Advanced SPM studies on the growth of ultrathin films of organic semiconductors at metal and dielectric interfaces

Many studies on the morphology, molecular orientation, device performance, substrate nature and growth parameter dependence have been carried out since the proposal of Sexithiophene (6T) for organic electronics [ ] However, these studies were mostly performed on films thicker than 20nm and without specifically addressing the relationship between morphology and molecular orientation within the nano and micro structures of ultrathin films of 0-3 monolayers. In 2004, the observation that in OFETs only the first few monolayers at the interface in contact with the gate insulator contribute to the charge transport [ ], underlined the importance to study submonolayer films and their evolution up to a few monolayers of thickness with appropriate experimental techniques. We present here a detailed Non-contact Atomic Force Microscopy and Scanning Tunneling Microscopy study on various substrates aiming at the investigation of growth mechanisms. Most reported similar studies are performed on ideal metals in UHV. However it is important to investigate the details of organic film growth on less ideal and even technological surfaces and device testpatterns. The present work addresses the growth of ultra thin organic films in-situ and quasi real-time by NC-AFM. An organic effusion cell is installed to evaporate the organic material directly onto the SPM sample scanning stage.

Ex situ X-­Ray absorption study of Li-­rich layered cathode material Li[Li0.2Mn0.56Ni0.16Co0.08]O2

The Li-rich layered transition metal oxides (LLOs) Li2MnO3-LiMO2 (M=Mn, Co, Ni, etc.) have drawn considerable attention as cathode materials for rechargeable lithium batteries. They generate large reversible capacities but the fundamental reaction mechanism and structural perturbations during cycling remain controversial. In the present thesis, ex situ X-ray absorption spectroscopy (XAS) measurements were performed on Li[Li0.2Mn0.56Ni0.16Co0.08]O2 at different stage of charge during electrochemical oxidation/reduction. K-edge spectra of Co, Mn and Ni were recorded through a voltage range of 3.7-4.8V vs. Li/Li+, which consist of X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Oxidation states during initial charge were discussed based on values from literature as well as XANES analysis. Information about bond distance, coordination number as well as corresponding Debye-Waller factor were extracted from Gnxas analysis of raw data in the EXAFS region. The possibility of oxygen participation in the initial charge was discussed. Co and Ni prove to take part in the oxidation/reduction process while Mn remain in the tetravalent state. The cathode material appears to retain good structural short-range order during charge-discharge. A resemblance of the pristine sample and sample 4 was discovered which was firstly reported for similar compounds.

Generalized Differential Quadrature Finite Element Method applied to Advanced Structural Mechanics

Over the years the Differential Quadrature (DQ) method has distinguished because of its high accuracy, straightforward implementation and general ap- plication to a variety of problems. There has been an increase in this topic by several researchers who experienced significant development in the last years. DQ is essentially a generalization of the popular Gaussian Quadrature (GQ) used for numerical integration functions. GQ approximates a finite in- tegral as a weighted sum of integrand values at selected points in a problem domain whereas DQ approximate the derivatives of a smooth function at a point as a weighted sum of function values at selected nodes. A direct appli- cation of this elegant methodology is to solve ordinary and partial differential equations. Furthermore in recent years the DQ formulation has been gener- alized in the weighting coefficients computations to let the approach to be more flexible and accurate. As a result it has been indicated as Generalized Differential Quadrature (GDQ) method. However the applicability of GDQ in its original form is still limited. It has been proven to fail for problems with strong material discontinuities as well as problems involving singularities and irregularities. On the other hand the very well-known Finite Element (FE) method could overcome these issues because it subdivides the computational domain into a certain number of elements in which the solution is calculated. Recently, some researchers have been studying a numerical technique which could use the advantages of the GDQ method and the advantages of FE method. This methodology has got different names among each research group, it will be indicated here as Generalized Differential Quadrature Finite Element Method (GDQFEM).

