Off-campus UMass Amherst users: To download 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 click the view more button below to purchase a copy of this dissertation from Proquest.
(Some titles may also be available free of charge in our Open Access Dissertation Collection, so please check there first.)
Aspects of network formation and property evolution in glassy polymer networks
Abstract
Experimental and theoretical characterization techniques are developed to illuminate relationships between molecular architecture, processing strategies, and physical properties of several model epoxy-amine systems. Just beyond the gel point partially cured networks are internally antiplasticized by unreacted epoxy and amine which leads to enhanced local chain packing and strain localization during deformation processes. Additional curing causes the antiplasticization to be removed, resulting in lower modulus, density, yield stress, and less strain localization. Physical and mechanical probes of network formation are discussed with respect to several different partially cured model epoxy-amine chemistries. The non-linear fracture energy release rate and the molecular architecture of virgin and healed epoxy networks are related through an effective crack length model. The inelastic component of the fracture energy release rate is attributed to the failure of network strands in a cohesive zone at the crack tip. Data from fracture and healing experiments are in good agreement with the model over more than three orders of magnitude. Changes in the shape of the process zone and deviation from planar crack growth cause deviations from the model for the toughest networks tested. Double network epoxies are created from stoichiometric blends of an epoxy resin cured sequentially with aliphatic and aromatic amine curing agents. Unreacted epoxide and aromatic amine functionality antiplasticize the partially cured materials. The thermal and mechanical properties of the fully cured networks vary according to composition. No evidence of phase separation is observed across the entire composition and conversion range. However, the breadth of the glass transition in the double networks increases due to the difference in the molecular stiffness of the two curing agents. Techniques are developed to monitor the evolution of residual stresses and strength in complex multicomponent epoxy-amine based coatings. The evolution of properties is attributed to loss of volatile small molecules from the coatings. The stresses that develop in biaxially constrained membranes are monitored through mechanical excitation. The strength of the membranes is determined by monitoring the size and shape of center cracks. This fracture analysis technique allows the evolution of stresses and toughness of the materials to be monitored simultaneously.
Subject Area
Materials science|Plastics
Recommended Citation
Detwiler, Andrew Thomas, "Aspects of network formation and property evolution in glassy polymer networks" (2011). Doctoral Dissertations Available from Proquest. AAI3482611.
https://scholarworks.umass.edu/dissertations/AAI3482611