High-strength steels manufactured via Laser Powder Bed Fusion: effect of post-process heat treatments and surface finishing on microstructure and mechanical properties

Laser Powder Bed Fusion (LPBF) permits the manufacturing of parts with optimized geometry, enabling lightweight design of mechanical components in aerospace and automotive and the production of tools with conformal cooling channels. In order to produce parts with high strength-to-weight ratio, high-strength steels are required. To date, the most diffused high-strength steels for LPBF are hot-work tool steels, maraging and precipitation-hardening stainless steels, featuring different composition, feasibility and properties. Moreover, LPBF parts usually require a proper heat treatment and surface finishing, to develop the desired properties and reduce the high roughness resulting from LPBF. The present PhD thesis investigates the effect of different heat treatments and surface finishing on the microstructure and mechanical properties of a hot-work tool steel and a precipitation-hardening stainless steel manufactured via LPBF. The bibliographic section focuses on the main aspects of LPBF, hot-work tool steels and precipitation-hardening stainless steels. The experimental section is divided in two parts. Part A addresses the effect of different heat treatments and surface finishing on the microstructure, hardness, tensile and fatigue behaviour of a LPBF manufactured hot-work tool steel, to evaluate its feasibility for automotive and racing components. Results indicated the possibility to achieve high hardness and strength, comparable to the conventionally produced steel, but a great sensitivity of fatigue strength on defects and surface roughness resulting from LPBF. Part B investigates the effect of different heat treatments on the microstructure, hardness, tensile and notch-impact behaviour of a LPBF produced precipitation-hardening stainless steel, to assess its feasibility for tooling applications. Results indicated the possibility to achieve high hardness and strength also through a simple Direct Aging, enabling heat treatment simplification by exploiting the microstructural features resulting from LPBF.

IDeS methodology applied to automotive component re-engineering focused on lightweight and high-strength by additive manufacturing

The project aims to gather an understanding of additive manufacturing and other manufacturing 4.0 techniques with an eyesight for industrialization. First the internal material anisotropy of elements created with the most economically feasible FEM technique was established. An understanding of the main drivers for variability for AM was portrayed, with the focus on achieving material internal isotropy. Subsequently, a technique for deposition parameter optimization was presented, further procedure testing was performed following other polymeric materials and composites. A replicability assessment by means of the use of technology 4.0 was proposed, and subsequent industry findings gathered the ultimate need of developing a process that demonstrate how to re-engineer designs in order to show the best results with AM processing. The latest study aims to apply the Industrial Design and Structure Method (IDES) and applying all the knowledge previously stacked into fully reengineer a product with focus of applying tools from 4.0 era, from product feasibility studies, until CAE – FEM analysis and CAM – DfAM. These results would help in making AM and FDM processes a viable option to be combined with composites technologies to achieve a reliable, cost-effective manufacturing method that could also be used for mass market, industry applications.

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.

In-situ and real time scanning probe microscopy of organic ultra thin films

In recent decades, Organic Thin Film Transistors (OTFTs) have attracted lots of interest due to their low cost, large area and flexible properties which have brought them to be considered the building blocks of the future organic electronics. Experimentally, devices based on the same organic material deposited in different ways, i.e. by varying the deposition rate of the molecules, show different electrical performance. As predicted theoretically, this is due to the speed and rate by which charge carriers can be transported by hopping in organic thin films, transport that depends on the molecular arrangement of the molecules. This strongly suggests a correlation between the morphology of the organic semiconductor and the performance of the OTFT and hence motivated us to carry out an in-situ real time SPM study of organic semiconductor growth as an almost unprecedent experiment with the aim to fully describe the morphological evolution of the ultra-thin film and find the relevant morphological parameters affecting the OTFT electrical response. For the case of 6T on silicon oxide, we have shown that the growth mechanism is 2D+3D, with a roughening transition at the third layer and a rapid roughening. Relevant morphological parameters have been extracted by the AFM images. We also developed an original mathematical model to estimate theoretically and more accurately than before, the capacitance of an EFM tip in front of a metallic substrate. Finally, we obtained Ultra High Vacuum (UHV) AFM images of 6T at lying molecules layer both on silicon oxide and on top of 6T islands. Moreover, we performed ex-situ AFM imaging on a bilayer film composed of pentacene (a p-type semiconductor) and C60 (an n-type semiconductor).

