This research aims to understand the reliability of Sn-Ag-Cu solder interconnects used in plastic ball grid array (PBGA) packages using microstructure evolution, laser moiré interferometry and finite-element modeling. A particle coarsening based microstructure evolution of the solder joint material during thermal excursions was studied for extended periods of time lasting for several months. The microstructure evolution and particle coarsening was quantified, and acceleration factors were determined between benign field-use conditions and accelerated thermal cycling (ATC) conditions for PBGA packages with different form factors and for two different lead-free solder alloys. A new technique using laser moiré interferometry was developed to assess the deformation behavior of Sn-Ag-Cu based solder joints during thermal excursions. This technique can used to estimate the fatigue life of solder joints quickly in a matter of few days instead of months and can be extended to cover a wide range of temperature regimes. Finite-element analysis (FEA) in conjunction with experimental data from the ATC for different lead-free PBGA packages was used to develop a fatigue life model that can be used to predict solder joint fatigue life for any PBGA package. The proposed model will be able to predict the mean number of cycles required for crack initiation and crack growth rate in a solder joint.

Automotive industry products portfolio includes a wide variety of complex‐shaped cast iron products, such as truck engine components, that need to withstand a constant trend of higher demands, especially urged by stricter environmental regulations on emissions. Combined with this continued demand on properties improvement, cast iron industry faces a process problem related to the lack of understanding of solidification and mechanisms behind defect formation. Casting products are highly affected by the product design and the manufacturing method itself, which governs the final microstructure and hence the final mechanical properties. Wall thickness of the moulding material strongly influences the solidification time, varying the microstructural coarseness, resulting in a component with different properties depending on the local shape of the casting. The main objective of this work is the characterization of the primary austenite microstructure and its coarsening process, which has been poorly documented in cast iron literature, to allow the prediction and control of these microstructural features present in the casting. The microstructural evolution of the primary austenite in hypoeutectic lamellar graphite iron (LGI) is studied under isothermal coarsening conditions. The dendritic microstructure suffered major morphological changes that included dendrite fragmentation, globularization, and coalescence. Empirical relations based on morphological parameters are introduced to predict the microstructural evolution of primary austenite. A novel technique for colour‐etching and semi‐automatic image analysis for the characterization of quenched dendritic microstructures in cast iron is presented. A new experimental technique for production of graphitic iron with varying nodularity is presented as a solution to control the production of compacted (CGI) and spheroidal graphite iron (SGI) under laboratory conditions. The nodularity evolution is controlled as a function of the holding time and the residual Mg, allowing the study of the primary solidification and primary microstructures of hypoeutectic CGI and SGI in future investigations.

