State-dependent diffusion coefficients and free energies for nucleation processes from Bayesian trajectory analysis

ABSTRACT

The rate of nucleation processes such as the freezing of a supercooled liquid or the condensation of supersaturated vapour is mainly determined by the height of the nucleation barrier and the diffusion coefficient for the motion across it. Here, we use a Bayesian inference algorithm for Markovian dynamics to extract simultaneously the free energy profile and the diffusion coefficient in the nucleation barrier region from short molecular dynamics trajectories. The specific example we study is the nucleation of vapour bubbles in liquid water under strongly negative pressures, for which we use the volume of the largest bubble as a reaction coordinate. Particular attention is paid to the effects of discretisation, the implementation of appropriate boundary conditions and the optimal selection of parameters. We find that the diffusivity is a linear function of the bubble volume over wide ranges of volumes and pressures, and is mainly determined by the viscosity of the liquid, as expected from the Rayleigh–Plesset theory for macroscopic bubble dynamics. The method is generally applicable to nucleation processes and yields important quantities for the estimation of nucleation rates in classical nucleation theory.     

Spherical void expansion in rubber-like materials: The stabilizing effects of viscosity and inertia

Dynamic cavitation is known to be a typical failure mechanism in rubber-like solids. While the mechanical behaviour of these materials is generally rate-dependent, the number of theoretical and numerical works addressing the problem of cavitation using nonlinear viscoelastic constitutive models is scarce. It has been only in recent years when some authors have suggested that cavitation in rubber-like materials is a dynamic fracture process strongly affected by the rate-dependent behaviour of the material because of the large strains and strain rates that develop near the cavity. In the present work we further investigate previous idea and perform finite element simulations to model the dynamic expansion of a spherical cavity embedded into a rubber-like ball and subjected to internal pressure. To describe the mechanical behaviour of the rubber-like material we have used an experimentally calibrated constitutive model which includes rate-dependent effects and material failure. The numerical results demonstrate that inertia and viscosity play a fundamental role in the cavitation process since they stabilize the material behaviour and thus delay failure.     

弹性板水下爆炸冲击载荷的修正虚拟流体方法分析

研究非接触水下爆炸中板结构厚度和密度对冲击载荷和空化演变的影响.将近期发展的修正的虚拟流体方法推广应用于处理可压缩流体与弹性板结构的非线性相互作用.研究发现,假设结构不发生断裂破坏,较小的板厚度或密度可以减弱爆炸波对结构的冲击,冲击载荷随着厚度或密度的增大非线性地趋向于固壁边界下的结果.而且较小的板厚度或密度可以促使空化较早形成,产生较大的空化区,并推迟和减弱空化破裂对结构的二次冲击.     

Compressible simulations of bubble dynamics with central-upwind schemes

This paper discusses the implementation of an explicit density-based solver, that utilises the central-upwind schemes for the simulation of cavitating bubble dynamic flows. It is highlighted that, in conjunction with the Monotonic Upstream-Centered Scheme for Conservation Laws (MUSCL) scheme they are of second order in spatial accuracy; essentially they are high-order extensions of the Lax–Friedrichs method and are linked to the Harten Lax and van Leer (HLL) solver family. Basic comparison with the predicted wave pattern of the central-upwind schemes is performed with the exact solution of the Riemann problem, for an equation of state used in cavitating flows, showing excellent agreement. Next, the solver is used to predict a fundamental bubble dynamics case, the Rayleigh collapse, in which results are in accordance to theory. Then several different bubble configurations were tested. The methodology is able to handle the large pressure and density ratios appearing in cavitating flows, giving similar predictions in the evolution of the bubble shape, as the reference.     

The influence of air content in water on ultrasonic cavitation field

Cavitation is a complex physical phenomenon affected by many factors, one of which is the gas dissolved in the medium. Researchers have given some efforts to the influence of gas content on sonoluminescence or some specific chemical reactions in and around the bubble, but limited work has been reported about the influence on the ultrasonic cavitation field distribution. In this work, the intensity distribution of the ultrasound field in a cleaning tank has been measured with the hydrophone. After analysed and visualised by MATLAB software, it was found that the cavitation intensity distribution in degassed water was much better than that in tap water. And further study proved that degassing process can improve the cavitation effect dramatically both in intensity and scope. Finally, the cavitation fields in mediums with different gas content were measured and the specific influence of air content on cavitation field was discussed.     

Sonication effects on non-radical reactions. A sonochemistry beyond the cavitation?

The kinetics of pH-independent hydrolysis of 4-methoxyphenyl dichloroacetate were investigated under ultrasonic irradiation with an application of 10% of the maximum power of the equipment and without sonication in acetonitrile–water binary mixtures with a content of acetonitrile ranging from 0.008 to 35 wt.%. Similar kinetic investigations were performed at intensities corresponding to 10%, 20%, 30%, 40%, and 50% of the input energy in solvent mixtures containing 10 wt.% and 25 wt.% acetonitrile. In parallel, the responses of KI and terephthalic acid dosimeters at applied irradiation levels were registered under the same experimental conditions. Significant kinetic sonication effects were found at sound intensities presumably not inducing cavitation in the solution. This result provides an experimental evidence of kinetic effects of ultrasound in the absence of cavitation. A disturbing impact of cavitation on the ultrasonic acceleration of the reaction was found. The implications of these findings were discussed.     

