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Grain growth competition during directional solidification of a polycrystal with hexagonal (hcp) symmetry (Mg-1wt%Gd alloy) is studied by phase-field modeling, exploring the effect of the temperature gradient G on the resulting grain boundary (GB) orientation selection. Results show that selection mechanisms and scaling laws derived for cubic (fcc, bcc) crystals also apply to hcp materials (within their basal plane), provided a re-estimation of fitting parameters and re-scaling to account for the sixfold symmetry. While grain growth competition remains stochastic with rare events of unexpected elimination or side-branching along the developing GBs, we also confirm an overall transition from a geometrical limit to a favorably oriented grain limit behavior with an increase of thermal gradient within the dendritic regime, and the progressive alignment of dendrites and GBs toward the temperature gradient direction with an increase of G during the dendritic-to-cellular morphological transition. Comparisons with original thin-sample directional solidification experiments show a qualitative agreement with PF results, yet with notable discrepancies, which nonetheless can be explained based on the stochastic variability of selected GB orientations, and the statistically limited experimental sample size. Overall, our results extend the understanding of GB formation and grain growth competition during solidification of hcp materials, and the effect of thermal conditions, nonetheless concluding on the challenges of extending the current studies to three dimensions, and the need for much broader (statistically significant) data sets of GB orientation selected under well-identified solidification conditions.

Slip transfer and blocking across grain boundaries was studied in a Ti foil with a strong rolling texture deformed in tension. Prior to deformation, the shape of the grains and the orientation of the grain boundaries were quantified through laboratory scale diffraction contrast tomography (LabDCT). Mechanical deformation led to the activation of prismatic slip, and slip transfer/blocking was assessed in > 300 grain boundaries by means of slip trace analysis and electron backscatter diffraction. A categorical model was employed to accurately assess slip transfer, and the "F1 score" of various slip transfer criteria proposed in the literature was evaluated for the first time from 3D grain boundary information. Remarkably, for the prismatic-dominated slip transfer in the current Ti sample, the results show that the best predictions of slip transfer/blocking are provided by the angle \k{appa}, which is directly related to the residual Burgers vector, and by the Luster-Morris parameter m'. In contrast, metrics based on the twist angle {\theta} and on the LRB criterion were not able to predict accurately slip transfer/blocking. Thus, the extensive analysis of the 3D grain boundary data and the novel application of LabDCT was able to help clarify the role of grain boundary orientation on the mechanisms of plastic deformation in polycrystals with strong prismatic-dominated slip.

The feasibility to manufacture scaffolds of poly-lactic acid reinforced with Zn particles by fused filament fabrication is demonstrated for the first time. Filaments of 2.85 mm in diameter of PLA reinforced with different weight fractions of $\mu$m-sized Zn - 1 wt. \% Mg alloy particles (in the range 3.5 to 17.5 wt. \%) were manufactured by a double extrusion in method in which standard extrusion is followed by a precision extrusion in a filament-maker machine. Filaments with constant diameter, negligible porosity and a homogeneous reinforcement distribution were obtained for Zn weight fractions of up to 10.5\%. It was found that the presence of Zn particles led to limited changes in the physico-chemical properties of the PLA that did not affect the window temperature for 3D printing nor the melt flow index. Thus, porous scaffolds could be manufactured by fused filament fabrication at 190\textdegree C with poly-lactic acid/Zn composites containing 3.5 and 7 wt. \% of Zn and at 170\textdegree C when the Zn content was 10.5 wt. \% with excellent dimensional accuracy and mechanical properties.

A phase-field model is developed to simulate the corrosion of Mg alloys in body fluids. The model incorporates both Mg dissolution and the transport of Mg ions in solution, naturally predicting the transition from activation-controlled to diffusion-controlled bio-corrosion. In addition to uniform corrosion, the presented framework captures pitting corrosion and accounts for the synergistic effect of aggressive environments and mechanical loading in accelerating corrosion kinetics. The model applies to arbitrary 2D and 3D geometries with no special treatment for the evolution of the corrosion front, which is described using a diffuse interface approach. Experiments are conducted to validate the model and a good agreement is attained against in vitro measurements on Mg wires. The potential of the model to capture mechano-chemical effects during corrosion is demonstrated in case studies considering Mg wires in tension and bioabsorbable coronary Mg stents subjected to mechanical loading. The proposed methodology can be used to assess the in vitro and in vivo service life of Mg-based biomedical devices and optimize the design taking into account the effect of mechanical deformation on the corrosion rate. The model has the potential to advocate further development of Mg alloys as a biodegradable implant material for biomedical applications.

The phase diagram of Al-Li-Cu system in the Al-rich region was determined by means of first-principles calculations and statistical mechanics. The mixing enthalpies of many configurations for different lattices in the whole Al-Li-Cu system were determined by density functional theory simulations to find the stable phases in the convex hull. They were fitted with a cluster expansion to calculate the free energy of the configurations with different compositions as a function of temperature in the Al-rich region (Al content > 40 at. %) by means of Monte Carlo simulations. It was found that the ground state phases in the Al-rich part of the Al-Li-Cu phase diagram were {\alpha}-Al, {\theta}' (Al2Cu), {\delta}' (Al3Li), {\delta} (AlLi) and T1 (Al6Cu4Li3), while {\theta}'' (Al3Cu), T1' (Al2CuLi) and Al3Cu2Li were found on the lowest mixing enthalpy surfaces of their lattices and were metastable. {\alpha}-Al, {\delta} and T1 are stable phases in the whole temperature range while {\delta}' becomes metastable at very low temperature and {\theta} (Al2Cu) replaces {\theta}' as the stable phase at approximately 550 K due to the vibrational entropic contribution. In addition, the phase diagram in the Al-rich region was built and it was shown in isothermal sections from 100 K to 900 K. They were in good agreement with the limited experimental data in the literature and provided new information regarding the stability, solubility and stoichiometry of the different phases. This information is important to understand the precipitation mechanisms during high temperature aging.

