DEVELOPMENT OF LI+ AND NA+ CONDUCTING CERAMICS AND CERAMIC STRUCTURES FOR USE IN SOLID STATE BATTERIES

A solid state lithium metal battery based on a lithium garnet material was developed, constructed and tested. Specifically, a porous-dense-porous trilayer structure was fabricated by tape casting, a roll-to-roll technique conducive to high volume manufacturing. The high density and thin center layer (< 20 μm) effectively blocks dendrites even over hundreds of cycles. The microstructured porous layers, serving as electrode supports, are demonstrated to increase the interfacial surface area available to the electrodes and increase cathode loading. Reproducibility of flat, well sintered ceramics was achieved with consistent powderbed lattice parameter and ball milling of powderbed. Together, the resistance of the LLCZN trilayer was measured at an average of 7.6 ohm-cm2 in a symmetric lithium cell, significantly lower than any other reported literature results. Building on these results, a full cell with a lithium metal anode, LLCZN trilayer electrolyte, and LiCoO2 cathode was cycled 100 cycles without decay and an average ASR of 117 ohm-cm2. After cycling, the cell was held at open circuit for 24 hours without any voltage fade, demonstrating the absence of a dendrite or short-circuit of any type. Cost calculations guided the optimization of a trilayer structure predicted that resulting cells will be highly competitive in the marketplace as intrinsically safe lithium batteries with energy densities greater than 300 Wh/kg and 1000 Wh/L for under $100/kWh. Also in the pursuit of solid state batteries, an improved Na+ superionic conductor (NASICON) composition, Na3Zr2Si2PO12, was developed with a conductivity of 1.9x10-3 S/cm. New super-lithiated lithium garnet compositions, Li7.06La3Zr1.94Y0.06O12 and Li7.16La3Zr1.84Y0.16O12, were developed and studied revealing insights about the mechanisms of conductivity in lithium garnets.

Meshfree Method for Prediction of Thermal Properties of Porous Ceramic Materials

In the presented thesis work, meshfree method with distance fields is applied to create a novel computational approach which enables inclusion of the realistic geometric models of the microstructure and liberates Finite Element Analysis(FEA) from thedependance on and limitations of meshing of fine microstructural feature such as splats and porosity.Manufacturing processes of ceramics produce materials with complex porosity microstructure.Geometry of pores, their size and location substantially affect macro scale physical properties of the material. Complex structure and geometry of the pores severely limit application of modern Finite Element Analysis methods because they require construction of spatial grids (meshes) that conform to the geometric shape of the structure. As a result, there are virtually no effective tools available for predicting overall mechanical and thermal properties of porous materials based on their microstructure. This thesis is a separate handling and controls of geometric and physical computational models that are seamlessly combined at solution run time. Using the proposedapproach we will determine the effective thermal conductivity tensor of real porous ceramic materials featuring both isotropic and anisotropic thermal properties. This work involved development and implementation of numerical algorithms, data structure, and software.

Vector self-pulsing in erbium-doped fiber lasers

Insight into instabilities of fiber laser regimes leading to complex self-pulsing operations is an opportunity to unlock the high power and dynamic operation tunability of lasers. Though many models have been suggested, there is no complete covering of self-pulsing complexity observed experimentally. Here, I further generalized our previous vector model of erbium-doped fiber laser and, for the first time, to the best of my knowledge, map tunability of complex vector self-pulsing on Poincare sphere (limit cycles and double scroll polarization attractors) for laser parameters, e.g., power, ellipticity of the pump wave, and in-cavity birefringence. Analysis validated by extensive numerical simulations demonstrates good correspondence to the experimental results on complex self-pulsing regimes obtained by many authors during the last 20 years.

Dissipative solitons in fiber lasers

Dissipative solitons (also known as auto-solitons) are stable, nonlinear, time-or space-localized solitary waves that occur due to the balance between energy excitation and dissipation. We review the theory of dissipative solitons applied to fiber laser systems. The discussion context includes the classical Ginzburg-Landau and Maxwell-Bloch equations and their modifications that allow describing laser-cavity-produced waves. Practical examples of laser systems generating dissipative solitons are discussed.

