arXiv subjects

Masao Iwamatsu

Publications and source records attributed to Masao Iwamatsu.

At least 37 records · Page 2Linked to original sources

arXiv2013

Heterogeneous nucleation on a completely wettable substrate

It is widely believed that heterogeneous nucleation occurs without an activation process when the surface is completely wettable. In this report, we review our previous work [J.Chem.Phys {\bf 134}, 234709 (2011)] to show that the critical nucleus (droplet) can exist and the activation process may be observable. In fact, a critical nucleus and a free energy barrier always exist if the surface potential or the disjoining pressure allows for the first-order pre-wetting transition on a completely wettable substrate where the contact angle is zero. Furthermore, the critical nucleus changes character from the critical nucleus of surface phase transition below bulk coexistence (undersaturation) to the critical nucleus of bulk heterogeneous nucleation above the coexistence (oversaturation) when it crosses the coexistence. In this paper the morphology and work of formation of a critical nucleus on a completely-wettable substrate are re-examined to point out the possibility of observing a critical droplet on a completely wettable substrate.

cond-mat.mtrl-sci↗

arXiv2012

The characterization of wettability of substrates by liquid nanodrops

Wettability of a substrates is characterized by a contact angle. Applicability of the simple formula developed by Derjaguin, which relates to the contact angle and disjoining pressure to nano-scale liquid droplets is reconsidered within the framework of the theory of the first-order wetting transition of volatile liquids. It is concluded that his formula is generally correct for large droplets on an incompletely-wettable substrate. But it can not be applied to nanodroplets, in particular, on a completely-wettable substrate. An effective contact angle can be defined even for the nanaodroplet. A formula similar to the Derjaguin formula is proposed by which we can calculate the contact angle of nanodorplets on both an incompletely- and a completely-wettable substrate for which the whole volume of the droplet is under the influence of the disjoining pressure.

cond-mat.soft↗

arXiv2012

Nucleation pathway of core-shell composite nucleus in size and composition space and in component space

The kinetics of nucleation of a core-shell composite nucleus that consists of a core of stable final phase surrounded by a wetting layer of intermediate metastable phase is studied using the kinetic theory of binary nucleation not only in the size and composition space but also in the component space. The steady-state solution of the Fokker-Planck equation is considered. Various formulas for the critical nucleus at the saddle point as well as for the post-critical nucleus are derived. The kinetics of nucleation at the saddle point is more appropriately characterized in the size and composition space, while the kinetics of the post-critical nucleus is more appropriately described in the component space. Although both the free-energy landscape and the reaction rates play decisive role to determine the kinetics of nucleation at the saddle point, the details of the free energy landscape are irrelevant to the kinetics of the post critical nucleus.

cond-mat.mtrl-sci↗

arXiv2012

Steady-state nucleation rate and flux of composite nucleus at saddle point

The steady-state nucleation rate and flux of composite nucleus at the saddle point is studied by extending the theory of binary nucleation. The Fokker-Planck equation that describes the nucleation flux is derived using the Master equation for the growth of the composite nucleus, which consists of the core of the final stable phase surrounded by a wetting layer of the intermediate metastable phase nucleated from a metastable parent phase recently evaluated by the author [J. Chem. Phys. {\bf 134}, 164508 (2011)]. The Fokker-Planck equation is similar to that used in the theory of binary nucleation, but the non-diagonal elements exist in the reaction rate matrix. First, the general solution for the steady-state nucleation rate and the direction of nucleation flux is derived. Next, this information is then used to study the nucleation of composite nucleus at the saddle point. The dependence of steady-state nucleation rate as well as the direction of nucleation flux on the reaction rate in addition to the free-energy surface is studied using a model free-energy surface. The direction of nucleation current deviates from the steepest-descent direction of the free-energy surface. The results show the importance of two reaction rate constants: one from the metastable environment to the intermediate metastable phase and the other from the metastable intermediate phase to the stable new phase. On the other hand, the gradient of the potential $Φ$ or the Kramers crossover function (the commitment or splitting probability) is relatively insensitive to reaction rates or free-energy surface.

cond-mat.mtrl-sci↗

arXiv2012

A note on the nucleation with multiple steps: Parallel and series nucleation

Parallel and series nucleation are the basic elements of the complex nucleation process when two saddle points exist on the free-energy landscape. It is pointed out that the nucleation rates follow formulas similar to those of parallel and series connection of resistors or conductors in an electric circuit. Necessary formulas to calculate individual nucleation rates at the saddle points and the total nucleation rate are summarized and the extension to the more complex nucleation process is suggested.