A generalized line tension model has been developed to estimate the critical resolved shear stress in precipitation hardened alloys. The model is based in previous line tension models for regular arrays of either impenetrable or shearable spherical precipitates that were expanded to take into account the effect of the elastic mismatch between the matrix and the precipitates. The model parameters are calibrated from dislocation dynamics simulations that covered a wide range of precipitate diameters and spacing as well as of the mismatch in elastic constants. This model is extended to deal with random arrays of monodisperse spherical precipitates by changing the geometrical parameters of the model by the averaged ones corresponding to the random distributions. The model predictions were in good agreement with the critical resolved shear stresses obtained from dislocation dynamics simulations of random spherical precipitates distributions for both impenetrable and shearable precipitates, providing a fast and accurate tool to predict precipitate strengthening in metallic alloys.

This work provides unambiguous evidence for the occurrence of icosahedral quasicrystal (iQC) enhanced nucleation during selective laser melting of gas atomized commercially-pure Ni powders. This solidification mechanism, which has only been recently reported in a few alloys and has to date never been observed in pure metals, consists on the solidification of grains of the primary phase on the facets of iQCs formed due to the presence of icosahedral short range order in the liquid. The occurrence of iQC enhanced nucleation has been inferred from the observation in the SLM processed pure Ni samples of an excess fraction of partially incoherent twin boundaries and of clusters of twinned grain pairs sharing common <110> five-fold symmetry axes. This work further evidences that additive manufacturing methods may constitute an invaluable tool for investigating the fundamentals of solidification and for the design of unprecedented grain boundary networks.

Slip transfer at grain boundaries and annealing twin boundaries was studied in polycrystalline Ni by means of slip trace analysis. Slip transfer or blocking was assessed in $>$ 200 boundaries and was related with geometrical criteria that establish the alignment between the active slip systems across the boundaries. It was found that slip transfer mainly occurs at low-angle regular grain boundaries and that a Luster-Morris parameter $>$ 0.8 stands for the best criterion to assess slip transfer. In the case of coherent or incoherent twin boundaries, slip transfer occurs when the residual Burgers vector is close to zero through dislocation cross-slip.

The effect of slip transfer on the flow strength of various FCC polycrystals was analyzed by means of computational homogenization of a representative volume element of the microstructure. The crystal behavior was governed by a physically-based crystal plasticity model in the framework of finite strains where slip transfer at grain boundaries was allowed between slip systems suitably oriented according to geometrical criteria. Conversely, slip transfer was blocked if the conditions for slip transfer were not fulfilled, leading to the formation of dislocation pile-ups. All the model parameters for each material were identified from either dislocation dynamics simulations or experimental data from the literature. Slip transfer led to a reduction in the flow stress of the polycrystals (as compared with the simulations with opaque grain boundaries) which was dependent on the fraction of translucent and transparent grain boundaries in the microstructure. Moreover, dislocation densities and Von Mises stresses were much higher around opaque grain boundaries, which become suitable places for damage nucleation. Finally, predictions of the Hall-Petch effect in Al, Ni, Cu and Ag polycrystals including slip transfer were in better agreement with the literature results, as compared with predictions assuming that all grain boundaries are opaque, particularly for small grain sizes ($<$ 20 $\mu$m).

The phase diagram of the Al-Li system was determined by means of first principles calculations in combination with the cluster expansion formalism and statistical mechanics. The ground state phases were determined from first principles calculations of fcc and bcc configurations in the whole compositional range while the phase transitions as a function of temperature were ascertained from the thermodynamic grand potential and the Gibbs free energies of the phases. Overall, the calculated phase diagram was in good agreement with the currently accepted experimental phase diagram but the simulations provided new insights that are important to optimize microstructure of these alloys by means of heat treatments. In particular, the structure of the potential GP zones, made up of Al0.5Li0.5 (001) monolayers embedded in Al matrix, was identified. It was found that Al3Li is a stable phase although the energy barrier for the transformation of Al3Li into AlLi is very small (a few meV) and can be overcome by thermal vibrations. Moreover, bcc AlLi was found to be formed by martensitic transformation of fcc configurations and Al3Li precipitates stand for favorable sites for the nucleation of AlLi because they contain the basic blocks of such fcc ordering. Finally, polynomial expressions of the Gibbs free energies of the different phases as a function of temperature and composition were given, so they can be used in mesoscale simulations of precipitation in Al-Li alloys.

Entering a new era of sustainable energy generation and consumption, new solutions for powering consumer electronics are required to tackle the limited capacity provided by the portable power sources employed nowadays. Hydrocarbon-fed micro-fuel cells represent a promising technology for this purpose, and micro-reactor technology can indeed enable their integration for portable applications. In this work, we present the design and fully scalable wafer-level fabrication of a MEMS-based catalytic micro-reactor, paving the way towards on-board hydrogen production for portable power generators. The device consists of an array of thousands of vertically-aligned micro-channels, 500 um in length and 50 um in diameter, for an overall superficial area per unit volume of 120 cm2 cm-3 and it embeds a thin-film heater for efficient reaction start-up. Functionalization of the active area was achieved by atomic layer deposition, resulting in the uniform coating of a Pt/Al2O3 heterogeneous catalyst. The temperature-dependent dimethyl ether (DME)-to-syngas conversion is tested through steam reforming (SR) and partial oxidation (POX) reactions. Here, conversion rates up to 74% and hydrogen selectivity of 60% are obtained by steam reforming at 650dC, while a specific volumetric hydrogen production of 4.5 mLH2 mL-1DME cm-3REACTOR at 600dC is obtained from DME POX in a standalone device tested by means of a 3D printed ceramic housing.

This work reports the design, manufacturing and catalytic activity characterization of a micro-reformer for hydrogen-rich gas generation integrated in portable-solid oxide fuel cells (u-SOFCs). The reformer has been designed as a silicon micro monolithic substrate compatible with the mainstream microelectronics fabrication technologies ensuring a cost-effective high reproducibility and reliability. Design and geometry of the system have been optimized comparing with the previous design, consisting in an array of more than 7x103 vertical through-silicon micro channels perfectly aligned (50 {um diameter) and a 5 W integrated serpentine heater consisting of three stacked metallic layers (TiW, W and Au) for perfect adhesion and passivation. Traditional fuels for SOFCs, such as ethanol or methanol, have been replaced by dimethyl ether (DME) and the chosen catalyst for DME conversion consists of Pd nanoparticles grafted on an alumina active support. The micro-channels have been coated by atomic layer deposition (ALD) with amorphous Al2O3 and the influence of rapid thermal processing (RTP) on such film has been studied. A customized ceramic 3D-printed holder has been designed to measure the specific hydrogen production rates, DME conversion and selectivity profiles of such catalyst at different temperatures.