Slow passage through thresholds in quantum dot lasers

A turn on of a quantum dot (QD) semiconductor laser simultaneously operating at the ground state (GS) and excited state (ES) is investigated both experimentally and theoretically. We find experimentally that the slow passage through the two successive laser thresholds may lead to significant delays in the GS and ES turn ons. The difference between the turn-on times is measured as a function of the pump rate of change and reveals no clear power law. This has motivated a detailed analysis of rate equations appropriate for two-state lasing QD lasers. We find that the effective time of the GS turn on follows an -1/2 power law provided that the rate of change is not too small. The effective time of the ES transition follows an -1 power law, but its first order correction in ln is numerically significant. The two turn ons result from different physical mechanisms. The delay of the GS transition strongly depends on the slow growth of the dot population, whereas the ES transition only depends on the time needed to leave a repellent steady state.

Theory and optimisation of 1.3 and 1.55 μm (Al)InGaAs metamorphic quantum well lasers

The use of InGaAs metamorphic buffer layers (MBLs) to facilitate the growth of lattice-mismatched heterostructures constitutes an attractive approach to developing long-wavelength semiconductor lasers on GaAs substrates, since they offer the improved carrier and optical confinement associated with GaAs-based materials. We present a theoretical study of GaAs-based 1.3 and 1.55 μm (Al)InGaAs quantum well (QW) lasers grown on InGaAs MBLs. We demonstrate that optimised 1.3 μm metamorphic devices offer low threshold current densities and high differential gain, which compare favourably with InP-based devices. Overall, our analysis highlights and quantifies the potential of metamorphic QWs for the development of GaAs-based long-wavelength semiconductor lasers, and also provides guidelines for the design of optimised devices.

Ceramic-veneered zirconia frameworks in full-arch implant rehabilitations: A 6-month to 5-year retrospective cohort study

Purpose: This was a retrospective cohort study designed to evaluate the clinical performance of ceramicveneered zirconia frameworks. Materials and Methods: Patients were recruited according to defined inclusion criteria. All patients were checked every 4 months from the time of definitive rehabilitation. At the end of 2013, all patients were rescheduled and rechecked for study purposes. The restorative procedures assessment was performed by previously established methods. The primary outcomes were the survival and success rates of the prosthesis. Descriptive statistics were used for the patient's demographics, implant distribution, and occurrence of complications. To study the survival and success of the prostheses, a Cox Regression analysis was used with a model constructed in a forward conditional stepwise mode. Predictive variables were included in the model, and adjusted survival curves were obtained for each outcome. Results: From 2008 to 2013, 75 patients were rehabilitated with 92 implant-supported, screw-retained, full-arch ceramic-veneered zirconia framework rehabilitations. The range of follow-up was between 6 months and 5 years. From the 92 full implant-supported screw-retained full-arch rehabilitations, Cox regression analysis indicated that within a 5-year time frame, the probability of framework fracture, major chipping, minor chipping, or any of the former combined to occur was 17.6%, 46.5%, 69.2%, and 90.5%, respectively. Conclusion: Results suggest zirconia as a suitable material for framework structure in implant-supported, full-arch rehabilitations. However, it experiences a high incidence of technical complications, mainly due to ceramic chipping. Further clinical studies should aim to ascertain the effects of clinical features and manufacturing procedures on the survival rates of these prostheses. © 2016 by Quintessence Publishing Co Inc.

Biomimetic topography in orthopaedic ceramic

The primary objective of this research was to perform an in vitro assessment of the ability of microscale topography to alter cell behaviour, with specific regard to producing favourable topography in an orthopaedic ceramic material suitable for implantation in the treatment of arthritis. Topography at microscale and nanoscale alters the bioactivity of the material. This has been used in orthopaedics for some time as seen with optimal pore size in uncemented hip and knee implants. This level of topography involves scale in hundreds of micrometres and allows for the ingrowth of tissue. Topography at smaller scale is possible thanks to progressive miniaturisation of technology. A topographic feature was created in a readily available clinically licensed polymer, Polycaprolcatone (PCL). The effect of this topography was assessed in vitro. The same topography was transferred to the latest generation composite orthopaedic ceramic, zirconia toughened alumina (ZTA). The fidelity of reproduction of the topography was examined using scanning electron microscopy (SEM) and atomic force microscopy (AFM). These investigations showed more accurate reproduction of the topography in PCL than ZTA with some material artefacts in the ZTA. Cell culture in vitro was performed on the patterned substrates. The response of osteoprogenitor cells was assessed using immunohistochemistry, real-time polymerase chain reaction and alizarin staining. These results showed a small effect on cell behaviour. Finally metabolic comparison was made of the effects created by the two different materials and the topography in each. The results have shown a reproducible topography in orthopaedic ceramics. This topography has demonstrated a positive osteogenic effect in both polycaprolactone and zirconia toughened alumina across multiple assessment modalities.

