Paleoenvironmental dynamics during the last 135.000 years at the Upper Jiloca basin area : the lacustrine record of "El Cañizar"

359 páginas - Tesis presentada para optar al grado de Doctor en Física Aplicada por la Universidad de ZaragozaPeer reviewe

CLIWOC multilingual meteorological dictionary

This dictionary is the first attempt to express the wealth of archaic logbook wind force terms in a form that is comprehensible to the modern-day reader. Oliver and Kington (1970) and Lamb (1982) have drawn attention to the importance of logbooks in climatic studies, and Lamb (1991) offered a conversion scale for early eighteenth century English wind force terms, but no studies have thus far pursued the matter to any greater depth. This text attempts to make good this deficiency, and is derived from the research undertaken by the CLIWOC project1 in which British, Dutch, French and Spanish naval and merchant logbooks from the period 1750 to 1850 were used to derive a global database of climatic information. At an early stage in the project it was apparent that many of the logbook weather terms, whilst conforming to a conventional vocabulary, possessed meanings that were unclear to twenty-first century readers or had changed over time. This was particularly the case for the important element of wind force; but no special plea is entered for the evolution in nautical vocabulary, which often reflected more wide-ranging changes in the respective native languages.The key objective was to translate the archaic vocabulary of the late eighteenth and early nineteenth century mariner into expressions directly comparable with the Beaufort Scale (see Appendix I). Only then could the projects scientific programme be embarked upon. This dictionary is the result of the largest undertaking into logbook studies that has yet been carried out. Several thousand logbooks from British, Dutch, French and Spanish archives were examined, and the exercise offered a unique opportunity to explore the vocabulary of the one hundred year period beginning in 1750. The logbooks from which the raw data have been abstracted range widely across the North and South Atlantic and the Indian Oceans. Only the Pacific, largely in consequence of the paucity of regular naval activity in that area, is not well represented. The range of climates encountered in this otherwise wide geographic domain gives ample opportunity for the full range of the mariners nautical weather vocabulary to be assessed, from the calms of the Equatorial regions, through the gales of the mid-latitude systems to the fearsome storms of the tropical latitudes. The Trade Winds belts, the Doldrums, the unsettled mid-latitudes, even the icy wastes of the high latitudes, are all embraced in this study. It is not here intended to pass any judgements on the climatological record of the logbooks, and this text seeks only to provide a means of understanding archaic wind force terms and, other than to indicate those items that were not commonly used, no information is given on the frequency with which different terms appeared in the logbooks. Attention is, furthermore, confined to Dutch, English, French and Spanish because these once great imperial powers were the only nations able to support wide-ranging ocean-going fleets with their attendant collections of logbooks and documents over this long period of time. The work is offered to the wider academic community in the hope that they will prove to be of as much value as it has been to the CLIWOC team

Correlation between Mn oxidation state and magnetic behavior in Mn/ZnO multilayers prepared by sputtering

Compositional, microstructural, and magnetic characterization of ZnO 30 Å/Mn x n multilayers prepared by sputtering is presented to study the observed ferromagnetism in the Mn-ZnO system. The nominal Mn layer thickness, x, is varied from 3 to 60 Å, while the number of bilayers, n, is increased to maintain the total amount of Mn constant. Microstructure information was deduced from x-ray reflectivity, Mn oxidation state was determined by x-ray absorption spectroscopy, and magnetic properties were measured over a temperature range of 5–400 K. Magnetic behavior of these samples is found to be related to the Mn layer thickness x. Multilayers with x 30 Å exhibit ferromagnetism with a Curie temperature above 400 K, while mostly paramagnetic behavior is obtained for x15 Å. Magnetic behavior is discussed in terms of electronic and structural parameters of samples. Mn-ZnO interface effect is related to the ferromagnetic order of the samples, but it is not a sufficient condition. The essential role of the Mn oxidation state in the magnetic behavior of this system is pointed out. It is shown a correlation between the obtained ferromagnetism and a Mn oxidation state close to 2+.Ministerio de Educación y Ciencias de España-MAT2003-01880 y MAT2006-0100

