Modelling the effect of acoustic waves on the thermodynamics and kinetics of phase transformation in a solution: Including mass transportation

Effects of acoustic waves on a phase transformation in a metastable phase were investigated in our previous work [S. R. Haqshenas, I. J. Ford, and N. Saffari, “Modelling the effect of acoustic waves on nucleation,” J. Chem. Phys. 145, 024315 (2016)]. We developed a non-equimolar dividing surface cluster model and employed it to determine the thermodynamics and kinetics of crystallisation induced by an acoustic field in a mass-conserved system. In the present work, we developed a master equation based on a hybrid Szilard-Fokker-Planck model, which accounts for mass transportation due to acoustic waves. This model can determine the kinetics of nucleation and the early stage of growth of clusters including the Ostwald ripening phenomenon. It was solved numerically to calculate the kinetics of an isothermal sonocrystallisation process in a system with mass transportation. The simulation results show that the effect of mass transportation for different excitations depends on the waveform as well as the imposed boundary conditions and tends to be noticeable in the case of shock waves. The derivations are generic and can be used with any acoustic source and waveform

Modelling the effect of acoustic waves on the thermodynamics and kinetics of phase transformation in a solution: Including mass transportation

Effects of acoustic waves on a phase transformation in a metastable phase were investigated in our previous work [S. R. Haqshenas, I. J. Ford, and N. Saffari, “Modelling the effect of acoustic waves on nucleation,” J. Chem. Phys. 145, 024315 (2016)]. We developed a non-equimolar dividing surface cluster model and employed it to determine the thermodynamics and kinetics of crystallisation induced by an acoustic field in a mass-conserved system. In the present work, we developed a master equation based on a hybrid Szilard-Fokker-Planck model, which accounts for mass transportation due to acoustic waves. This model can determine the kinetics of nucleation and the early stage of growth of clusters including the Ostwald ripening phenomenon. It was solved numerically to calculate the kinetics of an isothermal sonocrystallisation process in a system with mass transportation. The simulation results show that the effect of mass transportation for different excitations depends on the waveform as well as the imposed boundary conditions and tends to be noticeable in the case of shock waves. The derivations are generic and can be used with any acoustic source and waveform

Modelling the effect of acoustic waves on nucleation

A phase transformation in a metastable phase can be affected when it is subjected to a high intensity ultrasound wave. In this study we determined the effect of oscillation in pressure and temperature on a phase transformation using the Gibbs droplet model in a generic format. The developed model is valid for both equilibrium and non-equilibrium clusters formed through a stationary or non-stationary process. We validated the underlying model by comparing the predicted kinetics of water droplet formation from the gas phase against experimental data in the absence of ultrasound. Our results demonstrated better agreement with experimental data in comparison with classical nucleation theory. Then, we determined the thermodynamics and kinetics of nucleation and the early stage of growth of clusters in an isothermal sonocrystallisation process. This new contribution shows that the effect of pressure on the kinetics of nucleation is cluster size-dependent in contrast to classical nucleation theory

Modelling the effect of acoustic waves on nucleation

A phase transformation in a metastable phase can be affected when it is subjected to a high intensity ultrasound wave. In this study we determined the effect of oscillation in pressure and temperature on a phase transformation using the Gibbs droplet model in a generic format. The developed model is valid for both equilibrium and non-equilibrium clusters formed through a stationary or non-stationary process. We validated the underlying model by comparing the predicted kinetics of water droplet formation from the gas phase against experimental data in the absence of ultrasound. Our results demonstrated better agreement with experimental data in comparison with classical nucleation theory. Then, we determined the thermodynamics and kinetics of nucleation and the early stage of growth of clusters in an isothermal sonocrystallisation process. This new contribution shows that the effect of pressure on the kinetics of nucleation is cluster size-dependent in contrast to classical nucleation theory

Modelling the effect of acoustic waves on the thermodynamics and kinetics of crystal nucleation from a solution

A phase transformation in a metastable solution can be affected when it is subjected to high-intensity acoustic waves. Despite the extensive experimental evidence, the nature of this phenomenon has been little studied theoretically. This work aims to tackle this issue and develop the theoretical basis for investigating the thermodynamics and kinetics of crystallisation induced by an acoustic field. In the first part of thesis, we investigated the effect of acoustic waves on the thermodynamics of crystallisation by the aid of the Gibbs droplet model in a generic format. We have developed a new model based on non-equimolecular clusters which can overcome some of the shortcomings of the conventional form of the classical nucleation theory (CNT) in describing the thermodynamics of small clusters. The model is validated by comparing the predicted kinetics of water droplet formation from the gas phase against experimental data. Our results demonstrate a close agreement with experimental data, better than predictions by CNT. In the second part, we studied the kinetics of phase transformation in an acoustic field. We developed a master equation based on a hybrid Szilard-Fokker Planck model, which accounts for mass transportation due to acoustic waves. This model is employed to determine the kinetics of nucleation and the early stage of growth of clusters including the Ostwald ripening phenomenon in an isothermal sonocrystallisation process and is solved numerically for different scenarios in a system with and without mass transportation. Our results show that the effect of pressure on the kinetics of nucleation is cluster size-dependent in contrast to CNT. Furthermore, we calculated mass transportation for different excitations modelled as plane waves propagating in a semi-infinite medium which tends to be rather noticeable only in the case of shock waves. The derivations are generic and can be used with any acoustic source and waveform

