Development and characterization of non-oxide ceramic composites for mechanical and tribological applications

The main reasons for the attention focused on ceramics as possible structural materials are their wear resistance and the ability to operate with limited oxidation and ablation at temperatures above 2000°C. Hence, this work is devoted to the study of two classes of materials which can satisfy these requirements: silicon carbide -based ceramics (SiC) for wear applications and borides and carbides of transition metals for ultra-high temperatures applications (UHTCs). SiC-based materials: Silicon carbide is a hard ceramic, which finds applications in many industrial sectors, from heat production, to automotive engineering and metals processing. In view of new fields of uses, SiC-based ceramics were produced with addition of 10-30 vol% of MoSi2, in order to obtain electro conductive ceramics. MoSi2, indeed, is an intermetallic compound which possesses high temperature oxidation resistance, high electrical conductivity (21·10-6 Ω·cm), relatively low density (6.31 g/cm3), high melting point (2030°C) and high stiffness (440 GPa). The SiC-based ceramics were hot pressed at 1900°C with addition of Al2O3-Y2O3 or Y2O3-AlN as sintering additives. The microstructure of the composites and of the reference materials, SiC and MoSi2, were studied by means of conventional analytical techniques, such as X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (SEM-EDS). The composites showed a homogeneous microstructure, with good dispersion of the secondary phases and low residual porosity. The following thermo-mechanical properties of the SiC-based materials were measured: Vickers hardness (HV), Young’s modulus (E), fracture toughness (KIc) and room to high temperature flexural strength (σ). The mechanical properties of the composites were compared to those of two monolithic SiC and MoSi2 materials and resulted in a higher stiffness, fracture toughness and slightly higher flexural resistance. Tribological tests were also performed in two configurations disco-on-pin and slideron cylinder, aiming at studying the wear behaviour of SiC-MoSi2 composites with Al2O3 as counterfacing materials. The tests pointed out that the addition of MoSi2 was detrimental owing to a lower hardness in comparison with the pure SiC matrix. On the contrary, electrical measurements revealed that the addition of 30 vol% of MoSi2, rendered the composite electroconductive, lowering the electrical resistance of three orders of magnitude. Ultra High Temperature Ceramics: Carbides, borides and nitrides of transition metals (Ti, Zr, Hf, Ta, Nb, Mo) possess very high melting points and interesting engineering properties, such as high hardness (20-25 GPa), high stiffness (400-500 GPa), flexural strengths which remain unaltered from room temperature to 1500°C and excellent corrosion resistance in aggressive environment. All these properties place the UHTCs as potential candidates for the development of manoeuvrable hypersonic flight vehicles with sharp leading edges. To this scope Zr- and Hf- carbide and boride materials were produced with addition of 5-20 vol% of MoSi2. This secondary phase enabled the achievement of full dense composites at temperature lower than 2000°C and without the application of pressure. Besides the conventional microstructure analyses XRD and SEM-EDS, transmission electron microscopy (TEM) was employed to explore the microstructure on a small length scale to disclose the effective densification mechanisms. A thorough literature analysis revealed that neither detailed TEM work nor reports on densification mechanisms are available for this class of materials, which however are essential to optimize the sintering aids utilized and the processing parameters applied. Microstructural analyses, along with thermodynamics and crystallographic considerations, led to disclose of the effective role of MoSi2 during sintering of Zrand Hf- carbides and borides. Among the investigated mechanical properties (HV, E, KIc, σ from room temperature to 1500°C), the high temperature flexural strength was improved due to the protective and sealing effect of a silica-based glassy phase, especially for the borides. Nanoindentation tests were also performed on HfC-MoSi2 composites in order to extract hardness and elastic modulus of the single phases. Finally, arc jet tests on HfC- and HfB2-based composites confirmed the excellent oxidation behaviour of these materials under temperature exceeding 2000°C; no cracking or spallation occurred and the modified layer was only 80-90 μm thick.

