Piezoelectric and electroacoustic properties of Ti-doped AlN thin films as a function of Ti content

In this work we present the assessment of the structural and piezoelectric properties of Al(0.5-x)TixN0.5 compounds (titanium content menor que6% atomic), which are expected to possess improved properties than conventional AlN films, such as larger piezoelectric activity, thermal stability of frequency and temperature resistance. Al:Ti:N films were deposited from a twin concentric target of Al and Ti by reactive AC sputtering, which provided films with a radial gradient of the Ti concentration. The properties of the films were investigated as a function of their composition, which was measured by electron dispersive energy dispersive X-ray spectroscopy and Rutherford backscattering spectrometry. The microstructure and morphology of the films were assessed by X-ray diffraction and infrared reflectance. Their electroacoustic properties and dielectric constant were derived from the frequency response of BAW test resonators. Al:Ti:N films properties appear to be strongly dependent on the Ti content, which modifies the AlN wurtzite crystal structure leading to greater dielectric constant, lower sound velocities, lower electromechanical factor and moderately improved temperature coefficient of the resonant frequency.

Plausibility of a subglacial lake under Amundsenisen Icefield (Svalbard): spatially variable water content and sensitivity to thermal effect of snow and firn layers

Within our study of the plausibility of a subglacial lake under the Amundsenisen Icefield in Southern Spitzbergen, Svalbard achipelago (Glowacki et al., 2007), here we focus on the sensitivity of the system to the thermal effect of the firn and snow layers. Rough heat balance analysis shows that the firn layer plays an important role by driving the heat release to the atmosphere, so that its influence on the ice-water phase transition cannot be neglected (Bucchignani et al., 2012).

Study of the Saldanha Massif (MAR, 36 degrees 34 ' N): Constrains from rock magnetic and geophysical data

We present a study of the magnetic properties of a group of basalt samples from the Saldanha Massif (Mid-Atlantic Ridge - MAR - 36degrees 33' 54" N, 33degrees 26' W), and we set out to interpret these properties in the tectono-magmatic framework of this sector of the MAR. Most samples have low magnetic anisotropy and magnetic minerals of single domain grain size, typical of rapid cooling. The thermomagnetic study mostly shows two different susceptibility peaks. The high temperature peak is related to mineralogical alteration due to heating. The low temperature peak shows a distinction between three different stages of low temperature oxidation: the presence of titanomagnetite, titanomagnetite and titanomaghemite, and exclusively of titanomaghemite. Based on established empirical relationships between Curie temperature and degree of oxidation, the latter is tentatively deduced for all samples. Finally, swath bathymetry and sidescan sonar data combined with dive observations show that the Saldanha Massif is located over an exposed section of upper mantle rocks interpreted to be the result of detachment tectonics. Basalt samples inside the detachment zone often have higher than expected oxidation rates; this effect can be explained by the higher permeability caused by the detachment fault activity.

Characterization of the columbite precursor and (1-x)PMN-xPT powders prepared by Ti-modified columbite route

This study proposes to synthesize (1-x)PMN-xPT powders, where 0.10 < x < 0.45, using the T-modified columbite route. This methodology consists in the preparation of the MNT columbite precursor via the polymeric precursor method, followed by the solid state reaction with PbO to get the PMN-PT powders. It was verified that from 15 mol% of Ti, the MNT presents the coexistence of two main phases with different crystal symmetry: Rutile and Columbite. However, the synthesis of (1-x)PMN-xPT powders is not affected by this event. A detailed study of structural effects in MNT and PMN-PT powders as function of Ti content was made using the Rietveld method. It was also demonstrated that powders possess high chemical and microstructural homogeneity.