Monitoring of transient cavitation induced by ultrasound and intense pulsed light in presence of gold nanoparticles

One of the most important challenges in medical treatment is invention of a minimally invasive approach in order to induce lethal damages to cancer cells. Application of high intensity focused ultrasound can be beneficial to achieve this goal via the cavitation process. Existence of the particles and vapor in a liquid decreases the ultrasonic intensity threshold required for cavitation onset. In this study, synergism of intense pulsed light (IPL) and gold nanoparticles (GNPs) has been investigated as a means of providing nucleation sites for acoustic cavitation. Several approaches have been reported with the aim of cavitation monitoring. We conducted the experiments on the basis of sonochemiluminescence (SCL) and chemical dosimetric methods. The acoustic cavitation activity was investigated by determining the integrated SCL signal acquired over polyacrylamide gel phantoms containing luminol in the presence and absence of GNPs in the wavelength range of 400–500 nm using a spectrometer equipped with cooled charged coupled devices (CCD) during irradiation by different intensities of 1 MHz ultrasound and IPL pulses. In order to confirm these results, the terephthalic acid chemical dosimeter was utilized as well. The SCL signal recorded in the gel phantoms containing GNPs at different intensities of ultrasound in the presence of intense pulsed light was higher than the gel phantoms without GNPs. These results have been confirmed by the obtained data from the chemical dosimetry method. Acoustic cavitation in the presence of GNPs and intense pulsed light has been suggested as a new approach designed for decreasing threshold intensity of acoustic cavitation and improving targeted therapeutic effects.     

Electrochemical investigations of stable cavitation from bubbles generated during reduction of water

Megasonic cleaning is traditionally used for removal of particles from wafer surfaces in semiconductor industry. With the advancement of technology node, the major challenge associated with megasonic cleaning is to be able to achieve high cleaning efficiency without causing damage to fragile features. In this paper, a method based on electrochemistry has been developed that allows controlled formation and growth of a hydrogen bubbles close to a solid surface immersed in an aqueous solution irradiated with ∼1 MHz sound field. It has been shown that significant microstreaming from resonating size bubble can be induced by proper choice of transducer duty cycle. This method has the potential to significantly improve the performance of megasonic cleaning technology through generation of local microstreaming, interfacial and pressure gradient forces in close vicinity of conductive surfaces on wafers without affecting the transient cavitation responsible for feature damage.     

Acoustic and hydrodynamic cavitation assisted hydrolysis and valorisation of waste human hair for the enrichment of amino acids

Hair waste in large amount is produced in India from temples and saloons, India alone exported approximately 1 million kg of hair in 2010. Incineration and degradation of waste human hair leads to environmental concerns. The hydrothermal process is a conventional method for the production of hair hydrolysate. The hydrothermal process is carried out at a very high temperature and pressure, which causes the degradation of heat-sensitive essential amino acids, thereby depleting the nutritional value. This work deals with alkaline hydrolysis of human hair using acoustic and hydrodynamic cavitation, and comparison with the conventional method. The optimal operating conditions for highest efficiency was observed, for the hydrolysis of 1 g of sample hairs in 100 mL of solution, at 4:1 (KOH: hair) ratio, soaking time of 24 h, the ultrasonic power density of 600 W dm⁻³ (20 KHz frequency and input power 200 W) or hydrodynamic cavitation inlet pressure of 4 or 7 bars. Cavitation results in rupture of disulfide linkages in proteins and mechanical effects lead to cleavage of several hydrogen bonds breaking the keratin sheet structure in hair. Breakdown of bonds leads to a decrease in viscosity of the solution. 10% and 6% reduction in viscosity is obtained at optimal conditions for ultrasonic and hydrodynamic cavitation treatment, respectively. FTIR analysis of produced hair hydrolysate confirmed that the disulfide bonds in hair proteins are broken down during cavitation. The amino acid of hair hydrolysate, prepared using cavitation, has a relatively higher digestibility and nutritional value due to the enhancement of amino-acid content, confirmed using amino acid analysis. Cavitation assisted hair hydrolysate has a potential application in agricultural engineering as a fertilizer for improvement of the quality of the soil and land. Cavitation based hair hydrolysate can also be used as an environmentally friendly and economical source of essential amino acids and digestibles for animal or poultry feed.     

Numerical study on the desorption processes of oil droplets inside oil-contaminated sand under cavitation micro-jets

The removal of the adsorbed oil droplet is critical to deoiling treatment of oil-bearing solid waste. Ultrasonic cavitation is regarded as an extremely useful method to assist the oil droplets desorption in the deoiling treatment. In this paper, the effects of cavitation micro-jets on the oil droplets desorption were studied. The adsorbed states of oil droplets in the oil-contaminated sand were investigated using a microscope. Three representative absorbed states of the oil droplets can be summarized as: (1) the individual oil droplet adsorbed on the particle surface (2) the clustered oil droplets adsorbed on the particle surface; (3) the oil droplet adsorbed in a gap between particles. The micro-jet generation during the bubble collapse near a rigid wall under different acoustic pressure amplitudes at an ultrasonic frequency of 20 kHz was investigated numerically. The desorption processes of the oil droplets at the three representative absorbed states under micro-jets were also simulated subsequently. The results showed that the acoustic pressure has a great influence on the velocity of micro-jet, and the initial diameter of cavitation bubbles is significant for the cross-sectional area of micro-jets. The wall jet caused by a micro-jet impacting on the solid wall is the most important factor for the removal of the absorbed oil droplets. The oil droplet is broken by the jet impinging, and then it breaks away from the solid wall due to the shear force generated by the wall jet. In addition to a higher sound pressure, the cavitation bubble at a larger initial diameter is more important for the desorption of the clustered oil droplets. Conversely, the micro-jet generated by the cavitation bubble at a smaller initial diameter (0.1 mm) is more appropriate for the desorption of the oil droplet in a narrow or sharp-angled gap.