The Social Life of Pots. The reconstruction of ceramic production and distribution patterns of pottery assemblages in the Northern Levant during the Iron Age

The aim of the project is the creation of a new model for the analysis of the political and social structures of the Northern Levant during the Iron Age, through the study of the production and circulation of ceramics in urban and rural centers. The project includes an innovative approach compared to a traditional contextual and analytical study of ceramic material. The geographical area under consideration represents an ideal context for understanding these dynamics, as a place of interaction between culturally different but constantly communicating areas (Eastern Mediterranean, Syria, Upper Mesopotamia). They corresponds to present-day southeastern Turkey and northern Syria, with the Mediterranean coast and the Euphrates River as limits to the west and east, respectively. The chronological interval taken into consideration by the study extends from the twelfth century BC. to the seventh century BC, corresponding to a phase of political fragmentation of the region into small-medium state entities and their subsequent conquest by the Neo-Assyrian empire starting from the end of the ninth century BC.

Sustainability and environmental impact of the Italian ceramic tile industry

The increasing consumption rates among citizens and the uncontrolled exploitation of natural resources have made environmental pollution and management of waste the main problems facing humanity in its upcoming future. Together with generation of energy and transport, industrial production certainly plays a key role in the genesis of these problems. It is for this reason that the concepts of environmental, social and economic sustainability have emerged over the years as the cornerstones for future development. In light of this, the most forward-looking industries have begun to study their impact on environment and society in order to improve their performances and, at the same time, to anticipate the increasingly rigorous environmental regulations. In this work, various performance indicators related to the Italian ceramic tile sector will be presented and discussed. In particular, the emission factor of characteristic pollutants will be reported on a period of up to fifteen years while data regarding waste management, concentration of pollutants and emission legal limits for the last decade will be here disclosed as a result of a vast analysis on recorded data. The collected information describes the present level of performance of the ceramic tile manufacturing industries in Italy and shows how recycling is now a consolidated reality and how some pollutants, such as particulate matter, fluorine and lead are actually disappearing from production processes and how others, such as volatile organic compounds, are increasing instead. Moreover, the adoption of alternative raw materials for the production of ceramic tiles is discussed and the implementation of the recycling of various waste is addressed at experimental or industrial scale. Finally, the development of a new ceramic engobe with high content of waste glass (20%) is presented as an experimental example of reutilization of resources in the ceramic tile industry.

Study and development of BaCe0.65Zr0.20Y0.1503-Δ (BCZY) – Gd0.2Ce0.8O2-Δ (GDC) dense ceramic membranes sysyem for high temperature H2 purification

The first main conclusion drawn from this dissertation concerns the amount of Pt deposited on the asymmetric layer of membrane produced by tape casting porosity shaping method. Three different amounts were investigated (0.15, 1.5 and 4.5 mg cm-2 ). The most optimal performance, based on H2 permeation performances, was attained when 1.5 mg cm-2 of Pt was deposited on the porous layer, resulting in a 0.642 mL min-1 cm-2 permeated H2 when 80% H2 in He was employed as the feed. Pt deposition method is influenced by the concentration of the Pt precursor, which results in different morphology of the catalyst. The second development focused on further optimization on tape casting membranes concerning the solvent employed for the Pt catalyst deposition. The same concentration of Pt was employed, depositing 1.5 mg cm-2 on the porous side of the membrane, but a mixture of acetone and water was employed as solvent. This mixture allowed the suppression of effects leading to poorly dispersed particles. As a result, it was possible to achieve 0.74 mL min-1 cm-2 at 750°C with 50% H2 in He. Lastly, first-ever permeation performance measurements into an innovative ceramic membrane type for hydrogen separation was investigated. In-depth research was done on a group of hierarchically-structured BaCe0.65Zr0.20Y0.15O3-δ(BCZY) - Gd0.2Ce0.8O2-δ(GDC) membranes produced by freeze casting porosity shaping method. Membranes were investigated observing the effect of deposition solvent and the effect of porous layer thickness. Employing a mixture of Acetone and water resulted in better hydrogen permeation at temperatures (T > 650°C), reaching 0.26 mL min-1 cm-2 at 750°C with 50% H2 in He. The reduction of porous layer thickness led to a hydrogen flow of 0.33 mL min-1 cm-2 , at 750°C with 50% H2 in He.

Development And Shelf-life Determination Of Pasteurized, Microfiltered, Lactose Hydrolyzed Skim Milk.

