Combining phase field crystal methods with a Cahn-Hilliard model for binary alloys

During phase transitions certain properties of a material change, such as composition field and lattice-symmetry distortions. These changes are typically coupled, and affect the microstructures that form in materials. Here, we propose a 2D theoretical framework that couples a Cahn-Hilliard (CH) model describing the composition field of a material system, with a phase field crystal (PFC) model describing its underlying microscopic configurations. We couple the two continuum models via coordinate transformation coefficients. We introduce the transformation coefficients in the PFC method, to describe affine lattice deformations. These transformation coefficients are modeled as functions of the composition field. Using this coupled approach, we explore the effects of coarse-grained lattice symmetry and distortions on a phase transition process. In this paper, we demonstrate the working of the CH-PFC model through three representative examples: First, we describe base cases with hexagonal and square lattice symmetries for two composition fields. Next, we illustrate how the CH-PFC method interpolates lattice symmetry across a diffuse composition phase boundary. Finally, we compute a Cahn-Hilliard type of diffusion and model the accompanying changes to lattice symmetry during a phase transition process.Comment: 9 pages, 5 figure

Modeling Grain Boundaries using a Phase Field Technique

We propose a two dimensional frame-invariant phase field model of grain impingement and coarsening. One dimensional analytical solutions for a stable grain boundary in a bicrystal are obtained, and equilibrium energies are computed. We are able to calculate the rotation rate for a free grain between two grains of fixed orientation. For a particular choice of functional dependencies in the model the grain boundary energy takes the same analytic form as the microscopic (dislocation) model of Read and Shockley.Comment: 4 pages, 2 figure

Li-diffusion accelerates grain growth in intercalation electrodes: a phase-field study

Grain boundary migration is driven by the boundary's curvature and external loads such as temperature and stress. In intercalation electrodes an additional driving force results from Li-diffusion. That is, Li-intercalation induces volume expansion of the host-electrode, which is stored as elastic energy in the system. This stored energy is hypothesized as an additional driving force for grain boundaries and edge dislocations. Here, we apply the 2D Cahn-Hilliard$-$phase-field-crystal (CH-PFC) model to investigate the coupled interactions between highly mobile Li-ions and host-electrode lattice structure, during an electrochemical cycle. We use a polycrystalline FePO$_{4}$/ LiFePO$_{4}$ electrode particle as a model system. We compute grain growth in the FePO$_{4}$ electrode in two parallel studies: In the first study, we electrochemically cycle the electrode and calculate Li-diffusion assisted grain growth. In the second study, we do not cycle the electrode and calculate the curvature-driven grain growth. External loads, such as temperature and stress, did not differ across studies. We find the mean grain-size increases by $\sim11\%$ in the electrochemically cycled electrode particle. By contrast, in the absence of electrochemical cycling, we find the mean grain-size increases by $\sim2\%$ in the electrode particle. These CH-PFC computations suggest that Li-intercalation accelerates grain-boundary migration in the host-electrode particle. The CH-PFC simulations provide atomistic insights on diffusion-induced grain-boundary migration, edge dislocation movement and triple-junction drag-effect in the host-electrode microstructure.Comment: 11 pages, 9 figure

Thermodynamic phase-field model for microstructure with multiple components and phases: the possibility of metastable phases

A diffuse-interface model for microstructure with an arbitrary number of components and phases was developed from basic thermodynamic and kinetic principles and formalized within a variational framework. The model includes a composition gradient energy to capture solute trapping, and is therefore suited for studying phenomena where the width of the interface plays an important role. Derivation of the inhomogeneous free energy functional from a Taylor expansion of homogeneous free energy reveals how the interfacial properties of each component and phase may be specified under a mass constraint. A diffusion potential for components was defined away from the dilute solution limit, and a multi-obstacle barrier function was used to constrain phase fractions. The model was used to simulate solidification via nucleation, premelting at phase boundaries and triple junctions, the intrinsic instability of small particles, and solutal melting resulting from differing diffusivities in solid and liquid. The shape of metastable free energy surfaces is found to play an important role in microstructure evolution and may explain why some systems premelt at phase boundaries and phase triple junctions while others do not.Comment: 14 pages, 8 figure

