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We present TDS Simulator, a new software tool aimed at modelling thermal desorption spectroscopy (TDS) experiments. TDS is a widely used technique for quantifying key characteristics of hydrogen-material interactions, such as diffusivity and trapping. However, interpreting the output of TDS experiments is non-trivial and requires appropriate post-processing tools. This work introduces the first software tool capable of simulating TDS curves for arbitrary choices of material parameters and hydrogen trap characteristics, using the primary hydrogen diffusion and trapping models (Oriani, McNabb-Foster). Moreover, TDS Simulator contains a specific functionality for loading experimental TDS data and conducting the inverse calibration of a selected transport model, providing automatic estimates of the density and binding energy of each hydrogen trap type in the material. In its first version, TDS Simulator is provided as a MATLAB App, which is made freely available to the community and provides a simple graphical user interface (GUI) to make use of TDS Simulator straightforward. As reported in the present manuscript, the outputs of TDS Simulator have been extensively validated against literature data. Demonstrations of automatic determination of trap characteristics from experimental data through the optimisation tool are also provided. The present work enables an efficient and straightforward characterisation of hydrogen-material characteristics relevant to multiple applications, from nuclear fusion to the development of hydrogen-compatible materials for the hydrogen economy. TDS Simulator can be downloaded from https://mechmat.web.ox.ac.uk/codes.

Accelerated impressed current testing is the most common experimental method for assessing the susceptibility to corrosion-induced cracking, the most prominent challenge to the durability of reinforced concrete structures. Although it is well known that accelerated impressed current tests lead to slower propagation of cracks (with respect to corrosion penetration) than in natural conditions, which results in overestimations of the delamination/spalling time, the origins of this phenomenon have puzzled researchers for more than a quarter of a century. In view of recent experimental findings, it is postulated that the phenomenon can be attributed to the variability of rust composition and density, specifically to the variable ratio of the mass fractions of iron oxide and iron hydroxide-oxide, which is affected by the magnitude of the applied corrosion current density. Based on this hypothesis, a corrosion-induced cracking model for virtual impressed-current testing is presented. The simulation results obtained with the proposed model are validated against experimental data, showing good agreement. Importantly, the model can predict corrosion-induced cracking under natural conditions and thus allows for the calculation of a newly proposed crack width slope correction factor, which extrapolates the surface crack width measured during accelerated impressed current tests to corrosion in natural conditions.

A nonlinear phase-field model is developed to simulate corrosion damage. The motion of the electrode$-$ electrolyte interface follows the usual kinetic rate theory for chemical reactions based on the Butler-Volmer equation. The model links the surface polarization variation associated with the charging kinetics of an electric double layer (EDL) to the mesoscale transport. The effects of the EDL are integrated as a boundary condition on the solution potential equation. The boundary condition controls the magnitude of the solution potential at the electrode-electrolyte interface. The ion concentration field outside the EDL is obtained by solving the electro-diffusion equation and Ohm's law for the solution potential. The model is validated against the classic benchmark pencil electrode test. The framework developed reproduces experimental measurements of both pit kinetics and transient current density response. The model enables more accurate information on corrosion damage, current density, and environmental response in terms of the distribution of electric potential and charged species. The sensitivity analysis for different properties of the EDL is performed to investigate their role in the electrochemical response of the system. Simulation results show that the properties of the EDL significantly influence the transport of ionic species in the electrolyte.

This work overviews a new, recent success of phase-field modelling: its application to predicting the evolution of the corrosion front and the associated structural integrity challenges. Despite its important implications for society, predicting corrosion damage has been an elusive goal for scientists and engineers. The application of phase-field modelling to corrosion not only enables tracking the electrolyte-metal interface but also provides an avenue to explicitly simulate the underlying mesoscale physical processes. This lays the grounds for developing the first generation of mechanistic corrosion models, which can capture key phenomena such as film rupture and repassivation, the transition from activation- to diffusion-controlled corrosion, interactions with mechanical fields, microstructural and electrochemical effects, intergranular corrosion, material biodegradation, and the interplay with other environmentally-assisted damage phenomena such as hydrogen embrittlement.

A new model is presented to predict hydrogen-assisted fatigue. The model combines a phase field description of fracture and fatigue, stress-assisted hydrogen diffusion, and a toughness degradation formulation with cyclic and hydrogen contributions. Hydrogen-assisted fatigue crack growth predictions exhibit an excellent agreement with experiments over all the scenarios considered, spanning multiple load ratios, H2 pressures and loading frequencies. These are obtained without any calibration with hydrogen-assisted fatigue data, taking as input only mechanical and hydrogen transport material properties, the material's fatigue characteristics (from a single test in air), and the sensitivity of fracture toughness to hydrogen content. Furthermore, the model is used to determine: (i) what are suitable test loading frequencies to obtain conservative data, and (ii) the underestimation made when not pre-charging samples. The model can handle both laboratory specimens and large-scale engineering components, enabling the Virtual Testing paradigm in infrastructure exposed to hydrogen environments and cyclic loading.

A modelling framework for predicting carbonation-induced corrosion in reinforced concrete is presented. The framework constituents include a new model for water transport in cracked concrete, a link between corrosion current density and water saturation, and a theory for characterising concrete carbonation. The theoretical framework is numerically implemented using the finite element method and model predictions are extensively benchmarked against experimental data. The results show that the model is capable of accurately predicting carbonation progress, as well as wetting and drying of cracked and uncracked concrete, revealing a very good agreement with independent experiments from a set of consistent parameters. In addition, insight is gained into the evolution of carbonation penetration and corrosion current density under periodic wetting and drying conditions. Among others, we find that cyclic wetting periods significantly speed up the carbonation progress and that the induced corrosion current density is very sensitive to concrete saturation.