The present thesis deals with synthesis of free alloy nanoparticles in immiscible alloy systems by the process of laser ablation under a liquid. In this process the alloy target is submerged in a liquid and the plume formed by the laser beam interaction with the target is confined in the liquid. The nanoparticles formed inside this plume and get quenched by the surrounding liquid yielding suspension of nanoparticles in the liquid. By the addition of suitable surfactants, these nanoparticles can be protected from other reactions and their size can be controlled by preventing further growth. We have selected immiscible alloys for the present study. These alloys tend to phase separate in melt as well as in solid depending on the value of the positive heat of mixing. We have used two binary alloys for the present study. These are alloys in Ag-Cu system and Fe-Cu system. In both these systems, there are reports of formation of extended solid solution due to kinetic factors during nonequilibrium processing like rapid solidification and mechanical alloying. In the present thesis we report synthesis of alloy nanoparticles of different compositions and sizes in these two systems and explore the nature of the phases that form in the small (nano) particles and their evolutionary pathways leading to the final microstructure. Microscopic techniques, especially transmission electron microscope, were used for characterization of these nanoparticles. The phase evolution was further studied using in situ microscopic techniques. After introducing the thesis in the Chapter 1, we describe briefly the relevant literatures in Chapter 2. The experimental details, in particular the experimental set up for laser ablation with targets under liquid are described in chapter 3. This chapter also includes the experimental details of the characterization. Transmission electron microscopy was used as primary characterization tool in the present study. The Chapter 4 presents the result of our study of alloy nanoparticles in Fe-Cu system. This system exhibits a submerged liquid miscibility gap. Although we have studied alloy targets of different compositions, the results of alloy nanoparticles obtained from targets with compositions Cu-40at.%Fe and Cu-60at.%Fe were primarily presented in this chapter. The nanoparticles that were synthesized had a size range of approximately 40nm to more than 100 nm. These particles have spherical morphology. The measurements of local compositions of different locations in the particle indicate the presence of a layer of Fe3O4 oxide at the spherical surface. This layer is devoid of copper. Most of the copper exist in the core of the particle. Fe rich spherical particles of much smaller size (~15 nm) are found to be embedded in the copper rich core. The copper formed solid solution with Fe and a copper concentration gradient exists in the particle below oxide layer due to oxidation of Fe. In contrast the nanoparticles obtained from alloy target with composition Fe-40at.% Cu have a spherical morphology. These have a composite structure with a Fe core in addition to Fe3O4 oxide layer at the surface. We have attempted to explain the phase evolution taking into account under cooling of the melt condensate that forms in the plume and their subsequent solidification through submerged miscibility gap. The chapters 5-7 deals with alloys of Ag-Cu system. In Chapter 5, we have carried out a detailed study of morphological evolution of the nanoparticles of Ag-Cu system. After optimizing the ablation parameters using pure Ag and Cu targets, we have synthesized alloy nanoparticles using different target compositions over the entire range of compositions with sizes having a mode of 25 nm. The evolution of the two phase structure is shown to be composition dependent with particles near equiatomic composition exhibit solid solution with uniformly distributed segregations of composition (Cu & Ag rich) while copper rich alloys exhibit a core shell structure with outer layer being Ag rich. The isothermal experiments again reveal emergence of core-shell morphology at intermediate time for particles with equiatomic composition. In order to compare the results of Ag-Cu nanoparticles with particles produced by other techniques we have synthesized Ag-Cu nanoparticles of near equiatomic composition by chemical route using nitrate salts and NaBH4 as reducing agent. PVP was used as capping agent. The results are presented in chapter 6. Depending on time of reaction, it is possible to synthesis free alloy particles from 2-3 nm to a network of chains. The nanoparticles contain Ag rich and Ag deficient region with Ag tends to segregate near surface. We have also presented mechanism for the formation of chain structure with prolonged reaction. The thermodynamic basis of phase formation in the immiscible system and evolution of phases under nonequilibrium situation have been discussed in chapter 7. This also includes a model to estimate size dependent surface energy. The analysis presented allows a discussion of possible pathways for phase evolution observed in the present work. The thesis ends with a final chapter that discussed the critical issues remains to be addressed and possible future work.

<p>    </p> <p>In this thesis, a thermodynamically consistent phase field formulation was developed to identify the physical origin of interfacial transitions that drive macroscopic phenomena, start- ing at the single-particle length scale and building up to the polycrystalline length scale. At the single-particle length scale, the framework identified two interfacial phases that are stable at the surface of Sn nanoparticles: 1) a disordered interfacial phase, i.e., the experimentally observed premelted surface layer; and 2) an ordered surficial phase displaying a remnant de- gree of order in fully melted particles. Regimes of melting behavior as a function of particle size and temperature are discussed. To bridge the gap between single-particle and densified polycrystals, an analytical model was developed to capture the physical driving forces for densification during electric field-assisted sintering. Here, the model acknowledges the struc- tural contributions of particle-particle interfaces to the strength of mechanical, electrical, and surficial driving forces for densification, and shows good agreement with experimental flash sintering data. Finally, the theory was applied to polycrystalline LiCoO₂ (LCO) and shows that the experimentally observed metal-insulator transition is driven by grain bound- ary lithium segregation, the interfacial misorientation, and the size of the abutting grains. A critical misorientation as a function of the macroscopic lithium content exists above which the grain boundaries undergo a metal-insulating transition, suggesting that the fabrication of textured LCO microstructures will delay the metal-insulator transition. </p>

