also been studied. A difference in Kβ/Kα between the oxidation states of the analytes was only observed during the analysis of solutions of the metal species by EDXRF at the 98% level of confidence. Finally, the speciation and preconcentration of Cr(III) and Cr(VI) in waters has been performed by retention on Dowex 50W-X8 and Dowex 1-X8 followed by EDXRF determination. Efficient recoveries and preconcentration factors of up to 500 were achieved, leading to limits of detection of 30 µg/L for Cr(VI) and 40 µg/L for Cr(III). This method is simple, fast and inexpensive, allowing quantitative recoveries in the speciation of chromium in waste waters.
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24

Cussen, Edmund John. "The electronic properties of mixed metal oxides". Thesis, University of Oxford, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.301436.

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PANG, LOUIS SING KIM. "THE ELECTRONIC STRUCTURES OF ORGANOMETALLIC ALKYNE AND VINYLIDENE COMPLEXES AS DETERMINED BY X-RAY AND ULTRAVIOLET PHOTOELECTRON SPECTROSCOPY (CYCLOPENTADIENYL, VALENCE, MANGANESE, CORE, VANADIUM)". Diss., The University of Arizona, 1985. http://hdl.handle.net/10150/188072.

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The chemistry and bonding of alkynes and vinylidenes in organometallic complexes have been investigated. A variety of these complexes have been synthesized and characterized by X-ray crystallography, temperature-dependent NMR, molecular orbital calculations, and most importantly, HeI, HeII and MgKα photoelectron spectroscopy (PES). The core and valence ionizations are found to be very informative with regard to the relative bond strengths and stabilities of these complexes. The first step involved preparation of the series of complexes R-CpM(CO)₂(alkyne) (R-Cp = Cp, MeCp and Me₅Cp). When M = Mn, Re (alkyne = 3-hexyne, 2-butyne and hexafluoro-2-butyne), the molecular mirror plane bisects the alkyne (horizontal conformation). PES shows the alkyne (π(⊥)) orbital forms a filled-filled interaction with the frontier metal orbital which is significantly destabilized. The ionizations derived from the two alkyne π orbitals are not split. When M = V, the alkyne (C₂H₂, 3-hexyne, etc.) coincides with the molecular mirror plane (vertical conformation). PES shows the alkyne π(⊥) orbital donates electrons to the electron deficient vanadium and the metal backbonds strongly to the alkyne. Electronic factors controlling the conformations in the d⁶ manganese case has been much discussed in the literature. Another factor not previously identified is necessary for understanding the conformation in the d⁴ vanadium case. The energy of the LUMO reveals that this factor is donation of cyclopentadienyl electrons into an empty d orbital of the electron deficient vanadium. Rearrangement of alkyne complexes to terminal vinylidene and bridging vinylidene complexes, similar to reactions of organic molecules on metal surfaces, were also investigated. The series of [R-CpMn(CO)₂]₂(μC=CHR') (R' = H, Me) (Chapter 6) and CpMn(CO)₂(C=CHBuᵗ) (Chapter 7) complexes were prepared. PES showed that the terminal vinylidene ligand has less filled-filled interaction with the metal and stabilizes the metal more than the alkyne does. The bridging vinylidene accepts more electron density from the metals and stabilizes the metals more than the terminal vinylidene. The removal of antibonding electrons from the HOMO of the metal fragment by the bridging vinylidene leaves net metal-metal bonding interaction and forms a stable dimetallocyclopropane structure.
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26

MONTEIRO, NATALIA K. "Síntese e caracterização de manganita-cromita de lantânio dopada com rutênio para anodos de células a combustível de óxidos sólidos". reponame:Repositório Institucional do IPEN, 2011. http://repositorio.ipen.br:8080/xmlui/handle/123456789/10041.

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IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP
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27

Santos, Cássio Morilla dos. "Síntese e caracterização de compostos HoMn1-x(Ni,Co)xO3 /". Bauru : [s.n.], 2011. http://hdl.handle.net/11449/106644.

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Orientador: Paulo Noronha Lisboa-Filho
Banca: Fabio Furlan Ferreira
Banca: Manuel Henrique Lente
Banca: André Maurício Brinatti
Banca: Guinther Kellermann
O Programa de Pós graduação em Ciência e Tecnologia de Materiais, PosMat, tem carater institucional e integra as atividades de pesquisa em materiais de diversos campi da UNESP
Resumo: Nesse trabalho foi realizado o processo de síntese, e a caracterização estrutural e magnética de compostos HoMn1-x(Ni, Co)xO3 de estrutura perovskita. As sínteses das amostras foram realizadas por meio do método dos precursores poliméricos modificado. Após a síntese e a remoção do solvente, a resina polimérica formada foi tratada em 350ºC/4h para a remoção dos constituintes orgânicos, seguida de tratamentos térmicos em 500ºC/4h e 900ºC/20h para obtenção da fase cristalina. Para a caracterização estrutural foi utilizada a linha D10B-XPD do Laboratório Naiconal de Luz Síncrotron (LNLS), onde comprimentos de onda de raios X abaixo da borda de absorção do cobalto, do maganês e do níquel, foram utilizados. A formação das fases HoNi0.50Mn0.50O3, HoCo0.50O3 e HoNi0.25Co0.25Mn0.50O3, foram observadas pelas técnica da difração de raios X. Com o método de refinamento Reitveld para a amostra HoNi0.25Co0.25Mn0.50O3, foi determinado que o cobalto e o níquel apresentaram ocupações similares, no topo e na base da cela unitária, enquanto que o manganês ocupou preferencialmente o plano 002. A resposta magnética das amostras foi estudada através de curvas de magnetização em função da temperatura, e do campo magnético aplicado. As curvas ZFC demonstraram uma resposta paramagnética associada ao momento magnético do hólmio, além da coexistência de ferromagnetismo, antiferromagnetismos e ferrimagnetismo, devido às sub-redes formadas pelos metais de transição. As curvas FC evidenciaram o fenômeno da inversão de spin, associado à interação entre as sub-redes formadas pelos metais de transição com a sub-rede formada pela terra-rara, considerando um mecanismo de interação de troca antiferromagnética
Abstract: In this work was accomplished the syntheis process and structural and magnetic characterization of HoMn1-x(NiCo)xO3 compounds of pervskites structure. The sample synthesis were performed through modified polymeric precursos method. After synthesis and solvent removal, the polymer resin formed was treated at 350ºC/4h for organic constituents removal, followed by heating treatment at 500ºC/4h and 900ºC/20h to obtain the crystalline phase. For structural characterization, it was used D10B-XPD beam line of Laboratório Nacional de Luz Síncrotron (LNLS), where X-rays wavelengths below cobalt, manganeses and nickel absorption edge, were used. The formation of HoNi0.50Mn0.50O3, HoCo0.50O3 e HoNi0.25Co0.25Mn0.50O3 phases were observed by X-ray diffraction technique. By Rietveld refinement method for sample HoNi0.25Co0.25Mn0.50O3, it was determined that cobalt and nickel had similar occupations at the top and bottom of unit cell, while the manganeses preferentially occupied plan 002. The magnetic response of samples was studied through magnetization curves according to the temperature function and the applied magnetic field. The ZFC curves showed a paramagnetic response associated to holmium magnetic moment, and ferromagnetism, antiferromagnetism and ferrimagnetism coexistence, due to sublattices formed by transition metals. The FC curves evidenced the spin reversal phenomenon, associated to the interaction between the sublattice formed bu transition metals with sublattices formed by rare-earth, considering a mechanism of antiferromagnetic exchange interaction
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28