Advanced lithium battery chemistries for sustainable transportation

The specific energy of lithium-ion batteries (LIBs) is today 200 Wh/kg, a value not sufficient to power fully electric vehicles with a driving range of 400 km which requires a battery pack of 90 kWh. To deliver such energy the battery weight should be higher than 400 kg and the corresponding increase of vehicle mass would narrow the driving range to 280 km. Two main strategies are pursued to improve the energy of the rechargeable lithium batteries up to the transportation targets. The first is the increase of LIBs working voltage by using high-voltage cathode materials. The second is the increase of battery capacity by the development of a cell chemistry where oxygen redox reaction (ORR) occurs at the cathode and metal lithium is the anode (Li/O2 battery). This PhD work is focused on the development of high-voltage safe cathodes for LIBs, and on the investigation of the feasibility of Li/O2 battery operating with ionic liquid(IL)-based electrolytes. The use of LiMn1-xFexPO4 as high-voltage cathode material is discussed. Synthesis and electrochemical tests of three different phosphates, more safe cathode materials than transition metal oxides, are reported. The feasibility of Li/O2 battery operating in IL-based electrolytes is also discussed. Three aspects have been investigated: basic aspects of ORR, synthesis and characterization of porous carbons as positive electrode materials and study of limiting factors to the electrode capacity and cycle-life. Regarding LIBs, the findings on LiMnPO4 prepared by soluble precursors demonstrate that a good performing Mn-based olivine is viable without the coexistence of iron. Regarding Li/O2 battery, the oxygen diffusion coefficient and concentration values in different ILs were obtained. This work highlighted that the O2 mass transport limits the Li/O2 capacity at high currents; it gave indications on how to increase battery capacity by using a flow-cell and a porous carbon as cathode.

Sustainable improvement of water networks : to achieve best decisions for rehabilitation plans using advanced GIS and statistical techniques

Many of developing countries are facing crisis in water management due to increasing of population, water scarcity, water contaminations and effects of world economic crisis. Water distribution systems in developing countries are facing many challenges of efficient repair and rehabilitation since the information of water network is very limited, which makes the rehabilitation assessment plans very difficult. Sufficient information with high technology in developed countries makes the assessment for rehabilitation easy. Developing countries have many difficulties to assess the water network causing system failure, deterioration of mains and bad water quality in the network due to pipe corrosion and deterioration. The limited information brought into focus the urgent need to develop economical assessment for rehabilitation of water distribution systems adapted to water utilities. Gaza Strip is subject to a first case study, suffering from severe shortage in the water supply and environmental problems and contamination of underground water resources. This research focuses on improvement of water supply network to reduce the water losses in water network based on limited database using techniques of ArcGIS and commercial water network software (WaterCAD). A new approach for rehabilitation water pipes has been presented in Gaza city case study. Integrated rehabilitation assessment model has been developed for rehabilitation water pipes including three components; hydraulic assessment model, Physical assessment model and Structural assessment model. WaterCAD model has been developed with integrated in ArcGIS to produce the hydraulic assessment model for water network. The model have been designed based on pipe condition assessment with 100 score points as a maximum points for pipe condition. As results from this model, we can indicate that 40% of water pipeline have score points less than 50 points and about 10% of total pipes length have less than 30 score points. By using this model, the rehabilitation plans for each region in Gaza city can be achieved based on available budget and condition of pipes. The second case study is Kuala Lumpur Case from semi-developed countries, which has been used to develop an approach to improve the water network under crucial conditions using, advanced statistical and GIS techniques. Kuala Lumpur (KL) has water losses about 40% and high failure rate, which make severe problem. This case can represent cases in South Asia countries. Kuala Lumpur faced big challenges to reduce the water losses in water network during last 5 years. One of these challenges is high deterioration of asbestos cement (AC) pipes. They need to replace more than 6500 km of AC pipes, which need a huge budget to be achieved. Asbestos cement is subject to deterioration due to various chemical processes that either leach out the cement material or penetrate the concrete to form products that weaken the cement matrix. This case presents an approach for geo-statistical model for modelling pipe failures in a water distribution network. Database of Syabas Company (Kuala Lumpur water company) has been used in developing the model. The statistical models have been calibrated, verified and used to predict failures for both networks and individual pipes. The mathematical formulation developed for failure frequency in Kuala Lumpur was based on different pipeline characteristics, reflecting several factors such as pipe diameter, length, pressure and failure history. Generalized linear model have been applied to predict pipe failures based on District Meter Zone (DMZ) and individual pipe levels. Based on Kuala Lumpur case study, several outputs and implications have been achieved. Correlations between spatial and temporal intervals of pipe failures also have been done using ArcGIS software. Water Pipe Assessment Model (WPAM) has been developed using the analysis of historical pipe failure in Kuala Lumpur which prioritizing the pipe rehabilitation candidates based on ranking system. Frankfurt Water Network in Germany is the third main case study. This case makes an overview for Survival analysis and neural network methods used in water network. Rehabilitation strategies of water pipes have been developed for Frankfurt water network in cooperation with Mainova (Frankfurt Water Company). This thesis also presents a methodology of technical condition assessment of plastic pipes based on simple analysis. This thesis aims to make contribution to improve the prediction of pipe failures in water networks using Geographic Information System (GIS) and Decision Support System (DSS). The output from the technical condition assessment model can be used to estimate future budget needs for rehabilitation and to define pipes with high priority for replacement based on poor condition. rn

