Low voltage electroluminescence of terbium- and thulium-doped zinc oxide films

Strong interest in developing technology for visual information. stimulates research for thin film electroluminescent devices. Here, for the first time, we report that thulium- and terbium-doped zinc-oxide films are suitable for electroluminescence applications. Two different devices were assembled as lTO/LiF/ZnO:RE/LiF/Al or ITO/SiO2/ZnO:RE/SiO2/Al, where ZnO:RE is a film of zinc oxide containing 10 at% of Tb3+ or Tm3+. Electroluminescence spectra show that besides a broad emission band with maximum around 650 nm assigned to ZnO, also emission lines from Tb3+ at 484 nm (D-5(4) -> F-7(6)), 543 nm (D-5(4) -> F-7(6)), and 589 nm (D-5(4) -> F-7(4)), or from Tm3+ at 478 nm ((1)G(4) -> H-3(6)), and 511 mn (D-1(2) -> H-3(5)) were detected. Intensity of emission as function of applied voltage and current-voltage characteristic are shown and discussed. (c) 2005 Elsevier B.V. All rights reserved.

Determination of the activation energies of beef tallow and crude glycerin combustion using thermogravimetry

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Thermally activated dynamics of the tilts of the CuO6 octahedra, hopping of interstitial O, and possible instability towards the LTT phase in La2CuO4+δ

The anelastic spectrum (dynamic Young's modulus and elastic energy absorption) of La2CuO4+δ has been measured between 1 and 700 K with 0<δ<0.02. The spectrum of stoichiometric La2CuO4 in the low-temperature orthorhombic (LTO) phase is dominated by two intense relaxation processes which cause softenings of 16% around 150 K and 9% below 30 K at f∼1 kHz. The relaxation at 150 K is attributed to the presence of a fraction of the CuO6 octahedra which are able to change their tilted configuration by thermal activation between orientations which are nearly energetically equivalent, possibly within the twin boundaries. The relaxation below 30 K is governed by tunneling, and involves a considerable fraction of the lattice atoms. It is proposed that the double-well potentials for the low-temperature relaxation are created by the tendency of the LTO phase to form low-temperature tetragonal (LTT) domains, which however are not stabilized like when La is partially substituted with Ba. On doping with excess O, the relaxation rates of these processes are initially enhanced by hole doping, while their intensities are depressed by lattice disorder; an explanation of this behavior is provided. Excess O also causes two additional relaxation processes. The one appearing at lower values of δ is attributed to the hopping of single interstitial O2- ions, with a hopping rate equal to τ-1=2×10-14exp(-5600/T) s. The second process is slower and can be due to O pairs or other complexes containing excess O.

Determination of the activation energies of beef tallow and crude glycerin combustion using thermogravimetry

The present study deals with the determination of the activation energy for the thermal decomposition of two renewable fuels crude glycerin and beef tallow. The activation energies were investigated by using a thermogravimetric analyzer (TGA) in the temperature range of 25-600 degrees C in atmosphere of synthetic air. The TG curves of the thermal decomposition process of both samples were divided into several phases and the second, called PH2, was chosen for the kinetic study because it is associated with the combustion ignition. Differential Thermal Analysis (DTA) showed an endothermic event at the PH2 region for the crude glycerin corresponding to devolatilization, while for beef tallow, this step presented an exothermic event, called LTO (low-temperature oxidation), which is correlated with devolatilization followed by combustion. For the entire PH2, activation energy values for crude glycerin were between 90 kJ mol(-1) and 42 kJ mol(-1), while for the beef tallow they ranged from 50 kJ mol(-1) to 113 kJ mol (1). The activation energy values obtained at the pre-ignition stage - conversion between 0 and 0.45 - showed that the crude glycerin with higher values requires an additional energetic support at the start of combustion processes and the beef tallow ignites more easily, presenting lower values. According to the Wolfer's equation, a direct relation between the activation energy and the ignition delay is established and the results of this study provides useful data for the development and design of new combustion chambers and engines when non-traditional fuels are used as feedstock. (C) 2012 Elsevier Ltd. All rights reserved.

Taxibot: Analisi dei benefici derivanti dall'introduzione di un veicolo semi-robotico per dispatch towing. Un'applicazione all'aeroporto Guglielmo Marconi di Bologna.

