Oxidation and pyrolysis of methane and methyl formate in a plug flow reactor: computational and experimenal studies

Biodiesel represents a possible substitute to the fossil fuels; for this reason a good comprehension of the kinetics involved is important. Due to the complexity of the biodiesel mixture a common practice is the use of surrogate molecules to study its reactivity. In this work are presented the experimental and computational results obtained for the oxidation and pyrolysis of methane and methyl formate conducted in a plug flow reactor. The work was divided into two parts: the first one was the setup assembly whilst, in the second one, was realized a comparison between the experimental and model results; these last was obtained using models available in literature. It was started studying the methane since, a validate model was available, in this way was possible to verify the reliability of the experimental results. After this first study the attention was focused on the methyl formate investigation. All the analysis were conducted at different temperatures, pressures and, for the oxidation, at different equivalence ratios. The results shown that, a good comprehension of the kinetics is reach but efforts are necessary to better evaluate kinetics parameters such as activation energy. The results even point out that the realized setup is adapt to study the oxidation and pyrolysis and, for this reason, it will be employed to study a longer chain esters with the aim to better understand the kinetic of the molecules that are part of the biodiesel mixture.

Temperature measurements in turbulent pipe flow with cold wire anemometry

Passive scalars measurements in turbulent pipe flows are difficult to perform and only few experimental data are available in literature. The present thesis deals with the experimental acquisition and study of the first turbulent temperature profile inside the CICLoPE wind tunnel through cold wire anemometry technique at Reτ = 6000 and Reτ = 9500. This type of measurements provides not only useful data on temperature (and passive scalars) behaviour and statistics in turbulent pipe flows, but could be used also for temperature correction of turbulent velocity profiles. In the present work, subsequent acquisitions of temperature and velocity profiles has been performed at the same Reynolds number and in the same points, through cold wire and hot wire techniques respectively. Taking as reference data from both DNS and experimental campaigns, the activity has been carried out obtaining satisfactory results. We have verified the presence of turbulent temperature profile inside the CICLoPE wind tunnel and then studied its statistical and spectral behaviours obtaining results in agreement with existing data from Hishida, Nagano, and Ferro. Cold wire temperature data were then used to correct hot wire velocity data, obtaining a slightly improvement in the near wall region.

Study of a wind-wave numerical model and its integration with ocean and oil-spill numerical models

The ability to represent the transport and fate of an oil slick at the sea surface is a formidable task. By using an accurate numerical representation of oil evolution and movement in seawater, the possibility to asses and reduce the oil-spill pollution risk can be greatly improved. The blowing of the wind on the sea surface generates ocean waves, which give rise to transport of pollutants by wave-induced velocities that are known as Stokes’ Drift velocities. The Stokes’ Drift transport associated to a random gravity wave field is a function of the wave Energy Spectra that statistically fully describe it and that can be provided by a wave numerical model. Therefore, in order to perform an accurate numerical simulation of the oil motion in seawater, a coupling of the oil-spill model with a wave forecasting model is needed. In this Thesis work, the coupling of the MEDSLIK-II oil-spill numerical model with the SWAN wind-wave numerical model has been performed and tested. In order to improve the knowledge of the wind-wave model and its numerical performances, a preliminary sensitivity study to different SWAN model configuration has been carried out. The SWAN model results have been compared with the ISPRA directional buoys located at Venezia, Ancona and Monopoli and the best model settings have been detected. Then, high resolution currents provided by a relocatable model (SURF) have been used to force both the wave and the oil-spill models and its coupling with the SWAN model has been tested. The trajectories of four drifters have been simulated by using JONSWAP parametric spectra or SWAN directional-frequency energy output spectra and results have been compared with the real paths traveled by the drifters.

Testing of subgrid scale (SGS) models for large-eddy simulation (LES) of turbulent channel flow

Sub-grid scale (SGS) models are required in order to model the influence of the unresolved small scales on the resolved scales in large-eddy simulations (LES), the flow at the smallest scales of turbulence. In the following work two SGS models are presented and deeply analyzed in terms of accuracy through several LESs with different spatial resolutions, i.e. grid spacings. The first part of this thesis focuses on the basic theory of turbulence, the governing equations of fluid dynamics and their adaptation to LES. Furthermore, two important SGS models are presented: one is the Dynamic eddy-viscosity model (DEVM), developed by \cite{germano1991dynamic}, while the other is the Explicit Algebraic SGS model (EASSM), by \cite{marstorp2009explicit}. In addition, some details about the implementation of the EASSM in a Pseudo-Spectral Navier-Stokes code \cite{chevalier2007simson} are presented. The performance of the two aforementioned models will be investigated in the following chapters, by means of LES of a channel flow, with friction Reynolds numbers $Re_\tau=590$ up to $Re_\tau=5200$, with relatively coarse resolutions. Data from each simulation will be compared to baseline DNS data. Results have shown that, in contrast to the DEVM, the EASSM has promising potentials for flow predictions at high friction Reynolds numbers: the higher the friction Reynolds number is the better the EASSM will behave and the worse the performances of the DEVM will be. The better performance of the EASSM is contributed to the ability to capture flow anisotropy at the small scales through a correct formulation for the SGS stresses. Moreover, a considerable reduction in the required computational resources can be achieved using the EASSM compared to DEVM. Therefore, the EASSM combines accuracy and computational efficiency, implying that it has a clear potential for industrial CFD usage.

