1 research outputs found
Thermodynamics of heterogeneous crystal nucleation in contact and immersion modes
One of most intriguing problems of heterogeneous crystal nucleation in
droplets is its strong enhancement in the contact mode (when the foreign
particle is presumably in some kind of contact with the droplet surface)
compared to the immersion mode (particle immersed in the droplet). Many
heterogeneous centers have different nucleation thresholds when they act in
contact or immersion modes, indicating that the mechanisms may be actually
different for the different modes. Underlying physical reasons for this
enhancement have remained largely unclear. In this paper we present a model for
the thermodynamic enhancement of heterogeneous crystal nucleation in the
contact mode compared to the immersion one. To determine if and how the surface
of a liquid droplet can thermodynamically stimulate its heterogeneous
crystallization, we examine crystal nucleation in the immersion and contact
modes by deriving and comparing with each other the reversible works of
formation of crystal nuclei in these cases. As a numerical illustration, the
proposed model is applied to the heterogeneous nucleation of Ih crystals on
generic macroscopic foreign particles in water droplets at T=253 K. Our results
show that the droplet surface does thermodynamically favor the contact mode
over the immersion one. Surprisingly, our numerical evaluations suggest that
the line tension contribution to this enhancement from the contact of three
water phases (vapor-liquid-crystal) may be of the same order of magnitude as or
even larger than the surface tension contribution