Off-campus UMass Amherst users: To download campus access dissertations, please use the following link to log into our proxy server with your UMass Amherst user name and password.
Non-UMass Amherst users: Please talk to your librarian about requesting this dissertation through interlibrary loan.
Dissertations that have an embargo placed on them will not be available to anyone until the embargo expires.
Date of Award
Open Access Dissertation
Doctor of Philosophy (PhD)
Peter A. Monson
Confining walls induce qualitative changes in adsorbed fluids. Among the most intriguing phenomena is hysteresis, where a pore fills with fluid at a greater pressure than it empties. The causes and mechanisms by which this occurs are intensely investigated yet still poorly understood. Ordered mesoporous silicas, recently discovered materials with well-defined pore size distributions, provide an opportunity to deepen our understanding of the fundamental physics of the interaction of fluids with complex solids.
In part of this computational investigation we examine idealized pores. In agreement with other recent studies, we find that in 'inkbottle'-shaped pores, where a large cavity is accessible to the bulk fluid only by constrictions, there is no evidence of the long-hypothesized phenomenon of `pore blocking', where the constrictions inhibit fluid desorption from the cavity. We find that even in these simple systems the mechanism of hysteresis depends on pore characteristics, fluid properties and external conditions.
For silicas containing cylindrical holes of nearly uniform diameter, such as MCM-41, the state-of-the-art is to consider only a single pore, but the poor qualitative agreement of theoretical with experimental results has improved little as wall representations of increasing sophistication have been developed. Using only a one-dimensional potential, we reproduce features of isotherms, including in the hysteresis region, by averaging over a narrow distribution of pore sizes. The qualitative behavior is shown to be a collective phenomenon not representative of any individual pore. Adding surface roughness and a constriction to the pores yields results quantitatively nearly indistinguishable from experiments.
For materials larger than MCM-41, a continuum simulation proves too computationally taxing. Thus, a lattice model with adjustable fineness of site spacing is developed. It is found that a surprisingly low level of fineness is needed for confined systems to closely approximate continuum results. This model is applied to cubically symmetric materials, such as MCM-48 and SBA-16, finding that simulations are able to reproduce much of the qualitative behavior seen experimentally, but the lack of existing knowledge of the nature of silica walls proves to be a limiting factor.
Libby, Bradd E, "Understanding Adsorption In Mesoporous Materials Through Lattice-Based Density Functional Theory And Monte Carlo Simulation" (2009). Doctoral Dissertations 1896 - February 2014. 51.