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dc.contributor.advisor Chapman, Walter G
dc.creatorXi, Shun
dc.date.accessioned 2020-03-10T15:12:39Z
dc.date.available 2020-11-01T05:01:09Z
dc.date.created 2020-05
dc.date.issued 2020-03-06
dc.date.submitted May 2020
dc.identifier.citation Xi, Shun. "Multiscale and Multidimensional Thermodynamic Modeling of Block Copolymer Self-assembly in Solution." (2020) Diss., Rice University. https://hdl.handle.net/1911/108096.
dc.identifier.urihttps://hdl.handle.net/1911/108096
dc.description.abstract The study of block copolymer self-assembly in solution has been an active subject for years. As one of the most versatile molecules in nature, it is a chemical and biological building block for life. Lipids in aqueous solution self-organize to a bilayer structure that effectively compartmentalize cellular spaces for complex biochemical processes. Industrial products related to block copolymer self-assembly in solution have been created through intensive experimental and engineering efforts. Although models for block copolymer melts have been successful, a consistent theoretical understanding of block copolymers in solution has not kept with the applications. Challenges arise from its nature that block copolymer self-assembly in solution is a multiscale and multidimensional problem. Extremely diluted block copolymer solutions are homogeneous that can be well understood by an equation of state model. Inhomogeneity appears when the polymer concentration is above critical micelle concentration and the block copolymers form isolated micelles in dilute solution. Longrange ordered lyotropic liquid crystals of multidimensional mesophases are formed in concentrated solution when the block copolymers of individual micelles overlap. This thesis aims to develop a consistent thermodynamic model for block copolymer self-assembly in solution in multiscale and multidimension, based on a particular molecular density functional theory (DFT): interfacial statistical associating fluid theory (iSAFT). This DFT model ultimately predicts phase behaviors of self-assembly in solution, explains thermodynamic factors that influence the phase behaviors from a microscopic view at molecular level, and provides a guidance to design operating conditions and to select candidate materials for the related applications. Key contributions of this thesis include: 1. A quantitative approach to predict critical micelle concentrations and aggregation numbers of micelles of both diblock copolymers and triblock copolymers, and to explain inhomogeneous micellar solubilization in dilute aqueous solution; 2. Description of solvent regulated mesophase behaviors of block copolymers in solution having two-dimensional inhomogeneity, and how solvent selectivity and molecular packing parameter affect the phase behaviors in concentrated solution; 3. A new efficient numerical algorithm for molecular density functional theory with application to iSAFT to improve convergence, stability, and performance of DFT solution algorithm in cylindrical geometry.
dc.format.mimetype application/pdf
dc.language.iso eng
dc.subjectThermodynamics
Block copolymer
Self-assembly
dc.title Multiscale and Multidimensional Thermodynamic Modeling of Block Copolymer Self-assembly in Solution
dc.type Thesis
dc.date.updated 2020-03-10T15:12:40Z
dc.type.material Text
thesis.degree.department Chemical and Biomolecular Engineering
thesis.degree.discipline Engineering
thesis.degree.grantor Rice University
thesis.degree.level Doctoral
thesis.degree.name Doctor of Philosophy
dc.embargo.terms 2020-11-01
thesis.degree.major Chemical Physics


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