Mineralogy of microbially induced calcium carbonate precipitates formed using single cell drop-based microfluidics

Microbe-mineral interactions are ubiquitous and can facilitate major biogeochemical reactions that drive dynamic Earth processes such as rock formation. One example is microbially induced calcium carbonate precipitation (MICP) in which microbial activity leads to the formation of calcium carbonate precipitates. A majority of MICP studies have been conducted at the mesoscale but fundamental questions persist regarding the mechanisms of cell encapsulation and mineral polymorphism. Here, we are the first to investigate and characterize precipitates on the microscale formed by MICP starting from single ureolytic E. coli MJK2 cells in 25 µm diameter drops. Mineral precipitation was observed over time and cells surrounded by calcium carbonate precipitates were observed under hydrated conditions. Using Raman microspectroscopy, amorphous calcium carbonate (ACC) was observed first in the drops, followed by vaterite formation. ACC and vaterite remained stable for up to 4 days, possibly due to the presence of organics. The vaterite precipitates exhibited a dense interior structure with a grainy exterior when examined using electron microscopy. Autofluorescence of these precipitates was observed possibly indicating the development of a calcite phase. The developed approach provides an avenue for future investigations surrounding fundamental processes such as precipitate nucleation on bacteria, microbe-mineral interactions, and polymorph transitions.

Coupling of Computational Thermodynamics with Kinetic Models for Predictive Simulations of Materials Properties

We present successful examples of CALPHAD thermodynamics-based precipitation simulations for three important alloy groups: Single-crystal Ni-base superalloy, austenitic stainless steel and hardenable Al-alloy. Underlying physical models for special features, such as, energies of diffuse interfaces between coherent precipitates and matrix, precipitation of incoherent particles at grain boundaries, evolution of excess vacancies during quenching and continuous aging and their role for metastable precipitate nucleation, are discussed.

A design equation for low dosage additives that accelerate nucleation

Additives are used to control nucleation in many natural and industrial environments. However, the mechanisms by which additives inhibit or accelerate solute precipitate nucleation are not well understood. We propose an equation that predicts changes in nucleation barriers based on the adsorption properties and concentrations of trace additives. The equation shows that nucleant efficacy depends on the product of an adsorption equilibrium constant and the reduction in interfacial tension. Moreover, the two factors that determine the potency of additives are related to each other, suggesting that assays of just one property might facilitate additive design. We test the design equation for a Potts lattice gas model with surfactant-like additives in addition to solutes and solvents.

Finding Critical Nuclei in Phase Transformations by Shrinking Dimer Dynamics and its Variants

We investigate the critical nuclei morphology in phase transformation by combining two effective ingredients, with the first being the phase field modeling of the relevant energetics which has been a popular approach for phase transitions and the second being shrinking dimer dynamics and its variants for computing saddle points and transition states. In particular, the newly formulated generalized shrinking dimer dynamics is proposed by adopting the Cahn-Hilliard dynamics for the generalized gradient system. As illustrations, a couple of typical cases are considered, including a generic system modeling heterogeneous nucleation and a specific material system modeling the precipitate nucleation in FeCr alloys. While the standard shrinking dimer dynamics can be applied to study the non-conserved case of generic heterogeneous nucleation directly, the generalized shrinking dimer dynamics is efficient to compute precipitate nucleation in FeCr alloys due to the conservation of concentration. Numerical simulations are provided to demonstrate both the complex morphology associated with nucleation events and the effectiveness of generalized shrinking dimer dynamics based on phase field models.

The Influence of Mg and Ag on the Precipitation Kinetics and the Formation of the T1 Phase in Al-Cu-Li Alloys

Al-Cu-Li alloys are extensively used for aerospace applications. The main hardening phase is the T1phase that precipitates as thin platelets on {111}Alplanes. To facilitate its nucleation, different minor alloying elements are added and dislocations are introduced by cold deformation before the ageing treatment. The impact of these additions in combination with the presence of dislocations on precipitate nucleation and growth needs a deeper understanding. In this work, we investigated the precipitation kinetics of the T1phase in alloys containing a common content of Cu and Li and different contents of minor solutes (Mg, Ag) where these elements are present either together or independently. A general overview on the precipitation kinetics was achieved by in-situ small-angle X-ray scattering and hardness measurements. The evaluation of precipitation kinetics reveals that magnesium plays an important role during precipitation by enhancing nucleation kinetics. Additionally, a smaller yet measureable effect of Ag, both in the presence and absence of Mg has been evidenced.