Selective laser melting (SLM) is rapidly evolving to become a mainstream technology. However, the fundamental mechanisms of solidification and microstructure development inherent to the non-equilibrium conditions of this additive manufacturing method, which differ largely from those typical of conventional processing techniques, remain widely unknown. In this work, an in-depth characterization of the microstructure of Al7075 SLM processed samples, built from powder mixtures containing ZrH2 microparticles, demonstrates the occurrence of icosahedral quasicrystal-enhanced nucleation during laser fabrication. This solidification mechanism, only observed to date in cast Al-Zn and yellow gold alloys containing minute additions of Cr (Kurtuldu et al., 2013) or Ti (Chen et al. 2018), and Ir (Kurtuldu et al., 2014), is evidenced by the presence of an abnormally high fraction of twin boundaries and of five-fold orientation symmetry between twinned nearest neighbors lying within a matrix of equiaxed, randomly textured, ultrafine grains. This research attests to the wide range of possibilities offered by additive manufacturing methods for the investigation of novel physical metallurgy phenomena as well as for the design of advanced metals.

We briefly review the state-of-the-art in phase-field modeling of microstructure evolution. The focus is placed on recent applications of phase-field simulations of solid-state microstructure evolution and solidification that have been compared and/or validated with experiments. They show the potential of phase-field modeling to make quantitative predictions of the link between processing and microstructure. Finally, some current challenges in extending the application of phase-field models within the context of integrated computational materials engineering are mentioned.

The influence of Zr additions (in the form of ZrH2 particles) on the microstructure and mechanical properties of IN718 Ni-based superalloy manufactured by selective laser melting was explored. Fully dense alloys could be obtained by careful selection of the processing parameters. The addition of ZrH2 did not modify the microstructure of the alloy but introduced a dispersion of Zr-rich globular particles of approximately 50 nm in diameter which increased the strength of the as-printed material at ambient (23C) and high temperature (550C). Heat treatments of solubilisation followed by aging led to a fine dispersion of gamma" precipitates that controlled the strength of the alloy, which was independent of the addition of Zr. Moreover, dynamic strain ageing was found in the heat treated materials when deformed at 550C. Finally, the strength of the IN718 deformed perpendicular to the building direction was higher than that along the building direction, regardless of the heat treatment and temperature. Computational homogenization simulations showed that the anisotropy was associated with the strong texture.

The critical resolved shear stress of an Al 4 wt. \% Cu alloy containing a homogeneous distribution of $\theta''$ precipitates was determined by means of dislocation dynamics simulations. The size distribution, shape, orientation and volume fraction of the precipitates in the alloy were obtained from transmission electron microscopy observations while the parameters controlling the dislocation/precipitate interactions (elastic mismatch, transformation strains, dislocation mobility and cross-slip probability, etc.) were calculated from atomistic simulations. The precipitates were assumed to be either impenetrable or shearable by the dislocations, the latter characterized by a threshold shear stress that has to be overcome to shear the precipitate. The predictions of the simulations in terms of the critical resolved shear stress and of the dislocation/precipitate interaction mechanisms were in good agreement with the experimental results. It was concluded that the optimum strength of this alloy is attained with a homogeneous distribution of $\theta''$ precipitates whose average size ($\approx$ 40 nm) is at the transition between precipitate shearing and looping. Overall, the dislocation dynamics strategy presented in this paper is able to provide quantitative predictions of precipitate strengthening in metallic alloys.

In this article, we combine casting experiments and quantitative simulations to present a novel multiscale modeling approach to predict local primary dendritic spacings in metallic alloys solidified in conditions relevant to industrial casting processes. To this end, primary dendritic spacings were measured in instrumented casting experiments in Al-Cu alloys containing 1\,wt\% and 4\,wt\% of Cu, and they were compared to spacing stability ranges and average spacings in dendritic arrays simulated using phase-field (PF) and dendritic needle network (DNN) models. It is first shown that PF and DNN lead to similar results for the Al-1\,wt\%Cu alloy, using a dendrite tip selection constant calculated with PF in the DNN simulations. PF simulations cannot achieve quantitative predictions for the Al-4\,wt\%Cu alloy because they are too computationally demanding due to the large separation of scale between tip radius and diffusion length, a characteristic feature of non-dilute alloys. Nevertheless, the results of DNN simulations for non-dilute Al-Cu alloys are in overall good agreement with our experimental results as well as with those of an extensive literature review. Simulations consistently suggest a widening of the PDAS stability range with a decrease of the temperature gradient as the microstructure goes from cellular-dendrites to well-developed hierarchical dendrites.

Open-porous scaffolds of WE43 Mg alloy with a body-center cubic cell pattern were manufactured by laser powder bed fusion with different strut diameters. The geometry of the unit cells was adequately reproduced during additive manufacturing and the porosity within the struts was minimized. The microstructure of the scaffolds was modified by means of thermal solution and ageing heat treatments and was analysed in detail by means of X-ray microtomography, optical, scanning and transmission electron microscopy. Moreover, the corrosion rates and the mechanical properties of the scaffolds were measured as a function of the strut diameter and metallurgical condition. The microstructure of the as-printed scaffolds contained a mixture of Y-rich oxide particles and Rare Earth-rich intermetallic precipitates. The latter could be modified by heat treatments. The lowest corrosion rates of 2-3 mm/year were found in the as-printed and solution treated scaffolds and they could be reduced to ~0.1 mm/year by surface treatments using plasma electrolytic oxidation. The mechanical properties of the scaffolds improved with the strut diameter: the yield strength increased from 8 to 40 MPa and the elastic modulus improved from 0.2 to 0.8 GPa when the strut diameter increased from 275 \mu m to 800 \mu m. Nevertheless, the strength of the scaffolds without plasma electrolytic oxidation treatment decreased rapidly when immersed in simulated body fluid. In vitro biocompatibility tests showed surface treatments by plasma electrolytic oxidation were necessary to ensure cell proliferation in scaffolds with high surface-to-volume ratio.