VARGAS, REINALDO A. "Síntese e caracterização de manganito de neodímio dopado com estrôncio utilizado como catodo em células a combustível de óxido sólido de temperatura intermediaria". reponame:Repositório Institucional do IPEN, 2007. http://repositorio.ipen.br:8080/xmlui/handle/123456789/11567.

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IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP
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29

RIBEIRO, THATIANA G. D. "Sintese e caracterizacao de nanoparticulas magneticas de oxidos mistos de MnFesub(2)Osub(4) recobertas comm quitosona. Estudos da influencia na dopagem com Gdsup(3+) nas propriedades estruturais e magneticas". reponame:Repositório Institucional do IPEN, 2008. http://repositorio.ipen.br:8080/xmlui/handle/123456789/11515.

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Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP
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30

Feng, Xu. "Interaction of Na, O2, CO2 and water on MnO(100): Modeling a complex mixed oxide system for thermochemical water splitting". Diss., Virginia Tech, 2015. http://hdl.handle.net/10919/77378.

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A catalytic route to hydrogen production via thermochemical water splitting is highly desirable because it directly converts thermal energy into stored chemical energy in the form of hydrogen and oxygen. Recently, the Davis group at Caltech reported an innovative low-temperature (max 850C) catalytic cycle for thermochemical water splitting based on sodium and manganese oxides (Xu, Bhawe and Davis, PNAS, 2012). The key steps are thought to be hydrogen evolution from a Na2CO3/MnO mixture, and oxygen evolution by thermal reduction of solids formed by Na+ extraction from NaMnO2. Our work is aimed at understanding the fundamental chemical processes involved in the catalytic cycle, especially the hydrogen evolution from water. In this project, efforts are made to understand the interactions between the key components (Na, O2, CO2, and water) in the hydrogen evolution steps on a well-defined MnO(100) single crystal surface, utilizing x-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and temperature programmed desorption (TPD). While some of the behavior of the catalytic system is observed with the model system developed in this work, hydrogen is only produced from water in the presence of metallic sodium, in contrast to the proposal of Xu et al. that water splitting occurs from the reaction of water with a mixture of Na2CO3 and MnO. These differences are discussed in light of the different operating conditions for the catalytic system and the surface science model developed in this work.
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31

Eriksson, Therese. "The Structural Basis for Magnetic Order in New Manganese Compounds". Doctoral thesis, Uppsala : Acta Universitatis Upsaliensis : Univ.-bibl. [distributör], 2005. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-5746.

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32

Kiele, Sven. "Ladungs- und Orbitalordnungsphänomene in Übergangsmetalloxidverbindungen unter hydrostatischem Druck". Doctoral thesis, Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2006. http://nbn-resolving.de/urn:nbn:de:swb:14-1146138082235-46541.