Valutazione degli impatti economici ed ambientali derivanti dall'introduzione di un veicolo semi-robotico prodotto dall'israel aerospace industries che permette di eseguire il rullaggio con i motori principali dell'aeromobile spenti. Vengono valutati gli aspetti tecnici legate alle criticità e alle procedure di dispatch towing. Viene valutato il beneficio economico delle compagnie aeree derivante dal risparmio di cherosene.

Diagenesis of a light, tight-oil chert reservoir at the Ediacaran/Cambrian boundary, Sultanate of Oman

The Al Shomou Silicilyte Member (Athel Formation) in the South Oman Salt Basin shares many of the characteristics of a light, tight-oil (LTO) reservoir: it is a prolifi c source rock mature for light oil, it produces light oil from a very tight matrix and reservoir, and hydraulic fracking technology is required to produce the oil. What is intriguing about the Al Shomou Silicilyte, and different from other LTO reservoirs, is its position related to the Precambrian/Cambrian Boundary (PCB) and the fact that it is a ‘laminated chert‘ rather than a shale. In an integrated diagenetic study we applied microstructural analyses (SEM, BSE) combined with state-of-the-art stable isotope and trace element analysis of the silicilyte matrix and fractures. Fluid inclusion microthermometry was applied to record the salinity and minimum trapping temperatures. The microstructural investigations reveal a fi ne lamination of the silicilyte matrix with a mean lamina thickness of ca. 20 μm consisting of predominantly organic matter-rich and fi nely crystalline quartz-rich layers, respectively. Authigenic, micron-sized idiomorphic quartz crystals are the main matrix components of the silicilyte. Other diagenetic phases are pyrite, apatite, dolomite, magnesite and barite cements. Porosity values based on neutron density logs and core plug data indicate porosity in the silicilyte ranges from less than 2% to almost to 40%. The majority of the pore space in the silicilyte is related to (primary) inter-crystalline pores, with locally important oversized secondary pores. Pore casts of the silica matrix show that pores are extremely irregular in three dimensions, and are generally interconnected by a complex web or meshwork of fi ne elongate pore throats. Mercury injection capillary data are in line with the microstructural observations suggesting two populations of pore throats, with an effective average modal diameter of 0.4 μm. The acquired geochemical data support the interpretation that the primary source of the silica is the ambient seawater rather than hydrothermal or biogenic. A maximum temperature of ca. 45°C for the formation of microcrystalline quartz in the silicilyte is good evidence that the lithifi cation and crystallization of quartz occurred in the fi rst 5 Ma after deposition. Several phases of brittle fracturing and mineralization occurred in response to salt tectonics during burial. The sequences of fracture-fi lling mineral phases (dolomite - layered chalcedony – quartz – apatite - magnesite I+II - barite – halite) indicates a complex fl uid evolution after silicilyte lithifi cation. Primary, all-liquid fl uid inclusions in the fracturefi lling quartz are good evidence of growth beginning at low temperatures, i.e. ≤ 50ºC. Continuous precipitation during increasing temperature and burial is documented by primary two-phase fl uid inclusions in quartz cements that show brines at 50°C and fi rst hydrocarbons at ca. 70°C. The absolute timing of each mineral phase can be constrained based on U-Pb geochronometry, and basin modelling. Secondary fl uid inclusions in quartz, magnesite and barite indicate reactivation of the fracture system after peak burial temperature during the major cooling event, i.e. uplift, between 450 and 310 Ma. A number of fi rst-order trends in porosity and reservoir-quality distribution are observed which are strongly related to the diagenetic and fl uid history of the reservoir: the early in-situ generation of hydrocarbons and overpressure development arrests diagenesis and preserves matrix porosity. Chemical compaction by pressure dissolution in the fl ank areas could be a valid hypothesis to explain the porosity variations in the silicilitye slabs resulting in lower porosity and poorer connectivity on the fl anks of the reservoir. Most of the hydrocarbon storage and production comes from intervals characterized by Amthor et al. 114488 preserved micropores, not hydrocarbon storage in a fracture system. The absence of oil expulsion results in present-day high oil saturations. The main diagenetic modifi cations of the silicilyte occurred and were completed relatively early in its history, i.e. before 300 Ma. An instrumental factor for preserving matrix porosity is the diffi culty for a given slab to evacuate all the fl uids (water and hydrocarbons), or in other words, the very good sealing capacity of the salt embedding the slab.