Modelling the Physics of Bubble Nucleation in Histotripsy

This work aims to establish a theoretical framework for the modeling of bubble nucleation in histotripsy. A phenomenological version of the classical nucleation theory was parametrized with histotripsy experimental data, fitting a temperature-dependent activity factor that harmonizes theoretical predictions and experimental data for bubble nucleation at both high and low temperatures. Simulations of histotripsy pressure and temperature fields are then used in order to understand spatial and temporal properties of bubble nucleation at varying sonication conditions. This modeling framework offers a thermodynamic understanding on the role of the ultrasound frequency, waveforms, peak focal pressures, and duty cycle on patterns of ultrasound-induced bubble nucleation. It was found that at temperatures lower than 50 °C, nucleation rates are more appreciable at very large negative pressures such as -30 MPa. For focal peak-negative pressures of -15 MPa, characteristic of boiling histotripsy, nucleation rates grow by 20 orders of magnitude in the temperature interval 60 °C-100 °C

Mechanisms of nuclei growth in ultrasound bubble nucleation

This paper interrogates the intersections between bubble dynamics and classical nucleation theory (CNT) towards constructing a model that describes intermediary nucleation events between the extrema of cavitation and boiling. We employ Zeldovich's hydrodynamic approach to obtain a description of bubble nuclei that grow simultaneously via hydrodynamic excitation by the acoustic field and vapour transport. By quantifying the relative dominance of both mechanisms, it is then possible to discern the extent to which viscosity, inertia, surface tension and vapour transport shape the growth of bubble nuclei through non-dimensional numbers that naturally arise within the theory. The first non-dimensional number Φ12/Φ2 is analogous to the Laplace number, representing the balance between surface tension and inertial constraints to viscous effects. The second non-dimensional number δ represents how enthalpy transport into the bubble can reduce nucleation rates by cooling the surrounding liquid. This formulation adds to the current understanding of ultrasound bubble nucleation by accounting for bubble dynamics during nucleation, quantifying the physical distinctions between “boiling” and “cavitation” bubbles through non-dimensional parameters, and outlining the characteristic timescales of nucleation according to the growth mechanism of bubbles throughout the histotripsy temperature range. We observed in our simulations that viscous effects control the process of ultrasound nucleation in water-like media throughout the 0–120 °C temperature range, although this dominance decreases with increasing temperatures. Enthalpy transport was found to reduce nucleation rates for increasing temperatures. This effect becomes significant at temperatures above 30 °C and favours the creation of fewer nuclei that are larger in size. Conversely, negligible enthalpy transport at lower temperatures can enable the nucleation of dense clusters of small nuclei, such as cavitation clouds. We find that nuclei growth as modelled by the Rayleigh-Plesset equation occurs over shorter timescales than as modelled by vapour-dominated growth. This suggests that the first stage of bubble nuclei growth is hydrodynamic, and vapour transport effects can only be observed over longer timescales. Finally, we propose that this framework can be used for comparison between different experiments in bubble nucleation, towards standardisation and dosimetry of protocols

Benchmarking preconditioned boundary integral formulations for acoustics.

The boundary element method (BEM) is an efficient numerical method for simulating harmonic wave propagation. It uses boundary integral formulations of the Helmholtz equation at the interfaces of piecewise homogeneous domains. The discretization of its weak formulation leads to a dense system of linear equations, which is typically solved with an iterative linear method such as GMRES. The application of BEM to simulating wave propagation through large-scale geometries is only feasible when compression and preconditioning techniques reduce the computational footprint. Furthermore, many different boundary integral equations exist that solve the same boundary value problem. The choice of preconditioner and boundary integral formulation is often optimized for a specific configuration, depending on the geometry, material characteristics, and driving frequency. On the one hand, the design flexibility for the BEM can lead to fast and accurate schemes. On the other hand, efficient and robust algorithms are difficult to achieve without expert knowledge of the BEM intricacies. This study surveys the design of boundary integral formulations for acoustics and their acceleration with operator preconditioners. Extensive benchmarks provide valuable information on the computational characteristics of several hundred different models for multiple reflection and transmission of acoustic waves

Boundary integral formulations for acoustic modelling of high-contrast media

The boundary element method is an efficient algorithm for simulating acoustic propagation through homogeneous objects embedded in free space. The conditioning of the system matrix strongly depends on physical parameters such as density, wavespeed and frequency. In particular, high contrast in density and wavespeed across a material interface leads to an ill-conditioned discretisation matrix. Therefore, the convergence of Krylov methods to solve the linear system is slow. Here, specialised boundary integral formulations are designed for the case of acoustic scattering at high-contrast media. The eigenvalues of the resulting system matrix accumulate at two points in the complex plane that depend on the density ratio and stay away from zero. The spectral analysis of the Calderón preconditioned PMCHWT formulation yields a single accumulation point. Benchmark simulations demonstrate the computational efficiency of the high-contrast Neumann formulation for scattering at high-contrast media

Benchmarking preconditioned boundary integral formulations for acoustics

The boundary element method (BEM) is an efficient numerical method for simulating harmonic wave scattering. It uses boundary integral formulations of the Helmholtz equation at the interfaces of piecewise homogeneous domains. The discretisation of its weak formulation leads to a dense system of linear equations, which is typically solved with an iterative linear method such as GMRES. The application of BEM to simulating wave scattering at large-scale geometries is only feasible when compression and preconditioning techniques reduce the computational footprint. Furthermore, many different boundary integral equations exist that solve the same boundary value problem. The choice of preconditioner and boundary integral formulation is often optimised for a specific configuration, depending on the geometry, material characteristics, and driving frequency. On the one hand, the design flexibility for the BEM can lead to fast and accurate schemes. On the other hand, efficient and robust algorithms are difficult to achieve without expert knowledge of the BEM intricacies. This study surveys the design of boundary integral formulations for acoustics and their acceleration with operator preconditioners. Extensive benchmarking provide valuable information on the computational characteristics of several hundred different models for multiple scattering and transmission of acoustic wave fields