Relação entre resistência ao cisalhamento no plano e parâmetros processuais de co-cura de juntas em compósitos auto-reforçados de polietileno de matriz reprocessada

Este estudo investiga a otimização da resistência ao cisalhamento no plano de juntas de sobreposição co-curadas do compósito termoplástico unidirecional auto-reforçado de polietileno de baixa densidade reciclado reforçado por fibras de polietileno de ultra alto peso molecular através da relação desta resistência com os parâmetros processuais de prensagem a quente para a conformação da junta (pressão, temperatura, tempo e comprimento). A matriz teve sua estrutura química analisada para verificar potenciais degradações devidas à sua origem de reciclagem. Matriz e reforço foram caracterizados termicamente para definir a janela de temperatura de processamento de junta a ser estudada. A elaboração das condições de cura dos corpos de prova foi feita de acordo com a metodologia de Projeto de Experimento de Superfície de Resposta e a relação entre a resistência ao cisalhamento das juntas e os respectivos parâmetros de cura foi obtida através de equação de regressão gerada pelo método dos Mínimos Quadrados Ordinários. A caracterização mecânica em tração do material foi analisada micro e macromecanicamente. A análise química da matriz não demonstrou a presença de grupos carboxílicos que evidenciassem degradação por ramificações de cadeia e reticulação advindos da reciclagem do material. As metodologias de ensaio propostas demonstraram ser eficazes, podendo servir como base para a constituição de normas técnicas. Demonstrou-se que é possível obter juntas com resistência ótima ao cisalhamento de 6,88 MPa quando processadas a 1 bar, 115°C, 5 min e com 12 mm. A análise da fratura revelou que a ruptura por cisalhamento das juntas foi precedida por múltiplas fissuras longitudinais induzidas por sucessivos debondings, tanto dentro quanto fora da junta, devido à tensão transversal acumulada na mesma, proporcional a seu comprimento. A temperatura demonstrou ser o parâmetro de processamento mais relevante para a performance da junta, a qual é pouco afetada por variações na pressão e tempo de cura.

Strutture a pareti portanti in C. A. caratterizzate da elevate prestazioni sismiche

Per quanto riguarda le costruzioni in conglomerato cementizio armato gettato in opera, i sistemi strutturali più comunemente utilizzati sono quelli a telaio (con trasmissione di momento flettente), a setti portanti o una combinazione di entrambi. A partire dagli anni ’60, numerosissimi sono stati gli studi relativamente al comportamento sismico di strutture in c.a. a telaio. Lo stesso si può affermare per le costruzioni costituite da pareti miste a telai. In particolare, l’argomento della progettazione sismica di tali tipologie di edifici ha sempre riguardato soprattutto gli edifici alti nei quali, evidentemente, l’impiego delle pareti avveniva allo scopo di limitarne la elevata deformabilità. Il comportamento sismico di strutture realizzate interamente a pareti portanti in c.a. è stato meno studiato negli anni, nonostante si sia osservato che edifici realizzati mediante tali sistemi strutturali abbiano mostrato, in generale, pregevoli risorse di resistenza nei confronti di terremoti anche di elevata intensità. Negli ultimi 10 anni, l’ingegneria sismica si sta incentrando sull’approfondimento delle risorse di tipologie costruttive di cui si è sempre fatto largo uso in passato (tipicamente nei paesi dell’Europa continentale, in America latina, negli USA e anche in Italia), ma delle quali mancavano adeguate conoscenze scientifiche relativamente al loro comportamento in zona sismica. Tali tipologie riguardano sostanzialmente sistemi strutturali interamente costituiti da pareti portanti in c.a. per edifici di modesta altezza, usualmente utilizzati in un’edilizia caratterizzata da ridotti costi di realizzazione (fabbricati per abitazioni civili e/o uffici). Obiettivo “generale” del lavoro di ricerca qui presentato è lo studio del comportamento sismico di strutture realizzate interamente a setti portanti in c.a. e di modesta altezza (edilizia caratterizzata da ridotti costi di realizzazione). In particolare, le pareti che si intendono qui studiare sono caratterizzate da basse percentuali geometriche di armatura e sono realizzate secondo la tecnologia del cassero a perdere. A conoscenza dello scrivente, non sono mai stati realizzati, fino ad oggi, studi sperimentali ed analitici allo scopo di determinare il comportamento sismico di tali sistemi strutturali, mentre è ben noto il loro comportamento statico. In dettaglio, questo lavoro di ricerca ha il duplice scopo di: • ottenere un sistema strutturale caratterizzato da elevate prestazioni sismiche; • mettere a punto strumenti applicativi (congruenti e compatibili con le vigenti normative e dunque immediatamente utilizzabili dai progettisti) per la progettazione sismica dei pannelli portanti in c.a. oggetto del presente studio. Al fine di studiare il comportamento sismico e di individuare gli strumenti pratici per la progettazione, la ricerca è stata organizzata come segue: • identificazione delle caratteristiche delle strutture studiate, mediante lo sviluppo/specializzazione di opportune formulazioni analitiche; • progettazione, supervisione, ed interpretazione di una estesa campagna di prove sperimentali eseguita su pareti portanti in c.a. in vera grandezza, al fine di verificarne l’efficace comportamento sotto carico ciclico; • sviluppo di semplici indicazioni (regole) progettuali relativamente alle strutture a pareti in c.a. studiate, al fine di ottenere le caratteristiche prestazionali desiderate. I risultati delle prove sperimentali hanno mostrato di essere in accordo con le previsioni analitiche, a conferma della validità degli strumenti di predizione del comportamento di tali pannelli. Le elevatissime prestazioni riscontrate sia in termini di resistenza che in termini di duttilità hanno evidenziato come le strutture studiate, così messe a punto, abbiano manifestato un comportamento sismico più che soddisfacente.