Geological investigation of dykes in Shackleton Range, Antarctica

During the Geological Expedition to the Shackleton Range, Antarctica (GEISHA) in 1987/88, samples were taken from twenty-one basaltic dykes for palaeomagnetic investigations. The directions of characteristic remanent magnetization (ChRM) of the dykes were determined by thermal and alternating-field demagnetization of 268 cores drilled from the specimens collected. Moreover, on account of the hydrothermal and sometimes low-grade metamorphism of the dyke rock and the resulting partial modification of the primary magnetization, not only were comprehensive magnetic studies carried out, but also ore-microscopic examination. Only thus was it possible to achieve a reasonable assessment and interpretation of the remanent magnetization. Jurassic and Silurian-Devonian ages were confirmed for the dykes of the northern and northwestern Shackleton Range by comparison of the paleopole positions calculated on the basis of the ChRM of the dykes with the known pole positions for the eastern Antarctic, as well as with polar-wandering curves for Gondwana. Radiometric ages were also determined far some of the dykes. Middle and Late Proterozoic ages are postulated far the dykes in the Read Mountains. Conclusions on the geotectonic relations of the Shackleton Range can also be drawn from the palaeomagnetic data. It has been postulated that the main strike direction, which differs distinctly from that of the Ross orogen, is due to rotation or displacement of the Shackleton Range crustal block; however, this was not corroborated. The pole positions for the Shackleton Range agree with those of rocks of the same age from other areas of East Antarctica and its positions in the Palaeozoic-Mesozoic polar-wandering path for Gondwana are evidence against the idea of rotation and rather suggest that the position of the Shakleton Range crustal block is autochthonous.

Pole tip recession in linear tape systems

The tribology of linear tape storage system including Linear Tape Open (LTO) and Travan5 was investigated by combining X-ray Photoelectron Spectroscopy (XPS), Auger Electron Spectroscopy (AES), Optical Microscopy and Atomic Force Microscopy (AFM) technologies. The purpose of this study was to understand the tribology mechanism of linear tape systems then projected recording densities may be achieved in future systems. Water vapour pressure or Normalized Water Content (NWC) rather than the Relative Humidity (RH) values (as are used almost universally in this field) determined the extent of PTR and stain (if produced) in linear heads. Approximately linear dependencies were found for saturated PTR increasing with normalized water content increasing over the range studied using the same tape. Fe Stain (if produced) preferentially formed on the head surfaces at the lower water contents. The stain formation mechanism had been identified. Adhesive bond formation is a chemical process that is governed by temperature. Thus the higher the contact pressure, the higher the contact temperature in the interface of head and tape, was produced higher the probability of adhesive bond formation and the greater the amount of transferred material (stain). Water molecules at the interface saturate the surface bonds and makes adhesive junctions less likely. Tape polymeric binder formulation also has a significant role in stain formation, with the latest generation binders producing less transfer of material. This is almost certainly due to higher cohesive bonds within the body of the magnetic layer. TiC in the two-phase ceramic tape-bearing surface (AlTiC) was found to oxidise to form TiO2.The oxidation rate of TiC increased with water content increasing. The oxide was less dense than the underlying carbide; hence the interface between TiO2 oxide and TiC was stressed. Removals of the oxide phase results in the formation of three-body abrasive particles that were swept across the tape head, and gave rise to three-body abrasive wear, particularly in the pole regions. Hence, PTR and subsequent which signal loss and error growth. The lower contact pressure of the LTO system comparing with the Travan5 system ensures that fewer and smaller three-body abrasive particles were swept across the poles and insulator regions. Hence, lower contact pressure, as well as reducing stain in the same time significantly reduces PTR in the LTO system.

Piezoelectric and dielectric properties of Ce substituted La2Ti2O7 ceramics

The ferroelectric and dielectric properties of cerium (Ce) substituted La2Ti2O7 (LTO) have been investigated. Single phase, dense La2-xCexTi2O7 (x=0.15, 0.25, 0.35) ceramics were prepared by spark plasma sintering. The solubility limit of Ce in La2-xCexTi2O7 was found to be between 0.35 and 0.5. The a-, b- and c-axes of the unit cell decrease with increasing Ce substitution. The Curie point (Tc) of La2-xCexTi2O7 (x=0, 0.15, 0.25, 0.35) decreases and dielectric constant and loss increase with increasing Ce substitution. Cerium can increase the d33 of La2Ti2O7. The highest d33 was 3.9±0.1pC/N for La1.85Ce0.15Ti2O7 textured ceramic. © 2012 Elsevier Ltd.