Sviluppo e applicazione di un reattore di prepolimerizzazione in continuo

Presso lo stabilimento DOW di Correggio (che è una system house per la produzione di prepolimeri poliuretanici) la ricerca è attualmente incentrata sullo sviluppo su scala industriale di un reattore pilota continuo di tipo plug flow che andrà a sostituire i tradizionali processi BATCH, con un guadagno in termini di sicurezza e costi di investimento. In particolare, il progetto prevedeva di sperimentare le “ricette” attuali di prepolimeri per applicazioni nel settore della calzatura per valutarne l’equivalenza con quelli fatti in BATCH, e di calibrare un modello del reattore pilota che permetta di prevedere le prestazioni del reattore e supporti lo scale-up attraverso la raccolta di dati sperimentali (profili di temperatura, tempi di residenza, titolo di NCO del prodotto, ecc...). Alla conclusione del progetto è possibile affermare che la tecnologia è robusta, scalabile e rispetto ai sistemi di produzione attuale presenta una maggiore produttività, sicurezza e minori costi di investimento. At the DOW plant in Correggio, which is a system house for the production of polyurethane prepolymers, the research is currently focused on the develompment and application of a plug flow type continuos reactor that will replace the traditional BATCH processes, with advantages in terms of process safety an investment costs. In particular, the project aims were to test in the pilot plant the prepolymer receipts for footwear application, find out if the result products were similar or better than the ones made with BATCH reactor and harvest experimental data (such as temperatures profiles, reaction time, residual NCO value, etc...) in order to calibrate a model that will support the scale-up to the industrial plant. Now that the project is ended, it is possibile to assert that this tecnology is reliable, scalable, safer and cheaper than the old processes.

Mathematical Modeling to Investigate Antiarrhythmic Drug Side Effects: Rate-Dependence Role in Ionic Currents and Action Potentials Shape in the O’Hara Model

Sudden cardiac death due to ventricular arrhythmia is one of the leading causes of mortality in the world. In the last decades, it has proven that anti-arrhythmic drugs, which prolong the refractory period by means of prolongation of the cardiac action potential duration (APD), play a good role in preventing of relevant human arrhythmias. However, it has long been observed that the “class III antiarrhythmic effect” diminish at faster heart rates and that this phenomenon represent a big weakness, since it is the precise situation when arrhythmias are most prone to occur. It is well known that mathematical modeling is a useful tool for investigating cardiac cell behavior. In the last 60 years, a multitude of cardiac models has been created; from the pioneering work of Hodgkin and Huxley (1952), who first described the ionic currents of the squid giant axon quantitatively, mathematical modeling has made great strides. The O’Hara model, that I employed in this research work, is one of the modern computational models of ventricular myocyte, a new generation began in 1991 with ventricular cell model by Noble et al. Successful of these models is that you can generate novel predictions, suggest experiments and provide a quantitative understanding of underlying mechanism. Obviously, the drawback is that they remain simple models, they don’t represent the real system. The overall goal of this research is to give an additional tool, through mathematical modeling, to understand the behavior of the main ionic currents involved during the action potential (AP), especially underlining the differences between slower and faster heart rates. In particular to evaluate the rate-dependence role on the action potential duration, to implement a new method for interpreting ionic currents behavior after a perturbation effect and to verify the validity of the work proposed by Antonio Zaza using an injected current as a perturbing effect.

Pricing in stochastic-local volatility models with default

In recent years is becoming increasingly important to handle credit risk. Credit risk is the risk associated with the possibility of bankruptcy. More precisely, if a derivative provides for a payment at cert time T but before that time the counterparty defaults, at maturity the payment cannot be effectively performed, so the owner of the contract loses it entirely or a part of it. It means that the payoff of the derivative, and consequently its price, depends on the underlying of the basic derivative and on the risk of bankruptcy of the counterparty. To value and to hedge credit risk in a consistent way, one needs to develop a quantitative model. We have studied analytical approximation formulas and numerical methods such as Monte Carlo method in order to calculate the price of a bond. We have illustrated how to obtain fast and accurate pricing approximations by expanding the drift and diffusion as a Taylor series and we have compared the second and third order approximation of the Bond and Call price with an accurate Monte Carlo simulation. We have analysed JDCEV model with constant or stochastic interest rate. We have provided numerical examples that illustrate the effectiveness and versatility of our methods. We have used Wolfram Mathematica and Matlab.