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The thesis is dealing with the investigation of charge and orbital order and their behaviour under external pressure. Therefore, a new pressure cell has been developed which allows the observation of superlattice reflections corresponding to the order phenomena under pressure using scattering of high-energy synchrotron radiation. The maximum pressure that can be reached is 1.25 GPa. Until today there has been no possibility to conduct such studies of charge and orbital order superlattice reflections under pressure using x-ray scattering. The intensities of the reflections of the single crystalline samples are quite weak compared to fundamental peaks. Therefore the measurements are strongly affected by the absorption of the radiation in the pressure cell itself. Further difficulties result from the facts that low temperatures are needed and the sample has to be oriented in reciprocal space after being mounted into the cell. Therefore, the design of a compact clamp-type piston pressure cell was chosen here. The cell is made from a copper-beryllium alloy with the wall thickness reduced in the height of the sample volume. This allows the usage inside a closed-cycle cryostat mounted on a three-axis-diffractometer. Absorption effects are minimized due to the combination of reduced wall thickness and the usage of high energy synchrotron radiation (E = 100 keV at the beamline BW5 at HASYLAB/DESY). The new experimental technique was established and used for a study of two representatives of the transition metal oxide compounds, i.e. doped cuprates and manganites, which belong to the class of strongly correlated electron systems. The 1/8-doped cuprate La_{2-x}Ba_{x}CuO_{4} reveals an ordered state at low temperatures. Inside the CuO_{2} planes a combined order of charge stripes and antiferromagnetic spin stripes is observed. The ordering results from the interaction between charge, spin and lattice degrees of freedom. Here the lattice degrees of freedom play a major role. Particularly, a structural transition from an orthorhombic to a tetragonal symmetry is prerequisite for the observation of the ordered state. The cell constructed in this work allows a more exact analysis of the coupling between the crystal lattice and the formation of the charge and spin ordered phase. The manganite system Pr_{0.7}(Ca_{0.9}Sr_{0.1})_{0.3}MnO_{3} shows a strong magnetoresistive effect, called colossal magnetoresistance (CMR). In this system, several ordered phases can be found, which exhibit charge, spin and - since the orbital degree of freedom is also present in the manganites - additionally orbital ordering phenomena. In particular, an antiferromagnetically spin ordered insulating phase, which is connected to a charge- and orbital ordered state competes with a ferromagnetic metallic phase. This competition leads to a phase separation, which determines the properties of the sample. Both phases are strongly coupled to the lattice degrees of freedom, so that application of external pressure drastically affects the interplay between the different phases and allows a detailed study of the relation between the charge and orbital ordered phase and the crystal structure
Die vorliegende Arbeit befaßt sich mit dem Studium der Ordnungszustände von Ladungen und Orbitalen und deren Beeinflußung durch externen Druck. Als experimentelle Neuentwicklung wurde dafür eine Druckzelle entworfen, mit deren Hilfe die Beobachtung der jeweiligen Ordnungsphänomene unter Druck mittels der Streuung hochenergetischer Synchtrotronstrahlung möglich ist. Die Zelle erlaubt die Messung der orbitalen und Ladungsüberstrukturreflexe, welche aus den geordneten Zuständen resultieren, in einem Druckbereich bis 1.25 GPa. Die experimentelle Herausforderung ergibt sich hierbei aus der Tatsache, dass die Überstrukturreflexe im Vergleich zu den fundamentalen Reflexen der einkristallinen Proben sehr schwach sind und zusätzlich durch die Absorption im Mantelmaterial der Druckzelle stark beeinträchtigt werden. Darüber hinaus soll die Zelle bei tiefen Temperaturen einsetzbar und die Probe auch innerhalb der Zelle im reziproken Raum orientierbar sein. Bei dem hier realisierten Ansatz wurde für das Design daher der Typ einer kompakten Klemmdruckzelle aus einer Kupfer-Beryllium-Legierung gewählt, deren Zellwände im Bereich des Probenvolumens reduziert wurden. Dadurch ist der Einsatz der Zelle im Inneren eines Closed-Cycle-Kryostaten auf einem Einkristall-Diffraktometer möglich. Aufgrund der geringen Wandstärke der Zelle und der Nutzung von hochenergetischer Röntgenstrahlung (E = 100 keV am Messplatz BW5 des HASYLAB/DESY) werden Absorptionseffekte minimiert. Die neue Messmethode wurde im Rahmen der Arbeit etabliert und zur Untersuchung zweier wichtiger Übergangsmetalloxidverbindungen (dotierte Kuprate, Manganate), die zur Klasse der stark korrelierten Elektronensysteme gehören, eingesetzt. Das 1/8-dotierte Kupratsystem La_{2-x}Ba_{x}CuO_{4}, weist bei tiefen Temperaturen einen statisch geordneten Zustand auf. Innerhalb der CuO_{2}-Schichten des Kristalls ergibt sich eine Ordnung, bei der sich Streifen lokalisierter Löcher und antiferromagnetische Bereiche abwechseln. Ursache dieses Zustands ist das Wechselspiel von Ladungen, Spins und strukturellen Freiheitsgraden. Dabei spielen letztere eine herausgehobene Rolle. So ist insbesondere ein struktureller Übergang von einer orthorhombischen zu einer tetragonalen Phase Voraussetzung für die Beobachtung der Ordnung. Die in dieser Arbeit aufgebaute Druckzelle erlaubt eine genauere Analyse des Zusammenhangs zwischen Struktur des Kristalls und der Ausbildung der ladungs- und spingeordneten Phase. Das Manganatsystem Pr_{0.7}(Ca_{0.9}Sr_{0.1})_{0.3}MnO_{3}, zeichnet sich durch einen sehr starken magnetoresistiven Effekt aus, der auch als kolossaler Magnetowiderstand (CMR) bezeichnet wird. Auch hier kann bei tiefen Temperaturen eine geordnete Phase beobachtet werden. Allerdings spielt in diesem System zusätzlich der orbitale Freiheitsgrad der Elektronen eine entscheidende Rolle, so dass sich eine kombinierte Ladungs- und Orbitalordnung ergibt. Diese Phase, die isolierend und zusätzlich antiferromagnetisch geordnet ist, steht im direkten Wettbewerb zu einer ferromagnetischen Phase. Aus dieser Konkurrenz ergibt sich eine Tendenz zur Phasenseparation, deren Effekte die Eigenschaften des Kristalls dominieren. Da beide Phasen stark an die strukturellen Freiheitsgrade gekoppelt sind, läßt sich das Gleichgewicht zwischen ihnen durch externen Druck beeinflussen und die Abhängigkeit der ladungs- und orbitalgeordneten Phase von den strukturellen Eigenschaften des Kristalls im Detail untersuchen
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33

Lage, Marielle Hoalle Moreira Benevides. "Crescimento e caracterização de pontos quânticos de CdMnTe". Universidade Federal de Viçosa, 2013. http://locus.ufv.br/handle/123456789/4269.

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In the last decade, the growth of quantum dots has been studied with great interest in order to learn more about the basic physics of zero dimensional confinement and also due to their application in optoelectronic devices. The quantum dot energy levels can be controlled by changing the size, shape and material used, therefore its morphology plays an important role in determination of optical and electronic properties. In this study we used the molecular beam epitaxial technique (MBE) for producing CdMnTe quantum dots on silicon (111) substrates. To produce the samples, substrate temperature, growth time and manganese concentration were varied. The morphological and structural properties of the samples were analyzed by Atomic Force Microscopy (AFM) at the Laboratório Nacional de Nanotecnologia and by x- ray diffraction using the XRD2 beam line of the Laboratório Nacional de Luz Síncrontron (LNLS), in Campinas. The results showed that the substrate temperature influences the size dispersion of the islands, the growth time changes the size and the quality and the concentration of manganese affects mainly the quality of the quantum dots.
Na última década, tem-se estudado com grande interesse o crescimento de pontos quânticos com o intuito de conhecer mais sobre a física básica do confinamento zero dimensional e também devido a sua aplicação em dispositivos óptico-eletrônicos. Os níveis de energia podem ser controlados mudando o tamanho, a forma e o material utilizado, sendo assim a morfologia do ponto quântico desempenha um papel importante na determinação das propriedades ópticas do material estudado. Neste trabalho foi utilizada a técnica de crescimento epitaxial por feixe molecular (MBE) para a produção de pontos quânticos do semicondutor magnético diluído CdMnTe sobre substratos de silício (111). Para a produção das amostras, foram variados a temperatura do substrato, o tempo de crescimento e concentração de manganês. As propriedades morfológicas e estruturais das amostras foram analisadas através de Microscopia de Força Atômica (AFM) no Laboratório Nacional de Nanotecnologia, e através de difração de raios-x utilizando a linha XRD2 do Laboratório Nacional de Luz Síncrotron (LNLS), em Campinas. Os resultados mostraram que a temperatura do substrato influencia na dispersão de tamanhos das ilhas, o tempo de crescimento altera o tamanho e a qualidade e a concentração de manganês influencia principalmente a qualidade dos pontos quânticos.
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34

Martins, Da Silva Fernando Henrique. "Etude structurale, distribution cationique et état d'oxydation dans des nanoparticules magnétiques de ferrite du type coeur-coquille". Thesis, Paris 6, 2016. http://www.theses.fr/2016PA066102/document.