Combined experiments and computational modelling are used to increase understanding of the suitability of the Single-Edge Notch Tension (SENT) test for assessing hydrogen embrittlement susceptibility. The SENT tests were designed to provide the mode I threshold stress intensity factor ($K_{\text{th}}$) for hydrogen-assisted cracking of a C110 steel in two corrosive environments. These were accompanied by hydrogen permeation experiments to relate the environments to the absorbed hydrogen concentrations. A coupled phase-field-based deformation-diffusion-fracture model is then employed to simulate the SENT tests, predicting $K_{\text{th}}$ in good agreement with the experimental results and providing insights into the hydrogen absorption-diffusion-cracking interactions. The suitability of SENT testing and its optimal characteristics (e.g., test duration) are discussed in terms of the various simultaneous active time-dependent phenomena, triaxiality dependencies, and regimes of hydrogen embrittlement susceptibility.

Hydrogen embrittlement in metals (HE) is a serious challenge for the use of high strength materials in engineering practice and a major barrier to the use of hydrogen for global decarbonization. Here we describe the factors and variables that determine HE susceptibility and provide an overview of the latest understanding of HE mechanisms. We discuss hydrogen uptake and how it can be managed. We summarize hydrogen trapping and the techniques used for its characterization. We also review literature that argues that hydrogen trapping can be used to decrease HE susceptibility. We discuss the future research that is required to advance the understanding of HE and hydrogen trapping and to develop HE-resistant alloys.

An electro-chemo-mechanical phase-field formulation is developed to simulate pitting and stress corrosion in polycrystalline materials. The formulation incorporates dependencies of mechanical properties and corrosion potential on crystallographic orientation. The model considers the formation and charging dynamics of an electric double layer through a new general boundary condition for the solution potential. The potential of the model is demonstrated by simulating corrosion in polycrystalline materials with various grain morphology distributions. The results show that incorporating the underlying microstructure yields more extensive defects, faster defect kinetics, and irregular pit and crack shapes relative to a microstructurally-insensitive homogeneous material scenario.

In the race to reduce global CO2 emissions and achieve net-zero, chemomechanics must play a critical role in the technological development of current and next-generation batteries to improve their energy storage capabilities and their lifetime. Many degradation processes arise through mechanics via the development of diffusion-induced stress and volumetric strains within the various constituent materials in a battery. From particle cracking in lithium-ion batteries to lithium dendrite-based fracture of solid electrolytes in solid-state batteries, it is clear that significant barriers exist in the development of these energy storage systems, where chemomechanics plays a central part. To accelerate technological and scientific advances in this area, multi-scale and highly coupled multiphysics modelling must be carried out that includes mechanics-based phenomena. In this perspective article, we provide an introduction to chemomechanical modelling, the various physical problems that it addresses, and the issues that need to be resolved in order to expand its use within the field of battery technology.

In this work, we describe our contribution to the Purdue-SANDIA-LLNL \emph{Damage Mechanics Challenge}. The phase field fracture model is adopted to blindly estimate the failure characteristics of the challenge test, an unconventional three-point bending experiment on an additively manufactured rock resembling a type of gypsum. The model is formulated in a variationally consistent fashion, incorporating a volumetric-deviatoric strain energy decomposition, and the numerical implementation adopts a monolithic unconditionally stable solution scheme. Our focus is on providing an efficient and simple yet rigorous approach capable of delivering accurate predictions based solely on physical parameters. Model inputs are Young's modulus $E$, Poisson's ratio $\nu$, toughness $G_c$ and strength $\sigma_c$ (as determined by the choice of phase field length scale $\ell$). We show that a single mode I three-point bending test is sufficient to calibrate the model, and that the calibrated model can then reliably predict the force versus displacement responses, crack paths and surface crack morphologies of more intricate three-point bending experiments that are inherently mixed-mode. Importantly, our peak load, crack trajectory and crack surface morphology predictions for the challenge test, submitted before the experimental data was released, show a remarkable agreement with experiments. The characteristics of the challenge, and how changes in these can impact the predictive abilities of phase field fracture models, are also discussed.

Core-shell electrode particle designs offer a route to improved lithium-ion battery performance. However, they are susceptible to mechanical damage such as fracture and debonding, which can significantly reduce their lifetime. Using a coupled finite element model, we explore the impacts of diffusion-induced stresses on the failure mechanisms of an exemplar system with an NMC811 core and an NMC111 shell. In particular, we systematically compare the implications of assuming constant material properties against using Li concentration-dependent diffusion coefficient and partial molar volume. With constant material properties, our results show that smaller cores with thinner shells avoid debonding and fracture regimes. When factoring in a concentration-dependent partial molar volume, the maximum values of tensile hoop stress in the shell are found to be significantly lower than those predicted with constant properties, reducing the likelihood of fracture. Furthermore, with a concentration-dependent diffusion coefficient, significant barriers to full electrode utilisation are observed due to reduced lithium mobility at high states of lithiation. This provides a possible explanation for the reduced accessible capacity observed in experiments. Shell thickness is found to be the dominant factor in precluding structural integrity once the concentration dependency is accounted for. These findings shed new light on the performance and effective design of core-shell electrode particles.

We use a unique combination of electrochemical techniques to elucidate the dependency of hydrogen evolution reaction (HER) and absorption on pH and overpotential for iron and nickel. Impedance spectroscopy shows the dominance of the Volmer-Heyrovsky reaction pathway, challenging the common consideration of Volmer-Tafel dominance. Polarization slopes agree with the Volmer or Heyrovsky rate-determining step, with limitations at high overpotential. The evolution of steady-state permeation current density with overpotential is rationalised through newly-developed theory. Surface activity and absorption trends are captured. Combined with modelling, this work provides a path for quantifying hydrogen uptake and establishing an equivalent fugacity for aqueous electrolytes.