Precipitation in Mg-Zn alloys was analyzed by means of first principles calculations. Formation energies of symmetrically distinct hcp Mg1-xZnx (0 < x < 1) configurations were determined and potential candidates for Guinier-Preston zones coherent with the matrix were identified from the convex hull. The most likely structures were ranked depending on the interface energy along the basal plane. In addition, the formation energy and vibrational entropic contributions of several phases reported experimentally (Mg4Zn7, MgZn2 cubic, MgZn2 hexagonal, Mg21Zn25 and Mg2Zn11) were calculated. The formation energies of Mg4Zn7, MgZn2 cubic, and MgZn2 hexagonal Laves phases were very close because they were formed by different arrangements of rhombohedral and hexagonal lattice units. It was concluded that \beta_1^' precipitates were formed by a mixture of all of them. Nevertheless, the differences in the geometrical arrangements led to variations in the entropic energy contributions which determined the high temperature stability. It was found that the MgZn2 hexagonal Laves phase is the most stable phase at high temperature and, thus, \beta_1^' precipitates tend to transform into the \beta_2^' (MgZn2 hexagonal) precipitates with higher aging temperature or longer aging times. Finally, the equilibrium \beta phase (Mg21Zn25) was found to be a long-range order that precipitates the last one on account of the kinetic processes necessary to trigger the transformation from a short-range order phase \beta_2^' to \beta .

The mechanical properties of Cu/Nb metallic nanolaminates with different layer thickness (7, 16, 34 and 63 nm) were studied by means of micropillar compression tests from room temperature to 400 C. Both strain-rate jump and constant strain rate tests were carried out and they showed evidence of dynamic strain ageing in the nanolaminates with 7, 16 and 34 nm layer thickness deformed at 200 C. Dynamic strain ageing was accompanied by a reduction of the strain rate sensitivity to 0, high strength retention at 200 C and the development of shear localization of the deformation at low strains (5%-6%) that took place along the Nb layers in the nanolaminates. Atom probe tomography of the deformed specimens revealed the presence of O in solid solution in the Nb layers but not in the Cu layers. Thus, diffusion of O atoms to the mobile dislocations in Nb was found to be the origin of the dynamic strain ageing in the Cu/Nb nanolaminates around 200 C. This mechanism was not found at higher temperatures (400 C) because deformation was mainly controlled by stress-assisted diffusion in the Cu layers. This discovery shows a novel strategy to enhance the strength retention at high temperature of metallic nanolaminates through dynamic strain ageing of one the phases.

The fracture toughness of Al/SiC nanolaminates with different layer thicknesses (in the range 10 to 100 nm) was measured by means of micropillar splitting and bending of a notched beam. The crack plane was perpendicular to the layers in the former while notched beams with the notch parallel and perpendicular to the layers were milled in the latter. It was found that crack propagation parallel to the layers took place along the metal-ceramic interfaces and the toughness increased with the layer thickness due to the contribution of the plastic deformation of the Al layers. Crack propagation perpendicular to the layers showed evidence of crack deflection/arrest at the interface. The toughness in this orientation increased as the layer thickness decreased due to the higher density of interfaces except for the nanolaminates with 10 nm layer thickness. In the latter case, crack propagation took place along the weak columnar grain boundaries, leading to a marked reduction in toughness.

Room and high temperature mechanical properties of reactive magnetron sputtered TaSiN coatings were measured using nanoindentation (between 25C and 500C). Fracture toughness was also evaluated at a similar temperature range using the micropillar splitting method. The influence of the nitrogen concentration on the evolving phases and microstructure of the TaSiN coatings, before and after the high temperature testing, were examined by X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis. XRD spectra showed broad peaks with hexagonal $\gamma$-Ta2N as the main phase, with the cubic $\delta$-TaN phase emerging for higher N contents. Phase composition remained unchanged before and after the 500C tests. However, after the high temperature tests, TEM analysis showed the presence of an oxide surface layer, with a thickness that decreased (from 42 to 15 nm) with N content, due to residual oxygen diffusion, which replaces nitrogen to form amorphous SiOx. Beneath the oxide-rich surface layer, coatings exhibited a stable nanocrystalline columnar microstructure. Hardness and fracture toughness increased with N content, initially due to the formation of an amorphous Si-N tissue at grain boundaries, and for even higher N contents, due to the appearance of the hard cubic $\delta$-TaN phase. Hardness at 500C decreased only by 15%, while fracture toughness followed the opposite trend, due to increased plasticity with temperature. The optimum composition turned out to be Ta55Si10N35, which retained a hardness of 30 GPa at 500C, being also the toughest. These observations make this system very interesting for high temperature applications.

The influence of different types of precipitates (either Guinier-Preston zones, $\theta''$ or $\theta'$) on the critical resolved shear stress and strain hardening was determined by means of micropillar compression tests in an Al - 4 wt. \% Cu alloy. The size, shape and volume fraction of the precipitates were measured in each case. It was found that size effects were negligible for micropillars with diameter $\ge$ 5 $\mu$m. Micropillars with Guinier-Preston zones showed strain localization due to precipitate shearing. The best mechanical properties were obtained with either a fine dispersion of the $\theta''$ precipitates or a coarser dispersion of $\theta'$. Both precipitate shearing and Orowan loops were observed around the $\theta''$ precipitates and the micropillar strength was compatible with the predictions of the Orowan model. In the case of the alloy with $\theta'$ precipitates, the strengthening contribution associated with the transformation strain around the precipitates has to be included in the model to explain the experimental results. Finally, the micropillar compression tests in crystals with different orientations were used to calibrate a phenomenological crystal plasticity. This information was used to predict the mechanical properties of polycrystals by means of computational homogeneization.

