Theses and Dissertations


Satish Mishra

Issuing Body

Mississippi State University


Kundu, Santanu

Committee Member

Lacy Jr, Thomas E.

Committee Member

Rai, Neeraj

Committee Member

Meng, Dong

Date of Degree


Document Type

Dissertation - Open Access


Chemical Engineering

Degree Name

Doctor of Philosophy


James Worth Bagley College of Engineering


Dave C. Swalm School of Chemical Engineering


Physically assembled gels are widely applicable in the food industry, biomedical devices, drug delivery, and soft robotics due to their tunable mechanical properties and thermoreversibility. The mechanical responses of these gels originate from their microstructure. Therefore, factors affecting the gel microstructure like polymer molecular weight, solvent quality, and polymer concentration play a significant role in determining their mechanical behavior. Gel microstructure also changes during the deformations resulting in a deviation from the structure-property relationship established for the low deformations. During large deformations, other factors like stress relaxation, poroelasticity, and polymer chain entanglement contribute significantly to the gel response. This complexity extends to the understanding of their failure behavior that occurs at large deformations. The low strain mechanical behavior of gels is governed by load-bearing chain density. They are often represented with non-linear elastic models, which ignore the contribution from viscous dissipation, polymer entanglements, surface tension, and bond dissociation. In addition, the available theoretical models cannot capture the experimental conditions like boundary confinement, therefore, numerical simulations are useful to test the developed model by comparing with experimental observations. With this objective, the present dissertation is focused on understanding the failure of physically assembled gels that consists of an ABA-type triblock copolymer dissolved in a B-block (midblock) selective solvent. Here, gelation occurs as a result of relative difference in the solubility of A-blocks (endblocks) and B-blocks (midblocks) with solvent. The thermo-mechanical characterization of these gels was performed using rheology, cavitation rheology, and DSC. A custom-built experimental set-up was developed to conduct large deformation experiments like tensile tests, creep failure experiments, and fracture experiments with a predefined crack. To characterize the gel microstructure, small-angle x-ray/neutron techniques were used. A change in the gel microstructure during deformation was also captured. The microstructure of gels was tuned by varying temperature, polymer volume fraction, midblock length, and by addition of midblock homopolymer. Finite element simulations have been used to understand the effect of boundary confinement, surface tension, and viscous dissipation. The present work provides a better understanding of failure behavior in physically assembled gels through the polymer dynamics at nano-scale level.