We present a wrapper that allows Abaqus user material subroutines (UMATs) to be used as an External Material library in the software COMSOL Multiphysics. The wrapper, written in C language, transforms COMSOL's external material subroutine inputs and outputs into Fortran-coded Abaqus UMAT inputs and outputs, by means of a consistent variable transformation. This significantly facilitates conducting coupled, multi-physics studies employing the advanced material models that the solid mechanics community has developed over the past decades. We exemplify the potential of our new framework, UMAT4COMSOL, by conducting numerical experiments in the areas of elastoplasticity, hyperelasticity and crystal plasticity. The source code, detailed documentation and example tutorials are made freely available to download at www.empaneda.com/codes.

The phase field method has gathered significant attention in the past decade due to its versatile applications in engineering contexts, including fatigue crack propagation modeling. Particularly, the phase field cohesive zone method (PF-CZM) has emerged as a promising approach for modeling fracture behavior in quasi-brittle materials, such as concrete. The present contribution expands the applicability of the PF-CZM to include the modeling of fatigue-induced crack propagation. This study critically examines the validity of the extended PF-CZM approach by evaluating its performance across various fatigue behaviours, encompassing hysteretic behavior, S-N curves, fatigue creep curves, and the Paris law. The experimental investigations and validation span a diverse spectrum of loading scenarios, encompassing pre- and post-peak cyclic loading, as well as low- and high-cyclic fatigue loading. The validation process incorporates 2D and 3D boundary value problems, considering mode I and mixed-modes fatigue crack propagation. The results obtained from this study show a wide range of validity, underscoring the remarkable potential of the proposed PF-CZM approach to accurately capture the propagation of fatigue cracks in concrete-like materials. Furthermore, the paper outlines recommendations to improve the predictive capabilities of the model concerning key fatigue characteristics.

We combine welding process modelling with deformation-diffusion-fracture (embrittlement) simulations to predict failures in hydrogen transport pipelines. The focus is on the structural integrity of seam welds, as these are often the locations most susceptible to damage in gas transport infrastructure. Finite element analyses are conducted to showcase the ability of the model to predict cracking in pipeline steels exposed to hydrogen-containing environments. The validated model is then employed to quantify critical H$_2$ fracture pressures. The coupled, phase field-based simulations conducted provide insight into the role of existing defects, microstructural heterogeneity, and residual stresses. We find that under a combination of deleterious yet realistic conditions, the critical pressure at which fracture takes place can be as low as 15 MPa. These results bring new mechanistic insight into the viability of using the existing natural gas pipeline network to transport hydrogen, and the computational framework presented enables mapping the conditions under which this can be achieved safely.

A model for corrosion-induced cracking of reinforced concrete subjected to non-uniform chloride-induced corrosion is presented. The gradual corrosion initiation of the steel surface is investigated by simulating chloride transport considering binding. The transport of iron from the steel surface, its subsequent precipitation into rust, and the associated precipitation-induced pressure are explicitly modelled. Model results, obtained through finite element simulations, agree very well with experimental data, showing significantly improved accuracy over uniform corrosion modelling. The results obtained from case studies reveal that crack-facilitated transport of chlorides cannot be neglected, that the size of the anodic region must be considered, and that precipitate accumulation in pores can take years.

The influence of post-build processing on the hydrogen embrittlement behavior of additively manufactured (AM) 316L stainless steel fabricated using laser powder bed fusion was assessed at both room temperature and -50$^\circ$ C via uniaxial tensile experiments. In the absence of hydrogen at ambient temperature, all four evaluated AM conditions (as-built (AB), annealed (ANN), hot isostatic pressed (HIP), and HIP plus cold worked (CW) to 30\%) exhibit notably reduced ductility relative to conventionally manufactured (CM) 316L stainless steel. The AM material exhibits sensitivity to the build direction, both in the presence and absence of hydrogen, with a notable increase in yield strength in the X direction and enhanced ductility in the Z direction. Conversely, testing of non-charged specimens at -50$^\circ$ C revealed similar ductility between the CM, AB, ANN, and HIP conditions. Upon hydrogen charging, the ductility of all four AM conditions was found to be similar to that of CM 316L at ambient temperature, with the HIP condition actually exceeding the CM material. Critically, testing of hydrogen-charged samples at -50$^\circ$ C revealed that the ductility of the HIP AM 316L condition was nearly double that observed in the CM 316L. This improved performance persisted even after cold working, as the CW AM 316L exhibited comparable ductility to CM 316L at -50 C after hydrogen charging, despite having a 2-fold higher yield strength. Feritscope measurements suggest this increased performance is related to the reduced propensity for AM 316L to form strain-induced martensite during deformation, even after significant post-processing treatments. These results demonstrate that AM 316L can be post-processed using typical procedures to exhibit similar to or even improved resistance to hydrogen embrittlement relative to CM 316L.

Bio-chemical reactions enable the production of biomimetic materials such as sandstones. In the present study, microbiologically-induced calcium carbonate precipitation (MICP) is used to manufacture laboratory-scale specimens for fracture toughness measurement. The mode I and mixed-mode fracture toughnesses are measured as a function of cementation, and are correlated with strength, permeability and porosity. A micromechanical model is developed to predict the dependence of mode I fracture toughness upon the degree of cementation. In addition, the role of the crack tip $T$-stress in dictating kink angle and toughness is determined for mixed mode loading. At a sufficiently low degree of cementation, the zone of microcracking in the vicinity of the crack tip is sufficiently large for a crack tip $K$-field to cease to exist and for crack kinking theory to not apply. The interplay between cementation and fracture properties of sedimentary rocks is explained; this understanding underpins a wide range of rock fracture phenomena including hydraulic fracture.