The interaction between Mg edge basal dislocations and rod-shaped $\beta_1'$-MgZn$_2$ precipitates was studied by atomistic simulations using a new interatomic potential. The atomistic model was carefully built taking into account the experimental information about the orientation relationship between the matrix and the precipitate to ensure minimum energy interfaces. It was found that the dislocations initially overcame the precipitate by the formation of an Orowan loop that penetrated in the precipitate. The precipitate was finally sheared after several Orowan loops were piled-up. The number of loops necessary to shear the precipitate decreased as precipitate cross-section decreased and the temperature increased but was independent of the precipitate spacing. Precipitate shearing did not take place along well-defined crystallographic planes but it was triggered by the accumulation of the elastic energy in the precipitate which finally led to formation of an amorphous layer below and above the slip plane of the basal dislocations. The kink induced in the precipitate by this mechanism was in good agreement with transmission electron microscopy observations.

The thermodynamic properties of {\alpha}-Al and other phases (GP zones, {\theta}'', {\theta}' and {\theta}) in the Al-rich part of the Al-Cu system have been obtained by means of the cluster expansion formalism in combination with statistical mechanics. This information was used to build the Al-rich part of the Al-Cu phase-diagram taking into account vibrational entropic contributions for {\theta}', as those of the other phases were negligible. The simulation predictions of the phase boundaries between {\alpha}-Al and either {\theta}'', {\theta}' or {\theta} phases as a function of temperature are in good agreement with experimental data and extend the phase boundaries to a wider temperature range. The DFT calculations reveal the presence of a number of metastable Guinier-Preston-zone type configurations that may coexist with {\alpha}-Al and {\theta}'' at low temperatures. They also demonstrate that {\theta}' is the stable phase below 550K but it is replaced by {\theta} above this temperature due to the vibrational entropic contribution to the Gibbs energy of {\theta}'. This work shows how the combination of cluster expansion and statistical mechanics can be used to expand our knowledge of the phase diagram of metallic alloys and to provide Gibbs free energies of different phases that can be used as input in mesoscale simulations of precipitation.

The mechanisms of dislocation/precipitate interactions were analyzed in an Al-Cu alloy containing a homogeneous dispersion of $\theta'$ precipitates by means of discrete dislocation dynamics simulations. The simulations were carried out within the framework of the discrete-continuous method and the precipitates were assumed to be impenetrable by dislocations. The main parameters that determine the dislocation/precipitate interactions (elastic mismatch, stress-free transformation strains, dislocation mobility and cross-slip rate) were obtained from atomistic simulations, while the size, shape, spatial distribution and volume fraction of the precipitates were obtained from transmission electron microscopy. The predictions of the critical resolved shear stress (including the contribution of solid solution) were in agreement with the experimental results obtained by means of compression tests in micropillars of the Al-Cu alloy oriented for single slip. The simulations revealed that the most important contribution to the precipitation hardening of the alloy was provided by the stress-free transformation strains followed by the solution hardening and the Orowan mechanism due to the bow-out of the dislocations around the precipitates.

The mechanisms of dislocation/precipitate interaction as well as the critical resolved shear stress were determined as a function of temperature in a Mg-4 wt. % Zn alloy by means of micropillar compression tests. It was found that the mechanical properties were independent of the micropillar size when the cross-section was $>$ 3 x 3 $\mu$m$^2$. Transmission electron microscopy showed that deformation involved a mixture of dislocation bowing around the precipitates and precipitate shearing. The initial yield strength was compatible with the predictions of the Orowan model for dislocation bowing around the precipitates. Nevertheless, precipitate shearing was dominant afterwards, leading to the formation of slip bands in which the rod precipitates were transformed into globular particles, limiting the strain hardening. The importance of precipitate shearing increased with temperature and was responsible for the reduction in the mechanical properties of the alloy from 23C to 100C.

The slip transfer phenomenon was studied at the grain boundaries of pure Aluminum by means of slip trace analysis. Either slip transfer or blocked slip was analyzed in more than 250 grain boundaries and the likelihood of slip transfer between two slip systems across the boundary was assessed. The experimental results indicate that slip transfer was very likely to occur if the residual Burgers vector, $\Delta$b, was below 0.35b and the Luster- Morris parameter was higher than 0.9, and that the ratio of the Luster-Morris parameter and the residual Burgers vector has a threshold above which slip transfer is probable.

The mechanical behavior of closed-cell foams in compression is analyzed by means of the finite element simulation of a representative volume element of the microstructure. The digital model of the foam includes the most relevant details of the microstructure (relative density, cell size distribution and shape, fraction of mass in the struts and cell walls and strut shape), while the numerical simulation takes into account the influence of the gas pressure in the cells and of the contact between cell walls and struts during crushing. The model was validated by comparison with experimental results on isotropic and anisotropic polyurethane foams and it was able to reproduce accurately the initial stiffness, the plateau stress and the hardening region until full densification in isotropic and anisotropic foams. Moreover, it also provided good estimations of the energy dissipated and of the elastic energy stored in the foam as a function of the applied strain. Based on the simulation results, a simple analytical model was proposed to predict the mechanical behavior of closed-cell foams taking into the effect of the microstructure and of the gas pressure. An example of application of the simulation tool is presented to design foams with an optimum microstructure from the viewpoint of energy absorption for packaging.

The influence of the stress state on the cross-slip rate in Al was analyzed by means of molecular dynamics simulations and transition state theory. The activation energy barrier in the absence of thermal energy was determined through the nudged elastic band method while the cross-slip rates were determined using molecular dynamics simulations for different magnitudes of the Schmid stress on the cross-slip plane, and of the Escaig stresses on the cross-slip and glide planes. The enthalpy barrier and the effective attempt frequency were determined from the average rates of cross-slip obtained from the molecular dynamics simulations. It was found that the different stress states influence the cross-slip rate assuming harmonic transition state theory. Moreover, the theoretical contributions to the enthalpy barrier (configurational and due to the interaction of the applied stress with the local stress field created by the defect) were identified from the atomistic simulations while the entropic contribution to the activation energy could be estimated by the Meyer-Neldel rule. Based on these results, an analytical expression of the activation enthalpy for cross-slip in Al as a function of the different combinations of Schmid and Escaig stress states was developed and validated. This expression can be easily used in dislocation dynamics simulations to evaluate the probability of cross-slip of screw dislocation segments.

