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Microemulsions have important applications in various industries, including enhanced oil recovery, reactions, separations, drug delivery, cosmetics and foods. We investigated two different kinds of water-in-oil microemulsion systems, AOT (bis(2-ethylhexyl) sulfosuccinate) microemulsions with various counterions and perfluorocarbon-based microemulsion gels with triblock copolymers. In the AOT systems, we investigated the viscosity and interdroplet interactions in Ca(AOT)2, Mg(AOT)2 and KAOT microemulsions, and compared our results with the commonly-studied NaAOT/water/decane system. We attribute the differences in behavior to different hydration characteristics of the counterions, and we believe that the results are consistent with a previously proposed charge fluctuation model. Perfluorocarbons (PFCs) are of interest in a variety of biomedical applications as oxygen carriers. We have used triblock copolymer Pluronic® F127 to modify the rheology of PFC-based microemulsions, we have been able to form thermoreversible PFOB (perfluorooctyl bromide)-based gels, and have investigated the phase stability, rheology, microstructure, interactions, and gelation mechanism using scattering, rheometry, and microscopy. Finally, we attempted to use these data to understand the relationship between rheology and structure in soft attractive colloids.

Room temperature ionic liquids (ILs) are a unique class of solvents which are characterized by non-volatility, non-flammability, electrochemical stability and high ionic conductivity. These properties are highly desirable for ion-conducting electrolytes, and much work has focused on realizing their application in practical devices. In addition, hydrophilic and ionophilic polymers are generally miscible with ILs. The miscibility of ILs with ion-coordinating polymers makes ILs effective plasticizers for gel polymer electrolytes. Due to their unique properties, ILs present a means to realize the next generation of energy storage technology. In this dissertation, the fundamental interactions between poly(ethylene oxide) (PEO) and a variety of room temperature ILs were investigated. ILs with acidic protons were demonstrated to form a stronger interaction with PEO than ILs without such protons, suggesting that hydrogen bonding plays a dominant role for PEO miscibility with ILs. The hydrogen bonding interaction is selective for the PEO block of a PEO-b-PPO-b-PEO block copolymer (BCP). Therefore, blending these copolymers with the strongly interacting IL 1-butyl-3-methylimidazolium hexafluorophosphate ([BMI][PF6]) induced microphase separation into a well-ordered structure, whereas the neat copolymer is phase mixed. At sufficient quantities, the interaction between [BMI][PF6] and PEO suppresses PEO crystallinity entirely. In addition, the induced microphase separation may prove beneficial for ion conduction. Therefore, microphase separated copolymer/IL blends were investigated as potential gel polymer electrolytes. Cross-linkable block copolymers which microphase separate when blended with [BMI][PF6] were synthesized by modifying PPO-b-PEO-b-PPO copolymers with methacrylate end-groups. Cross-linking these copolymers while swollen with an IL generates ion gels with high ionic conductivities. The copolymer/IL blends vary from a well-ordered, strongly microphase separated state to a poorly ordered and weakly microphase separated state, depending upon the molecular weight. Stronger microphase separation results in higher mechanical strength upon cross-linking. However, this does not greatly affect ion conductivity. Nor is conductivity affected by forming gels from cross-linked PEO homopolymers when compared to BCPs. It was found that BCPs can be beneficial in producing gel electrolytes by allowing sequestration of phase selective cross-linkers away from the conducting block. Cross-linker molecules that are selective for the PPO blocks can be used to increase the mechanical strength of the gels with only a small effect on the conductivity. When cross-linkers that partition to the mixed PEO/IL block are used, the conductivity decreases by nearly a factor of 2. These studies show how ILs interact with PEO and how gel polymer electrolytes can be constructed with the IL [BMI][PF6]. While BCPs cannot directly be used to increase ion conductivity, they do allow for greater mechanical strength without sacrificing conductivity. This suggests many new approaches that may be used to simultaneously achieve high ionic conductivity and mechanical strength in solid and gel polymer electrolytes.

Polylactide (PLA) is a biodegradable and biocompatible polymer which is attracting much attention for environmental issues imposed by the petroleum-based polymers. PLA can be used as medical polymer in surgical sutures, implants tissue and many other areas. However, one of the main shortcomings of PLA is its brittleness in nature and relatively poor mechanical properties, which often limits its further application. It is generally accepted for polymeric materials that some mechanical properties of oriented structures can be improved as the molecular weight of PLA increases. The outcome of this thesis will provide the knowhow to achieve ultrahigh molecular weight of polylactides, and further to improve the mechanical properties and extend its range of applications. In this work, different catalytic systems for the synthesis of ultra-high molecular weight (UHMW) polylactide are considered. For the catalytic systems considered, the reaction conditions and initiators are investigated. The resulting molecular characteristics and mechanical properties of the synthesized polymers will be evaluated. On the contrary to the brittle nature of PLA, Poly(ε-carprolactone) (PCL) is elastic and flexible with a relatively low melting point (60 oC) and low glass transition temperature (-60 oC). Hence, ultra-high molecular weight PCL will be also synthesized by using the same catalytic systems employed for achieving UHMWPLAs. PCL is also used in different biomedical applications, such as in scaffolds for tissue engineering. It is well documented that the complementary physical properties of PLA and PCL have the potential to enhance toughness of PLA. To enhance the toughness and mechanical properties of the block copolymers attempt is made to synthesize ultra-high molar mass of the two polymers in the block copolymer. But their molar masses (and consequently their mechanical properties) are always on the low side. For this reason, the synthesis of high molecular mass PLA and PCL multiblocks will be attempted. Furthermore, it is interesting to study the synthesis of high molar masses PLLA and PDLA stereoblocks especially their ability to crystallize during the polymerization and test the possibility to prepare stereocomplex only during synthesis. The resulting molecular characteristics and mechanical properties of the synthesized multiblock-polymers will be also evaluated.