Chemistry of primary and secondary phases in intraplate basalts and volcaniclastic sediments at DSDP Leg 89 Holes

Electron microprobe data are presented for clinopyroxenes, plagioclases, palagonites, smectites, celadonites, and zeolites in Hole 462A sheet-flow basalts and Site 585 volcaniclastic sediments. Glomerocrystic clinopyroxenes in Hole 462A are predominantly Ti-poor augites with minor fractionation to ferroaugites in rim portions. Quenched plumose clinopyroxenes show considerable variation from Ca-rich to Ca-poor augites, although all are characterized by being Tirich and Cr-poor relative to the glomerocrysts. Two differentiated series of Site 585 pyroxene compositions, calcic augite and diopside-salite, demonstrate the coexistence, in the vitric and lithic clasts, of tholeiitic and alkali basalt types, respectively. Plagioclase compositions in all samples are mainly labradorites, although some zoned Hole 462A glomerocrysts range from An73 to An20 and are characterized by high Mg and Fe contents in the more calcic varieties. The K content of the plagioclases is highest in the more sodic crystals, although the overall higher orthoclase component of Site 585 plagioclases reflects the generally higher bulk-rock K content. The compositions of both secondary smectites and celadonites are similar irrespective of the alteration location (glass, matrix, vesicles, etc.), although brown smectites replacing interstitial glass have marginally higher total Fe contents than pale green and yellow smectites. Analyzed zeolites are mainly phillipsites with variable alkali content, and, together with associated celadonite, represent late-stage alteration repositories for K under mildly oxidizing conditions. The compositions of both early and late secondary minerals are typical of those formed by the submarine alteration of basaltic rocks at low temperatures.

Geochemical mass-balance and oxygen-isotope constrains on silcrete formation and its paleoclimatic implications in Southern Australia

Two geographically distinct silcrete associations are present in southern Australia, inland and eastern; these were sampled in central South Australia and central Victoria, respectively, At each site, both silicified and immediately adjacent unsilicified parent material were collected. Analytical data from these pairs were used to construct isocons, assuming Zr immobility, and to calculate the volume change and amount of silica introduced during silicification, These results, together with whole-rock oxygen isotope compositions, were used to determine the delta(18)O of th, introduced silica, The results show that the eastern silcretes in central Victoria are probably linked genetically to the associated basalts, weathering of which supplied the introduced silica, This conclusion is based on the close spatial connection between the two, as well as the substantial amount of introduced silica in the silcretes (greater than in the inland silcretes), resulting in volume increases in some eastern silcretes, Oxygen isotopic calculations for the silcretes indicate that the silica precipitated from groundwaters at temperatures slightly higher than present conditions. Silcrete formation apparently occurred during the Miocene and Pliocene (basalts in Victoria younger than Pliocene lack associated silcrete) and may reflect the much wetter climate in southeastern Australia at that time. The inland silcretes of central South Australia can be divided into pedogenic (the most common) and groundwater varieties. The pedogenic silcretes, which show typical soil features like columnar and nodular textures, contain moderate amounts of introduced silica that precipitated by evaporation from saline groundwaters, For the groundwater silcretes, which have massive textures and formed at or close to the water table, insufficient data are available to determine the mode of formation. The inland pedogenic silcretes have probably been farming from the Eocene-Miocene to the present, implying that conditions of seasonally high evaporation have occurred in central Australia during this time period. Thus silcrete formation depends on a complex interplay between climate and silica supply, and it is impossible to generalize that the presence of silcrete is indicative of a particular climate. Likewise, the elemental composition of silcretes, particularly Ti content, is not necessarily of climatic significance, Nevertheless, detailed geochemical and oxygen isotopic studies of a silcrete and its parent material can elucidate the mechanisms of silcrete formation, and if evaporation is indicated as a major factor in silcrete formation, then the climate at the time was likely to have been at least seasonally arid.