cond-mat.mtrl-sci↗

arXiv2011

Heterogeneous critical nucleation on a completely-wettable substrate

Heterogeneous nucleation of a new bulk phase on a flat substrate can be associated with the surface phase transition called wetting transition. When this bulk heterogeneous nucleation occurs on a completely-wettable flat substrate with a zero contact angle, the classical nucleation theory predicts that the free energy barrier of nucleation vanishes. In fact, there always exist a critical nucleus and a free energy barrier as the first-order pre-wetting transition will occur even when the contact angle is zero. Furthermore, the critical nucleus changes its character from the critical nucleus of surface phase transition below bulk coexistence (undersaturation) to the critical nucleus of bulk heterogeneous nucleation above the coexistence (oversaturation) when it crosses the coexistence. Recently, Sear [J.Chem.Phys {\bf 129}, 164510 (2008)] has shown by a direct numerical calculation of nucleation rate that the nucleus does not notice this change when it crosses the coexistence. In our work the morphology and the work of formation of critical nucleus on a completely-wettable substrate are re-examined across the coexistence using the interface-displacement model. Indeed, the morphology and the work of formation changes continuously at the coexistence. Our results support the prediction of Sear and will rekindle the interest on heterogeneous nucleation on a completely-wettable substrate.

cond-mat.soft↗

arXiv2011

Free-energy landscape of nucleation with an intermediate metastable phase studied using capillarity approximation

Capillarity approximation is used to study the free-energy landscape of nucleation when an intermediate metastable phase exists. The critical nucleus that corresponds to the saddle point of the free-energy landscape as well as the whole free-energy landscape can be studied using this capillarity approximation, and various scenarios of nucleation and growth can be elucidated. In this study we consider a model in which a stable solid phase nucleates within a metastable vapor phase when an intermediate metastable liquid phase exists. We predict that a composite critical nucleus that consists of a solid core and a liquid wetting layer as well as pure liquid and pure solid critical nuclei can exist depending not only on the supersaturation of the liquid phase relative to that of the vapor phase but also on the wetting behavior of the liquid surrounding the solid. The existence of liquid critical nucleus indicates that the phase transformation from metastable vapor to stable solid occurs via the intermediate metastable liquid phase, which is quite similar to the scenario of nucleation observed in proteins and colloidal systems. By studying the minimum-free-energy path on the free-energy landscape, we can study the evolution of the composition of solid and liquid within nuclei not limited to the critical nucleus.

cond-mat.mtrl-sci↗

arXiv2010

Stability of critical bubble in stretched fluid of square-gradient density-functional model with triple-parabolic free energy

The square-gradient density-functional model with triple-parabolic free energy, that was used previously to study the homogeneous bubble nucleation [J. Chem. Phys. 129, 104508 (2008)], is used to study the stability of the critical bubble nucleated within the bulk under-saturated stretched fluid. The stability of the bubble is studied by solving the Schrödinger equation for the fluctuation. The negative eigenvalue corresponds to the unstable growing mode of the fluctuation. Our results show that there is only one negative eigenvalue whose eigenfunction represents the fluctuation that corresponds to the isotropically growing or shrinking nucleus. In particular, this negative eigenvalue survives up to the spinodal point. Therefore the critical bubble is not fractal or ramified near the spinodal.

cond-mat.soft↗

arXiv2010

Cell dynamics modeling of phase transformation and metastable phase formation

The phase transition kinetics in three phase systems was investigated using the numerically efficient cell dynamics method. A phasefield model with a simple analytical free energy and single order parameter was used to study the kinetics and the thermodynamics of a three-phase system. This free energy is able to achieve three phases coexistence, which for simplicity we call α, βand γphases. Our study focused on the kinetics of phase transition rather than the nucleation of a seed of a new phase that was introduced into the matrix of the old phase when the relative stability of the three phases were changed. We found dynamical as well as kinetically arrested static scenarios in the appearance of the macroscopic metastable phase. A few other interesting scenarios of the kinetics of phase transition in this three-phase system will be demonstrated and discussed.