Dynamics of Bora wind over the Adriatic sea: atmospheric water balance and role of air-sea fluxes and orography

The Bora wind is a mesoscale phenomenon which typically affects the Adriatic Sea basin for several days each year, especially during winter. The Bora wind has been studied for its intense outbreak across the Dinaric Alps. The properties of the Bora wind are widely discussed in the literature and scientific papers usually focus on the eastern Adriatic coast where strong turbulence and severe gust intensity are more pronounced. However, the impact of the Bora wind can be significant also over Italy, not only in terms of wind speed instensity. Depending on the synoptic pressure pattern (cyclonic or anticyclonic Bora) and on the season, heavy snowfall, severe storms, storm surges and floods can occur along the Adriatic coast and on the windward flanks of the Apennines. In the present work five Bora cases that occurred in recent years have been selected and their evolution has been simulated with the BOLAM-MOLOCH model set, developed at ISAC-CNR in Bologna. Each case study has been addressed by a control run and by several sensitivity tests, performed with the purpose of better understanding the role played by air-sea latent and sensible heat fluxes. The tests show that the removal of the fluxes induces modifications in the wind approching the coast and a decrease of the total precipitation amount predicted over Italy. In order to assess the role of heat fluxes, further analysis has been carried out: column integrated water vapour fluxes have been computed along the Italian coastline and an atmospheric water balance has been evaluated inside a box volume over the Adriatic Sea. The balance computation shows that, although latent heat flux produces a significant impact on the precipitation field, its contribution to the balance is relatively minor. The most significant and lasting case study, that of February 2012, has been studied in more detail in order to explain the impressive drop in the total precipitation amount simulated in the sensitivity tests with removed heat fluxes with respect to the CNTRL run. In these experiments relative humidity and potential temperature distribution over different cross-sections have been examined. With respect to the CNTRL run a drier and more stable boundary layer, characterised by a more pronounced wind shear at the lower levels, has been observed to establish above the Adriatic Sea. Finally, in order to demonstrate that also the interaction of the Bora flow with the Apennines plays a crucial role, sensitivity tests varying the orography height have been considered. The results of such sensitivity tests indicate that the propagation of the Bora wind over the Adriatic Sea, and in turn its meteorological impact over Italy, is influenced by both the large air-sea heat fluxes and the interaction with the Apennines that decelerate the upstream flow.

A study of the turbulence of the neutral medium in two nearby spiral galaxies

The width of the 21 cm line (HI) emitted by spiral galaxies depends on the physical processes that release energy in the Interstellar Medium (ISM). This quantity is called velocity dispersion (σ) and it is proportional first of all to the thermal kinetic energy of the gas. The accepted theoretical picture predicts that the neutral hydrogen component (HI) exists in the ISM in two stable phases: a cold one (CNM, with σ~0.8 km/s) and a warm one (WNM, with σ~8 km/s). However, this is called into question by the observation that the HI gas has usually larger velocity dispersions. This suggests the presence of turbulence in the ISM, although the energy sources remain unknown. In this thesis we want to shed new light on this topic. We have studied the HI line emission of two nearby galaxies: NGC6946 and M101. For the latter we used new deep observations obtained with the Westerbork radio interferometer. Through a gaussian fitting procedure, we produced dispersion maps of the two galaxies. For both of them, we compared the σ values measured in the spiral arms with those in the interarms. In NGC6946 we found that, in both arms and interarms, σ grows with the column density, while we obtained the opposite for M 101. Using a statistical analysis we did not find a significant difference between arm and interarm dispersion distributions. Producing star formation rate density maps (SFRD) of the galaxies, we studied their global and local relations with the HI kinetic energy, as inferred from the measured dispersions. For NGC6946 we obtained a good log-log correlation, in agreement with a simple model of supernova feedback driven turbulence. This shows that in this galaxy turbulent motions are mainly induced by the stellar activity. For M 101 we did not find an analogous correlation, since the gas kinetic energy appears constant with the SFRD. We think that this may indicate that in this galaxy turbulence is driven also by accretion of extragalactic material.