Mechanical properties of structural materials are highly correlated to their microstructure. The relationship between microstructure and mechanical properties can be established experimentally. The growing need for structural materials in industry promotes the study of microstructural evolution of materials by design using computational approaches. This thesis presents the microstructural evolution of two different structural materials. The first uses a genetic algorithm approach to study the microstructural evolution of a high-temperature nickel-based oxide-dispersion-strengthened (ODS) alloy. The chosen Ni-20Cr ODS system has nano Y2O3 particles for dispersion strengthening and submicron Al2O3 for composite strengthening. Synergistic effects through the interaction of small dispersoids and large reinforcements improved high-temperature strength. Optimization considered different weight factors on low temperature strength, ductility, and high temperature strength. Simulation revealed optimal size and volume fraction of dispersoids and reinforced particles. Ni-20Cr-based alloys were developed via mechanical alloying for computational optimization and validation. The Ni-20Cr-1.2Y2O3-5Al2O3 alloy exhibited significant reduction in the minimum creep rate (on the order of 10-9 s-1) at 800oC and 100 MPa. The second considers the microstructural evolution of AA 7050 alloy during friction stir welding (FSW). Modeling the FSW process includes thermal, material flow, microstructural and strength modeling. Three-dimensional material flow and heat transfer model was developed for friction stir welding process of AA 7050 alloy to predict thermal histories and extent of deformation. Peak temperature decreases with the decrease in traverse speed at constant advance per revolution, while the increase in tool rotation rate enhances peak temperature. Shear strain is higher than the longitudinal and transverse strain for lower traverse speed and tool rotation rate; whereas for higher traverse speed and tool rotation rate, shear and normal strain acquire similar values. Precipitation distribution simulation using TC-PRISMA predicts the presence of η' and η in the as-received AA 7050-T7451 alloy and mostly η in the friction stir welded AA7050 alloy, which results in the lower predicted strength of friction stir welded alloy. Further, development of modeling assists in process optimization and innovation, and enhances the progression rate. Accelerating the development process requires coupling experimental methods with predictive modeling. The overall purpose of this work was to develop an integrated computational model with predictive capabilities. In the present work, an application tool to predict thermal histories during FSW of AA7050 was developed using COMSOL software.

Le besoin pressant de substitution du plomb dans les alliages de soudure a conduit à une introduction très rapide de nouveaux alliages sans plomb dont la connaissance en termes de comportement n'est pas assez approfondie. En effet, d'autres problématiques sont apparues (l'augmentation de la température du procédé de soudage, trop grand choix disponible dans les alliages alternatifs) alors que les problèmes relatifs aux alliages actuels sont restés sans réponse (le changement incessant de la microstructure des alliages de soudure, la méthodologie empirique prédisant la durée de vie). Tous les paramètres cités ci-dessus modifient la stabilité et la fiabilité des performances spécifiques de l'alliage de soudure et par conséquence, de tout le module électronique.De plus, avec la miniaturisation de l'électronique et les conditions d'environnement de plus en plus sévères, ces obstacles deviennent critiques et les solutions actuelles ne sont plus compatibles. Les demandes de ce marché deviennent donc de plus en plus strictes en termes de prédiction de durée de vie et de contrôle de fiabilité.L'objectif de ce projet est de comprendre et de concevoir une nouvelle formulation d'alliage sans plomb afin de développer une alternative à l'alliage plombé haute température et un alliage pour les applications haute fiabilité et en accord avec les directives gouvernementales. Des approches expérimentales avancées comme la nano-indentation, le suivi de l'évolution de la microstructure par SEM et par EDS mapping, l'étude des effets du vieillissement thermique sur la croissance de la taille des grains avec de la lumière croisée polarisée de microscopie optique etc seront utilisées pour développer un alliage sans plomb qui convienne aux exigences des applications automobile et pipeline / The urgent need for removing lead from solder alloys led to the very fast introduction of lead-free solder alloys without a deep knowledge of their behaviour. As a consequence, additional issues raised (increased thermally induced problems during soldering process, a too wide range of possible available alternative alloy formulations), while problems related to current solder alloys remained unsolved (the constant change of the solder alloy microstructure, empirical predicting lifetime methodology). All the above mentioned issues alter stability and reliability of the application specific performances of the solder alloy, and subsequently of the whole electronic module. These problems become critical and are no longer compatible, as the market goes towards miniaturization and harsh environment conditions. These market trends now require stricter life time prediction and reliability control. Objective of this project is to understand and design a novel lead-free solder formulation to develop a potential alternative to lead-based high temperature melting point solder for high reliability requirements and in accordance with governmental directives. An advanced experimental approach like nanoindentation, microstructure evolution with SEM and EDS mapping, thermal aging effects on continuous grain size growth with cross polarized light of optical microscopy etc. would be implemented to develop doped-SAC lead-free solders for the best-fit to requirements in automotives and pipelines applications