The influence of grain size on the flow stress of various FCC polycrystals (Cu, Al, Ag and Ni) has been analyzed by means of computational homogenization of a representative volume element of the microstructure using a FFT approach in combination with a strain gradient crystal plasticity model. The density of geometrically necessary dislocations resulting from the incompatibility of plastic deformation among different crystals was obtained from the Nye tensor, which was efficiently obtained from the curl operation in the Fourier space. The simulation results were in good agreement with the experimental data for Cu, Al, Ag and Ni polycrystals for grain sizes > 20 microns and strains < 5% and provided a physical explanation for the higher strengthening provided by grain boundaries in Al and Ni, as compared with Cu and Ag. The investigation demonstrates how the combination of FFT with strain gradient crystal plasticity can be used to include effect of grain boundaries in the mechanical behavior of polycrystals using realistic representative volume elements of the microstructure.

The effect of slip transfer on the deformation mechanisms of Al bicrystals was explored using a rate-dependent dislocation-based crystal plasticity model. Three different types of grain boundaries (GBs) were included in the model by modifying the rate of dislocation accumulation near the GB in the Kocks-Mecking law, leading to fully-opaque (dislocation blocking), fully-transparent and partially-transparent GBs. In the latter, slip transmission is only allowed in pairs of SS in neighbour grains that are suitably oriented for slip transfer according to the Luster-Morris parameter. Modifications of the GB character led to important changes in the deformation mechanisms at the GB. In general, bicrystals with fully-opaque boundaries showed an increase in the dislocation density near the GB, which was associated with an increase in the Von Mises stress. In contrast, the dislocation pile-ups and the stress concentration were less pronounced in the case of partially-transparent boundaries as the slip in one grain can progress into the next grain with some degree of continuity. No stress concentrations were found at these boundaries for fully-transparent boundaries, and there was continuity of strain across the boundary, which is not typical of most experimentally observed GBs. Simulations of ideal bicrystals oriented for favorable slip transfer on the most highly favored slip system in grains with high Schmid factors for slip transfer depends on the number of active SS in operation in the neighborhood and that most boundaries will lead to nearly opaque conditions while some boundaries will be transparent. Finally, the model was applied to a particular experimentally observed GB in which slip transfer was clearly operating indicating that the model predicted a nearly transparent GB.

Taper-free InP twinning superlattice (TSL) nanowires with an average twin spacing of ~ 13 nm were grown along the zinc-blende close-packed [111] direction using metalorganic vapor phase epitaxy. The mechanical properties and fracture mechanisms of individual InP TSL nanowires in tension were ascertained by means of in situ uniaxial tensile tests in a transmission electron microscope. The elastic modulus, failure strain and tensile strength along the [111] direction were determined. No evidence of inelastic deformation mechanisms was found before fracture, which took place in a brittle manner along the twin boundary. The experimental results were supported by molecular dynamics simulations of the tensile deformation of the nanowires that also showed that the fracture of twinned nanowires occurred in the absence of inelastic deformation mechanisms by the propagation of a crack from the nanowire surface along the twin boundary.

A scale bridging strategy based in molecular statics and molecular dynamics simulations in combination with transition state theory has been developed to determine the flow stress of Al-Cu alloy containing Guinier-Preston zones. The athermal contribution to the flow stress was determined from the Taylor model, while the thermal contribution was obtained from the obstacle strength and the free energy barrier. These two magnitudes were obtained by means of molecular statics and molecular dynamics simulations of the interaction of edge dislocations with Guinier-Preston zones in two different orientations. The predictions of the model were compared with experimental data and were in reasonable agreement, showing the potential of atomistic simulations in combination with transition state theory to predict the flow stress of metallic alloys strengthened with precipitates.

The influence of solute atoms (Al and Zn) on the deformation mechanisms and the critical resolved shear stress for basal slip in Mg alloys at 298 K and 373 K was ascertained by micropillar compression tests in combination with high-throughput processing techniques based on the diffusion couples. It was found that the presence of solute atoms enhances the size effect at 298 K as well as the localization of deformation in slip bands, which is associated with large strain bursts in the resolved shear stress ($\tau_{RSS}$)-strain ($\epsilon$) curves. Deformation in pure Mg and Mg alloys was more homogeneous at 373 K and the influence of the micropillar size on the critical resolved shear stress was much smaller. In this latter case, it was possible to determine the effect of solute content on the critical resolved shear stress for basal slip in Mg-Al and Mg-Zn alloys.

Slip transfer across grain boundaries was studied in annealed polycrystalline Al foils deformed in uniaxial tension by means of the analysis of the slip traces on the specimen surface. Grain orientations and selected grain boundary misorientations were measured on both surfaces of the sample using electron back-scattered diffraction mapping. It was found that most of the grains were within 15{\deg} of a cube orientation and approximately half of the grains percolated through the specimen thickness. The Luster-Morris m' parameter (that can be computed from the surface grain orientation) was used to assess the likelihood of slip transfer across boundaries. It was found that transfer across grain boundaries was rare in near-cube oriented grains, and convincing evidence was only found when m' > 0.97, which corresponds to low-angle boundaries with <15{\deg} misorientation. This behavior was explained by the presence of many active slip slips in near-cube oriented grains that favor self-accommodation of the grain shape to the evolving boundary conditions imposed by neighboring grains instead of promoting slip transfer across the boundary. These results indicate that the alignment between slip planes and slip directions across the boundary is not the only important metric to determine the threshold for slip transfer, as the particular details of deformation in each grain (such as the number of available slip systems) also must be considered.

The effect of grain size on the flow strength of FCC polycrystals was analyzed by means of computational homogenization. The mechanical behavior of each grain was dictated by a dislocation-based crystal plasticity model in the context of finite strain plasticity and takes into the account the formation of pile-ups at grain boundaries. All the model parameters have a clear physical meaning and were identified for different FCC metals from dislocation dynamics simulations or experiments. It was found that the influence of the grain size on the flow strength of FCC polycrystals was mainly dictated by the similitude coefficient $K$ that establishes the relationship between the dislocation mean free path and the dislocation density in the bulk. Finally, the modelling approach was validated by comparison with experimental results of the effect of grain size on the flow strength of Ni, Al, Cu and Ag.