Advanced polymeric materials for applications in technical equipment for snow sports

The thesis is divided in three chapters, each one covering one topic. Initially, the thermo-mechanical and impact properties of materials used for back protectors have been analysed. Dynamical mechanical analysis (DMTA) has shown that materials used for soft-shell protectors present frequency-sensitive properties. Furthermore, through impact tests, the shock absorbing characteristics of the materials have been investigated proving the differences between soft and hard-shell protectors; moreover it has been demonstrated that the materials used for soft-shell protectors maintain their protective properties after multi-impacts. The second chapter covers the effect of the visco-elastic properties of the thermoplastic polymers on the flexural and rebound behaviours of ski boots. DMTA analysis on the materials and flexural and rebound testing on the boots have been performed. A comparison of the results highlighted a correlation between the visco-elastic properties and the flexural and rebound behaviour of ski boots. The same experimental methods have been used to investigate the influence of the design on the flexural and rebound behaviours. Finally in the third chapter the thermoplastic materials employed for the construction of ski boots soles have been characterized in terms of chemical composition, hardness, crystallinity, surface roughness and coefficient of friction (COF). The results showed a relation between material hardness and grip, in particular softer materials provide more grip with respect to harder materials. On the contrary, the surface roughness has a negative effect on friction because of the decrease in contact area. The measure of grip on inclined wet surfaces showed again a relation between hardness and grip. The performance ranking of the different materials has been the same for the COF and for the slip angle tests, indicating that COF can be used as a parameter for the choice of the optimal material to be used for the soles of ski boots.

Modelling, diagnostics and experimental analysis of plasma assisted processes for material treatment

This work presents results from experimental investigations of several different atmospheric pressure plasmas applications, such as Metal Inert Gas (MIG) welding and Plasma Arc Cutting (PAC) and Welding (PAW) sources, as well as Inductively Coupled Plasma (ICP) torches. The main diagnostic tool that has been used is High Speed Imaging (HSI), often assisted by Schlieren imaging to analyse non-visible phenomena. Furthermore, starting from thermo-fluid-dynamic models developed by the University of Bologna group, such plasma processes have been studied also with new advanced models, focusing for instance on the interaction between a melting metal wire and a plasma, or considering non-equilibrium phenomena for diagnostics of plasma arcs. Additionally, the experimental diagnostic tools that have been developed for industrial thermal plasmas have been used also for the characterization of innovative low temperature atmospheric pressure non equilibrium plasmas, such as dielectric barrier discharges (DBD) and Plasma Jets. These sources are controlled by few kV voltage pulses with pulse rise time of few nanoseconds to avoid the formation of a plasma arc, with interesting applications in surface functionalization of thermosensitive materials. In order to investigate also bio-medical applications of thermal plasma, a self-developed quenching device has been connected to an ICP torch. Such device has allowed inactivation of several kinds of bacteria spread on petri dishes, by keeping the substrate temperature lower than 40 degrees, which is a strict requirement in order to allow the treatment of living tissues.