Die vorliegende Arbeit zeigt einen Weg, Kupfer und einphasige Kupferlegierungen mit stark verzwillingten Gefügen durch ein technisch relevantes Umformverfahren herzustellen. Der Drahtzug bildet dabei aufgrund seines Spannungszustands und der entsprechenden Texturentwicklung in kubischflächenzentrierten Metallen ein ideales Umformverfahren, um einen Großteil des Gefüges durch mechanische Zwillingsbildung zu verfeinern. Für die Aktivierung der Zwillingsbildung in reinem Kupfer unter den untersuchten Werkstoffvarianten sind Temperaturen nahe der Temperatur des flüssigen Stickstoffs notwendig. Um den Drahtzug in flüssigem Stickstoff umzusetzen, wurden verschiedene Feststoffschmiermittel auf ihre Eignung hin getestet. Die Textur der mit Stickstoffkühlung hergestellten Halbzeuge ist durch eine dreifache Fasertextur bestehend aus <111>-, <001>- und <115>-Fasertexturkomponente charakterisiert. Anhand der strengen Orientierungsverhältnisse konnte der Volumenanteil von verzwillingtem Material bestehend aus Matrixkörnern und Verformungszwillingen auf 71 vol% durch röntgenografische Globaltexturmessungen abgeschätzt werden, wobei das Volumenverhältnis von Zwillingen zu Matrix bei knapp 0,7:1 liegt. Die Zwillinge zeigen eine breite Zwillingslamellenweitenverteilung von wenigen Nanometern bis einige 100 nm im höchstverformten Stadium. Durch die Absenkung der Umformtemperatur und die daraus resultierende Aktivierung der Zwillingsbildung kann die Zugfestigkeit von reinem Kupfer um 140 MPa im Vergleich zu einem ohne Kühlung hergestellten Draht auf 582 MPa erhöht werden. Dabei reduziert sich die elektrische Leitfähigkeit um 6,5% gegenüber einem grobkorngeglühten Kupfer. Eine Absenkung der Stapelfehlerenergie auf 30 mJ/m² in CuAl2 führt zur Aktivierung der mechanischen Zwillingsbildung beim Drahtzug ohne Kühlung. Durch diese Aktivierung der Zwillingsbildung kann bei fortschreitender Verringerung der Stapelfehlerenergie wie in CuAl7 die Zugfestigkeit des umgeformten Drahtes auf weit über 1 GPa erhöht werden. Das entsprechende Gefüge ist dabei ultrafeinkörnig.

Sn-Pb solder has long been used in the Electronics industry. But, due to its toxic nature and environmental effects, certain restrictions are made on its use and therefore many researchers are looking to replace it. Sn-3.0Ag-0.5Cu (SAC) solders are suggested as lead-free replacements but their coarse microstructure and formation of hard and brittle Inter-Metallic Compounds (IMCs) like Ag₃Sn and Cu₆Sn₅ have limited their use in high temperature applications. In this research work, RE elements, mostly lanthanum (La), are used as potential additives to SAC alloys. They reduce the surface free energy, refine the grain size and improve the mechanical and wetting properties of SAC alloys. An extensive experimental work has been performed on the microstructure evolution, bulk mechanical properties, individual phase (matrix and IMCs) mechanical properties, creep behavior and wettability performance of the SAC and SAC-La alloys, with different (La) doping. SEM and EDS have been used to follow the continuous growth of the IMCs at 150°C and 200°C and thus provide a quantitative measure in terms of their size, spacing and volume fraction. Grain size is measured at regular intervals starting from 10 hours up to 200 hours of thermal aging using Optical Microscope with cross polarized light. Bulk mechanical properties are evaluated using tensile tests at low strain rates. Individual phase mechanical properties like Young's modulus, hardness, strain rate sensitivity index and bulge effects are characterized with nanoindentation from 100 µN up to 5000 µN loadings at different temperatures of 25°C, 45°C, 65°C and 85°C. Creep experiments are performed at elevated temperatures with good fitting of Dorn creep and back-stress creep models. Activation energy measurements are made at 40°C, 80°C and 120°C. Wettability testing on copper substrates is used for surface tension, wetting force and contact angle measurements of SAC and SAC-La doped alloys at 250°C and 260°C.