Photonic Crystals: Numerical Predictions of Manufacturable Dielectric Composite Architectures

Photonic properties depend on both dielectric contrast in a microscopic composite and the arrangement of the microstructural components. No theory exists for direct prediction of photonic properties, and so progress relies on numerical methods combined with insight into manufacturable composite architectures. We present a discussion of effective photonic crystal production techniques and several numerical methods to predict dispersion relations of hypothetical but fabricable structures.Singapore-MIT Alliance (SMA

Realising the technological promise of smartphones in addiction research and treatment: An ethical review

Background Smartphone technologies and mHealth applications (or apps) promise unprecedented scope for data collection, treatment intervention, and relapse prevention when used in the field of substance abuse and addiction. This potential also raises new ethical challenges that researchers, clinicians, and software developers must address. Aims This paper aims to identify ethical issues in the current uses of smartphones in addiction research and treatment. Methods A search of three databases (PubMed, Web of Science and PsycInfo) identified 33 studies involving smartphones or mHealth applications for use in the research and treatment of substance abuse and addiction. A content analysis was conducted to identify how smartphones are being used in these fields and to highlight the ethical issues raised by these studies. Results Smartphones are being used to collect large amounts of sensitive information, including personal information, geo-location, physiological activity, self-reports of mood and cravings, and the consumption of illicit drugs, alcohol and nicotine. Given that detailed information is being collected about potentially illegal behaviour, we identified the following ethical considerations: protecting user privacy, maximising equity in access, ensuring informed consent, providing participants with adequate clinical resources, communicating clinically relevant results to individuals, and the urgent need to demonstrate evidence of safety and efficacy of the technologies. Conclusions mHealth technology offers the possibility to collect large amounts of valuable personal information that may enhance research and treatment of substance abuse and addiction. To realise this potential researchers, clinicians and app-developers must address these ethical concerns to maximise the benefits and minimise risks of harm to users

Classifying the mechanisms of electrochemical shock in ion-intercalation materials

“Electrochemical shock” – the electrochemical cycling-induced fracture of materials – contributes to impedance growth and performance degradation in ion-intercalation batteries, such as lithium-ion. Using a combination of micromechanical models and acoustic emission experiments, the mechanisms of electrochemical shock are identified, classified, and modeled in targeted model systems with different composition and microstructure. A particular emphasis is placed on mechanical degradation occurring in the first electrochemical cycle. Three distinct mechanisms of electrochemical shock are identified, and a fracture mechanics failure criterion is derived for each mechanism. In a given material system, crystal symmetry and phase-behavior determine the active mechanisms. A surprising result is that electrochemical shock in commercial lithium-storage materials occurs by mechanisms that are insensitive to the electrochemical cycling rate. This fundamental understanding of electrochemical shock leads naturally to practical design criteria for battery materials and microstructures that improve performance and energy storage efficiency. These microstructure and crystal chemical design criteria are demonstrated experimentally for spinel materials such as LiMn2O4 and LiMn1.5Ni0.5O4. A case study of LiMn1.5Ni0.5O4 is presented, in which small changes in composition that have negligible impact on electrochemical properties induce a significant change in phase behavior that allow electrochemical shock at relevant electrochemical cycling rates to be avoided. Although lithium-storage materials are used as model systems for experimental study, the physical phenomena are common to other ion-intercalation systems, including sodium- and magnesium-storage compounds

