This thesis is on molecular dynamics studies of drying suspensions of bidisperse nanoparticle mixtures. I first use an explicit solvent model to investigate how the structure of the dry film depends on the evaporation rate of the solvent and the initial volume fractions of the nanoparticles. My simulation results show that the particle mixtures stratify according to their sizes when the suspensions are quickly dried, consistent with the prediction of recent theories. I further show that stratification can be controlled using thermophoresis induced by a thermal gradient imposed on the drying suspension. To model larger systems on longer time scales, I explore implicit solvent models of drying particle suspensions in which the solvent is treated as a uniform viscous background and the liquid-vapor interface is replaced by a potential barrier that confines all the solutes in the solution. Drying is then modeled as a process in which the location of the confining potential is moved. In order to clarify the physical foundation of this moving interface method, I analyze the meniscus on the outside of a circular cylinder and apply the results to understand the capillary force experienced by a spherical particle at a liquid-vapor interface. My analyses show that the capillary force is approximately linear with the displacement of the particle from its equilibrium location at the interface. An analytical expression is derived for the corresponding spring constant that depends on the surface tension and lateral span of the interface and the particle radius. I further show that with a careful mapping, both explicit and implicit solvent models yield similar stratification behavior for drying suspensions of bidisperse particles. Finally, I apply the moving interface method based on an implicit solvent to study the drying of various soft matter solutions, including a solution film of a mixture of polymers and nanoparticles, a suspension droplet of bidisperse nanoparticles, a solution droplet of a polymer blend, and a solution droplet of diblock copolymers. / PHD / Drying is a ubiquitous phenomenon. In this thesis, I use molecular dynamics methods to simulate the drying of a suspension of a bidisperse mixture of nanoparticles that have two different radii. First, I use a model in which the solvent is included explicitly as point particles and the nanoparticles are modeled as spheres with finite radii. Their trajectories are generated by numerically solving the Newtonian equations of motion for all the particles in the system. My simulations show that the bidisperse nanoparticle mixtures stratify according to their sizes after drying. For example, a “small-on-top” stratified film can be produced in which the smaller nanoparticles are distributed on top of the larger particles in the drying film. I further use a similar model to demonstrate that stratification can be controlled by imposing a thermal gradient on the drying suspension. I then map an explicit solvent system to an implicit one in which the solvent is treated as a uniform viscous background and only the nanoparticles are kept. The physical foundation of this mapping is clarified. I compare simulations using the explicit and implicit solvent models and show that similar stratification behavior emerge in both models. Therefore, the implicit solvent model can be applied to study much larger systems on longer time scales. Finally, I apply the implicit solvent model to study the drying of various soft matter solutions, including a solution film of a mixture of polymers and nanoparticles, a droplet of a bidisperse nanoparticle suspension, a solution droplet of a polymer blend, and a droplet of a diblock copolymer solution.
| Identifer | oai:union.ndltd.org:VTETD/oai:vtechworks.lib.vt.edu:10919/87435 |
| Date | 04 February 2019 |
| Creators | Tang, Yanfei |
| Contributors | Physics, Cheng, Shengfeng, Täuber, Uwe C., Pitt, Mark L., Hanna, James |
| Publisher | Virginia Tech |
| Source Sets | Virginia Tech Theses and Dissertation |
| Detected Language | English |
| Type | Dissertation |
| Format | ETD, application/pdf, application/pdf, application/pdf, application/pdf |
| Rights | In Copyright, http://rightsstatements.org/vocab/InC/1.0/ |
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