Interaction of fine particles and nanoparticles with red blood cells visualized with advanced microscopic techniques

So far, little is known about the interaction of nanoparticles with lung cells, the entering of nanoparticles, and their transport through the blood stream to other organs. The entering and localization of different nanoparticles consisting of differing materials and of different charges were studied in human red blood cells. As these cells do not have any phagocytic receptors on their surface, and no actinmyosin system, we chose them as a model for nonphagocytic cells to study how nanoparticles penetrate cell membranes. We combined different microscopic techniques to visualize fine and nanoparticles in red blood cells: (I) fluorescent particles were analyzed by laser scanning microscopy combined with digital image restoration, (II) gold particles were analyzed by conventional transmission electron microscopy and energy filtering transmission electron microscopy, and (III) titanium dioxide particles were analyzed by energy filtering transmission electron microscopy. By using these differing microscopic techniques we were able to visualize and detect particles < or = 0.2 microm and nanoparticles in red blood cells. We found that the surface charge and the material of the particles did not influence their entering. These results suggest that particles may penetrate the red blood cell membrane by a still unknown mechanism different from phagocytosis and endocytosis.

Advanced mechanics of materials with microstructure

The study of advanced materials aimed at improving human life has been performed since time immemorial. Such studies have created everlasting and greatly revered monuments and have helped revolutionize transportation by ushering the age of lighter–than–air flying machines. Hence a study of the mechanical behavior of advanced materials can pave way for their use for mankind’s benefit. In this school of thought, the aim of this dissertation is to broadly perform two investigations. First, an efficient modeling approach is established to predict the elastic response of cellular materials with distributions of cell geometries. Cellular materials find important applications in structural engineering. The approach does not require complex and time-consuming computational techniques usually associated with modeling such materials. Unlike most current analytical techniques, the modeling approach directly accounts for the cellular material microstructure. The approach combines micropolar elasticity theory and elastic mixture theory to predict the elastic response of cellular materials. The modeling approach is applied to the two dimensional balsa wood material. Predicted properties are in good agreement with experimentally determined properties, which emphasizes the model’s potential to predict the elastic response of other cellular solids, such as open cell and closed cell foams. The second topic concerns intraneural ganglion cysts which are a set of medical conditions that result in denervation of the muscles innervated by the cystic nerve leading to pain and loss of function. Current treatment approaches only temporarily alleviate pain and denervation which, however, does not prevent cyst recurrence. Hence, a mechanistic understanding of the pathogenesis of intraneural ganglion cysts can help clinicians understand them better and therefore devise more effective treatment options. In this study, an analysis methodology using finite element analysis is established to investigate the pathogenesis of intraneural ganglion cysts. Using this methodology, the propagation of these cysts is analyzed in their most common site of occurrence in the human body i.e. the common peroneal nerve. Results obtained using finite element analysis show good correlation with clinical imaging patterns thereby validating the promise of the method to study cyst pathogenesis.

MODEL UPDATING AND STRUCTURAL HEALTH MONITORING OF HORIZONTAL AXIS WIND TURBINES VIA ADVANCED SPINNING FINITE ELEMENTS AND STOCHASTIC SUBSPACE IDENTIFICATION METHODS