cond-mat.mtrl-sci↗

arXiv2009

Minimum free-energy path of homogenous nucleation from the phase-field equation

The minimum free-energy path (MFEP) is the most probable route of the nucleation process on the multidimensional free-energy surface. In this study, the phase-field equation is used as a mathematical tool to deduce the minimum free-energy path (MFEP) of homogeneous nucleation. We use a simple square-gradient free-energy functional with a quartic local free-energy function as an example and study the time evolution of a single nucleus placed within a metastable environment. The time integration of the phase-field equation is performed using the numerically efficient cell-dynamics method. By monitoring the evolution of the size of the nucleus and the free energy of the system simultaneously, we can easily deduce the free-energy barrier as a function of the size of the sub- and the super-critical nucleus along the MFEP.

cond-mat.mtrl-sci↗

arXiv2009

Critical cavity in the stretched fluid studied using square-gradient density-functional model with triple-parabolic free energy

The generic square-gradient density-functional model with triple-parabolic free energy is used to study the stability of a cavity introduced into the stretched liquid. The various properties of the critical cavity, which is the largest stable cavity within the liquid, are compared with those of the critical bubble of the homogeneous bubble nucleation. It is found that the size of the critical cavity is always smaller than that of the critical bubble, while the work of formation of the former is always higher than the latter in accordance with the conjectures made by Punnathanam and Corti [J. Chem. Phys. {\bf 119}, 10224 (2003)] deduced from the Lennard-Jones fluids. Therefore their conjectures about the critical cavity size and the work of formation would be more general and valid even for other types of liquid such as metallic liquid or amorphous. However, the scaling relations they found for the critical cavity in the Lennard-Jones fluid are marginally satisfied only near the spinodal.

cond-mat.soft↗

arXiv2008

Scaling properties of critical bubble of homogeneous nucleation in stretched fluid of square-gradient density-functional model with triple-parabolic free energy

The square-gradient density-functional model with triple-parabolic free energy is used to study homogeneous bubble nucleation in a stretched liquid to check the scaling rule for the work of formation of the critical bubble as a function of scaled undersaturation $Δμ/Δμ_{\rm spin}$, the difference in chemical potential $Δμ$ between the bulk undersaturated and saturated liquid divided by $Δμ_{\rm spin}$ between the liquid spinodal and saturated liquid. In contrast to our study, a similar density-functional study for a Lennard-Jones liquid by Shen and Debenedetti [J. Chem. Phys. {\bf 114}, 4149 (2001)] found that not only the work of formation but other various quantities related to the critical bubble show the scaling rule, however, we found virtually no scaling relationships in our model near the coexistence. Although some quantities show almost perfect scaling relations near the spinodal, the work of formation divided by the value deduced from the classical nucleation theory shows no scaling in this model even though it correctly vanishes at the spinodal. Furthermore, the critical bubble does not show any anomaly near the spinodal as predicted many years ago. In particular, our model does not show diverging interfacial width at the spinodal, which is due to the fact that compressibility remains finite until the spinodal is reached in our parabolic models.

cond-mat.soft↗

arXiv2008

Direct numerical simulation of homogeneous nucleation and growth in a phase-field model using cell dynamics method

Homogeneous nucleation and growth in a simplest two-dimensional phase field model is numerically studied using the cell dynamics method. Whole process from nucleation to growth is simulated and is shown to follow closely the Kolmogorov-Johnson-Mehl-Avrami (KJMA) scenario of phase transformation. Specifically the time evolution of the volume fraction of new stable phase is found to follow closely the KJMA formula. By fitting the KJMA formula directly to the simulation data, not only the Avrami exponent but the magnitude of nucleation rate and, in particular, of incubation time are quantitatively studied. The modified Avrami plot is also used to verify the derived KJMA parameters. It is found that the Avrami exponent is close to the ideal theoretical value m=3. The temperature dependence of nucleation rate follows the activation-type behavior expected from the classical nucleation theory. On the other hand, the temperature dependence of incubation time does not follow the exponential activation-type behavior. Rather the incubation time is inversely proportional to the temperature predicted from the theory of Shneidman and Weinberg [J. Non-Cryst. Solids {\bf 160}, 89 (1993)]. A need to restrict thermal noise in simulation to deduce correct Avrami exponent is also discussed.

cond-mat.mtrl-sci↗

arXiv2007

Dynamics of condensation of wetting layer in time-dependent Ginzburg-Landau model

The dynamics of liquid condensation on a substrate or within a capillary is studied when the wetting film grows via interface-limited growth. We use a phenomenological time-dependent Ginzburg-Landau (TDGL)-type model with long-range substrate potential. Using an order parameter, which does not directly represent the density, we can derive an analytic formula for the interfacial growth velocity that is directly related to the substrate potential. Using this analytic expression the growth of wetting film is shown to conform to a power-law-type growth, which is due to the presence of a long-range dispersion force.