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Nous explorons les propriétés structurales de nanoparticules cœur-coquille, avec un cœur de ferrite MFe2O4 (M = Mn et Co) ou de ferrite mixte Mn-Zn. Ces nanoparticules sont obtenues par co-précipitation hydrothermique et sont dispersées en milieu acide par un traitement de surface empirique au nitrate ferrique, protégeant les nanograins contre une dissociation chimique par une fine couche superficielle de maghémite. La fraction volumique du cœur, de la coquille et l’épaisseur de la couche superficielle sont déterminées par dosage chimique. Nous suivons les changements structurels des nanocristaux de MnFe2O4 et CoFe2O4, pendant la durée du traitement de surface, tandis que ceux des nanoparticules de ferrite mixte Mn-Zn sont étudiés en fonction de leur teneur en zinc. Diffraction de rayons-x et de neutrons sont utilisées pour déterminer les paramètres de structure, en particulier la diffusion de cations dans les interstices de la ferrite spinelle. Pour un haut degré de fiabilité, des raffinements de Rietveld sont réalisés. Les distances inter-atomiques, l’état d’oxydation moyen et le degré d’inversion sont déterminés par spectroscopie d’absorption des rayons-x. Morphologie, cristallinité et taille des nanoparticules de ferrite mixte Mn-Zn sont étudiées par TEM/HRTEM et par diffraction des électrons. Dans les nanoparticules MnFe2O4 et de ferrite mixte Mn-Zn, on constate la présence de cations Mn3+ en environnement octaédrique, responsables de déformations anisotropes (effet Jahn-Teller). Le degré d’inversion obtenu ici diffère de celui du bulk en raison de la réduction à l’échelle nanométrique et de l'augmentation du rapport surface/volume pendant le processus de synthèse
Structural properties of core-shell ferrite nanoparticles MFe2O4 (M = Mn and Co) and Mn-Zn ferrite nanoparticles are here investigated. The nanoparticles are synthesized by hydrothermal co-precipitation and are dispersed in acid medium thanks to an empirical surface treatment by ferric nitrate, which prevents the chemical dissociation by a thin maghemite layer incorporated at the surface of the nano-grains. Chemical titrations allow us to calculate volume fractions of core and shell, as well as the surface-layer thickness. Structural changes induced by the surface treatment are followed as a function of treatment duration in MnFe2O4 and CoFe2O4 nanocrystals. Whereas structural changes in Mn-Zn ferrite nanoparticles are investigated as a function of zinc content. X-ray and Neutron diffractions are used to determine the structural parameters, in particular cationic distribution in the spinel ferrite sites. Precise structural information with high degree of reliability is obtained by Rietveld refinements. To investigate the local structure of these materials, X-ray Absorption Spectroscopy measurements are performed, allowing determining interatomic distances, mean oxidation state and inversion degree. Morphology, crystallinity and size of mixed-ferrite nanoparticles are investigated by TEM/HRTEM and electron diffraction. In Mn-Zn ferrite nanoparticles, the presence of Mn3+ in octahedral environment is responsible for anisotropic distortions, known as Jahn-Teller effect. The inversion degree obtained in this work diverges from the bulk values due to the reduction to nanoscale and to the increase of the surface/volume ratio, associated to the synthesis process
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35

Kiele, Sven. "Ladungs- und Orbitalordnungsphänomene in Übergangsmetalloxidverbindungen unter hydrostatischem Druck: Diffraktometrische Studien mit Synchrotronstrahlung". Doctoral thesis, Technische Universität Dresden, 2005. https://tud.qucosa.de/id/qucosa%3A24697.