Modelli semplificati per valutazione di vulnerabilità sismica di strutture in muratura

L'obiettivo della tesi è stato quello di indagare il complesso problema della vulnerabilità sismica dei ponte in muratura ad arco utilizzando modelli semplificati. Dopo una descrizione dei materiali da costruzione impiegati nella realizzazione e dei principali elementi dei un ponti in muratura, si è indirizzato lo studio di un ponte ad arco situato nel comune di San Marcello Pistoiese. Viene mostrato un modello numerico che permette di descrivere il comportamento strutturale del ponte sotto azione sismica e di valutare la capacità di carico del ponte sottoposto ad una azione trasversale. In un secondo momento viene descritta la realizzazione di un modello in scala del ponte, che è stato sottoposto a prove distruttive effettuate per valutare la capacità di carico del ponte rispetto ad un ipotetica azione orizzontale. Si è cercato poi di inquadrare il problema in un modello teorico che faccia riferimento all'analisi limite. Esso descrive un cinematismo di collasso a telaio che prende spunto dal quadro fessurativo del modello in muratura. Infine sono stati presentati modelli FEM numerici in ordine di complessità crescente, cercando di inquadrare il comportamento meccanico del prototipo del ponte. Tre tipi di modelli sono rappresentati: un telaio incernierato alle estremità costituito da elementi beam con resistenza alla flessione . Il secondo tipo è costituito da una reticolare equivalente che mima lo schema del ponte ed è formato solo da bielle. Infine, il terzo tipo cerca di descrivere l'intero modello con elementi tridimensionali.

Studio degli effetti della mordenzatura con acido fluoridrico sul disilicato di litio utilizzato in odontoiatria

Scopo dello studio: valutare i cambiamenti indotti da diversi trattamenti di mordenzatura sulla morfologia superficiale e sulla microstruttura di due vetro-ceramiche a base disilicato di litio (IPS e.max® Press e IPS e.max® CAD) ed esaminarne gli effetti sia sull’adesione con un cemento resinoso che sulla resistenza alla flessione. Materiali e metodi: Settanta dischetti (12 mm di diametro, 2 mm di spessore) di ogni ceramica sono stati preparati e divisi in 5 gruppi: nessun trattamento (G1), HF 5% 20s (G2), HF 5% 60s (G3), HF 9.6% 20s (G4), HF 9.6% 60s (G5). Un campione per ogni gruppo è stato analizzato mediante profilometro ottico e osservato al SEM. Per gli altri campioni è stato determinato lo shear bond strength (SBS) con un cemento resinoso. Dopo l’SBS test, i campioni sono stati caricati fino a frattura utilizzando il piston-on-three-ball test per determinarne la resistenza biassiale alla flessione. Risultati: L’analisi morfologica e microstrutturale dei campioni ha rivelato come diversi trattamenti di mordenzatura producano delle modifiche nella rugosità superficiale che non sono direttamente collegate ad un aumento dei valori di adesione e dei cambiamenti microstrutturali che sono più rilevanti con l’aumento del tempo di mordenzatura e di concentrazione dell’acido. I valori medi di adesione (MPa) per IPS e.max® CAD sono significativamente più alti in G2 e G3 (21,28 +/- 4,9 e 19,55 +/- 5,41 rispettivamente); per IPS e.max® Press, i valori più elevati sono in G3 (16,80 +/- 3,96). La resistenza biassiale alla flessione media (MPa) è più alta in IPS e.max® CAD (695 +/- 161) che in IPS e.max® Press (588 +/- 117), ma non è non influenzata dalla mordenzatura con HF. Conclusioni: il disilicato di litio va mordenzato preferibilmente con HF al 5%. La mordenzatura produce alcuni cambiamenti superficiali e microstrutturali nel materiale, ma tali cambiamenti non ne influenzano la resistenza in flessione.