Quantifying Li-content for compositional tailoring of lithium ferrite ceramics

Owing to their multiple applications, lithium ferrites are relevant materials for several emerging technologies. For instance, LiFeO2 has been spotted as an alternative cathode material in Li-ion batteries, while LiFe5O8 is the lowest damping ferrite, holding promise in the field of spintronics. The Li-content in lithium ferrites has been shown to greatly affect the physical properties, and in turn, the performance of functional devices based on these materials. Despite this, lithium content is rarely accurately quantified, as a result of the low number of electrons in Li hindering its identification by means of routine materials characterization methods. In the present work, magnetic lithium ferrite powders with Li:Fe ratios of 1:1, 1:3 and 1:5 have been synthesized, successfully obtaining phase-pure materials (LiFeO2 and LiFe5O8), as well as a controlled mixture of both phases. The powders have been compacted and subsequently sintered by thermal treatment (Tmax = 1100 {\deg}C) to fabricate dense pellets which preserve the original Li:Fe ratios. Li-content on both powders and pellets has been determined by two independent methods: (i) Rutherford backscattering spectroscopy combined with nuclear reaction analysis and (ii) Rietveld analysis of powder X-ray diffraction data. With good agreement between both techniques, it has been confirmed that the Li:Fe ratios employed in the synthesis are maintained in the sintered ceramics. The same conclusion is drawn from spatially-resolved confocal Raman microscopy experiments on regions of a few microns. Field emission scanning electron microscopy has evidenced the substantial grain growth taking place during the sintering process - mean particle sizes rise from about 600 nm in the powders up to 3.8(6) um for dense LiFeO2 and 10(2) um for LiFe5O8 ceramics

Quantifying Li-content for compositional tailoring of lithium ferrite ceramics

Owing to their multiple applications, lithium ferrites are relevant materials for several emerging technologies. For instance, LiFeO2 has been spotted as an alternative cathode material in Li-ion batteries, while LiFe5O8 is the lowest damping ferrite, holding promise in the field of spintronics. The Li-content in lithium ferrites has been shown to greatly affect the physical properties, and in turn, the performance of functional devices based on these materials. Despite this, lithium content is rarely accurately quantified, as a result of the low number of electrons in Li hindering its identification by means of routine materials characterization methods. In the present work, magnetic lithium ferrite powders with Li:Fe ratios of 1:1, 1:3 and 1:5 have been synthesized, successfully obtaining phase-pure materials (LiFeO2 and LiFe5O8), as well as a controlled mixture of both phases. The powders have been compacted and subsequently sintered by thermal treatment (Tmax = 1100 ◦C) to fabricate dense pellets which preserve the original Li:Fe ratios. Li-content on both powders and pellets has been determined by two independent methods: (i) Rutherford backscattering spectroscopy combined with nuclear reaction analysis and (ii) Rietveld analysis of powder X-ray diffraction data. With good agreement between both techniques, it has been confirmed that the Li:Fe ratios employed in the synthesis are maintained in the sintered ceramics. The same conclusion is drawn from spatially-resolved confocal Raman microscopy experiments on regions of a few microns. Field emission scanning electron microscopy has evidenced the substantial grain growth taking place during the sintering process – mean particle sizes rise from ≈ 600 nm in the powders up to 3.8(6) μm for dense LiFeO2 and 10(2) μm for LiFe5O8 ceramics. Additionally, microstructural analysis has revealed trapped pores inside the grains of the sintered ceramics, suggesting that grain boundary mobility is governed by surface diffusion. Vibrating sample magnetometry on the ceramic samples has confirmed the expected soft ferrimagnetic behavior of LiFe5O8 (with Ms = 61.5(1) Am2/kg) and the paramagnetic character of LiFeO2 at room temperature. A density of 92.7(6)% is measured for the ceramics, ensuring the mechanical integrity required for both their direct utilization in bulk shape and their use as targets for thin-film depositionThis work has been supported by grants RTI2018-095303-B-C51 and RTI2018-095303-A-C52 funded by MCIN/AEI/ 10.13039/ 501100011033 and by “ERDF A way of making Europe” and grants PID20210124585NB-C31, PID2021–124585NB-C32 and PID2021- 124585NB-C33 funded by MCIN/AEI/ 10.13039/501100011033 and by the “European Union NextGenerationEU/PRTR”. C.G.-M. acknowledges financial support from grant FJC2018–035532-I funded by MCIN/ AEI/ 10.13039/501100011033 and grant RYC2021–031181-I funded by MCIN/AEI/10.13039/501100011033 and by the “European Union NextGenerationEU/PRTR”. A.S. acknowledges financial support from the Comunidad de Madrid for an “Atracción de Talento Investigador” contract No. 2017-t2/IND5395 and grant RYC2021-031236-I funded by MCIN/AEI/10.13039/501100011033 and by the “European Union NextGenerationEU/PRTR”. A.Q. acknowledges financial support from grant RYC-2017023320 funded by MCIN/AEI/ 10.13039/ 501100011033 and by “ESF Investing in your future”. The authors acknowledge support from CMAM for beamtime proposals with codes STD019/20, STD026/20 and STD033/2