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The thesis is dealing with the investigation of charge and orbital order and their behaviour under external pressure. Therefore, a new pressure cell has been developed which allows the observation of superlattice reflections corresponding to the order phenomena under pressure using scattering of high-energy synchrotron radiation. The maximum pressure that can be reached is 1.25 GPa. Until today there has been no possibility to conduct such studies of charge and orbital order superlattice reflections under pressure using x-ray scattering. The intensities of the reflections of the single crystalline samples are quite weak compared to fundamental peaks. Therefore the measurements are strongly affected by the absorption of the radiation in the pressure cell itself. Further difficulties result from the facts that low temperatures are needed and the sample has to be oriented in reciprocal space after being mounted into the cell. Therefore, the design of a compact clamp-type piston pressure cell was chosen here. The cell is made from a copper-beryllium alloy with the wall thickness reduced in the height of the sample volume. This allows the usage inside a closed-cycle cryostat mounted on a three-axis-diffractometer. Absorption effects are minimized due to the combination of reduced wall thickness and the usage of high energy synchrotron radiation (E = 100 keV at the beamline BW5 at HASYLAB/DESY). The new experimental technique was established and used for a study of two representatives of the transition metal oxide compounds, i.e. doped cuprates and manganites, which belong to the class of strongly correlated electron systems. The 1/8-doped cuprate La_{2-x}Ba_{x}CuO_{4} reveals an ordered state at low temperatures. Inside the CuO_{2} planes a combined order of charge stripes and antiferromagnetic spin stripes is observed. The ordering results from the interaction between charge, spin and lattice degrees of freedom. Here the lattice degrees of freedom play a major role. Particularly, a structural transition from an orthorhombic to a tetragonal symmetry is prerequisite for the observation of the ordered state. The cell constructed in this work allows a more exact analysis of the coupling between the crystal lattice and the formation of the charge and spin ordered phase. The manganite system Pr_{0.7}(Ca_{0.9}Sr_{0.1})_{0.3}MnO_{3} shows a strong magnetoresistive effect, called colossal magnetoresistance (CMR). In this system, several ordered phases can be found, which exhibit charge, spin and - since the orbital degree of freedom is also present in the manganites - additionally orbital ordering phenomena. In particular, an antiferromagnetically spin ordered insulating phase, which is connected to a charge- and orbital ordered state competes with a ferromagnetic metallic phase. This competition leads to a phase separation, which determines the properties of the sample. Both phases are strongly coupled to the lattice degrees of freedom, so that application of external pressure drastically affects the interplay between the different phases and allows a detailed study of the relation between the charge and orbital ordered phase and the crystal structure.
Die vorliegende Arbeit befaßt sich mit dem Studium der Ordnungszustände von Ladungen und Orbitalen und deren Beeinflußung durch externen Druck. Als experimentelle Neuentwicklung wurde dafür eine Druckzelle entworfen, mit deren Hilfe die Beobachtung der jeweiligen Ordnungsphänomene unter Druck mittels der Streuung hochenergetischer Synchtrotronstrahlung möglich ist. Die Zelle erlaubt die Messung der orbitalen und Ladungsüberstrukturreflexe, welche aus den geordneten Zuständen resultieren, in einem Druckbereich bis 1.25 GPa. Die experimentelle Herausforderung ergibt sich hierbei aus der Tatsache, dass die Überstrukturreflexe im Vergleich zu den fundamentalen Reflexen der einkristallinen Proben sehr schwach sind und zusätzlich durch die Absorption im Mantelmaterial der Druckzelle stark beeinträchtigt werden. Darüber hinaus soll die Zelle bei tiefen Temperaturen einsetzbar und die Probe auch innerhalb der Zelle im reziproken Raum orientierbar sein. Bei dem hier realisierten Ansatz wurde für das Design daher der Typ einer kompakten Klemmdruckzelle aus einer Kupfer-Beryllium-Legierung gewählt, deren Zellwände im Bereich des Probenvolumens reduziert wurden. Dadurch ist der Einsatz der Zelle im Inneren eines Closed-Cycle-Kryostaten auf einem Einkristall-Diffraktometer möglich. Aufgrund der geringen Wandstärke der Zelle und der Nutzung von hochenergetischer Röntgenstrahlung (E = 100 keV am Messplatz BW5 des HASYLAB/DESY) werden Absorptionseffekte minimiert. Die neue Messmethode wurde im Rahmen der Arbeit etabliert und zur Untersuchung zweier wichtiger Übergangsmetalloxidverbindungen (dotierte Kuprate, Manganate), die zur Klasse der stark korrelierten Elektronensysteme gehören, eingesetzt. Das 1/8-dotierte Kupratsystem La_{2-x}Ba_{x}CuO_{4}, weist bei tiefen Temperaturen einen statisch geordneten Zustand auf. Innerhalb der CuO_{2}-Schichten des Kristalls ergibt sich eine Ordnung, bei der sich Streifen lokalisierter Löcher und antiferromagnetische Bereiche abwechseln. Ursache dieses Zustands ist das Wechselspiel von Ladungen, Spins und strukturellen Freiheitsgraden. Dabei spielen letztere eine herausgehobene Rolle. So ist insbesondere ein struktureller Übergang von einer orthorhombischen zu einer tetragonalen Phase Voraussetzung für die Beobachtung der Ordnung. Die in dieser Arbeit aufgebaute Druckzelle erlaubt eine genauere Analyse des Zusammenhangs zwischen Struktur des Kristalls und der Ausbildung der ladungs- und spingeordneten Phase. Das Manganatsystem Pr_{0.7}(Ca_{0.9}Sr_{0.1})_{0.3}MnO_{3}, zeichnet sich durch einen sehr starken magnetoresistiven Effekt aus, der auch als kolossaler Magnetowiderstand (CMR) bezeichnet wird. Auch hier kann bei tiefen Temperaturen eine geordnete Phase beobachtet werden. Allerdings spielt in diesem System zusätzlich der orbitale Freiheitsgrad der Elektronen eine entscheidende Rolle, so dass sich eine kombinierte Ladungs- und Orbitalordnung ergibt. Diese Phase, die isolierend und zusätzlich antiferromagnetisch geordnet ist, steht im direkten Wettbewerb zu einer ferromagnetischen Phase. Aus dieser Konkurrenz ergibt sich eine Tendenz zur Phasenseparation, deren Effekte die Eigenschaften des Kristalls dominieren. Da beide Phasen stark an die strukturellen Freiheitsgrade gekoppelt sind, läßt sich das Gleichgewicht zwischen ihnen durch externen Druck beeinflussen und die Abhängigkeit der ladungs- und orbitalgeordneten Phase von den strukturellen Eigenschaften des Kristalls im Detail untersuchen.
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36

Ledieu, Julian. "The five-fold surface of the icosahedral Al←7←0Pd←2←1Mn←9 quasicrystal". Thesis, University of Liverpool, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.343756.

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Larguet, Nour-Eddine. "Contribution à l'étude de la formation de l'état quasicristallin". Rouen, 1995. http://www.theses.fr/1995ROUES025.

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Le retour à l'équilibre d'une solution solide sursaturée contenant 2 à 3 at % de Mn d'une part et l'effet du recuit à 530° C sur la structure de la phase T2 du système Al-Li-Cu d'autre part ont été étudiés par diffraction X in-situ et par M. E. T. Dans le système Al-Mn et pour la première fois, la précipitation d'une phase quasicristalline à partir d'une solution solide sursaturée a été mise en évidence. Elle constitue une étape intermédiaire métastable du retour à l'équilibre vers la phase stable Al6Mn. La teneur en Mn de cette phase a été déterminée par des mesures en diffraction X et par MET/EdX. La valeur obtenue comprise entre 9,4 et 10,8 at%, est fonction de la concentration nominale de l'alliage et fixe ainsi la limite inférieure de formation d'une structure quasicristalline dans le système Al-Mn. Dans le système Al-Li-Cu des échantillons de composition Al6Li3Cu, ayant subi des recuits isothermes à 530°C sous 40 atm. D'argon, ont été étudiés. Nous avons entrepris une étude quantitative des écarts au modèle du quasicristal parfait par des mesures de diffraction X à température ambiante. Le recuit prolongé élimine progressivement les défauts de type phason, accompagnant une modification de la composition chimique de la phase T2. Des modèles de structures approximantes ont été simulés par un calcul des spectres de diffraction électronique et de rayons X. Les modèles les plus proches de l'expérience correspondent à des approximants orthorhombiques d'ordre (5/3, 5/3, 3/2) pour l'alliage brut de coulée et (8/5, 5/3, 5/3) pour le matériau recuit. Les paramètres de maille varient de 50 à 60 ang
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38

Paul, Alexander. "Manganese as a site factor for epiphytic lichens". Doctoral thesis, [S.l.] : [s.n.], 2005. http://webdoc.sub.gwdg.de/diss/2005/paul.