Studio elettrofisiologico di modificazioni a lungo termine della forza della trasmissione sinaptica nel sistema nervoso centrale

Il nucleo accumbens (NAc), il maggior componente del sistema mesocorticolimbico, è coinvolto nella mediazione delle proprietà di rinforzo e nella dipendenza da diverse sostanze d’abuso. Le sinapsi glutammatergiche del NAc possono esprimere plasticità, tra cui una forma di depressione a lungo termine (LTD) dipendente dagli endocannabinoidi (eCB). Recenti studi hanno dimostrato un’interazione tra le vie di segnalazione del sistema eCB e quelle di altri sistemi recettoriali, compreso quello serotoninergico (5-HT); la vasta colocalizzazione di recettori serotoninergici e CB1 nel NAc suggerisce la possibilità di un’interazione tra questi due sistemi. In questo studio abbiamo riscontrato che una stimolazione a 4 Hz per 20 minuti (LFS-4Hz) delle afferenze glutammatergiche in fettine cerebrali di ratto, induce una nuova forma di eCB-LTD nel core del NAc, che richiede l’attivazione dei recettori CB1 e 5-HT2 e l’apertura dei canali del Ca2+ voltaggio-dipendenti di tipo L. Inoltre abbiamo valutato che l’applicazione esogena di 5-HT (5 M, 20 min) induce una LTD analoga (5-HT-LTD) a livello delle stesse sinapsi, che richiede l’attivazione dei medesimi recettori e l’apertura degli stessi canali del Ca2+; LFS-4Hz-LTD e 5-HT-LTD sono reciprocamente saturanti. Questi risultati suggeriscono che la LFS-4Hz induce il rilascio di 5-HT, che si lega ai recettori 5-HT2 a livello postsinaptico incrementando l’influsso di Ca2+ attraverso i canali voltaggio-dipendenti di tipo L e la produzione e il rilascio di 2-arachidonoilglicerolo; l’eCB viaggia a ritroso e si lega al recettore CB1 a livello presinaptico, causando una diminuzione duratura del rilascio di glutammato, che risulta in una LTD. Queste osservazioni possono essere utili per comprendere i meccanismi neurofisiologici che sono alla base della dipendenza da sostanze d’abuso, della depressione maggiore e di altre malattie psichiatriche caratterizzate dalla disfunzione della neurotrasmissione di 5-HT nel NAc.

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.

Smantellamento di un reattore di potenza gas-grafite di I generazione: metodologie e tecnologie di rimozione della grafite e smantellamento del nocciolo

Il presente lavoro di tesi ha riguardato lo studio dello smantellamento di un reattore gas grafite di potenza di I Gen. L’indagine è stata focalizzata in particolare al recupero della grafite irraggiata che ne costituisce il core. Viene presentata una descrizione referenziata del reattore e dei suoi componenti per mettere in evidenza la particolare architettura e le specifiche problematiche ad essa correlate. A valle di un’indagine sulle esperienze internazionali in merito al decommissioning e allo smantellamento di questi tipi di reattori, si forniscono una possibile sequenza di accesso alla cavità del reattore e una procedura per il suo smantellamento; si descrivono sommariamente le tecnologie di taglio e di handling, attualmente allo stato dell’arte, considerate come più idonee a questo tipo di applicazione. Vengono descritte le principali criticità della grafite nuclear grade ed illustrati i fenomeni caratteristici che ne determinano l’evoluzione nel reattore. Sulla base dei dati resi disponibili dalla Sogin S.p:A. e ricorrendo ai dati di letteratura per quelli non disponibili, è stato effettuato un assessment della grafite irraggiata costituente il nocciolo del reattore, rivolto in particolare a determinarne le caratteristiche meccaniche e la resistenza residua post-irraggiamento. Per valutare la possibilità di prelevare la grafite dal nocciolo è stato ipotizzato un dispositivo di presa che agganci per attrito i blocchi di grafite del moderatore attraverso il canale assiale. Infine è stata valutata la fattibilità di tale metodo attraverso una serie di simulazioni agli elementi finiti dirette a verificare la resistenza del blocco in varie condizioni di carico e vincolo. Come risultato si è dimostrata la fattibilità, almeno in via preliminare, del metodo proposto, determinando l’inviluppo di utilizzo del dispositivo di presa nonché la compatibilità del metodo proposto con le tecnologie di handling precedentemente individuate.