Numerical and experimental investigation of structural stiffness influence on ratcheting convection cell in granular soils under cyclic loading

Lateral cyclic loaded structures in granular soils can lead to an accumulation of irreversible strains by changing their mechanical response (densification) and forming a closed convective cell in the upper layer of the bedding. In the present thesis the convective cell dimension, formation and grain migration inside this closed volume have been studied and presented in relation to structural stiffness and different loads. This relation was experimentally investigated by applying a cyclic lateral force to a scaled flexible vertical element embedded in dry granular soil. The model was monitored with a camera in order to derive the displacement field by means of the PIV technique. Modelling large soil deformation turns out to be difficult, using mesh-based methods. Consequently, a mesh-free approach (DEM) was chosen in order to investigate the granular flow with the aim of extracting interesting micromechanical information. In both the numerical and experimental analyses the effect of different loading magnitudes and different dimensions of the vertical element were considered. The main results regarded the different development, shape and dimensions of the convection cell and the surface settlements. Moreover, the Discrete Element Method has proven to give satisfactory results in the modelling of large deformation phenomena such as the ratcheting convective cell.

Economic and Environmental Optimization of Ornamental Stone Block Cutting with a 3D Algorithm

This thesis focuses on finding the optimum block cutting dimensions in terms of the environmental and economic factors by using a 3D algorithm for a limestone quarry in Foggia, Italy. The environmental concerns of quarrying operations are mainly: energy consumption, material waste, and pollution. The main economic concerns are the block recovery, the selling prices, and the production costs. Fractures adversely affect the block recovery ratio. With a fracture model, block production can be optimized. In this research, the waste volume produced by quarrying was minimised to increase the recovery ratio and ensure economic benefits. SlabCutOpt is a software developed at DICAM–University of Bologna for block cutting optimization which tests different cutting angles on the x-y-z planes to offer up alternative cutting methods. The program tests several block sizes and outputs the optimal result for each entry. By using SlabCutOpt, ten different block dimensions were analysed, the results indicated the maximum number of non-intersecting blocks for each dimension. After analysing the outputs, the block named number 1 with the dimensions ‘1mx1mx1m’ had the highest recovery ratio as 43% and the total Relative Money Value (RMV) with a value of 22829. Dimension number 1, also had the lowest waste volume, with a value of 3953.25 m3, for the total bench. For cutting the total bench volume of 6932.25m3, the diamond wire cutter had the lowest dust emission values for the block with the dimension ‘2mx2mx2m’, with a value of 24m3. When compared with the Eco-Label standards, block dimensions having surface area values lower than 15m2, were found to fit the natural resource waste criteria of the label, as the threshold required 25% of minimum recovery [1]. Due to the relativity of production costs, together with the Eco-Label threshold, the research recommends the selection of the blocks with a surface area value between 6m2 and 14m2.

Tutte's 5-flow conjecture

The aim of this thesis is to show and put together the results, obtained so far, useful to tackle a conjecture of graph theory proposed in 1954 by William Thomas Tutte. The conjecture in question is Tutte's 5-flow conjecture, which states that every bridgeless graph admits a nowhere-zero 5-flow, namely a flow with non-zero integer values between -4 and 4. We will start by giving some basics on graph theory, useful for the followings, and proving some results about flows on oriented graphs and in particular about the flow polynomial. Next we will treat two cases: graphs embeddable in the plane $\mathbb{R}^2$ and graphs embeddable in the projective plane $\mathbb{P}^2$. In the first case we will see the correlation between flows and colorings and prove a theorem even stronger than Tutte's conjecture, using the 4-color theorem. In the second case we will see how in 1984 Richard Steinberg used Fleischner's Splitting Lemma to show that there can be no minimal counterexample of the conjecture in the case of graphs in the projective plane. In the fourth chapter we will look at the theorems of François Jaeger (1976) and Paul D. Seymour (1981). The former proved that every bridgeless graph admits a nowhere-zero 8-flow, the latter managed to go even further showing that every bridgeless graph admits a nowhere-zero 6-flow. In the fifth and final chapter there will be a short introduction to the Tutte polynomial and it will be shown how it is related to the flow polynomial via the Recipe Theorem. Finally we will see some applications of flows through the study of networks and their properties.

Experimental characterization of a planar jet by hot-wire anemometry

The study of turbulence is also nowadays a problem that does not have solution from the mathematical point of view due to the lack of solution to link the mean part of the flow with the fluctuating one. To solve this problem, in the CICLoPE laboratory of Predappio, experiments on different type of jets are performed in order to derive a closure model able to close our mathematical model. One of the most interesting type of jet that could be studied is the planar turbulent free jet which is a two dimensional canonical jet characterized by the self-similarity condition of the velocity profiles. To study this particular jet, a new facility was built. The aim of this project is to characterize the jet at different distances from the nozzle exit, for different values of Reynolds number, to demonstrate that the self-similarity condition is respected. To do that, the evaluation of quantities such as spreading rate, centerline velocity decay and relation between fluctuations and mean part of the flow has to be obtain. All these parameters could be detected thanks to the use of single and X hot-wire anemometry with which it is possible to analyzed the fluctuating behaviour of the flow by associating to an electric signal a physical variable expressed in terms of velocity. To justify the data obtain by the measures, a comparison with results coming from the literature has to be shown.