The segment of the world population showing permanent or temporary lactose intolerance is quite significant. Because milk is a widely consumed food with an high nutritional value, technological alternatives have been sought to overcome this dilemma. Microfiltration combined with pasteurization can not only extend the shelf life of milk but can also maintain the sensory, functional, and nutritional properties of the product. This studied developed a pasteurized, microfiltered, lactose hydrolyzed (delactosed) skim milk (PMLHSM). Hydrolysis was performed using β-galactosidase at a concentration of 0.4mL/L and incubation for approximately 21h at 10±1°C. During these procedures, the degree of hydrolysis obtained (>90%) was accompanied by evaluation of freezing point depression, and the remaining quantity of lactose was confirmed by HPLC. Milk was processed using a microfiltration pilot unit equipped with uniform transmembrane pressure (UTP) ceramic membranes with a mean pore size of 1.4 μm and UTP of 60 kPa. The product was submitted to physicochemical, microbiological, and sensory evaluations, and its shelf life was estimated. Microfiltration reduced the aerobic mesophilic count by more than 4 log cycles. We were able to produce high-quality PMLHSM with a shelf life of 21 to 27d when stored at 5±1°C in terms of sensory analysis and proteolysis index and a shelf life of 50d in regard to total aerobic mesophile count and titratable acidity.

Photodynamic Antimicrobial Effects Of Bis-indole Alkaloid Indigo From Indigofera Truxillensis Kunth (leguminosae).

Multidrug-resistant microbial infections represent an exponentially growing problem affecting communities worldwide. Photodynamic therapy is a promising treatment based on the combination of light, oxygen, and a photosensitizer that leads to reactive oxygen species production, such as superoxide (type I mechanism) and singlet oxygen (type II mechanism) that cause massive oxidative damage and consequently the host cell death. Indigofera genus has gained considerable interest due its mutagenic, cytotoxic, and genotoxic activity. Therefore, this study was undertaken to investigate the effect of crude extracts, alkaloidal fraction, and isolated substance derived from Indigofera truxillensis in photodynamic antimicrobial chemotherapy on the viability of bacteria and yeast and evaluation of mechanisms involved. Our results showed that all samples resulted in microbial photoactivation in subinhibitory concentration, with indigo alkaloid presenting a predominant photodynamic action through type I mechanism. The use of CaCl2 and MgCl2 as cell permeabilizing additives also increased gram-negative bacteria susceptibility to indigo.

Estudo por espectroscopia micro-Raman dos mecanismos de separação de fase em vidros fosfatos de metais de transição

Glass-ceramics are prepared by controlled separation of crystal phases in glasses, leading to uniform and dense grain structures. On the other hand, chemical leaching of soluble crystal phases yields porous glass-ceramics with important applications. Here, glass/ceramic interfaces of niobo-, vanado- and titano-phosphate glasses were studied by micro-Raman spectroscopy, whose spatial resolution revealed the multiphase structures. Phase-separation mechanisms were also determined by this technique, revealing that interface composition remained unchanged as the crystallization front advanced for niobo- and vanadophosphate glasses (interface-controlled crystallization). For titanophosphate glasses, phase composition changed continuously with time up to the equilibrium composition, indicating a spinodal-type phase separation.

Avaliação in vitro do aparelho DIAGNOdent para diagnóstico oclusal

The aim of this study was to determine the effectiveness and reliability of laser fluorescence measurements in relation to occlusal caries diagnosis. DIAGNOdent 2095 (Kavo, Biberach, Germany), which has been developed especially for caries diagnosis, was utilized. Five (5) teeth were examined in the pilot test; after that, ten (10) teeth were examined in order to calibrate both examiners. Data were obtained from 66 teeth (36 molars and 30 premolars), totalizing 144 sites identified through photographs of the occlusal surfaces. Reproducibility was evaluated in 10 teeth. The interexaminer Spearman correlation (r) was 0.89 and the intra-examiner, 0.93 and 0.97 (examiner A and B, respectively). Validation was carried out by histological examination (stereomicroscope). For the two examiners the sensitivity of the device was relatively high, varying from 0.81 to 1.00, while specificity varied according to which validation criterion was used (0.77 - 0.86: enamel lesion / 0.52 - 0.59: dentin lesion). It was concluded that DIAGNodent presented good capacity of identifying any alteration of the dental surface, nevertheless it presents the disadvantage of accomplishing many false-positive diagnosis when the validation criterion is dentin lesion.