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39

Kang, Kyongha. "Crystalline structure, and magnetic and magneto-optical properties of MnSbBi thin films". Thesis, University of Oxford, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.365438.

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40

Pajot, Ségolène. "Synthèse et caractérisation d’oxydes lamellaires riches en lithium et en manganèse obtenus sous la forme de gradients de concentration pour les batteries Li-ion". Thesis, Bordeaux, 2016. http://www.theses.fr/2016BORD0277/document.

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Ce travail présente la mise en oeuvre d’un protocole de synthèse de gradients deconcentration dans les oxydes lamellaires riches en Li et en Mn. Le but a été dedévelopper la formation d’oxydes lamellaires riches en Li et Mn au coeur des agrégatssphériques du matériau actif et, en se rapprochant de la surface, d’enrichir lacomposition de l’oxyde lamellaire en Co et en Ni, afin de combiner une forte densitéd’énergie (apportée par le coeur du gradient) et une excellente stabilité thermique etstructurale (apportée par la surface du gradient). La synthèse a été réalisée en deuxétapes, une co-précipitation pour former un carbonate de métaux de transition suivied’une calcination à haute température pour obtenir le matériau actif lithié. L’influencede différents paramètres (pH, débit d’injection, taille du réacteur, composition, …) surla nature du carbonate à gradient de concentration ainsi formé a été étudiée. De lamême façon, le contrôle du ratio Li/M (ici M = Ni, Co, Mn), de la température et de ladurée de calcination s’est révélé important pour parvenir à maintenir le gradient deconcentration dans le matériau lithié. Le ratio Li/M est également déterminant pourcontrôler la nature des matériaux obtenus (lamellaire - spinelle ou lamellaire –lamellaire). Des caractérisations extrêmement pointues, et complexes à mettre enoeuvre, ont été menées afin d’obtenir des informations pertinentes sur la distributiondes phases au sein des agrégats (composition et structure), de la surface au coeur dugradient : différentes techniques de microscopie (EPMA, MEB-EDX et FIB-STEM) ontainsi été largement utilisées. Les matériaux les plus intéressants ont été étudiés enbatteries Lithium-ion avec une électrode de graphite à la négative, les performancesélectrochimiques et la stabilité thermique à l’état chargé de la batterie sont largementdiscutées par rapport à l’état de l’art et notamment au matériau de coeur riche en Li eten Mn
This work describes in details the implementation of the synthesis protocol for theformation of Li- and Mn-rich layered oxides with concentration-gradients. The purposewas to develop the synthesis of Li- and Mn-rich layered oxides in the bulk of sphericalaggregates of active material and, moving to the surface, to enrich the layered oxides’composition with Co and Ni, in order to combine a high energy density (provided bythe bulk) and an excellent thermal and structural stability (provided by the surface).The synthesis was performed in two steps, a coprecipitation to form a transition metalcarbonate followed by a calcination at high temperature to obtain the lithiated activematerial. The influence of several parameters (pH, feeding rate, size of the reactor,composition …) on the nature of the carbonates formed with concentration-gradientswas studied. Similarly, the control of the Li/M ratio (with M = Ni, Co, Mn) and of thetemperature and duration of calcination was revealed to be important to maintain theconcentration-gradient in the lithiated materials. The Li/M ratio is also the keyparameter to control the nature of the materials obtained (layered - spinel or layered -layered). Advanced characterizations, complex to be implemented, were performed inorder to obtain in-depth information on the distribution of phases within the aggregates(composition and structure), from the bulk to the surface: complementary microscopytechniques (EPMA, SEM-EDS and FIB-STEM) were widely used. The most interestingmaterials were studied in Lithium-ion batteries with graphite at the negative electrode,their electrochemical performance and the thermal stability in the charged state of thebattery were compared to the state of art, and particularly to the bulk Li and Mn-richlayered oxide
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41

Kunický, Daniel. "Studium struktury vysokonapěťových katodových materiálů pro lithno iontové akumulátory metodou rentgenové strukturní analýzy". Master's thesis, Vysoké učení technické v Brně. Fakulta elektrotechniky a komunikačních technologií, 2018. http://www.nusl.cz/ntk/nusl-377135.

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This diploma thesis deals with the X-Ray crystallography study of structural changes within lithium-ion cells. First part consists of the theoretical discussion about the structural changes in commerce lithium-ion cells with focus on X-Ray crystallography. Then the ex situ, in situ and operando terms are discussed. Verification of the XRD usage is realized on the LiFePO4 material. Experimental part deals with the optimization and preparation of electrochemical cells and the measurements. Finally, results of the Rietveld analysis are discussed.
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42

Charenton, Jean-Claude. "Synthèse et caractérisation structurale et physico-chimique de quelques variétés non-stoechiométriques de bioxyde de manganèse". Grenoble 1, 1987. http://www.theses.fr/1987GRE10089.

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Compose etudiees : axmnoy, zh::(2)o a = na, k, rb, cs, mn (phyllomanganates) et mno::(1,93-1,98), zh::(2)o (type mno::(2) nongamma epsilon ). Pour les phyllomanganates, l'etude des variations des parametres cristallins et de la teneur en eau z en fonction de la temperature t et de l'hygrometrie rh confirme la structure lamellaire. Mesures de conductivite en fonction de t et rh. La structure des composes de type mno::(2) nongamma epsilon est basee sur une intercroissance de reseaux de type rutile et ramsdellite
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43

CASINI, JULIO C. S. "Influência da substituição do cobalto por estanho e cobre na microestrutura e propriedades elétricas em ligas a base de LaMgAlMnCoNi". reponame:Repositório Institucional do IPEN, 2015. http://repositorio.ipen.br:8080/xmlui/handle/123456789/24068.