Mechanical and electrochemical response of all-solid-state lithium-ion batteries

All-solid-state rechargeable lithium-ion batteries have attracted much interest because they have features particularly favorable for large-scale application to automotive applications and to stationary load-leveling for intermittent power generation from solar or wind energy. The replacement of an organic liquid electrolyte with a nonflammable and more reliable inorganic solid electrolyte (SE) simplifies the battery design and improves safety and durability of the system [1]. However, the mechanical behavior of such electrodes will be considerably different than their liquid electrolyte counterparts. Direct stacking of solid-state cells enables the achievement of high operating voltages in a reduced volume. Furthermore, all-solid-state batteries allow the use of large-capacity electrode materials, for instance, sulfur positive electrode paired with a lithium metal negative electrode, which are difficult to employ in conventional liquid electrolyte batteries. A key development to the success of all-solid-state batteries is a SE with high Li+ ion conductivity at room Temperature [2, 3, 4]. In recent years, several SEs having the same level of conductivity as organic liquid electrolytes have been discovered and tested with many active materials. The durability of a cohering solid–solid interface between electrode and electrolyte is likely to be important practical consideration. Notwithstanding the several techniques have been investigated to increase the contact area at the interface [5], interface cohesion and its effects on the rate capability and the overall performance throughout the expected life cycles needs to be maintained. This research focuses on the development of a nonlinear continuum model able to account for the combined effects of Li diffusion and for the consequent isotropic or anisotropic volumetric expansion of the hosting material. The electrode and electrolyte are modeled as idealized as elastic-viscoplastic materials, with elastic properties varying with lithium concentration. A discrete approximation of such a model has been implemented (in the framework of finite elements) to simulate mechanical and elctrochemical response of the system. Side reactions being mostly inhibited in all-solid cells, the battery life depends in larger measure on the mechanical integrity of the composite system [6]. As physical values for the SE’s mechanical behavior are not available, our calculations indicate trends of how mechanical reliability will depend on temperature-dependent viscoelastic behavior. When mechanical properties become available, they can be used directly in our model. Of relevant practical interest is thus the prediction of stress, plastic flow, and damage within the bulk and in particular at the electrode–electrolyte interface. KEY WORDS Lithium ion batteries, All-solid-state batteries, Electrochemical–mechanical continuum model, Diffusion, Elasto-viscoplastic material REFERENCES [1] Kazunori Takada. Progress and prospective of solid-state lithium batteries. Acta Materialia. 2013, 61(3), 759–770. [2] Bates, J.B., Dudney, N.J., Neudecker, B., Ueda, A., Evans, C.D. Thin-film lithium and lithium-ion batteries. Solid State Ionics. 2000, 135(1–4), 33–45. [3] Yoshikatsu Seino, Tsuyoshi Ota, Kazunori Takada, Akitoshi Hayashi, and Masahiro Tatsumisago. A sulphide lithium super ion conductor is superior to liquid ion conductors for use in rechargeable batteries. Energy Environ. Sci. 2014, 7, 627–631. [4] Noriaki Kamaya, Kenji Homma, Yuichiro Yamakawa, Masaaki Hirayama, Ryoji Kanno, Masao Yonemura, Takashi Kamiyama, Yuki Kato, Shigenori Hama, Koji Kawamoto, Akio Mitsui. A lithium superionic conductor. Nature Mater. 2011, 10(9), 682–686. [5] Masahiro Tatsumisago, Motohiro Nagao, Akitoshi Hayashi. Recent development of sulfide solid electrolytes and interfacial modification for all-solid-state rechargeable lithium batteries. J Asian Ceram Soc. 2013, 1(1), 17–25. [6] Akitoshi Hayashi, Kousuke Noi, Atsushi Sakuda, Masahiro Tatsumisago. Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries. Nature Commun. 2012, 3

Atomistic Simulations of Metallic Cluster Coalescence

A new computational method is introduced to investigate the stresses developed in the island-coalescence stage of polycrystalline film formation during deposition. The method uses molecular dynamics to examine the behavior of clusters of atoms both in free space and on substrates. Continuum treatments used in previous models may not be applicable at small length scales or low dimensionality. In atomistic simulations, the effects of surface diffusion, bond straining and defect formation can be directly studied. TEM experiments will be used to evaluate the validity of the simulation model.Singapore-MIT Alliance (SMA

Mechanical Properties of Bulk Metallic Glasses and Composites

We have studied the mechanical properties of monolithic bulk metallic glasses and composite in the La based alloys. La₈₆₋yAl₁₄(Cu, Ni)y (y=24 to 32) alloy systems was used to cast the in-situ structure and subsequently tested under compression. We found that the ductility of the monolithic is actually poorer than that of the fully crystalline composite.Singapore-MIT Alliance (SMA