Randomness in the void distribution within a ductile metal complicates quantitative modeling of damage following the void growth to coalescence failure process. Though the sequence of micro-mechanisms leading to ductile failure is known from unit cell models, often based on assumptions of a regular distribution of voids, the effect of randomness remains a challenge. In the present work, mesoscale unit cell models, each containing an ensemble of four voids of equal size that are randomly distributed, are used to find statistical effects on the yield surface of the homogenized material. A yield locus is found based on a mean yield surface and a standard deviation of yield points obtained from 15 realizations of the four-void unit cells. It is found that the classical GTN model very closely agrees with the mean of the yield points extracted from the unit cell calculations with random void distributions, while the standard deviation $\textbf{S}$ varies with the imposed stress state. It is shown that the standard deviation is nearly zero for stress triaxialities $T\leq1/3$, while it rapidly increases for triaxialities above $T\approx 1$, reaching maximum values of about $\textbf{S}/\sigma_0\approx0.1$ at $T \approx 4$. At even higher triaxialities it decreases slightly. The results indicate that the dependence of the standard deviation on the stress state follows from variations in the deformation mechanism since a well-correlated variation is found for the volume fraction of the unit cell that deforms plastically at yield. Thus, the random void distribution activates different complex localization mechanisms at high stress triaxialities that differ from the ligament thinning mechanism forming the basis for the classical GTN model. A method for introducing the effect of randomness into the GTN continuum model is presented, and an excellent comparison to the unit cell yield locus is achieved.

This study presents CFD simulations of biomass dust explosions in a newly developed experimental 1 m$^3$ silo apparatus with variable venting, designed and fabricated to operate similarly to the explosivity test standards. The aim of the study is to validate a CFD model under development and investigate its capability to capture the transient effects of a vented explosion. The model is based on OpenFOAM and solves the multiphase (gas-particle) flow using an Eulerian-Lagrangian approach in a two-way regime. It considers the detailed thermochemical conversion of biomass, including moisture evaporation, devolatilization, and char oxidation, along with the homogeneous combustion of gases, turbulence, and radiative heat transfer. The explosion is analyzed in all stages, i.e., dust cloud dispersion, ignition, closed explosion, and vented explosion. The results indicate excellent agreement between the CFD model and experimental tests throughout the sequence. Our findings highlight the critical role of particle size in dust cloud distribution and pre-ignition turbulence, which significantly influences flame dynamics and the explosion itself. This model shows great promise and encourages its application for future investigations of biomass dust explosions in larger-scale geometries, especially in venting situations that fall out of the scope of the NFPA 68 or EN 14491 standards, and to help design effective safety measures to prevent such incidents.

We present a new theoretical and computational framework for modelling electro-chemo-mechanical fracture. The model combines a phase field description of fracture with a fully coupled characterisation of electrolyte behaviour, surface chemical reactions and stress-assisted diffusion. Importantly, a new physics-based formulation is presented to describe electrolyte-containing phase field cracks, appropriately capturing the sensitivity of electrochemical transport and reaction kinetics to the crack opening height. Unlike other existing methods, this approach is shown to accurately capture the results obtained with discrete fracture simulations. The potential of the electro-chemo-mechanical model presented is demonstrated by particularising it to the analysis of hydrogen embrittlement in metallic samples exposed to aqueous electrolytes. The finite element implementation takes as nodal degrees-of-freedom the electrolyte potential, the concentrations of relevant ionic species, the surface coverage, the concentration of diluted species, the displacement field and the phase field order parameter. Particular attention is devoted to improve stability and efficiency, resulting in the development of strategies for avoiding ill-constrained degrees of freedom and lumped integration schemes that eliminate numerical oscillations. The numerical experiments conducted showcase the ability of the model to deliver assumptions-free predictions for systems involving both free-flowing and crack-contained electrolytes. The results obtained highlight the role of electrolyte behaviour in driving the cracking process, evidencing the limitations of existing models.

The presence of hydrogen traps within a metallic alloy influences the rate of hydrogen diffusion. The electro-permeation (EP) test can be used to assess this: the permeation of hydrogen through a thin metallic sheet is measured by suitable control of hydrogen concentration on the front face and by recording the flux of hydrogen that exits the rear face. Additional insight is achieved by the more sophisticated three stage EP test: the concentration of free lattice hydrogen on the front face is set to an initial level, is then dropped to a lower intermediate value and is then restored to the initial level. The flux of hydrogen exiting the rear face is measured in all three stages of the test. In the present study, a transient analysis is performed of hydrogen permeation in a three stage EP test, assuming that lattice diffusion is accompanied by trapping and de-trapping. The sensitivity of the three stage EP response to the depth and density of hydrogen traps is quantified. A significant difference in permeation response can exist between the first and third stages of the EP test when the alloy contains a high number density of deep traps.

We present a new mechanistic framework for corrosion-induced cracking in reinforced concrete that resolves the underlying chemo-mechanical processes. The framework combines, for the first time, (i) a model for reactive transport and precipitation of dissolved Fe2+ and Fe3+ ions in the concrete pore space, (ii) a precipitation eigenstrain model for the pressure caused by the accumulation of precipitates (rusts) under pore confinement conditions, (iii) a phase-field model calibrated for the quasi-brittle fracture behaviour of concrete, and (iv) a damage-dependent diffusivity tensor. Finite element model predictions show good agreement with experimental data from impressed current tests under natural-like corrosion current densities.

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.

This paper investigates the effect of moisture content upon the degradation behaviour of composite materials. A coupled phase field framework considering moisture diffusion, hygroscopic expansion, and fracture behaviour is developed. This multi-physics framework is used to explore the damage evolution of composite materials, spanning the micro-, meso- and macro-scales. The micro-scale unit-cell model shows how the mismatch between the hygroscopic expansion of fibre and matrix leads to interface debonding. From the meso-scale ply-level model, we learn that the distribution of fibres has a minor influence on the material properties, while increasing moisture content facilitates interface debonding. The macro-scale laminate-level model shows that moisture induces a higher degree of damage on the longitudinal ply relative to the transverse ply. This work opens a new avenue to understand and predict environmentally-assisted degradation in composite materials.