Precipitation during high temperature aging of Al-Cu alloys is analyzed by means of the integration of classical nucleation theory and phase-field simulations into a multiscale modelling approach based on well-established thermodynamics principles. In particular, thermal stability of ${\theta}''$, ${\theta}'$ and ${\theta}$ precipitates was assessed from first principles calculations of the Helmholtz free energy while homogeneous and heterogeneous nucleation of ${\theta}''$ and ${\theta}'$ was analysed using classical nucleation theory. Precipitate growth was finally computed by means of mesoscopic phase-field model. The model parameters that determine quantitatively the driving forces for each transformation were obtained by means of first principles calculations and computational thermodynamics. The predictions of the models were in good agreement with experimental results and provided a comprehensive understanding of the precipitation pathway in Al-Cu alloys. It is envisaged that the strategy presented in this investigation can be used in the future to design optimum microstructures based on the information of the different energy contributions obtained from first principles calculations.

The mechanisms of deformation and failure of Cu/Nb nanolaminates manufactured by accumulated roll bonding were analysed using in-situ TEM mechanical tests. Dog-bone small-scale tensile specimens were prepared using a FIB-based technique with the layers parallel and perpendicular to the loading axis. Load, deformation and TEM micrographs were recorded during the in-situ TEM mechanical tests. The specimens deformed parallel to the layers presented very high strain hardening and ductility while those deformed in the perpendicular orientation were more brittle. These results were rationalized in terms of the deformation and fracture mechanisms observed during the tests.

The interaction between edge dislocations and Guinier-Preston zones in an Al-Cu alloy was analyzed by means of atomistic simulations. The different thermodynamic functions that determine the features of these obstacles for the dislocation glide were computed using molecular statics, molecular dynamics and the nudged elastic band method. It was found that Guinier-Preston zones are sheared by dislocations and the rate at which dislocations overcome the precipitate is controlled by the activation energy, $\Delta U$, in agreement with the postulates of the harmonic transition state theory. Moreover, the entropic contribution to the Helmholtz activation free energy was in the range 1.3-1.8$k_b$, which can be associated with the typical vibrational entropy of solids. Finally, an estimation of the initial shear flow stress as a function of temperature was carried out from the thermodynamic data provided by the atomistic simulations. Comparison with experimental results showed that the effect of the random precipitate distribution and of the dislocation character and dislocation/precipitation orientation has to be taken into account in the simulations to better reproduce experiments.

The mechanisms of dislocation/precipitate interaction were studied by means of discrete dislocation dynamics within a multiscale approach. Simulations were carried out using the discrete continuous method in combination with a fast Fourier transform solver to compute the mechanical fields. The original simulation strategy was modified to include straight dislocation segments by means of the field dislocation mechanics method and was applied to simulate the interaction of an edge dislocation with a $\theta'$ precipitate in an Al-Cu alloy. It was found that the elastic mismatch has a negligible influence on the dislocation/precipitate interaction in the Al-Cu system. Moreover, the influence of the precipitate aspect ratio and orientation was reasonably well captured by the simple Orowan model in the absence of the stress-free transformation strain. Nevertheless, the introduction of the stress-free transformation strain led to dramatic changes in the dislocation/precipitate interaction and in the critical resolved shear stress to overcome the precipitate, particularly in the case of precipitates with small aspect ratio. The new multiscale approach to study the dislocation/precipitate interactions opens the possibility to obtain quantitative estimations of the strengthening provided by precipitates in metallic alloys taking into account the microstructural details.

The mechanical behavior of nanotwinned Cu was studied through indentation creep and constant strain rate indentation tests from 25 $^\circ$C to 200 $^\circ$C. The results showed an enhanced strain rate sensitivity of nanotwinned Cu with temperature, which was higher than that found in coarse-grained Cu. Transmission electron microscopy revealed the same deformation mechanism in the whole temperature range: confined dislocation slip between coherent twin boundaries and formation of dislocation pile-ups at the coherent twin boundaries. The mechanisms responsible for large increase in strain rate sensitivity of nanotwinned Cu with temperature were discussed to the light of experimental observations.

A multidisciplinary approach is presented to analyse the precipitation process in a model Al-Cu alloy. Although this topic has been extensively studied in the past, most of the investigations are focussed either on transmission electron microscopy or on thermal analysis of the processes. The information obtained from these techniques cannot, however, provide a coherent picture of all the complex transformations that take place during decomposition of supersaturated solid solution. Thermal analysis, high resolution dilatometry, (high resolution) transmission electron microscopy and density functional calculations are combined to study precipitation kinetics, interfacial energies, and the effect of second phase precipitates on the mechanical strength of the alloy. Data on both the coherent and semi-coherent orientations of the {\theta}"/Al interface are reported for the first time. The combination of the different characterization and modelling techniques provides a detailed picture of the precipitation phenomena that take place during aging and of the different contributions to the strength of the alloy. This strategy can be used to analyse and design more complex alloys.

This paper reviews the current state-of-the-art in the simulation of the mechanical behavior of polycrystalline materials by means of computational homogenization. The key ingredients of this modelling strategy are presented in detail starting with the parameters needed to describe polycrystalline microstructures and the digital representation of such microstructures in a suitable format to perform computational homogenization. The different crystal plasticity frameworks that can describe the physical mechanisms of deformation in single crystals (dislocation slip and twinning) at the microscopic level are presented next. This is followed by the description of computational homogenization methods based on mean-field approximations by means of the viscoplastic self-consistent approach, or on the full-field simulation of the mechanical response of a representative polycrystalline volume element by means of the finite element method or the fast Fourier transform-based method. Multiscale frameworks based on the combination of mean-field homogenization and the finite element method are presented next to model the plastic deformation of polycrystalline specimens of arbitrary geometry under complex mechanical loading. Examples of application to predict the strength, fatigue life, damage, and texture evolution under different conditions are presented to illustrate the capabilities of the different models. Finally, current challenges and future research directions in this field are summarized.

