Dynamics of Irreversible Particle Adsorption to Fluid Interfaces

Fuente: arXiv
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Autori principali: Pasquet, Marina, Fu, Yu, Frechette, Joelle
Natura: Preprint
Pubblicazione: 2025
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author Pasquet, Marina
Fu, Yu
Frechette, Joelle
author_facet Pasquet, Marina
Fu, Yu
Frechette, Joelle
contents Understanding the dynamic adsorption of colloidal particles at fluid interfaces is essential for applications ranging from emulsion stabilization to interfacial assembly of functional materials. Adsorption dynamics is often described through diffusion-limited models (such as the Ward-Tordai framework) along with assuming dynamic equilibrium between the adsorbed and dispersed particles. However, most experiments show that particle adsorption is irreversible, and diffusion-limited models fail as the surface coverage goes beyond the dilute limit where particle crowding limits further adsorption. Here, we present a unified model that captures the transition from diffusion-limited to kinetic-limited regimes by coupling diffusion with a Random Sequential Adsorption (RSA)-based boundary condition that accounts for irreversible adsorption and particle blocking for a spherical droplet. Using both a microtensiometer and pendant drop tensiometry, we measure dynamic interfacial tension changes for 3-(Trimethoxysilyl)propyl methacrylate (TPM) particles at the toluene/water interface across a range of bulk concentrations, drop sizes, and particle functionalization. Our analysis shows that the adsorption flux becomes increasingly hindered as the surface area fills, in agreement with RSA predictions. Furthermore, we calculate the Thiele modulus as a dimensionless number that quantifies the relative importance of adsorption kinetics to diffusion. We find that above a critical surface coverage, adsorption becomes reaction-limited, marking a transition to kinetically controlled dynamics. This approach provides a predictive framework for particle adsorption at fluid interfaces and highlights the necessity of moving beyond equilibrium diffusion-limited models.
format Preprint
id arxiv_https___arxiv_org_abs_2507_21026
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Dynamics of Irreversible Particle Adsorption to Fluid Interfaces
Pasquet, Marina
Fu, Yu
Frechette, Joelle
Soft Condensed Matter
Materials Science
Understanding the dynamic adsorption of colloidal particles at fluid interfaces is essential for applications ranging from emulsion stabilization to interfacial assembly of functional materials. Adsorption dynamics is often described through diffusion-limited models (such as the Ward-Tordai framework) along with assuming dynamic equilibrium between the adsorbed and dispersed particles. However, most experiments show that particle adsorption is irreversible, and diffusion-limited models fail as the surface coverage goes beyond the dilute limit where particle crowding limits further adsorption. Here, we present a unified model that captures the transition from diffusion-limited to kinetic-limited regimes by coupling diffusion with a Random Sequential Adsorption (RSA)-based boundary condition that accounts for irreversible adsorption and particle blocking for a spherical droplet. Using both a microtensiometer and pendant drop tensiometry, we measure dynamic interfacial tension changes for 3-(Trimethoxysilyl)propyl methacrylate (TPM) particles at the toluene/water interface across a range of bulk concentrations, drop sizes, and particle functionalization. Our analysis shows that the adsorption flux becomes increasingly hindered as the surface area fills, in agreement with RSA predictions. Furthermore, we calculate the Thiele modulus as a dimensionless number that quantifies the relative importance of adsorption kinetics to diffusion. We find that above a critical surface coverage, adsorption becomes reaction-limited, marking a transition to kinetically controlled dynamics. This approach provides a predictive framework for particle adsorption at fluid interfaces and highlights the necessity of moving beyond equilibrium diffusion-limited models.
title Dynamics of Irreversible Particle Adsorption to Fluid Interfaces
topic Soft Condensed Matter
Materials Science
url https://arxiv.org/abs/2507.21026