Velocity structure and seismic anisotropy in the crust and upper mantle from Receiver Function analysis: three case studies in Italy

The research for this PhD project consisted in the application of the RFs analysis technique to different data-sets of teleseismic events recorded at temporary and permanent stations located in three distinct study regions: Colli Albani area, Northern Apennines and Southern Apennines. We found some velocity models to interpret the structures in these regions, which possess very different geologic and tectonics characteristics and therefore offer interesting case study to face. In the Colli Albani some of the features evidenced in the RFs are shared by all the analyzed stations: the Moho is almost flat and is located at about 23 km depth, and the presence of a relatively shallow limestone layer is a stable feature; contrariwise there are features which vary from station to station, indicating local complexities. Three seismic stations, close to the central part of the former volcanic edifice, display relevant anisotropic signatures­­­ with symmetry axes consistent with the emplacement of the magmatic chamber. Two further anisotropic layers are present at greater depth, in the lower crust and the upper mantle, respectively, with symmetry axes directions related to the evolution of the volcano complex. In Northern Apennines we defined the isotropic structure of the area, finding the depth of the Tyrrhenian (almost 25 km and flat) and Adriatic (40 km and dipping underneath the Apennines crests) Mohos. We determined a zone in which the two Mohos overlap, and identified an anisotropic body in between, involved in the subduction and going down with the Adiratic Moho. We interpreted the downgoing anisotropic layer as generated by post-subduction delamination of the top-slab layer, probably made of metamorphosed crustal rocks caught in the subduction channel and buoyantly rising toward the surface. In the Southern Apennines, we found the Moho depth for 16 seismic stations, and highlighted the presence of an anisotropic layer underneath each station, at about 15-20 km below the whole study area. The moho displays a dome-like geometry, as it is shallow (29 km) in the central part of the study area, whereas it deepens peripherally (down to 45 km); the symmetry axes of anisotropic layer, interpreted as a layer separating the upper and the lower crust, show a moho-related pattern, indicated by the foliation of the layer which is parallel to the Moho trend. Moreover, due to the exceptional seismic event occurred on April 6th next to L’Aquila town, we determined the Vs model for two station located next to the epicenter. An extremely high velocity body is found underneath AQU station at 4-10 km depth, reaching Vs of about 4 km/s, while this body is lacking underneath FAGN station. We compared the presence of this body with other recent works and found an anti-correlation between the high Vs body, the max slip patches and earthquakes distribution. The nature of this body is speculative since such high velocities are consistent with deep crust or upper mantle, but can be interpreted as a as high strength barrier of which the high Vs is a typical connotation.

Studio del processo CVI/CVD per lo sviluppo di compositi ceramici rinforzati a fibra lunga

The most relevant thermo-mechanical properties of SiC or C based CFCCs are high strength, high toughness, low weight, high reliability, thermal shock and fatigue resistance. Thanks to these special characteristics, the CFCCs are the best candidates to substitute metals and monolithic ceramics, traditionally employed to realize components in energy, aeronautic and nuclear fields. Among the commonly techniques for the CFCCs production, CVI still represents the most significant one. Its main advantages are the versatility, the high quality deposits and the fact that it is conducted under mild temperature conditions. On the other hand, this technique is quite complex, therefore the set up of all process parameters needs long development time. The main purpose of the present study was to analyze the parameters controlling the CVD and CVI processes. Specifically, deposition and infiltration of SiC and Py-C tests were conducted on non-porous and porous substrates. The experiments were performed with a pilot size Isothermal/Isobaric CVI plant, designed and developed by ENEA. To guarantee the control of the process parameters, a previously optimization of the plant was needed. Changing temperature, pressure, flow rates and methane/hydrogen ratio, the Py-C deposition rate value, for an optimal fibre/matrix interphase thickness, was determined. It was also underlined the hydrogen inhibiting effect over the Py-C deposition rate. Regarding SiC morphologies, a difference between the inner and outer substrate surfaces was observed, as a consequence of a flow rate non-uniformity. In the case of the Cf/C composites development, the key parameter of the CVI process was the gas residence time. In fact, the hydrogen inhibiting effect was evident only with high value of residence time. Furthermore, lower the residence time more homogeneous the Py-C deposition rate was obtained along the reaction chamber axis. Finally, a CVD and CVI theoretical modelling was performed.

