Interface liquid nucleation

Johans et al. derived a model for diffusion-controlled electrodeposition at liquid-liquid interface taking into account the development of diffusion fields in both phases [91]. The current transients exhibited rising portions followed by planar diffusion-controlled decay. These features are very similar to those commonly observed in three-dimensional nucleation of metals onto solid electrodes [173-175]. The authors reduced aqueous ammonium tetrachloropalladate by butylferrocene in DCE. The experimental transients were in good agreement with the theoretical ones. The nucleation rate was considered to depend exponentially on the applied potential and a one-electron step was found to be rate determining. The results were taken to confirm the absence of preferential nucleation sites at the liquid-liquid interface. Other nucleation work at the liquid-liquid interface has described the formation of two-dimensional metallic films with rather interesting fractal shapes [176]. 

Increasing the temperature or lowering the pressure on a superheated liquid will increase the probability of nucleation. Also, the presence of solid surfaces enhances the probability because it is often easier to form a critical-sized embryo at a solid-liquid interface than in the bulk of the liquid. Nucleation in the bulk is referred to as homogeneous nucleation whereas if the critical-sized embryo forms at a solid-liquid (or liquid-liquid) interface, it is termed heterogeneous nucleation. Normal boiling processes wherein heat transfer occurs through the container wall to the liquid always occur by heterogeneous nucleation. 

Low energy surfaces—e.g., Teflon, Mylar, etc.—are apparently ineffective nucleating agents. When polymers are cooled in contact with these surfaces, nucleation is precluded at the S-L interface and is apparently initiated in the bulk. Sufficient supercooling has not occurred at the solid-liquid interface to nucleate the interfacial region before nucleation occurs in the bulk. Apparently, this is the reason for the lack of a well defined transcrystalline region when polyethylene is nucleated against a... 

Hejazi SR, Hosseini HR, Sasani Ghamsari M. The role of reactants and droplet interfaces on nucleation and growth of ZnO nanorods synthesized by vapor—liquid—solid (VLS) mechanism. J Alloys Compd 2008 455 353-7. 

Note that the third term in this expression, which is associated with the wall/liquid interfacial energy, is subtracted from the other two terms because this interface is replaced by the solid/wall interface upon nucleation of the particle. From the interfacial energy force balance derived in Equation 6.17, we can relate the interfacial energy terms to the contact angle 9 via... 

Preexisting surfaces (e.g. aerosol or dust particles), ions or large polymer molecules greatly accelerate the rate of nucleation by lowering W, defined by Eq. (2). Such surfaces accomplish this by reducing the amount of work required to provide the interface in nucleation (since a surface already exists) while ions accomplish this (especially with polar molecules) by dielectric polarization so that the barrier W can be lowered to the point where a single ion can induce the formation of a macroscopic liquid drop. This represents almost the ultimate in amplification and detection. 

This section represents a continuation of Section VII-5, which dealt primarily with the direct estimation of surface quantities at a solid-gas interface. Although in principle some of the methods described there could be applied at a solid-liquid interface, very little has been done apart from the study of the following Kelvin effect and nucleation studies, discussed in Chapter IX. 

Heat transfer by nucleate boiling is an important mechanism in the vaporization of liqmds. It occurs in the vaporization of liquids in kettle-type and natural-circulation reboilers commonly usea in the process industries. High rates of heat transfer per unit of area (heat flux) are obtained as a result of bubble formation at the liquid-solid interface rather than from mechanical devices external to the heat exchanger. There are available several expressions from which reasonable values of the film coefficients may be obtained. 

Note that this equation has two energy terms that did not appear in eqn. (7.1). The first, Tir Cl - cos 0)Ycs> is the energy needed to create the new interface between the catalyst and the solid. The second, - rr (l - cos 0)Ycu is the energy released because the area of the catalyst-liquid interface is smaller after nucleation than it was before. 

Thermodynamic and mechanical equilibrium on a curved vapor-liquid interface requires a certain degree of superheat in order to maintain a given curvature. Characteristics of homogeneous and heterogeneous nucleation can be estimated in the frame of classical theory of kinetics of nucleation (Volmer and Weber 1926 Earkas 1927 Becker and Doring 1935 Zel dovich 1943). The vapor temperature in the bubble Ts.b can be computed from equations (Bankoff and Flaute 1957 Cole 1974 Blander and Katz 1975 Li and Cheng 2004) for homogeneous nucleation in superheated liquids... 

Second, the molecular orientation of the fiber and the prepolymer matrix is important. The rate of crystal nucleation at the fiber-matrix interface depends on the orientation of matrix molecules just prior to their change of phase from liquid to solid. Thus, surface-nucleated morphologies are likely to dominate the matrix stmcture. 

In the first step, lipid model membranes have been generated (Fig. 15) on the air/liquid interface, on a glass micropipette (see Section VIII.A.1), and on an aperture that separates two cells filled with subphase (see Section VIII.A.2). Further, amphiphilic lipid molecules have been self-assembled in an aqueous medium surrounding unilamellar vesicles (see Section VIII.A.3). Subsequently, the S-layer protein of B. coagulans E38/vl, B. stearother-mophilus PV72/p2, or B. sphaericus CCM 2177 have been injected into the aqueous subphase (Fig. 15). As on solid supports, crystal growth of S-layer lattices on planar or vesicular lipid films is initiated simultaneously at many randomly distributed nucleation... 

Despite the fact that the electrodeposition of copper and silver at the water-DCE and the water-dichloromethane interfaces has been generally regarded as the first experimental evidence for heterogeneous ET at externally biased ITIES [171], a very limited amount of work has dealt with this type of process. This reaction has also theoretical interest because the molecular liquid-liquid interface can be seen as an ideal substrate for electrochemical nucleation studies due to the weak interactions between the interface and the newly formed phase and the lack of preferential nucleation sites always present at metallic electrodes. 

Equation (2-14) provides a way to calculate the liquid temperature in equilibrium with the ready-to-grow bubble if the saturation pressure or temperature, the value of B, and the cavity radius are known (Shai, 1967). Several modified versions of nucleation criteria have since been advanced. An example is the model proposed by Lorenta et al. (1974), which takes into account both the geometric shape of the cavity and the wettability of the surface (in terms of contact angle < >). Consider an idealized conical cavity with apex angle ip, and a liquid with a flat front penetrating into it (Fig. 2.3a). Assume that once the vapor is trapped in by the liquid front, the interface readjusts to form a cap with radius of curvature rn. Conservation of vapor... 

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