Functional alkali tantalate 2D structures for microelectronics and related applications

Alkali tantalates and niobates, including K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, are a very promising ferroic family of lead-free compounds with perovskite-like structures. Their versatile properties make them potentially interesting for current and future application in microelectronics, photocatalysis, energy and biomedics. Among them potassium tantalate, KTaO3 (KTO), has been raising interest as an alternative for the well-known strontium titanate, SrTiO3 (STO). KTO is a perovskite oxide with a quantum paraelectric behaviour when electrically stimulated and a highly polarizable lattice, giving opportunity to tailor its properties via external or internal stimuli. However problems related with the fabrication of either bulk or 2D nanostructures makes KTO not yet a viable alternative to STO. Within this context and to contribute scientifically to the leverage tantalate based compounds applications, the main goals of this thesis are: i) to produce and characterise thin films of alkali tantalates by chemical solution deposition on rigid Si based substrates, at reduced temperatures to be compatible with Si technology, ii) to fulfil scientific knowledge gaps in these relevant functional materials related to their energetics and ii) to exploit alternative applications for alkali tantalates, as photocatalysis. In what concerns the synthesis attention was given to the understanding of the phase formation in potassium tantalate synthesized via distinct routes, to control the crystallization of desired perovskite structure and to avoid low temperature pyrochlore or K-deficient phases. The phase formation process in alkali tantalates is far from being deeply analysed, as in the case of Pb-containing perovskites, therefore the work was initially focused on the process-phase relationship to identify the driving forces responsible to regulate the synthesis. Comparison of phase formation paths in conventional solid-state reaction and sol-gel method was conducted. The structural analyses revealed that intermediate pyrochlore K2Ta2O6 structure is not formed at any stage of the reaction using conventional solid-state reaction. On the other hand in the solution based processes, as alkoxide-based route, the crystallization of the perovskite occurs through the intermediate pyrochlore phase; at low temperatures pyrochlore is dominant and it is transformed to perovskite at >800 °C. The kinetic analysis carried out by using Johnson-MehlAvrami-Kolmogorow model and quantitative X-ray diffraction (XRD) demonstrated that in sol-gel derived powders the crystallization occurs in two stages: i) at early stage of the reaction dominated by primary nucleation, the mechanism is phase-boundary controlled, and ii) at the second stage the low value of Avrami exponent, n ~ 0.3, does not follow any reported category, thus not permitting an easy identification of the mechanism. Then, in collaboration with Prof. Alexandra Navrotsky group from the University of California at Davis (USA), thermodynamic studies were conducted, using high temperature oxide melt solution calorimetry. The enthalpies of formation of three structures: pyrochlore, perovskite and tetragonal tungsten bronze K6Ta10.8O30 (TTB) were calculated. The enthalpies of formation from corresponding oxides, ∆Hfox, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -203.63 ± 2.84 kJ/mol, - 358.02 ± 3.74 kJ/mol, and -1252.34 ± 10.10 kJ/mol, respectively, whereas from elements, ∆Hfel, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol, and -13393.04 ± 31.15 kJ/mol, respectively. The possible decomposition reactions of K-deficient KTa2.2O6 pyrochlore to KTaO3 perovskite and Ta2O5 (reaction 1) or to TTB K6Ta10.8O30 and Ta2O5 (reaction 2) were proposed, and the enthalpies were calculated to be 308.79 ± 4.41 kJ/mol and 895.79 ± 8.64 kJ/mol for reaction 1 and reaction 2, respectively. The reactions are strongly endothermic, indicating that these decompositions are energetically unfavourable, since it is unlikely that any entropy term could override such a large positive enthalpy. The energetic studies prove that pyrochlore is energetically more stable phase than perovskite at low temperature. Thus, the local order of the amorphous precipitates drives the crystallization into the most favourable structure that is the pyrochlore one with similar local organization; the distance between nearest neighbours in the amorphous or short-range ordered phase is very close to that in pyrochlore. Taking into account the stoichiometric deviation in KTO system, the selection of the most appropriate fabrication / deposition technique in thin films technology is a key issue, especially concerning complex ferroelectric oxides. Chemical solution deposition has been widely reported as a processing method to growth KTO thin films, but classical alkoxide route allows to crystallize perovskite phase at temperatures >800 °C, while the temperature endurance of platinized Si wafers is ~700 °C. Therefore, alternative diol-based routes, with distinct potassium carboxylate precursors, was developed aiming to stabilize the precursor solution, to avoid using toxic solvents and to decrease the crystallization temperature of the perovskite phase. Studies on powders revealed that in the case of KTOac (solution based on potassium acetate), a mixture of perovskite and pyrochlore phases is detected at temperature as low as 450 °C, and gradual transformation into monophasic perovskite structure occurs as temperature increases up to 750 °C, however the desired monophasic KTaO3 perovskite phase is not achieved. In the case of KTOacac (solution with potassium acetylacetonate), a broad peak is detected at temperatures <650 °C, characteristic of amorphous structures, while at higher temperatures diffraction lines from pyrochlore and perovskite phases are visible and a monophasic perovskite KTaO3 is formed at >700 °C. Infrared analysis indicated that the differences are due to a strong deformation of the carbonate-based structures upon heating. A series of thin films of alkali tantalates were spin-coated onto Si-based substrates using diol-based routes. Interestingly, monophasic perovskite KTaO3 films deposited using KTOacac solution were obtained at temperature as low as 650 °C; films were annealed in rapid thermal furnace in oxygen atmosphere for 5 min with heating rate 30 °C/sec. Other compositions of the tantalum based system as LiTaO3 (LTO) and NaTaO3 (NTO), were successfully derived as well, onto Si substrates at 650 °C as well. The ferroelectric character of LTO at room temperature was proved. Some of dielectric properties of KTO could not be measured in parallel capacitor configuration due to either substrate-film or filmelectrode interfaces. Thus, further studies have to be conducted to overcome this issue. Application-oriented studies have also been conducted; two case studies: i) photocatalytic activity of alkali tantalates and niobates for decomposition of pollutant, and ii) bioactivity of alkali tantalate ferroelectric films as functional coatings for bone regeneration. Much attention has been recently paid to develop new type of photocatalytic materials, and tantalum and niobium oxide based compositions have demonstrated to be active photocatalysts for water splitting due to high potential of the conduction bands. Thus, various powders of alkali tantalates and niobates families were tested as catalysts for methylene blue degradation. Results showed promising activities for some of the tested compounds, and KNbO3 is the most active among them, reaching over 50 % degradation of the dye after 7 h under UVA exposure. However further modifications of powders can improve the performance. In the context of bone regeneration, it is important to have platforms that with appropriate stimuli can support the attachment and direct the growth, proliferation and differentiation of the cells. In lieu of this here we exploited an alternative strategy for bone implants or repairs, based on charged mediating signals for bone regeneration. This strategy includes coating metallic 316L-type stainless steel (316L-SST) substrates with charged, functionalized via electrical charging or UV-light irradiation, ferroelectric LiTaO3 layers. It was demonstrated that the formation of surface calcium phosphates and protein adsorption is considerably enhanced for 316L-SST functionalized ferroelectric coatings. Our approach can be viewed as a set of guidelines for the development of platforms electrically functionalized that can stimulate tissue regeneration promoting direct integration of the implant in the host tissue by bone ingrowth and, hence contributing ultimately to reduce implant failure.