Phase field fracture models have seen widespread application in the last decade. Among these applications, its use to model the evolution of fatigue cracks has attracted particular interest, as fatigue damage behaviour can be predicted for arbitrary loading histories, dimensions and complexity of the cracking phenomena at play. However, while cycle-by-cycle calculations are remarkably flexible, they are also computationally expensive, hindering the applicability of phase field fatigue models for technologically-relevant problems. In this work, a computational framework for accelerating phase field fatigue calculations is presented. Two novel acceleration strategies are proposed, which can be used in tandem and together with other existing acceleration schemes from the literature. The computational performance of the proposed methods is documented through a series of 2D and 3D boundary value problems, highlighting the robustness and efficiency of the framework even in complex fatigue problems. The observed reduction in computation time using both of the proposed methods in tandem is shown to reach a speed-up factor of 32, with a scaling trend enabling even greater reductions in problems with more load cycles.

Computational modelling of metal-electrolyte reactions is central to the understanding and prediction of a wide range of physical phenomena, yet this is often challenging owing to the presence of numerical oscillations that arise due to dissimilar reaction rates. The ingress of hydrogen into metals is a paradigmatic example of a technologically-relevant phenomenon whose simulation is compromised by the stiffness of the reaction terms, as reaction rates vary over orders of magnitude and this significantly limits the time increment size. In this work, we present a lumped integration scheme for electro-chemical interface reactions that does not suffer from numerical oscillations. The scheme integrates the reactions in a consistent manner, while it also decouples neighbouring nodes and allows for larger time increments to be used without oscillations or convergence issues. The stability and potential of our scheme is demonstrated by simulating hydrogen ingress over a wide range of reaction rate constants and environmental conditions. While previous hydrogen uptake predictions were limited to time scales of minutes, the present lumped integration scheme enables conducting simulations over tens of years, allowing us to reach steady state conditions and quantify hydrogen ingress for time scales relevant to practical applications.

We present a novel computational framework to simulate the electromechanical response of self-sensing carbon nanotube (CNT)-based composites experiencing fracture. The computational framework combines electrical-deformation-fracture finite element modelling with a mixed micromechanics formulation. The latter is used to estimate the constitutive properties of CNT-based composites, including the elastic tensor, fracture energy, electrical conductivity, and linear piezoresistive coefficients. These properties are inputted into a coupled electro-structural finite element model, which simulates the evolution of cracks based upon phase-field fracture. The coupled physical problem is solved in a monolithic manner, exploiting the robustness and efficiency of a quasi-Newton algorithm. 2D and 3D boundary value problems are simulated to illustrate the potential of the modelling framework in assessing the influence of defects on the electromechanical response of meso- and macro-scale smart structures. Case studies aim at shedding light into the interplay between fracture and the electromechanical material response and include parametric analyses, validation against experiments and the simulation of complex cracking conditions (multiple defects, crack merging). The presented numerical results showcase the efficiency and robustness of the computational framework, as well as its ability to model a large variety of structural configurations and damage patterns. The deformation-electrical-fracture finite element code developed is made freely available to download.

We present a generalised phase field formulation for predicting high-cycle fatigue in metals. Different fatigue degradation functions are presented, together with new damage accumulation strategies, to account for (i) a typical S-N curve slope, (ii) the fatigue endurance limit, and (iii) the mean stress effect. The numerical implementation exploits an efficient quasi-Newton monolithic solution strategy and Virtual S-N curves are computed for both smooth and notched samples. The comparison with experiments reveals that the model can accurately predict fatigue lives and endurance limits, as well as naturally capture the influence of the stress concentration factor and the load ratio.

This paper presents a surrogate modelling technique based on domain partitioning for Bayesian parameter inference of highly nonlinear engineering models. In order to alleviate the computational burden typically involved in Bayesian inference applications, a multielement Polynomial Chaos Expansion based Kriging metamodel is proposed. The developed surrogate model combines in a piecewise function an array of local Polynomial Chaos based Kriging metamodels constructed on a finite set of non-overlapping subdomains of the stochastic input space. Therewith, the presence of non-smoothness in the response of the forward model (e.g.~ nonlinearities and sparseness) can be reproduced by the proposed metamodel with minimum computational costs owing to its local adaptation capabilities. The model parameter inference is conducted through a Markov chain Monte Carlo approach comprising adaptive exploration and delayed rejection. The efficiency and accuracy of the proposed approach are validated through two case studies, including an analytical benchmark and a numerical case study. The latter relates the partial differential equation governing the hydrogen diffusion phenomenon of metallic materials in Thermal Desorption Spectroscopy tests.

The relative efficacy of electrochemical permeation (EP) and isothermal desorption spectroscopy (ITDS) methods for determining the hydrogen diffusivity is investigated using cold-rolled pure iron. The diffusivities determined from 13 first transient and 8 second transient EP experiments, evaluated using the conventional lag and breakthrough time methods, are compared to the results of 10 ITDS experiments. Results demonstrate that the average diffusivity is similar between the second EP transient and ITDS, which are distinctly increased relative to the first EP transient. However, the coefficient of variation for the ITDS experiments is reduced by 2 and 3-fold relative to the first and second EP transients, confirming the improved repeatability of ITDS diffusivity measurements. The source of the increased error in EP measurements is systematically evaluated, revealing an important influence of assumed electrochemical boundary conditions on the analysis and interpretation of EP experiments.

We present a theoretical and numerical scheme that enables quantifying hydrogen ingress in metals for arbitrary environments and defect geometries. This is achieved by explicitly resolving the electrochemical behaviour of the electrolyte, the hydrogen and corrosion reactions, the kinetics of surface adsorption, and hydrogen uptake, diffusion and trapping in mechanically-deforming solids. This new framework is used to produce maps that relate the absorbed hydrogen with the applied potential, specimen geometry and fluid velocity. We also present simplified versions of our generalised model, and benchmark predictions of these and other existing models against the generalised electro-chemo-mechanical results, establishing regimes of validity.