A microstructure-based model that accounts for the effect of grain size has been developed to study the effect of grain size on the fatigue life of Inconel 718 alloys. The fatigue behavior of two alloys with different grain size was determined by means of uniaxial cyclic deformation tests under fully-reversed deformation ($R_\varepsilon$ = -1) at 400$^\circ$C in the low cycle fatigue regime. The model was based in the determination of the fatigue indicator parameter (based on the local crystallographic strain energy dissipated per cycle) by means of computational homogenization of a representative volume element of the microstructure. The mechanical response of the single crystal within the polycrystal was modelled through a phenomenological crystal plasticity model which was modified to account for the effect of grain size on the monotonic and cyclic hardening/softening mechanisms. The microstructure-based crack initiation model parameters were calibrated from the experimental tests of the material with fine grain size. The results of the fatigue simulations were in good agreement with the experimental results in terms of the cyclic stress-strain curves and of the number of cycles for fatigue crack initiation. The model did not show any grain size effect on the fatigue life for the largest cyclic strain ranges while the predicted fatigue life predicted was considerably longer in the case of the microstructure with fine grain size for the lowest strain ranges, in quantitative agreement with experimental data. These differences were attributed to changes in the deformation modes between homogeneous plastic deformation at large cyclic strain ranges and localized plasticity in a few grains at low cyclic strain ranges.

The effect of grain size on the flow stress of FCC polycrystals is analyzed by means of a multiscale strategy based on computational homogenization of the polycrystal aggregate. The mechanical behavior of each crystal is given by a dislocation-based crystal plasticity model in which the critical resolved shear stress follows the Taylor model. The generation and annihilation of dislocations in each slip system during deformation is given by the Kocks-Mecking model, which was modified to account for the dislocation storage at the grain boundaries. Polycrystalline Cu is selected to validate the simulation strategy and all the model parameters are obtained from dislocation dynamics simulations or experiments at lower length scales and the simulation results were in good agreement with experimental data in the literature. The model is applied to explore the influence of different microstructural factors (initial dislocation density, width of the grain size distribution, texture) on the grain size effect. It is found that the initial dislocation density, $\rho_i$, plays a dominant role in the magnitude of the grain size effect and that dependence of flow stress with an inverse power of grain size ($\sigma_ y -\sigma_\infty \propto d_g^{-x}$) breaks down for large initial dislocation densities ($> 10^{14}$ m$^{-2}$) and grain sizes $d_g > $ 40 $\mu$m in FCC metals. However, it was found that the grain size contribution to the strength followed a power-law function of the dimensionless parameter $d_g\sqrt{\rho_i}$ for small values of the applied strain ($<$ 2 \%), in agreement with previous theoretical considerations for size effects in plasticity.

The mechanical properties and deformation mechanisms of Cu/Nb nanoscale metallic multilayers (NMMs) manufactured by accumulative roll bonding (ARB) are studied at 25C and 400C. Cu/Nb NMMs with individual layer thicknesses between 7 and 63 nm were tested by in-situ micropillar compression inside a scanning electron microscope Yield strength, strain-rate sensitivities and activation volumes were obtained from the pillar compression tests. The deformed micropillars were examined under scanning and transmission electron microscopy in order to examine the deformation mechanisms active for different layer thicknesses and temperatures. The analysis suggests that room temperature deformation was determined by dislocation glide at larger layer thicknesses and interface-related mechanisms at the thinner layer thicknesses. The high temperature compression tests, in contrast, revealed superior thermo-mechanical stability and strength retention for the NMMs with larger layer thicknesses with deformation controlled by dislocation glide. A remarkable transition in deformation mechanism occurred as the layer thickness decreased, to a deformation response controlled by diffusion processes along the interfaces, which resulted in temperature-induced softening. A deformation mechanism map, in terms of layer thickness and temperature, is proposed from the results obtained in this investigation.

A microstructure-based model is presented to predict the fatigue life of polycrystalline metallic alloys which present a bilinear Coffin-Manson relationship. The model is based in the determination of the maximum value of a fatigue indicator parameter obtained from the plastic energy dissipated by cycle in the microstructure. The fatigue indicator parameter was obtained by means of the computational homogenization of a representative volume element of the microstructure using a crystal-plasticity finite element model. The microstructure-based model was applied to predict the low cyclic fatigue behavior of IN718 at 400$^\circ$C which exhibits a bilinear Coffin-Manson relationship under the assumption that this behavior is triggered by a transition from highly localized plasticity at low cyclic strain amplitudes to more homogeneous deformation at high cyclic strain amplitudes. The model predictions were in very good agreement with the experimental results for a wide range of cyclic strain amplitudes and two strain ratios ($R_\epsilon$ = 0 and -1) and corroborated the initial hypothesis. Moreover, they provided a micromechanical explanation for the influence of the strain ratio on the fatigue life at low cyclic strain amplitudes.

The mechanical behaviour and deformation mechanisms of magnetron-sputtered Zr/Nb nanoscale multilayers were analysed as a function of the periodicity (L = 10 and 75 nm) and annealing time at 350C (2-336 hrs). The strength of the as-deposited multilayers was independent of the layer thickness and it was controlled by the co-deformation of the Zr and Nb layers. Annealing led to transformation of the Zr layers into ZrO2 after a few hours, while the Nb layers oxidised at a much slower rate. The volumetric expansion associated with the oxidation led to the formation of cracks at the interfaces and within the ZrO2 layers for the multilayers with L = 75 nm but not in the case of L = 10 nm. The nanoindentation hardness increased significantly after annealing due to the contribution of the residual stresses associated with the volume increase due to oxidation and to the higher strength of the oxides. The strength increase after annealing, as measured by micropillar compression tests, was smaller than that measured by nanoindentation, as it did not include the contribution of the residual stresses, which were relieved during micropillar fabrication. The nanolaminate with L = 10 nm presented the highest strength and toughness as damage during oxidation was suppressed, and a deformation mechanism controlled by the formation of shear bands.

Atomistic simulations were carried out to analyze the interaction between $< a>$ basal dislocations and precipitates in Mg-Al alloys and the associated strengthening mechanisms., Comment: Due to the limitations of the interatomic potential used, it was not possible to ensure the accuracy of some of the results in the paper