Title: Physical properties of ultrafine-grained magnesium based alloys prepared by various severe plastic deformation techniques Author: Jitka Stráská Department / Institute: Department of Physics of Materials Supervisor of the doctoral thesis: Doc. RNDr. Miloš Janeček, CSc. Abstract: The objective of the doctoral thesis is the complex investigation of ultrafine-grained magnesium alloy AZ31 prepared by two different severe plastic deformation techniques, in particular the hot extrusion followed by equal-channel angular pressing (EX-ECAP) and high pressure torsion (HPT). These severe plastic deformation methods, and as well as many others, are described in detail in the introductory theoretical section. Experimental results are summarized in the following experimental part of the thesis. Mechanical properties, lattice defect structure and especially microstructure were investigated using various experimental techniques. Thermal stability of ultrafine-grained microstructure of AZ31 after EX-ECAP was investigated and the activation energies for grain growth in different temperature ranges were calculated using kinetic equation for grain growth and Arrhenius equation. Results from the dislocation density measurements proved temperature ranges of the recovery and the following grain growth. Results from the...

Out of the known aerospace metal and alloys, Aluminium (Al) and Titanium (Ti) are important due to their unique combination of properties, such as strength, ductility and corrosion resistance etc. For these reasons, welding of these two materials, especially in the butt and lap configuration, has a significant impact for structural applications. However, welding of Al to Ti is a challenge due to wide differences in their physical properties and properties of the brittle intermetallic that are formed. Such problems in Ti-Al weld can be minimized if the temperature of welding is reduced. Therefore, many solid-state welding processes have been introduced for this system in the past few decades. Amongst these processes, Friction Stir Welding (FSW) is among the most appropriate for dissimilar materials in the butt and lap configuration, as this process involves lower temperature of processing. The present thesis is an attempt to address the issues pertaining to the friction stir welding of commercially pure Al and Ti. Though these commercially pure materials are seldom used in actual applications, where alloys such as Ti-6Al-4V and Al 2219 (and their variants) are used, this work is done to get a fundamental understanding of the underlying mechanisms during Friction Stir Welding (FSW). The study has been extended to the effect of using a thin strip of other metallic materials between Al and Ti. These inserts are likely to play a role in the formation of intermetallic and control the after effects of the formation of these intermetallic. Two metals have been chosen for this purpose, namely Zinc (Zn) and Niobium (Nb). The thesis has 8 chapters that attempts to systematically understand the process of FSW of cp-Al to cp-Ti. In Chapter 1 of the thesis, the FSW process is introduced with an emphasis on important parameters that control the welding process. In addition, a brief introduction of Al-Ti binary system is also given. Literature related to conventional solid state welding processes and friction stir welding process is presented in Chapter 2. In this chapter, previous works on the FSW of various materials is reviewed, with more emphasis on welding of aluminium to titanium. At the end of the chapter the scope and motivation of the present investigation has been outlined Chapter 3 includes the experimental details involved in the present study. In addition to the details of the processes and various characterization techniques used in the present investigation, the basic principles involved in various techniques, names as X-ray tomography, Scanning Electron Microscopy (SEM) with Electron Back-Scattered Diffraction (EBSD), X-Ray Diffraction (XRD) and Electron Probe Micro-Analysis (EPMA) have also been given. Micro-hardness and tensile tests results are also reported in this chapter. A detailed study on FSW of Al and Ti is presented in chapter 4 of the thesis. The effect of process parameters on the evolution of microstructure and mechanical properties has been reported. A bottom-up approach on experimentally determining the “process window” is presented. The results emphasises on the distribution of titanium fragments and intermetallic particles in the nugget zone and their influence on mechanical properties of the weld. The microstructural evolution in the matrix is also detailed. The most noteworthy observation is substantial grain refinement in the nugget zone due to the presence of fine fragments of titanium and intermetallic. Cross-tensile tests of the samples welded under the optimised conditions fail in the retreating side of the aluminium material and has strength more than the parent material. The last section in this chapter deals with thermal stability of the microstructures. Chapter 5 deals with the use of Zn as interlayer between Al and Ti. The microstructural evolution and its effect on the mechanical properties have been examined. The investigations clearly show that FSW of Al and Ti with Zn interlayer has superior mechanical properties compared to Al-Ti welds without interlayer. The resulting microstructure has a better thermal stability. The use of Nb as interlayer has been studied in chapter 6. The microstructural investigation of the nugget zone reveals that Nb interlayer does not readily form solid solution with any of the base materials and Nb gets distributed more heterogeneously compared to Ti itself. This has led to a reduction in the strength of the weld, however, the ductility increases The thermal stability of the microstructure is poor compared to FSW of Al to Ti with Zn interlayer. In chapter 7, salient features of the different micro-mechanism operating during FSW of the investigated combinations has been discussed in detail. Finally, the outcome of the thesis has been summarized and scope for future investigation is outlined in chapter 8.