Towards eco-friendly batteries: concepts for lithium and sodium ion batteries

Several possibilities are arising aiming the development of “greener”, more sustainable energy storage systems. One point is the completely water-based processing of battery electrodes, thus being able to renounce the use of toxic solvents in the preparation process. Despite its advantage of lower cost and eco-friendlyness, there is the need of similar mechanical and electrochemichal behavior for boosting this preparation mode. Another point – accompanying the water-based processing - is the replacement of solvent-based polymer binders by water-based ones. These binders can be based on fluorinated, crude-oil based polymers on the one side, but also on naturally abundant and economic friendly biopolymers. The most common anode materials, graphite and lithium titanate (LTO), have been subjected a water-based preparation route with different binder systems. LTO is a promising anode material for lithium ion batteries (LIBs), as it shows excellent safety characteristics, does not form a significant SEI and its volume change upon intercalation of lithium ions is negligible. Unfortunately, this material suffers from a rather low electric conductivity - that is why an intensive study on improved current collector surfaces for LTO electrodes was performed. In order to go one step ahead towards sustainable energy storage, anode and cathode active materials for a sodium ion battery were synthesized. Anode active material resulted in a successful product which was then subjected to further electrochemical tests. In this PhD work the development of “greener” energy storage possibilities is tested under several aspects. The ecological impact of raw materials and required battery components is examined in detail.