Ti-6Al-4V is a titanium alloy with excellent properties for lightweight applications and its production through Additive Manufacturing processes is attractive for different industrial sectors. In this work, the influence of mechanical properties on the notch fracture resistance of Ti-6Al-4V produced by Selective Laser Melting is numerically investigated. Literature data is used to inform material behaviour. The as-built brittle behaviour is compared to the enhanced ductile response after heat treatment (HT) and hot isostatic pressing (HIP) post-processes. A Phase Field framework is adopted to capture damage nucleation and propagation from two different notch geometries and a discussion on the influence of fracture energy and the characteristic length is carried out. In addition, the influence of oxygen uptake is analysed by reproducing non-inert atmospheres during HT and HIP, showing that oxygen shifts fracture to brittle failures due to the formation of an alpha case layer, especially for the V-notch geometry. Results show that a pure elastic behaviour can be assumed for the as-built SLM condition, whereas elastic-plastic phenomena must be modelled for specimens subjected to heat treatment or hot isostatic pressing. The present brittle Phase Field framework coupled with an elastic-plastic constitutive analysis is demonstrated to be a robust prediction tool for notch fracture after different post-processing routes.

The Brazilian test has been extremely popular while prompting significant debate. The main source of controversy is rooted in its indirect nature; the material tensile strength is inferred upon assuming that cracking initiates at the centre of the sample. Here, we use the Griffith criterion and finite element analysis to map the conditions (jaws geometry and material properties) that result in the nucleation of a centre crack. Unlike previous studies, we do not restrict ourselves to evaluating the stress state at the disk centre; the failure envelope of the generalised Griffith criterion is used to establish the crack nucleation location. We find that the range of conditions where the Brazilian test is valid is much narrower than previously assumed, with current practices and standards being inappropriate for a wide range of rock-like materials. The results obtained are used to develop a protocol that experimentalists can follow to obtain a valid estimate of the material tensile strength. This is showcased with specific case studies and examples of valid and invalid tests from the literature. Furthermore, the uptake of this protocol is facilitated by providing a MATLAB App that determines the validity of the experiment for arbitrary test conditions.

Due to its computational robustness and versatility, the phase field fracture model has become the preferred tool for predicting a wide range of cracking phenomena. However, in its conventional form, its intrinsic tension-compression symmetry in damage evolution prevents its application to the modelling of compressive failures in brittle and quasi-brittle solids, such as concrete or rock materials. In this work, we present a general methodology for decomposing the phase field fracture driving force, the strain energy density, so as to reproduce asymmetrical tension-compression fracture behaviour. The generalised approach presented is particularised to the case of linear elastic solids and the Drucker-Prager failure criterion. The ability of the presented model to capture the compressive failure of brittle materials is showcased by numerically implementing the resulting strain energy split formulation and addressing four case studies of particular interest. Firstly, insight is gained into the capabilities of the model in predicting friction and dilatancy effects under shear loading. Secondly, virtual direct shear tests are conducted to assess fracture predictions under different pressure levels. Thirdly, a concrete cylinder is subjected to uniaxial and triaxial compression to investigate the influence of confinement. Finally, the localised failure of a soil slope is predicted and the results are compared with other formulations for the strain energy decomposition proposed in the literature. The results provide a good qualitative agreement with experimental observations and demonstrate the capabilities of phase field fracture methods to predict crack nucleation and growth under multi-axial loading in materials exhibiting asymmetric tension-compression fracture behaviour.

There is a need for computational models capable of predicting meltwater-assisted crevasse growth in glacial ice. Mass loss from glaciers and ice sheets is the largest contributor to sea-level rise and iceberg calving due to hydrofracture is one of the most prominent yet less understood glacial mass loss processes. To overcome the limitations of empirical and analytical approaches, we here propose a new phase field-based computational framework to simulate crevasse growth in both grounded ice sheets and floating ice shelves. The model incorporates the three elements needed to mechanistically simulate hydrofracture of surface and basal crevasses: (i) a constitutive description incorporating the non-linear viscous rheology of ice, (ii) a phase field formulation capable of capturing cracking phenomena of arbitrary complexity, such as 3D crevasse interaction, and (iii) a poro-damage representation to account for the role of meltwater pressure on crevasse growth. A stress-based phase field model is adopted to reduce the length-scale sensitivity, as needed to tackle the large scales of iceberg calving, and to adequately predict crevasse growth in tensile stress regions of incompressible solids. The potential of the computational framework presented is demonstrated by addressing a number of 2D and 3D case studies, involving single and multiple crevasses, and considering both grounded and floating conditions. The computational framework presented opens new horizons in the modelling of iceberg calving and, due to its ability to incorporate incompressible behaviour, can be readily incorporated into numerical ice sheet models for projecting sea-level rise.

Determination of the explosion severity parameters of biomass is crucial for the safety management and dust explosion risk assessment of biomass-processing industries. These are commonly determined following experimental tests in the 20L sphere according to the international standards. Recently, CFD simulations have emerged as a reliable alternative to predict the explosion behavior with good accuracy and reduced labor and capital. In this work, numerical simulations of biomass dust explosions are conducted with the open-source CFD code OpenFOAM. The multi-phase (gas-solid) flow is treated in an Eulerian-Lagrangian framework, using a two-way coupling regime and considering the reactions of biomass conversion (moisture evaporation, devolatilization, and char oxidation), the combustion of volatile gases, and convective and radiative heat transfer. The model is validated with pressure-time and concentration-dependent experimental measurements of two biomass samples. Results suggest that the characteristics of the cold-flow (\i.e. turbulence levels, actual dust concentration, spatial distribution of the dust cloud, and turbophoresis effect) govern the course of the explosion process, and depend strongly on particle size, dust concentration, and ignition delay time effects. These findings may be relevant in the design of better dust explosion testing devices and to the reexamination of the guidelines for the operation of the experiment. Finally, a thorough discussion on the explosion pressures, degree of biomass conversion, flame temperature, flame propagation patterns, and the dust agglomeration effect is presented.

