Synthesis and Characterization of Diblock Copolymer Templated Iron Oxide Nanoparticles

Abstract

Templating ordered assemblies of magnetic oxide nanoparticles within self-assembled diblock copolymers of varying morphologies is an important problem with a wide applicability such as in electromagnetics, optical devices, metal catalysts, medicine and biology. In this thesis, the effects of different polymer structures on particle ordering and resultant magnetic properties have been investigated using various microstructure and magnetic characterization tools. Ring-opening metathesis polymerization (ROMP) of norbornene and functionalized norbornene monomers has been used to synthesize diblock copolymers of narrow polydispersities using Grubbs' catalyst. These block copolymers can be used as templates to form inorganic nanoparticles. In this research, the structural and physical understanding of the inorganic-copolymer system was studied by small-angle neutron and x-ray scattering techniques and transmission electron microscopy. Synthesis of $\gamma$-Fe$_2$O$_3$ nanoparticles has been achieved within novel block copolymers of (norbornene)-b-(deuterated norbornene dicarboxylic) acid and (norbornene methanol)-(norbornene dicarboxylic acid). The polymer morphologies were controlled by varying the volume fractions of the constituent blocks. The pure norbornene based diblock copolymer morphologies were demonstrated by electron microscopy for the first time. Spherical, cylindrical and lamellar morphologies of these novel diblock copolymers were reported. The block ratios of the synthesized polymers were determined using gel permeation chromatography - light scattering, elemental analysis and UV-VIS spectroscopy. Solution phase doping and submersion of thin films in metal salt solutions were employed as metal doping methods and the observed nanoparticle structures were compared to those of the undoped copolymer morphologies. This project reports on the types of templating structures and dispersion of the nanoparticles. The effects of particle interactions on the microphase separation and magnetic properties were also investigated. The knowledge gained from understanding the templating mechanism in block copolymer / iron oxide nanocomposites can be applied to other similar systems for a variety of biological and catalyst applications.