Nucleation in Sessile Saline Microdroplets: Induction Time Measurement via Deliquescence-Recrystallization Cycling

TL;DR

This paper introduces a novel, statistically robust method for measuring induction times in sessile microdroplets, enabling detailed analysis of nucleation kinetics and confinement effects with high reproducibility.

Contribution

The work presents a new approach combining deliquescence-recrystallization cycling and image analysis to accurately measure independent nucleation events in microdroplets, addressing previous challenges in statistical reproducibility.

Findings

Microdroplet interactions can be eliminated by controlling humidity.

Induction times follow a Weibull distribution after outlier removal.

Smaller droplets require higher supersaturation for nucleation.

Abstract

Induction time, a measure of how long one will wait for nucleation to occur, is an important parameter in quantifying nucleation kinetics and its underlying mechanisms. Due to the stochastic nature of nucleation, efficient methods for measuring large number of independent induction times are needed to ensure statistical reproducibility. In this work, we present a novel approach for measuring and analyzing induction times in sessile arrays of microdroplets via deliquescence/recrystallization cycling. With the help of a recently developed image analysis protocol, we show that the interfering diffusion-mediated interactions between microdroplets can be eliminated by controlling the relative humidity, thereby ensuring independent nucleation events. Moreover, possible influence of heterogeneities, impurities, and memory effect appear negligible as suggested by our 2-cycle experiment. Further statistical analysis (k-sample Anderson-Darling test) reveals that upon identifying possible outliers, the dimensionless induction times obtained from different datasets (microdroplet lines) obey the same distribution and thus can be pooled together to form a much larger dataset. The pooled dataset showed an excellent fit with the Weibull function, giving a mean supersaturation at nucleation of 1.61 and 1.85 for the 60pL and 4pL microdroplet respectively. This confirms the effect of confinement where smaller systems require higher supersaturations to nucleate. Both the experimental method and the data-treatment procedure presented herein offer promising routes in the study of fundamental aspects of nucleation kinetics, particularly confinement effects, and are adaptable to other salts, pharmaceuticals, or biological crystals of interest.