We present a combined phase field and cohesive zone formulation for hydrogen embrittlement that resolves the polycrystalline microstructure of metals. Unlike previous studies, our deformation-diffusion-fracture modelling framework accounts for hydrogen-microstructure interactions and explicitly captures the interplay between bulk (transgranular) fracture and intergranular fracture, with the latter being facilitated by hydrogen through mechanisms such as grain boundary decohesion. We demonstrate the potential of the theoretical and computational formulation presented by simulating inter- and trans-granular cracking in relevant case studies. Firstly, verification calculations are conducted to show how the framework predicts the expected qualitative trends. Secondly, the model is used to simulate recent experiments on pure Ni and a Ni-Cu superalloy that have attracted particular interest. We show that the model is able to provide a good quantitative agreement with testing data and yields a mechanistic rationale for the experimental observations.

We present a mechanistic theory for predicting void evolution in the Li metal electrode during the charge and discharge of all-solid-state battery cells. A phase field formulation is developed to model vacancy annihilation and nucleation, and to enable the tracking of the void-Li metal interface. This is coupled with a viscoplastic description of Li deformation, to capture creep effects, and a mass transfer formulation accounting for substitutional (bulk and surface) Li diffusion and current-driven flux. Moreover, we incorporate the interaction between the electrode and the solid electrolyte, resolving the coupled electro-chemical-mechanical problem in both domains. This enables predicting the electrolyte current distribution and thus the emergence of local current 'hot spots', which act as precursors for dendrite formation and cell death. The theoretical framework is numerically implemented, and single and multiple void case studies are carried out to predict the evolution of voids and current hot spots as a function of the applied pressure, material properties and charge (magnitude and cycle history). For both plating and stripping, insight is gained into the interplay between bulk diffusion, Li dissolution and deposition, creep, and the nucleation and annihilation of vacancies. The model is shown to capture the main experimental observations, including not only key features of electrolyte current and void morphology but also the sensitivity to the applied current, the role of pressure in increasing the electrode-electrolyte contact area, and the dominance of creep over vacancy diffusion.

Electrode particle cracking is one of the main phenomena driving battery capacity degradation. Recent phase field fracture studies have investigated particle cracking behaviour. However, only the beginning of life has been considered and effects such as damage accumulation have been neglected. Here, a multi-physics phase field fatigue model has been developed to study crack propagation in battery electrode particles undergoing hundreds of cycles. In addition, we couple our electrochemo-mechanical formulation with X-ray CT imaging to simulate fatigue cracking of realistic particle microstructures. Using this modelling framework, non-linear crack propagation behaviour is predicted, leading to the observation of an exponential increase in cracked area with cycle number. Three stages of crack growth (slow, accelerating and unstable) are observed, with phenomena such as crack initialisation at concave regions and crack coalescence having a significant contribution to the resulting fatigue crack growth rates. The critical values of C-rate, particle size and initial crack length are determined, and found to be lower than those reported in the literature using static fracture models. Therefore, this work demonstrates the importance of considering fatigue damage in battery degradation models and provides insights on the control of fatigue crack propagation to alleviate battery capacity degradation.

We present a phase field-based electro-chemo-mechanical formulation for modelling mechanics-enhanced corrosion and hydrogen-assisted cracking in elastic-plastic solids. A multi-phase-field approach is used to present, for the first time, a general framework for stress corrosion cracking, incorporating both anodic dissolution and hydrogen embrittlement mechanisms. We numerically implement our theory using the finite element method and defining as primary kinematic variables the displacement components, the phase field corrosion order parameter, the metal ion concentration, the phase field fracture order parameter and the hydrogen concentration. Representative case studies are addressed to showcase the predictive capabilities of the model in various materials and environments, attaining a promising agreement with benchmark tests and experimental observations. We show that the generalised formulation presented can capture, as a function of the environment, the interplay between anodic dissolution- and hydrogen-driven failure mechanisms; including the transition from one to the other, their synergistic action and their individual occurrence. Such a generalised framework can bring new insight into environment-material interactions and the understanding of stress corrosion cracking, as demonstrated here by providing the first simulation results for Gruhl's seminal experiments.

We investigate the influence of microstructural traps in hydrogen-assisted fatigue crack growth. To this end, a new formulation combining multi-trap stress-assisted diffusion, mechanism-based strain gradient plasticity and a hydrogen- and fatigue-dependent cohesive zone model is presented and numerically implemented. The results show that the ratio of loading frequency to effective diffusivity governs fatigue crack growth behaviour. Increasing the density of \emph{beneficial} traps, not involved in the fracture process, results in lower fatigue crack growth rates. The combinations of loading frequency and carbide trap densities that minimise embrittlement susceptibility are identified, providing the foundation for a rational design of hydrogen-resistant alloys.

We present a novel micromechanics-based phase field approach to model crack initiation and propagation in carbon nanotube (CNT) based composites. The constitutive mechanical and fracture properties of the nanocomposites are first estimated by a mean-field homogenisation approach. Inhomogeneous dispersion of CNTs is accounted for by means of equivalent inclusions representing agglomerated CNTs. Detailed parametric analyses are presented to assess the effect of the main micromechanical properties upon the fracture behaviour of CNT-based composites. The second step of the proposed approach incorporates the previously estimated constitutive properties into a phase field fracture model to simulate crack initiation and growth in CNT-based composites. The modelling capabilities of the framework presented is demonstrated through three paradigmatic case studies involving mode I and mixed mode fracture conditions.