cond-mat.soft↗

arXiv2007

Cell dynamics simulation of droplet and bridge formation within striped nano-capillaries

The kinetics of droplet and bridge formation within striped nano-capillaries is studied when the wetting film grows via interface-limited growth. The phenomenological time-dependent Ginzburg-Landau (TDGL)-type model with thermal noise is used and numerically solved using the cell dynamics method. The model is two-dimensional and consists of undersaturated vapor confined within a nano-capillary made of two infinitely wide flat substrates. The surface of the substrate is chemically heterogeneous with a single stripe of lyophilic domain that exerts long-range attractive potential to the vapor molecule. The dynamics of nucleation and subsequent growth of droplet and bridge can be simulated and visualized. In particular, the evolution of the morphology from droplet or bump to bridge is clearly identified. Crucial role played by the substrate potential on the morphology of bridge of nanoscopic size is clarified. Nearly temperature-independent evolution of capillary condensation is predicted when the interface-limited growth dominates. In addition, it is shown that the dynamics of capillary condensation follows the scenario of capillary condensation proposed by Everett and Haynes three decades ago.

cond-mat.soft↗

arXiv2007

Scenarios of heterogeneous nucleation and growth studied by cell dynamics simulation

The dynamics of phase transformation due to homogeneous nucleation has long been analyzed using the classic Kolmogorov-Johnson-Mehl-Avrami (KJMA) theory. However, the dynamics of phase transformation due to heterogeneous nucleation has not been studied systematically even though it is vitally important technologically. In this report, we study the dynamics of heterogeneous nucleation theoretically and systematically using the phenomenological time-dependent Ginzburg-Landau (TDGL)-type model combined with the cell dynamics method. In this study we focus on the dynamics of phase transformation when the material is sandwiched by two supporting substrates. This model is supposed to simulates phase change storage media. Since both homogeneous and heterogeneous nucleation can occur simultaneously, we predict a few scenarios of phase transformation including: homogeneous-nucleation regime, heterogeneous-nucleation regime, and the homogeneous-heterogeneous coexistence regime. These predictions are directly confirmed by numerical simulation using the TDGL model. The outcome of the study was that the KJMA formula has limited use when heterogeneous nucleation exist, but it could still give some information about the microscopic mechanism of phase transformation at various stages during phase transformation.

cond-mat.mtrl-sci↗

arXiv2005

Contact angle hysteresis of cylindrical drops on chemically heterogeneous striped surfaces

Contact angle hysteresis of a macroscopic droplet on a heterogeneous but flat substrate is studied using the interface displacement model. First, the apparent contact angle of a droplet on a heterogeneous surface under the condition of constant volume is considered. By assuming a cylindrical liquid-vapor surface (meniscus) and minimizing the total free energy, we derive an equation for the apparent contact angle, which is similar but different from the well-known Cassie's law. Next, using this modified Cassie's law as a guide to predict the behavior of a droplet on a heterogeneous striped surface, we examine several scenarios of contact angle hysteresis using a periodically striped surface model. By changing the volume of the droplet, we predict a sudden jump of the droplet edge, and a continuous change of the apparent contact angle at the edge of two stripes. Our results suggest that as drop volume is increased (advancing contact lines), the predominant drop configuration observed is the one whose contact angle is large; whereas, decreasing drop volume from a large value (receding contact lines) yields drop configuration that predominantly exhibit the smaller contact angle.

cond-mat.soft↗

arXiv2005

The validity of Cassie's law: A simple exercise using a simplified model

The contact angle of a macroscopic droplet on a heterogeneous but flat substrate is studied using the interface displacement model which can lead to the augmented Young-Laplace equation. Droplets under the condition of constant volume as well as constant vapor pressure are considered. By assuming a cylindrical liquid-vapor surface (meniscus) and minimizing the total free energy of the interface displacement model, we derive an equation which is similar but different from the well known Cassie's law. Our modified Cassie's law is essentially the same as the formula obtained previously by Marmur [J.Colloid Interface Sci. {\bf 168}, 40 (1994)]. A few consequences from this modified Cassie's law will be briefly described in the following sections of this paper. Several sets of recent experimental results seem to support the validity of our modified Cassie's law.

cond-mat.soft↗