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Tese (Doutorado em Tecnologia Nuclear)
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Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP
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Mancini, Lucia. "Étude des défauts dans les quasicristaux en utilisant les aspects nouveaux de l'imagerie aux rayons X associés aux sources synchrotron de troisième génération". Université Joseph Fourier (Grenoble ; 1971-2015), 1998. http://www.theses.fr/1998GRE10077.

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Nous avons etudie les defauts dans des quasicristaux d'al-pd-mn a symetrie icosaedrique, en utilisant les nouvelles possibilites de l'imagerie aux rayons x associees aux proprietes des sources synchrotron de 3#e#m#e generation. Nous avons observe par imagerie de fresnel (radiographie et microtomographie en contraste de phase) des heterogeneites, trous et precipites, dans le volume des grains. Les trous ont des tailles et des distances discretes. Les topographies aux rayons x ont montre des contrastes a deux lobes et des objets complexes avec un contraste sous forme de boucles (boucles). Nous avons observe que les recuits a haute temperature (750 c) effectues sur les grains peuvent produire la formation de precipites lamellaires, cristallins et pauvres en pd. Ils se developpent au fur et a mesure que l'on recuit les echantillons pres des surfaces ou des trous presents dans l'echantillon. La topographie combinee avec l'imagerie de fresnel a permis d'etablir une correlation entre les defauts structuraux et les heterogeneites dans les grains bruts de croissance ou apres recuit. Des experiences topographiques in situ, dans un four, ont montre que les boucles ont un comportement inhabituel par rapport aux defauts cristallins, le contraste variant de maniere reversible lors de recuits courts. Les images enregistrees pendant des longs recuits (plusieurs heures) montrent une augmentation irreversible de la taille et densite de ces boucles. Ces defauts n'ont jamais ete observes a une echelle plus petite, par met, qui ne montre que des lignes de dislocation qui n'evoluent pas en fonction de la temperature. La simulation d'images, un outil puissant pour l'interpretation des topographies, nous a permis de donner une premiere interpretation a une partie des contrastes observes dans les grains quasicristallins examines.
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45

Ludvigsson, Mikael. "Materials for future power sources". Doctoral thesis, Uppsala University, Department of Chemistry, 2000. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-498.

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Proton exchange membrane fuel cells and lithium polymer batteries are important as future power sources in electronic devices, vehicles and stationary applications. The development of these power sources involves finding and characterising materials that are well suited r the application.

The materials investigated in this thesis are the perfluorosulphonic ionomer NafionTM (DuPont) and metal oxides incorporated into the membrane form of this material. The ionomer is used as polymer electrolyte in proton exchange membrane fuel cells (PEMFC) and the metal oxides are used as cathode materials in lithium polymer batters (LPB).

Crystallinity in cast Nafion films can be introduced by ion beam exposure or aging. Spectroscopic investigations of the crystallinity of the ionomer indicate that the crystalline regions contain less water than amorphous regions and this could in part explain the drying out of the polymer electrolyte membrane in a PEMFC.

Spectroscopic results on the equilibrated water uptake and the state of water in thin cast ionomer films indicate that there is a full proton transfer from the sulphonic acid group in the ionomer when there is one water molecule per sulphonate group.

The LPB cathode materials, lithium manganese oxide and lithium cobalt oxide, were incorporated in situ in Nafion membranes. Other manganese oxides and cobalt oxides were incorporated in situ inside the membrane. Ion-exchange experiments from HcoO2 to LiCoO2 within the membrane were also successful.

Fourier transform infrared spectroscopy, Raman spectroscopy and X-ray diffraction were used for the characterisation of the incorporated species and the Nafion film/membrane.

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46

Boulineau, Adrien. "Contribution à la compréhension de la structure de Li2MnO3, de ses défauts et de phases dérivées". Thesis, Bordeaux 1, 2008. http://www.theses.fr/2008BOR13747/document.

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Afin de mieux comprendre les évolutions structurales mises en évidence dans les oxydes lamellaires de formule générale Li1+x(Ni0.425Mn0.425Co0.15)O2 utilisés comme électrode positive pour batterie lithium-ion, la structure du composé Li2MnO3 a été étudiée en détail. Obtenu selon différentes voies de synthèses, réalisées à différentes températures, ce matériau qui peut être considéré comme un matériau model à fait l’objet d’une étude cristallographique où l’utilisation de la microscopie électronique a été privilégiée. Deux types de défauts ont été identifiés. D’une part, l’existence de fautes d’empilement au sein du matériau a été démontrée. Leurs conséquences sur les clichés de diffraction électronique et les diagrammes de diffraction des rayons-X ont étés expliquées permettant d’unifier les controverses présentent à ce sujet dans la littérature. D’autre part, l’étude de la stabilité thermique du composé Li2MnO3 a mis en évidence l’apparition de défauts de type « phase spinelle » en surface des grains lorsque la température de traitement thermique devient supérieure ou égale à 900°C. Le traitement du matériau par la voie acide a pu être étudié et le mécanisme de désintercalation chimique du lithium par la voie acide a finalement pu être précisé. Il est montré que ce mécanisme est le même quelle que soit la taille des particules
In order to get a better understanding of the complex structural evolutions occurring in the layered oxides like Li1+x(Ni0.425Mn0.425Co0.15)O2 materials when they are used as positive electrodes in lithium batteries, the structure of Li2MnO3 has been studied in detail. Obtained from several synthesis ways, annealed at various temperatures, this compound that can be considered as a model one regarding these complex materials has been the object of a crystallographic study where the use of electron microscopy was privileged. Two kinds of defects could be identified. From one part, the existence of stacking faults in the Li2MnO3 material has been proved and they have been visualized for the first time. Their consequences on X ray and electron diffraction patterns are explained allowing the unification of discrepancies existing in the bibliography. For other part, the study of the thermal stability of Li2MnO3 evidenced the appearance of spinel type defects when the annealing treatment is performed above 900°C. Finally the delithiation by acid leaching is studied and the lithium extraction mechanism is clarified. It is shown that this mechanism is the same whatever the particle size is
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47

Chaluvadi, Sandeep kumar. "Influence of the epitaxial strain on magnetic anisotropy in LSMO thin films for spintronics applications". Thesis, Normandie, 2017. http://www.theses.fr/2017NORMC248/document.

