Related Experiment Video
Updated: Nov 25, 2025

Challenges in Rheological Characterization of Highly Concentrated Suspensions — A Case Study for Screen-printing Silver Pastes
Published on: April 10, 2017
Entropy production in model colloidal suspensions under shear via the fluctuation theorem
Caroline Desgranges1, Jerome Delhommelle1
1Department of Chemistry, New York University, New York, New York 10003, USA and Department of Chemistry & Molecular Simulation of NonEquilibrium Processes (MSNEP), Suite 2300, Tech Accelerator, University of North Dakota, Grand Forks, North Dakota 58202, USA.
Abstract:
Dissipative systems often exhibit novel and unexpected properties. This is, for instance, the case of simple liquids, which, when subjected to shear and after reaching a steady state, can exhibit a negative entropy production over finite length scales and timescales. This result, among others, is captured by nonequilibrium relations known as fluctuation theorems. Using nonequilibrium molecular dynamics simulations, we examine how, by fine-tuning the properties of the components of a complex fluid, we can steer the nonequilibrium response of the fluid. More specifically, we show how we control the nonequilibrium probability distribution for the shear stress and, in turn, how often states with a negative entropy production can occur. To achieve this, we start by characterizing how the size for the liquid matrix impacts the probability of observing negative entropy states, as well as the timescale over which these can be observed. We then measure how the addition of larger particles to this liquid matrix, i.e., simulating a model colloidal suspension, results in an increase in the occurrence of such states. This suggests how modifications in the composition of the mixture and in the properties of its components lead to an increase in the probability of observing states of negative entropy production and, thus, for the system to run in reverse.
Related Concept Videos
Colloids and Suspensions
Entropy
Theories of Dissolution: The Danckwerts' Model and Interfacial Barrier Model
Entropy and Solvation
Colloidal precipitates
Second Law of Thermodynamics