Experimental and numerical investigation on short and long term performance of macro-synthetic fibre reinforced concrete materials

Fibre Reinforced Concretes are innovative composite materials whose applications are growing considerably nowadays. Being composite materials, their performance depends on the mechanical properties of both components, fibre and matrix and, above all, on the interface. The variables to account for the mechanical characterization of the material, could be proper of the material itself, i.e. fibre and concrete type, or external factors, i.e. environmental conditions. The first part of the research presented is focused on the experimental and numerical characterization of the interface properties and short term response of fibre reinforced concretes with macro-synthetic fibers. The experimental database produced represents the starting point for numerical models calibration and validation with two principal purposes: the calibration of a local constitutive law and calibration and validation of a model predictive of the whole material response. In the perspective of the design of sustainable admixtures, the optimization of the matrix of cement-based fibre reinforced composites is realized with partial substitution of the cement amount. In the second part of the research, the effect of time dependent phenomena on MSFRCs response is studied. An extended experimental campaign of creep tests is performed analysing the effect of time and temperature variations in different loading conditions. On the results achieved, a numerical model able to account for the viscoelastic nature of both concrete and reinforcement, together with the environmental conditions, is calibrated with the LDPM theory. Different type of regression models are also elaborated correlating the mechanical properties investigated, bond strength and residual flexural behaviour, regarding the short term analysis and creep coefficient on time, for the time dependent behaviour, with the variable investigated. The experimental studies carried out emphasize the several aspects influencing the material mechanical performance allowing also the identification of those properties that the numerical approach should consider in order to be reliable.

Subsidence history, thermal maturity, and structural inversion of the Greater Caucasus-Kura-Adjara-Trialeti basin system of central-eastern Georgia

This study aims at defining the tectonic evolution of a portion of the Caucasian region, in Georgia, which experienced a complex pattern of deformation events throughout Mesozoic and Cenozoic times. An integrated approach was applied to unravel the thermo-tectonic history of three inverted sedimentary basins from burial to exhumation. Additionally, this dissertation provides examples of structural inversion of sedimentary basins in response to far-field transmission of compressional stresses away from collision zones, contributing to elucidate the dynamics of stress partitioning during continental collisions. The Adjara-Trialeti fold-and-thrust belt in south-western Georgia results from the structural inversion of a Middle Eocene continental back-arc rift basin opened as a consequence of the Northern Neotethys slab rollback. This study quantitatively defines the subsidence and exhumation history of the Adjara-Trialeti basin, constraining its Middle Miocene inception of structural inversion. The western Kura Basin is a flexural foreland basin trapped between the Lesser Caucasus to the south and the Greater Caucasus to the north. This study constrains successive and competing episodes of flexural subsidence during Oligocene-Miocene times, followed by partial inversion through thick- and thin-skinned tectonics in response to continued convergence between the adjacent, oppositely verging orogenic belts. The Greater Caucasus results from the structural inversion of a Jurassic continental back-arc basin, but the timing of its growth is still debated. An across-strike transect in its southern central domain was studied, indicating that this sector of the Greater Caucasus experienced two phases of structural inversion during Late Cretaceous-Paleocene and Late Miocene times. Overall, the dataset presented in this dissertation points to a complex and episodic history of incremental deformation, characterised by successive phases of extensional and compressional tectonics which developed in response to sequential terrane accretion at the southwestern margin of Eurasia since Late Cretaceous times, eventually determining the current configuration of the Arabia-Eurasia collision zone.

Embedded systems and advanced signal processing for Acousto- Ultrasonic Inspections