Sondagem de Belverde (Cenozóico, Península de Setúbal, Portugal). Diagrafias

In the aim of the project "Recognition of the Miocene of the distal region of the Lower Tagus Basin through a borehole with continuous sampling", Temperature, Natural Gamma Ray, Neutron (almost in all the borehole), Sonic, SP and SPR (in two small sections in upper and lower parts of the Miocene Series) geophysical logs were carried on. Interpretation of those logs and comparison with chronological, lithostratigraphical, micropaleontological and clay mineraIs data; helped in the definition of depositional sequences and to obtain paleoenvironmental reconstructions that could lead to a better understanding of the evolution of the Setúbal Península and Lisboa regions Miocene gulf. Log data agree with the lithologic succession observed in the Belverde borehole, essentially silty sandstones/sandy siltstones (with variable clay content) to clays, often with marly intercalations. Sonic logs (and Neutron logs, in general) reflect the sediments porosity. The higher acoustic velocities are often related to compact/massive layers as claystones and/or limestones and rather fossiliferous marly layers. Lower values are obtained for porous, silty sandstones (fossiliferous and with scarce clay content) and bio-calcareous sandstones. As indicative, we obtained the mean values of 2500-3000m/s for the higher velocities and 1300-1600m/s for the lowest ones. ln Natural Gamma Ray log, the radiation peaks can be correlated to often fossiliferous marly micaceous layers. Radioactive micas are present. It seems that the gamma peaks and the depositional sequences previously defined for the Lower Tagus Basin (see Antunes et al., 1999, 2000; Pais et al., 2002) can be correlated, taking also into account the whole available micropaleontological, palynological and isotopic evidence.

Development of a satellite based PM10 concentration product for urban areas

Dissertação para obtenção do Grau de Doutor em Engenharia do Ambiente

Impact of carbon/nitrogen feeding strategy on polyhydroxyalkanoates production using mixed microbial cultures

Polyhydroxyalkanoates (PHA) production using mixed microbial cultures (MMC) requires a multi-stage process involving the microbial selection of PHA-storing microorganisms, typically operated in sequencing batch reactors (SBR), and an accumulation reactor. Since low-cost renewable feedstocks used as process feedstock are often nitrogen-deficient, nutrient supply in the selection stage is required to allow for microbial growth. In this context, the possibility to uncouple nitrogen supply from carbon feeding within the SBR cycle has been investigated in this study. Moreover, three different COD:N ratios (100:3.79, 100:3.03 and 100:2.43) were tested in three different runs which also allowed the study of COD:N ratio on the SBR performance. For each run, a synthetic mixture of acetic and propionic acids at an overall organic load rate of 8.5 gCOD L-1 d-1 was used as carbon feedstock, whereas ammonium sulfate was the nitrogen source in a lab-scale sequence batch reactor (SBR) with 1 L of working volume. Besides, a sludge retention time (SRT) of 1 d was used as well as a 6 h cycle length. The uncoupled feeding strategy significantly enhanced the selective pressure towards PHA-storing microorganisms, resulting in a two-fold increase in the PHA production (up to about 1.3 gCOD L-1). A high storage response was observed for the two runs with the COD:N ratios (gCOD:gN) of 100:3.79 and 100:3.03, whereas the lowest investigated nitrogen load resulted in very poor performance in terms of polymer production. In fact, strong nitrogen limitation caused fungi to grow and a very poor storage ability by microorganisms that thrived in those conditions. The COD:N ratio also affected the polymer composition, indeed the produced poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) showed a variable HV content (1-20 %, w/w) among the three runs, lessening as the COD:N increased. This clearly suggests the possibility to use the COD:N ratio as a tool for tuning polymer properties regardless the composition of the feedstock.

Recrystallisation rims in zircon (Valle d'Arbedo, Switzerland): an integrated cathodoluminescence, LA-ICP-MS, SHRIMP, and TEM study

Recrystallization rims are a common feature of zircon crystals that underwent metamorphism. We present a microstructural and microchemical study of partially recrystallized zircon grains collected in polymetamorphic migmatites (Valle d'Arbedo, Ticino, Switzerland). The rims are bright in cathodo-luminescence (CL), with sharp and convex contacts characterized by inward-penetrating embayments transgressing igneous zircon cores. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) data and transmission electron microscopy (TEM) imaging indicate that the rims are chemically and microstructurally different from the cores. The rims are strongly depleted in REE, with concentrations up to two orders of magnitude lower than in the cores, indicating a significant loss of REE during zircon recrystallization. Enrichment in non-formula elements, such as Ca, has not been observed in the rims. The microstructure of zircon cores shows a dappled intensity at and below the 100 nm scale, possibly due to radiation damage. Other defects such as pores and dislocations are absent in the core except at healed cracks. Zircon rims are mostly dapple-free, but contain nanoscale pores and strain centers, interpreted as fluid inclusions and chemical residues, respectively. Sensitive high-resolution ion microprobe (SHRIMP) U-Pb ages show that the recrystallization of the rims took place >200 Ma ago when the parent igneous zircon was not metamict. The chemical composition and the low-Ti content of the rims indicate that they form at sub-solidus temperatures (550-650 degrees C). Recrystallization rims in Valle d'Arbedo zircon are interpreted as the result of the migration of chemical reaction fronts in which fluid triggered in situ and contemporaneous interface-coupled dissolution-reprecipitation mechanisms. This study indicates that strong lattice strain resulting from the incorporation of a large amount of impurities and structural defects is not a necessary condition for zircon to recrystallize. Our observations suggest that the early formation of recrystallization rims played a major role in preserving zircon from the more recent Alpine metamorphic overprint.

