Intramolecular conflict : conformation and self-assembly of architecturally complex macromolecules in solution

The solution behavior of linear polymer chains is well understood, having been the subject of intense study throughout the previous century. As plastics have become ubiquitous in everyday life, polymer science has grown into a major field of study. The conformation of a polymer in solution depends on the molecular architecture and its interactions with the surroundings. Developments in synthetic techniques have led to the creation of precision-tailored polymeric materials with varied topologies and functionalities. In order to design materials with the desired properties, it is imperative to understand the relationships between polymer architecture and their conformation and behavior. To meet that need, this thesis investigates the conformation and self-assembly of three architecturally complex macromolecular systems with rich and varied behaviors driven by the resolution of intramolecular conflicts. First we describe the development of a robust and facile synthetic approach to reproducible bottlebrush polymers (Chapter 2). The method was used to produce homologous series of bottlebrush polymers with polynorbornene backbones, which revealed the effect of side-chain and backbone length on the overall conformation in both good and theta solvent conditions (Chapter 3). The side-chain conformation was obtained from a series of SANS experiments and determined to be indistinguishable from the behavior of free linear polymer chains. Using deuterium-labeled bottlebrushes, we were able for the first time to directly observe the backbone conformation of a bottlebrush polymer which showed self-avoiding walk behavior. Secondly, a series of SANS experiments was conducted on a homologous series of Side Group Liquid Crystalline Polymers (SGLCPs) in a perdeuterated small molecule liquid crystal (5CB). Monodomain, aligned, dilute samples of SGLCP-b-PS block copolymers were seen to self-assemble into complex micellar structures with mutually orthogonally oriented anisotropies at different length scales (Chapter 4). Finally, we present the results from the first scattering experiments on a set of fuel-soluble, associating telechelic polymers. We observed the formation of supramolecular aggregates in dilute (≤0.5wt%) solutions of telechelic polymers and determined that the choice of solvent has a significant effect on the strength of association and the size of the supramolecules (Chapter 5). A method was developed for the direct estimation of supramolecular aggregation number from SANS data. The insight into structure-property relationships obtained from this work will enable the more targeted development of these molecular architectures for their respective applications.

A Study on iron-based amorphous alloys : alloy development, thermodynamics and soft magnetism

Metallic glass has since its debut been of great research interest due to its profound scientific significance. Magnetic metallic glasses are of special interest because of their promising technological applications. In this thesis, we introduced a novel series of Fe-based alloys and offer a holistic review of the physics and properties of these alloys. A systematic alloy development and optimization method was introduced, with experimental implementation on transition metal based alloying system. A deep understanding on the influencing factors of glass forming ability was brought up and discussed, based on classical nucleation theory. Experimental data of the new Fe-based amorphous alloys were interpreted to further analyze those influencing factors, including reduced glass transition temperature, fragility, and liquid-crystal interface free energy. Various treatments (fluxing, overheating, etc.) were discussed for their impacts on the alloying systems' thermodynamics and glass forming ability. Multiple experimental characterization methods were discussed to measure the alloys' soft magnetic properties. In addition to theoretical and experimental investigation, we also gave a detailed numerical analysis on the rapid-discharge-heating-and-forming platform. It is a novel experimental system which offers extremely fast heating rate for calorimetric characterization and alloy deformation.

Experimental study on inertial effects in liquid-solid flows

This thesis presents experimental measurements of the rheological behavior of liquid-solid mixtures at moderate Reynolds (defined by the shear rate and particle diameter) and Stokes numbers, ranging from 3 ≤ Re ≤ 1.6 × 10³ and 0.4 ≤ St ≤ 195. The experiments use a specifically designed Couette cylindrical rheometer that allows for probing the transition from transporting a pure liquid to transporting a dense suspension of particles. Measurements of the shear stress are presented for a wide range of particle concentration (10 to 60% in volume) and for particle to fluid density ratio between 1 and 1.05. The effective relative viscosity exhibits a strong dependence on the solid fraction for all density ratios tested. For density ratio of 1 the effective viscosity increases with Stokes number (St) for volume fractions (φ) lower than 40% and becomes constant for higher φ. When the particles are denser than the liquid, the effective viscosity shows a stronger dependance on St. An analysis of the particle resuspension for the case with a density ratio of 1.05 is presented and used to predict the local volume fraction where the shear stress measurements take place. When the local volume fraction is considered, the effective viscosity for settling and no settling particles is consistent, indicating that the effective viscosity is independent of differences in density between the solid and liquid phase. Shear stress measurements of pure fluids (no particles) were performed using the same rheometer, and a deviation from laminar behavior is observed for gap Reynolds numbers above 4× 10³, indicating the presence of hydrodynamic instabilities associated with the rotation of the outer cylinder. The increase on the effective viscosity with Stokes numbers observed for mixtures with φ ≤ 30% appears to be affected by such hydrodynamic instabilities. The effective viscosity for the current experiments is considerably higher than the one reported in non-inertial suspensions.