Wind energy has been one of the most growing sectors of the nation’s renewable energy portfolio for the past decade, and the same tendency is being projected for the upcoming years given the aggressive governmental policies for the reduction of fossil fuel dependency. Great technological expectation and outstanding commercial penetration has shown the so called Horizontal Axis Wind Turbines (HAWT) technologies. Given its great acceptance, size evolution of wind turbines over time has increased exponentially. However, safety and economical concerns have emerged as a result of the newly design tendencies for massive scale wind turbine structures presenting high slenderness ratios and complex shapes, typically located in remote areas (e.g. offshore wind farms). In this regard, safety operation requires not only having first-hand information regarding actual structural dynamic conditions under aerodynamic action, but also a deep understanding of the environmental factors in which these multibody rotating structures operate. Given the cyclo-stochastic patterns of the wind loading exerting pressure on a HAWT, a probabilistic framework is appropriate to characterize the risk of failure in terms of resistance and serviceability conditions, at any given time. Furthermore, sources of uncertainty such as material imperfections, buffeting and flutter, aeroelastic damping, gyroscopic effects, turbulence, among others, have pleaded for the use of a more sophisticated mathematical framework that could properly handle all these sources of indetermination. The attainable modeling complexity that arises as a result of these characterizations demands a data-driven experimental validation methodology to calibrate and corroborate the model. For this aim, System Identification (SI) techniques offer a spectrum of well-established numerical methods appropriated for stationary, deterministic, and data-driven numerical schemes, capable of predicting actual dynamic states (eigenrealizations) of traditional time-invariant dynamic systems. As a consequence, it is proposed a modified data-driven SI metric based on the so called Subspace Realization Theory, now adapted for stochastic non-stationary and timevarying systems, as is the case of HAWT’s complex aerodynamics. Simultaneously, this investigation explores the characterization of the turbine loading and response envelopes for critical failure modes of the structural components the wind turbine is made of. In the long run, both aerodynamic framework (theoretical model) and system identification (experimental model) will be merged in a numerical engine formulated as a search algorithm for model updating, also known as Adaptive Simulated Annealing (ASA) process. This iterative engine is based on a set of function minimizations computed by a metric called Modal Assurance Criterion (MAC). In summary, the Thesis is composed of four major parts: (1) development of an analytical aerodynamic framework that predicts interacted wind-structure stochastic loads on wind turbine components; (2) development of a novel tapered-swept-corved Spinning Finite Element (SFE) that includes dampedgyroscopic effects and axial-flexural-torsional coupling; (3) a novel data-driven structural health monitoring (SHM) algorithm via stochastic subspace identification methods; and (4) a numerical search (optimization) engine based on ASA and MAC capable of updating the SFE aerodynamic model.

Aluminum - Bronze Compacts and their Possible Use as a Bearing Material

In the modern aspect of powder metallurgy, the first use of a sintering process was in making filaments for incandescent electric lamps.In the short while from the day of Edison to the pres­ent, the science of working with metal powders has advanced by leaps and bounds.

Development of a novel material flow simulation model for the integration of spatial and process relevant information

Simulation techniques are almost indispensable in the analysis of complex systems. Materials- and related information flow processes in logistics often possess such complexity. Further problem arise as the processes change over time and pose a Big Data problem as well. To cope with these issues adaptive simulations are more and more frequently used. This paper presents a few relevant advanced simulation models and intro-duces a novel model structure, which unifies modelling of geometrical relations and time processes. This way the process structure and their geometric relations can be handled in a well understandable and transparent way. Capabilities and applicability of the model is also presented via a demonstrational example.

Serial [18F]-fluoromisonidazole PET during radiochemotherapy for locally advanced head and neck cancer and its correlation with outcome.

PURPOSE The aim was to assess changes of tumour hypoxia during primary radiochemotherapy (RCT) for head and neck cancer (HNC) and to evaluate their relationship with treatment outcome. MATERIAL AND METHODS Hypoxia was assessed by FMISO-PET in weeks 0, 2 and 5 of RCT. The tumour volume (TV) was determined using FDG-PET/MRI/CT co-registered images. The level of hypoxia was quantified on FMISO-PET as TBRmax (SUVmaxTV/SUVmean background). The hypoxic subvolume (HSV) was defined as TV that showed FMISO uptake ⩾1.4 times blood pool activity. RESULTS Sixteen consecutive patients (T3-4, N+, M0) were included (mean follow-up 31, median 44months). Mean TBRmax decreased significantly (p<0.05) from 1.94 to 1.57 (week 2) and 1.27 (week 5). Mean HSV in week 2 and week 5 (HSV2=5.8ml, HSV3=0.3ml) were significantly (p<0.05) smaller than at baseline (HSV1=15.8ml). Kaplan-Meier plots of local recurrence free survival stratified at the median TBRmax showed superior local control for less hypoxic tumours, the difference being significant at baseline and after 2weeks (p=0.031, p=0.016). CONCLUSIONS FMISO-PET documented that in most HNC reoxygenation starts early during RCT and is correlated with better outcome.