Non Destructive Testing (NDT) and Structural Health Monitoring (SHM) are becoming essential in many application contexts, e.g. civil, industrial, aerospace etc., to reduce structures maintenance costs and improve safety. Conventional inspection methods typically exploit bulky and expensive instruments and rely on highly demanding signal processing techniques. The pressing need to overcome these limitations is the common thread that guided the work presented in this Thesis. In the first part, a scalable, low-cost and multi-sensors smart sensor network is introduced. The capability of this technology to carry out accurate modal analysis on structures undergoing flexural vibrations has been validated by means of two experimental campaigns. Then, the suitability of low-cost piezoelectric disks in modal analysis has been demonstrated. To enable the use of this kind of sensing technology in such non conventional applications, ad hoc data merging algorithms have been developed. In the second part, instead, imaging algorithms for Lamb waves inspection (namely DMAS and DS-DMAS) have been implemented and validated. Results show that DMAS outperforms the canonical Delay and Sum (DAS) approach in terms of image resolution and contrast. Similarly, DS-DMAS can achieve better results than both DMAS and DAS by suppressing artefacts and noise. To exploit the full potential of these procedures, accurate group velocity estimations are required. Thus, novel wavefield analysis tools that can address the estimation of the dispersion curves from SLDV acquisitions have been investigated. An image segmentation technique (called DRLSE) was exploited in the k-space to draw out the wavenumber profile. The DRLSE method was compared with compressive sensing methods to extract the group and phase velocity information. The validation, performed on three different carbon fibre plates, showed that the proposed solutions can accurately determine the wavenumber and velocities in polar coordinates at multiple excitation frequencies.

Numerical and experimental analysis of 3D printed smart structures and systems

Three dimensional (3D) printers of continuous fiber reinforced composites, such as MarkTwo (MT) by Markforged, can be used to manufacture such structures. To date, research works devoted to the study and application of flexible elements and CMs realized with MT printer are only a few and very recent. A good numerical and/or analytical tool for the mechanical behavior analysis of the new composites is still missing. In addition, there is still a gap in obtaining the material properties used (e.g. elastic modulus) as it is usually unknown and sensitive to printing parameters used (e.g. infill density), making the numerical simulation inaccurate. Consequently, the aim of this thesis is to present several work developed. The first is a preliminary investigation on the tensile and flexural response of Straight Beam Flexures (SBF) realized with MT printer and featuring different interlayer fiber volume-fraction and orientation, as well as different laminate position within the sample. The second is to develop a numerical analysis within the Carrera' s Unified Formulation (CUF) framework, based on component-wise (CW) approach, including a novel preprocessing tool that has been developed to account all regions printed in an easy and time efficient way. Among its benefits, the CUF-CW approach enables building an accurate database for collecting first natural frequencies modes results, then predicting Young' s modulus based on an inverse problem formulation. To validate the tool, the numerical results are compared to the experimental natural frequencies evaluated using a digital image correlation method. Further, we take the CUF-CW model and use static condensation to analyze smart structures which can be decomposed into a large number of similar components. Third, the potentiality of MT in combination with topology optimization and compliant joints design (CJD) is investigated for the realization of automated machinery mechanisms subjected to inertial loads.

Analytical methods for modeling elastic metasurfaces

This dissertation aims at developing advanced analytical tools able to model surface waves propagating in elastic metasurfaces. In particular, four different objectives are defined and pursued throughout this work to enrich the description of the metasurface dynamics. First, a theoretical framework is developed to describe the dispersion properties of a seismic metasurface composed of discrete resonators placed on a porous medium considering part of it fully saturated. Such a model combines classical elasticity theory, Biot’s poroelasticity and an effective medium approach to describe the metasurface dynamics and its coupling with the poroelastic substrate. Second, an exact formulation based on the multiple scattering theory is developed to extend the two-dimensional classical Lamb’s problem to the case of an elastic half-space coupled to an arbitrary number of discrete surface resonators. To this purpose, the incident wavefield generated by a harmonic source and the scattered field generated by each resonator are calculated. The substrate wavefield is then obtained as solutions of the coupled problem due to the interference of the incident field and the multiple scattered fields of the oscillators. Third, the above discussed formulation is extended to three-dimensional contexts. The purpose here is to investigate the dynamic behavior and the topological properties of quasiperiodic elastic metasurfaces. Finally, the multiple scattering formulation is extended to model flexural metasurfaces, i.e., an array of thin plates. To this end, the resonant plates are modeled by means of their equivalent impedance, derived by exploiting the Kirchhoff plate theory. The proposed formulation permits the treatment of a general flexural metasurface, with no limitation on the number of plates and the configuration taken into account. Overall, the proposed analytical tools could pave the way for a better understanding of metasurface dynamics and their implementation in engineered devices.