Ethylene copolymers are widely used as packaging materials, adhesives and specialty polymers for well-regarded cost savings, durability, chemical resistance, and hot melt character. This work examines the use of diester monomers known as malonates to determine the plausibility of utilizing an uncommon monomer class for producing novel ethylene copolymers. Ethylene is copolymerized with diethyl methylene malonate—a simple malonate representative of more complex and highly modified malonate monomers and macromers—to produce ethylene-co-diethyl methylene malonate in a range of molecular weights. Ethylene-co-diethyl methylene malonate is analyzed to determine physical properties such as glass transition temperature, chain length and monomer incorporation. Successful copolymerization occurred under a range of temperatures and pressures in tetrahydrofuran, diethyl carbonate, and dimethyl carbonate. The produced polymers were found to have a molecular weight of 15-46 kg/mol, a glass transition temperature of 7°C, a melting temperature of 108°C, and a cold crystallization temperature of 64°C. The high concentration of a radical source inhibitor in the diethyl methylene malonate monomer solution negatively impacted molecular weight and ethylene incorporation.

Laser lithography was used to create novel patterns in thin diblock copolymer films. These patterns were characterized and an examination of their formation and growth was conducted. The patterns occurred only in diblock films, due to the interaction between thermal gradient induced Marangoni flow and the self assembly of the molecules. Growth of the patterns was found to be strongly dependent on absorbed power. The impact of film thickness on pattern growth was mainly due to the corresponding changes in sample reflectance, however a periodic patterning was observed suggesting that growth is also dependent on the amount of 'excess' material (over that required to form complete lamella) available. It was also shown that the pattern growth can occur independently of laser lithography and the Marangoni effect, though laser lithography was required to direct this growth. / Thesis / Master of Applied Science (MASc)

Indium tin oxide is a transparent conductive oxide electrode which is widely used for organic electronics. Morphology of ITO plays an important role in the performance of organic electronics. To understand the influence of the substrate morphology in device performance, a controllable route for producing periodic and aperiodic roughness of ITO surfaces are necessary. In this thesis, this was attempted by using various approaches to forming ITO nanostructures. Initially, ITO was deposited by a traditional sputtering procedure. However, the roughness distribution of the sputtered ITO resulted in a s Gaussian distribution, unsuitable to further studies of roughness. ITO nanostructures can also be formed by depositing ITO nanoparticles on an ITO sub- strates. Using acetate and chloride precursors, ITO films were produced from solution and formed into nanoparticles using the reverse micelles deposition approach. The acetate route (InAc+SnCl2+ethanol), was the most successful prior to the nanoparticle formation, showing high quality ITO with bixbyte crystal structure and Sn percentages of 20%, low enough to form a conductive film. Nanoparticles were fabricated with diblock copolymer reverse micelles(PS-b-P2VP). Reverse micelles were found to act as a nano reactor, restricting the size of nanoparticles by having hydrophilic reactants undergo chemical reactions inside the micelles. However, nanoparticles from the reverse micelles revealed Sn percentages much above 20%. This was attributed to the solubility difference of the precursors leading to displacing or preventing of pre- cursor loading into the reverse micelles. The change of the stirring time, the micelles concentration, the sequence of precursors loading, and the weight of precursors were not found to affect the Sn concentration; moreover, large variations in Sn concentrations were observed. From quantitative nano mechanical testing of the micelles, a maximum load amount for the precursors was observed, confirming that the high concentration of Sn was likely due to the solubility differences between the precursors and their ability to penetrate the micelle. By manipulating the nanoparticles distribution through spin coating speeds, micelles concentration, and deposited volume, several degrees of order were obtained, though hexagonal packing was not observed. In general, even though Sn concentration were found to be above 20%, nanoparticles were successfully fabricated with reverse micelles, confirming that the reverse micelle technique is a good strategy for future studies of roughness. / Thesis / Master of Applied Science (MASc)

Thesis advisor: Jia Niu / This dissertation discusses two main projects focusing on synthesizing degradable vinyl copolymers. The first project describes the development of a general approach to synthesizing degradable vinyl random copolymers through photocontrolled radical ring-opening cascade copolymerization (rROCCP). The rROCCP of a macrocyclic allylic sulfone with acrylates or acrylamides mediated by visible light at ambient temperature achieved near-unity comonomer reactivity ratios over the entire range of feed compositions. Such a powerful approach provides degradable vinyl random copolymers with comparable material properties to their non-degradable counterparts. Experimental and computational evidence also revealed an unusual reversible inhibition of chain propagation by in situ generated sulfur dioxide (SO2), which was successfully overcome by reducing the solubility of SO2 during polymerization. The second project depicts a general method for organocatalyzed photocontrolled radical copolymerization of a macrocyclic allylic sulfone and various types of vinyl monomers, including acrylates, acrylamides, styrene, and methacrylate. Catalyzed by Eosin Y under visible light irradiation, copolymerization of the macrocyclic allylic sulfone and acrylic monomers displayed near unity comonomer reactivity ratios by fitting the copolymer composition to the Beckingham-Sanoya-Lynd integrated model. The macrocyclic allylic sulfone was also successfully copolymerized with styrene or methyl methacrylate to generate degradable polystyrene and poly(methyl methacrylate). These degradable vinyl copolymers exhibited tunable thermal properties correlated with the incorporation of degradable main-chain diester motif. / Thesis (PhD) — Boston College, 2023. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.