Giunzione mediante laser di materiali difficili, ibridi ed a struttura cellulare

Lo studio presentato in questa sede concerne applicazioni di saldatura LASER caratterizzate da aspetti di non-convenzionalità ed è costituito da tre filoni principali. Nel primo ambito di intervento è stata valutata la possibilità di effettuare saldature per fusione, con LASER ad emissione continua, su pannelli Aluminum Foam Sandwich e su tubi riempiti in schiuma di alluminio. Lo studio ha messo in evidenza numerose linee operative riguardanti le problematiche relative alla saldatura delle pelli esterne dei componenti ed ha dimostrato la fattibilità relativa ad un approccio di giunzione LASER integrato (saldatura seguita da un post trattamento termico) per la realizzazione della giunzione completa di particolari tubolari riempiti in schiuma con ripristino della struttura cellulare all’interfaccia di giunzione. Il secondo ambito di intervento è caratterizzato dall’applicazione di una sorgente LASER di bassissima potenza, operante in regime ad impulsi corti, nella saldatura di acciaio ad elevato contenuto di carbonio. Lo studio ha messo in evidenza come questo tipo di sorgente, solitamente applicata per lavorazioni di ablazione e marcatura, possa essere applicata anche alla saldatura di spessori sub-millimetrici. In questa fase è stato messo in evidenza il ruolo dei parametri di lavoro sulla conformazione del giunto ed è stata definita l’area di fattibilità del processo. Lo studio è stato completato investigando la possibilità di applicare un trattamento LASER dopo saldatura per addolcire le eventuali zone indurite. In merito all’ultimo ambito di intervento l’attività di studio si è focalizzata sull’utilizzo di sorgenti ad elevata densità di potenza (60 MW/cm^2) nella saldatura a profonda penetrazione di acciai da costruzione. L’attività sperimentale e di analisi dei risultati è stata condotta mediante tecniche di Design of Experiment per la valutazione del ruolo preciso di tutti i parametri di processo e numerose considerazioni relative alla formazione di cricche a caldo sono state suggerite.

Messa a punto e validazione di metodiche analitiche per la determinazione di micotossine in matrici biologiche mediante UPLC-MS/MS

La presenza di micotossine nelle materie prime desta grande preoccupazione a causa delle importanti implicazioni nella sicurezza di alimenti e mangimi. Lo scopo di questo lavoro è stato quello di mettere a punto e validare una metodica analitica rapida e semplice, in cromatografia liquida ad ultra prestazione accoppiata a spettrometria di massa-tandem (UPLC-MS/MS), per la determinazione simultanea di differenti micotossine: aflatossine (B1, B2, G1, G2), ocratossina A, fumonisine (B1, B2), deossinivalenolo e zearalenone in matrici biologiche. Il metodo sviluppato per l’analisi di campioni di mangime secco per cani ha mostrato prestazioni adeguate ed è stato applicato a 49 campioni reperibili in commercio, al fine di valutare la sua efficacia e di ottenere alcuni dati preliminari sulla contaminazione da micotossine in alimenti per cani disponibili sul mercato italiano. Lo studio ha evidenziato una percentuale alta di campioni positivi, contenenti principalmente fumonisine, deossinivalenolo e ocratossina A; tutti i tenori si sono dimostrati inferiori al limite di legge previsto (Racc. CE 576/2006). Una seconda metodica è stata messa a punto e validata per l’identificazione e la quantificazione micotossine in campioni di formaggio; per questa matrice è stata inserita anche l’aflatossina M1, specifica dei prodotti lattiero - caseari. Le differenti proprietà chimico-fisiche degli analiti e la complessità della matrice hanno implicato alcune difficoltà nello sviluppo della metodica. Tuttavia, il metodo validato si è mostrato rapido, semplice ed affidabile ed è stato applicato a diversi tipi di formaggi per verificarne la versatilità. I risultati preliminari hanno mostrato l’assenza di contaminazione da parte delle micotossine in oggetto. Entrambi i metodi si sono dimostrati utili per il monitoraggio di contaminanti in matrici complesse ad oggi ancora poco studiate.