A Caltech Library Service

Reshaping Elastomers with Light: First Principles Model of Diffusion-Induced Deformation


Turner, Ryan Matthew (2012) Reshaping Elastomers with Light: First Principles Model of Diffusion-Induced Deformation. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/RVVD-2J26.


Elastomeric photopolymers are a new class of materials originally developed at Caltech for use as intraocular lenses. These materials consist of a host network swollen with short-chain, photoreactive "macromers." Using a light source for selective photopolymerization, gradients in free macromer molecules are created, driving diffusion-induced shape change. Although models exist for external flow of solvent into a swelling gel or for gel deswelling caused by externally imposed forces, no known model exists to account for reaction-induced diffusion-deformation for a force-free material in which solvent can neither enter nor leave. To predict this unique reaction-diffusion-induced shape change, we propose a simple "two-component" model which treats macromer as converting directly into network strands. This model is first shown to be in good agreement with experimental data on the equilibrium swelling of elastomeric photopolymers. We then use mixture theory to develop constitutive laws for the system stress and the flux of macromer by ensuring that the second law of thermodynamics holds. Finally, we implement the theory to a variety of problems - including a finite-element model of the light-adjustable lens - in each case systematically detailing the relative importance of the material parameters on the magnitude and rate of shape change. We determined that the shape change depends upon the rate of consumption of macromer (specified by the initial extent of reaction profile and the initial volume fraction of macromer) and is independent of the network modulus or the macromer molar mass. In addition, we found that the macromer molar mass serves only to determine the rate at which the deformation proceeds, whereas the network modulus serves to determine the magnitude of the internal forces experienced in the photopolymer.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:light-adjustable lens, photopolymer, diffusion, deformation, finite-element, elastomer, theory
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemical Engineering
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Kornfield, Julia A.
Thesis Committee:
  • Kornfield, Julia A. (chair)
  • Wang, Zhen-Gang
  • Brady, John F.
  • Selinger, Robin L. B.
Defense Date:12 February 2012
Record Number:CaltechTHESIS:04192012-094254839
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:6947
Deposited By: Ryan Turner
Deposited On:30 Jun 2014 18:13
Last Modified:03 Oct 2019 23:55

Thesis Files

PDF - Final Version
See Usage Policy.


Repository Staff Only: item control page