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Nous présentons une étude des effets de contrainte induits par l’épitaxie dans des couches minces La1-xSrxMnO3 (LSMO) (001) (x = 0.33) pour 3 épaisseurs de films (50, 25 et 12 nm) déposés par Ablation Laser Pulsée (PLD) sur différents substrats tels que SrTiO3 (STO) (001), STO buffered MgO (001), NdGaO3 (NGO) (110) et (LaAlO3)0.3(Sr2AlTaO6)0.7 (LSAT) (001). L’étude est complétée par l’effet de la composition sur les propriétés magnétiques de couches minces de La1-xSrxMnO3 avec x=0,33 et 0,38 déposées par Epitaxie à Jets Moléculaires (MBE). Des caractérisations par diffraction de rayons X (XRD), et microscopie à force atomique (AFM), des mesures de résistivité électrique en quatre points en fonction de la température, d’aimantation par magnetometrie à SQUID (Superconducting Quantum Interference Device) et d’anisotropie magnétique par magnétométrie magnéto-optique Kerr vectorielle (MOKE) sont présentées. Les évolutions angulaires de l’anisotropie magnétique, de l’aimantation à rémanence, du champ coercitif et du champ de renversement d’aimantation ont ainsi pu être analysées pour des films épitaxiés LSMO de différentes épaisseurs. Des études en fonction de la température complètent les données. L’origine de l’anisotropie (magnétique, magnétocristalline, magnétostrictive ou liée aux effets de marches et d’angle de désorientation du substrat) est finalement discutée
We report a quantitative analysis of thickness dependent epitaxial strain-induced effects in La1-xSrxMnO3 (LSMO) (001) (x = 0.33) thin films of thicknesses (50, 25 and 12 nm) grown on various single crystal substrates such as SrTiO3 (STO) (001), STO buffered MgO (001), NdGaO3 (NGO) (110) and (LaAlO3)0.3(Sr2AlTaO6)0.7 (LSAT) (001) by Pulsed Laser Deposition (PLD) technique. We also report the composition dependent magnetic properties of LSMO thin films with x = 0.33 and 0.38 in particular grown onto LSAT (001) substrate by Molecular Beam Epitaxy (MBE). The study mainly includes measurements such as X-ray Diffraction (XRD), Atomic Force Microscopy (AFM), temperature dependent four-probe resistivity, magnetization properties by Superconducting Quantum Interference Device (SQUID), magnetic anisotropy by Magneto-Optical Kerr Magnetometry (MOKE). Our results highlight the detailed study of angular evolution and thickness dependent magnetic anisotropy, remanence, coercivity and switching field in epitaxial LSMO thin films. Temperature-dependent studies are also performed on few selected films. We will also discuss the cause of magnetic anisotropy in LSMO films i.e., magneto-crystalline and magnetostriction anisotropy and the effects of steps or substrate mis-cut induced anisotropy
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48

GALDINO, GABRIEL S. "Influência do PR na microestrutura e propriedades elétricas em ligas à base de LaPrMgAlMnCoNi utilizadas em baterias de Ni-HM". reponame:Repositório Institucional do IPEN, 2011. http://repositorio.ipen.br:8080/xmlui/handle/123456789/10080.

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Made available in DSpace on 2014-10-09T12:34:31Z (GMT). No. of bitstreams: 0
Made available in DSpace on 2014-10-09T14:00:26Z (GMT). No. of bitstreams: 0
Dissertação (Mestrado)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP
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49

El, Amrani Mohamed. "Synthèse et caractérisation spectroscopique d oxydes multiferroïques.Y1-xInxMn1-yFeyO3 et RCrO3 (R = terre rare)". Thesis, Tours, 2014. http://www.theses.fr/2014TOUR4046/document.

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Dans les multiferroïques coexistent au moins deux ordres ferroïques différents (ferromagnétique, ferroélectrique, ferroélasticité et ferrotoroïdicité) ou anti-ferroïques. Ces différentes propriétés peuvent être couplées ou non. Parmi ces matériaux, les plus étudiés sont ceux présentant un ordre magnétique et un ordre ferroélectrique. La présence d’un couplage magnétoélectrique entre ces deux ordres, permet de contrôler la polarisation par l’application d’un champ magnétique et inversement. Cependant très peu de ces matériaux ont des températures de transition supérieures à la température ambiante. Ces matériaux multiferoïques peuvent être séparés en deux catégories : la première regroupe les matériaux où les transitions des deux ordres sont indépendantes ; la deuxième regroupe les matériaux dont la transition ferroélectrique est liée à la mise en ordre magnétique. Dans cette thèse nous nous sommes intéressés à deux types d’oxyde multiferroïques dont l’un appartient à la première catégorie (YMnO3) et l’autre à la deuxième (RCrO3)
In multiferroics, at least two different ferroic orders coexist (ferromagnetic, ferroelectric, ferroelastici and ferrotoroidici) or anti-ferroic. These different properties can be coupled or not. Among these materials, the most studied are those with magnetic and ferroelectric orders. The presence of magnetoelectric coupling between these two orders, allows one to control the polarization by the application of a magnetic field and vice versa. However very few of these materials have transition temperatures above room temperature. These multiferoics materials can be separated into two categories : the first one includes the materials where the transitions of both orders are independent ; the second comprises the materials the ferroelectric transition of which is related to magnetic ordering. In this thesis we have studied two types of multiferroic oxides, one belongs to the first category (YMnO3) and the other to the second (RCrO3 )
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50

Caignaert, Vincent. "Non-stoechiometrie par creation de lacunes anioniques : oxydes mixtes de manganese et de fer, de structure apparentee a la perovskite". Caen, 1986. http://www.theses.fr/1986CAEN2007.

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Etude des possibilites d'ecarts a la stoechiometrie sur le sous reseau anionique des perovskites amn::(1-x) fe::(x)o::(3-y) (a=ca, sr, ba) par diffraction x et neutron, microscopie electronique haute resolution, spectre moessbauer et mesures magnetiques. Caracterisation de plusieurs types d'ordre des lacunes oxygene en fonction du cation a et du taux de mn
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