Epitaxial integration of CoFe₂O₄ thin films on Si (001) surfaces using TiN buffer layers

Epitaxial cobalt ferrite thin films with strong in-plane magnetic anisotropy have been grown on Si (001) substrates using a TiN buffer layer. The epitaxial films have been grown by ion beam sputtering using either metallic, CoFe₂, or ceramic, CoFe₂2O₄, targets. X-ray diffraction (XRD) and Rutherford spectrometry (RBS) in random and channeling configuration have been used to determine the epitaxial relationship CoFe₂O₄ [100]/TiN [100]/Si [100]. Mossbauer spectroscopy, in combination with XRD and RBS, has been used to determine the composition and structure of the cobalt ferrite thin films. The TiN buffer layer induces a compressive strain in the cobalt ferrite thin films giving rise to an in-plane magnetic anisotropy. The degree of in- plane anisotropy depends on the lattice mismatch between CoFe₂O₂ and TiN, which is larger for CoFe₂O₄ thin films grown on the reactive sputtering process with ceramic targets

Induced ferromagnetism in Mn3N2 phase embedded in Mn/Si3N4 multilayers

Room temperature ferromagnetism has been obtained for different sets of Mn/Si3N4 multilayers prepared by sputtering. In order to find the most suitable conditions to stabilize the ferromagnetic ordering in this system, the evolution of the magnetic properties has been studied for films in which the Si3N4 layer thickness was maintained constant while that of the Mn layer was varied, Mn tm/Si3N4 3.4 nm n, and conversely, in Mn 0.7 nm/Si3N4 tsn 43 samples, in which the Mn layer thickness was kept constant while varying the Si3N4 layer thickness. Structural, compositional, electronic and magnetic characterizations have been performed by means of x-ray reflectometry, Rutherford backscattering spectrometry, x-ray photoemission spectroscopy, x-ray absorption, and superconducting quantum interference device for further knowledge of the magnetic-structural relationship in this system. Our results show that the peculiar magnetic behavior of these films is mainly related to the stabilization of a slightly distorted Mn3N2 phase that is induced by the Si3N4 at the interfaces. For samples with larger Mn layer thickness, metallic Mn and Mn3N2 phases coexist, which leads to a reduction of the total magnetization per Mn atom due to the presence of metallic Mn. For small Mn layer thickness tm 0.86 nm, where noncontinuous Mn3N2 layers are formed, the magnetization decreases noticeably due to the superparamagnetic size limit. It has been found that the best conditions for the stabilization of the ferromagnetism in this system occur when both, the manganese-rich and the silicon nitride layers, are continuous and with similar thickness, close to 3.5 nm.Ministerio de Educación y Ciencia de España-MAT2006-01004, MAT2008-06542-C04-01, MAT2008-06765-C02-02, S-0505/MAT/0194, Consolider 2010_26400 y Nanoselect CSD2007-0004