Heated Optical Fiber for Distributed Soil-Moisture Measurements: A Lysimeter Experiment

An Actively Heated Fiber Optics (AHFO) method to estimate soil moisture is tested and the analysis technique improved on. The measurements were performed in a lysimeter uniformly packed with loam soil with variable water content profiles. In the first meter of the soil profi le, 30 m of fiber optic cable were installed in a 12 loops coil. The metal sheath armoring the fiber cable was used as an electrical resistance heater to generate a heat pulse, and the soil response was monitored with a Distributed Temperature Sensing (DTS) system. We study the cooling following three continuous heat pulses of 120 s at 36 W m(-1) by means of long-time approximation of radial heat conduction. The soil volumetric water contents were then inferred from the estimated thermal conductivities through a specifically calibrated model relating thermal conductivity and volumetric water content. To use the pre-asymptotic data we employed a time correction that allowed the volumetric water content to be estimated with a precision of 0.01-0.035 (m(3) m(-3)). A comparison of the AHFO measurements with soil-moisture measurements obtained with calibrated capacitance-based probes gave good agreement for wetter soils [discrepancy between the two methods was less than 0.04 (m(3) m(-3))]. In the shallow drier soils, the AHFO method underestimated the volumetric water content due to the longertime required for the temperature increment to become asymptotic in less thermally conductive media [discrepancy between the two methods was larger than 0.1 (m(3) m(-3))]. The present work suggests that future applications of the AHFO method should include longer heat pulses, that longer heating and cooling events are analyzed, and, temperature increments ideally be measured with higher frequency.

Studies on Ilmenite of Chavara and Manavalakurichi Deposites, Southwest Coast of India

The present work attempts to trace the variation in the physical and chemical behavior of ilmenite, since its release from country rocks and subsequent transportation to the coast through the progressive weathering environments of laterite, sedimentary rocks, rivers and estuarine systems. Since the hinterland of the study area consists of crystalline and sedimentary rocks and their weathered forms (laterites), the contribution of each lithological system to the beach placer is attempted. The results of the study show that the most magnetic fraction contains more content of altered phases than the relatively unweathered fractions. The fractions separated above 0.35A define a high grade of ilmenite ore enriched in Ti content. The lattice volume generally decreases with alteration. The magnetic studies revels that the Chavara ilmenite are found to be made up to low magnetic crops with about 46% of the bulk ilmenite constituted by fractions separated at above 0.35A. In the Manavalakurichi ilmenite on the other hand, around 91% of the beach ilmenite is made of fractions separated at or below 0.3A

Correction of atmospheric delay effects in radar interferometry using a nested mesoscale atmospheric model

The temporal variability of the atmosphere through which radio waves pass in the technique of differential radar interferometry can seriously limit the accuracy with which the method can measure surface motion. A forward, nested mesoscale model of the atmosphere can be used to simulate the variable water content along the radar path and the resultant phase delays. Using this approach we demonstrate how to correct an interferogram of Mount Etna in Sicily associated with an eruption in 2004-5. The regional mesoscale model (Unified Model) used to simulate the atmosphere at higher resolutions consists of four nested domains increasing in resolution (12, 4, 1, 0.3 km), sitting within the analysis version of a global numerical model that is used to initiate the simulation. Using the high resolution 3D model output we compute the surface pressure, temperature and the water vapour, liquid and solid water contents, enabling the dominant hydrostatic and wet delays to be calculated at specific times corresponding to the acquisition of the radar data. We can also simulate the second-order delay effects due to liquid water and ice.