We investigate the role of microstructural bridging on the fracture toughness of composite materials. To achieve this, a new computational framework is presented that integrates phase field fracture and cohesive zone models to simulate fibre breakage, matrix cracking and fibre-matrix debonding. The composite microstructure is represented by an embedded cell at the vicinity of the crack tip, whilst the rest of the sample is modelled as an anisotropic elastic solid. The model is first validated against experimental data of transverse matrix cracking from single-notched three-point bending tests. Then, the model is extended to predict the influence of grain bridging, brick-and-mortar microstructure and 3D fibre bridging on crack growth resistance. The results show that these microstructures are very efficient in enhancing the fracture toughness via fibre-matrix debonding, fibre breakage and crack deflection. In particular, the 3D fibre bridging effect can increase the energy dissipated at failure by more than three orders of magnitude, relative to that of the bulk matrix; well in excess of the predictions obtained from the rule of mixtures. These results shed light on microscopic bridging mechanisms and provide a virtual tool for developing high fracture toughness composites.

We present a phase field-based framework for modelling fatigue damage in Shape Memory Alloys (SMAs). The model combines, for the first time: (i) a generalised phase field description of fracture, incorporating multiple phase field formulations, (ii) a constitutive model for SMAs, based on a Drucker-Prager form of the transformation surface, and (iii) a fatigue degradation function, with damage driven by both elastic and transformation strains. The theoretical framework is numerically implemented, and the resulting linearised system is solved using a robust monolithic scheme, based on quasi-Newton methods. Several paradigmatic boundary value problems are addressed to gain insight into the role of transformation stresses, stress-strain hysteresis and temperature. Namely, we compute $\Delta \varepsilon-N$ curves, quantify Paris law parameters and predict fatigue crack growth rates in several geometries. In addition, the potential of the model for solving large-scale problems is demonstrated by simulating the fatigue failure of a 3D lattice structure.

The diffusivity of hydrogen in cold-rolled pure iron is investigated using permeation and desorption methods. Electrochemical charging, electro-permeation and thermal desorption spectroscopy (TDS) experiments are conducted. Firstly, the relation between the charging current and the hydrogen concentration is established. Secondly, permeation experiments are conducted at 22, 40 and 67{\deg}C to quantify the diffusivity dependence on temperature. Finally, the diffusivity is estimated by using two types of desorption experiments and Fick's law: (i) a `rest time' method, by which we measure the hydrogen content of samples held at room temperature for different times, and (ii) isothermal desorption experiments at temperatures ranging from 22 to 80{\deg}C, fitting the resulting desorption rate versus time curves. Good agreement is obtained between the isothermal desorption and permeation approaches, with observed differences discussed and rationalised. Moreover, measured diffusivity values for cold-rolled pure iron are also found to be comparable to those reported in the literature. This work demonstrates that isothermal desorption experiments are a convenient approach to determine hydrogen diffusivity over a wide range of temperatures, as facilitated by new TDS systems with fast heating rates.

We present a generalised phase field-based formulation for predicting fatigue crack growth in metals. The theoretical framework aims at covering a wide range of material behaviour. Different fatigue degradation functions are considered and their influence is benchmarked against experiments. The phase field constitutive theory accommodates the so-called AT1, AT2 and phase field-cohesive zone (PF-CZM) models. In regards to material deformation, both non-linear kinematic and isotropic hardening are considered, as well as the combination of the two. Moreover, a monolithic solution scheme based on quasi-Newton algorithms is presented and shown to significantly outperform staggered approaches. The potential of the computational framework is demonstrated by investigating several 2D and 3D boundary value problems of particular interest. Constitutive and numerical choices are compared and insight is gained into their differences and similarities. The framework enables predicting fatigue crack growth in arbitrary geometries and for materials exhibiting complex (cyclic) deformation and damage responses. The finite element code developed is made freely available at www.empaneda.com/codes.

In this study, we use the mechanism-based strain gradient plasticity theory to evaluate both crack tip dislocation density behaviour and the coupled effect of the material plastic properties and the intrinsic material length on non-linear amplitude factors. The two planar classical stress-strain states are examined, namely, plane strain and plane stress, both under pure mode I and pure mode II loading conditions. The constitutive relations are based on Taylor's dislocation model, which enables gaining insights into the role of the increased dislocation density associated with large gradients in plastic strain near cracks. The material model is implemented in a commercial finite element (FE) software package using a user subroutine, and the nonlinear stress intensity factors (SIF) are evaluated as a function of the intrinsic material length, characterising the scale at which gradient effects become significant. As a result of the FE calculations of dislocation density distributions, the effects of both the fracture mode and the stress-strain state are determined. In pure mode I, the geometrically necessary dislocation (GND) density is located symmetrically with respect to the blunted crack tip. On the contrary, under pure mode II, the GND density becomes concentrated in the blunted and sharp parts of the crack tip. In this case, fracture initiation is shown to be likely to occur near the blunted region of the crack tip, where both the stress triaxiality and the GND density are at their maximum. The relation between the equilibrium state of dislocation densities and the intrinsic material length as well as the plastic SIF as a function of the work hardening exponent is discussed.

We present a new mechanistic, phase field-based formulation for predicting hydrogen embrittlement. The multi-physics model developed incorporates, for the first time, a Taylor-based dislocation model to resolve the mechanics of crack tip deformation. This enables capturing the role of dislocation hardening mechanisms in elevating the tensile stress, hydrogen concentration and dislocation trap density within tens of microns ahead of the crack tip. The constitutive strain gradient plasticity model employed is coupled to a phase field formulation, to simulate the fracture process, and to a multi-trap hydrogen transport model. The analysis of stationary and propagating cracks reveals that the modelling framework presented is capable of adequately capturing the sensitivity to the hydrogen concentration, the loading rate, the material strength and the plastic length scale. In addition, model predictions are compared to experimental data of notch tensile strength versus hydrogen content on a high-strength steel; a very good agreement is attained. We define and implement both atomistic-based and phenomenological hydrogen degradation laws and discuss similarities, differences and implications for the development of parameter-free hydrogen embrittlement models.