Polyferrocenylsilane (PFS) diblock copolymers self-assemble in selective solvents to form one-dimensional micelles for a broad range of polymer compositions and experimental conditions, driven by the crystallization of the PFS block that forms the micelle core. The most striking feature of these micelles is that they remain active for further growth. They can be extended in length when additional polymer, dissolved in a good solvent, is added to a solution of the pre-existing micelles. This thesis describes several studies investigating the factors that affect the growth and fragmentation of PFS diblock copolymer micelles in solution, with a particular emphasis on polyisoprene-PFS (PI-PFS) diblock copolymers. The goal of my research was trying to provide deeper understanding of this crystallization-driven self-assembly (CDSA) process. In an attempt to understand the growth kinetics of the PI-PFS cylindrical micelles, I added tiny amount of short micelle seeds into supersaturated solution of the same polymer, and followed the micelle growth by light scattering. The data analysis showed that the increase of micelle length could be described by an expression with two exponential decay terms. In another attempt to examine the factors that may affect the growth behavior of the PI-PFS micelles, I found that PI-PFS long micelles underwent fragmentation when they were subjected to external stimuli, e.g. addition of polar solvent, or heating. During the course of studying the effect of heating on the micelles, I developed a new approach to generate cylindrical micelles with controllable and uniform length, a one-dimensional analogue of self-seeding of crystalline polymers. I carried out a systematic study to investigate the self-seeding behavior of PFS block copolymers.

Polyferrocenylsilane (PFS) diblock copolymers self-assemble in selective solvents to form one-dimensional micelles for a broad range of polymer compositions and experimental conditions, driven by the crystallization of the PFS block that forms the micelle core. The most striking feature of these micelles is that they remain active for further growth. They can be extended in length when additional polymer, dissolved in a good solvent, is added to a solution of the pre-existing micelles. This thesis describes several studies investigating the factors that affect the growth and fragmentation of PFS diblock copolymer micelles in solution, with a particular emphasis on polyisoprene-PFS (PI-PFS) diblock copolymers. The goal of my research was trying to provide deeper understanding of this crystallization-driven self-assembly (CDSA) process. In an attempt to understand the growth kinetics of the PI-PFS cylindrical micelles, I added tiny amount of short micelle seeds into supersaturated solution of the same polymer, and followed the micelle growth by light scattering. The data analysis showed that the increase of micelle length could be described by an expression with two exponential decay terms. In another attempt to examine the factors that may affect the growth behavior of the PI-PFS micelles, I found that PI-PFS long micelles underwent fragmentation when they were subjected to external stimuli, e.g. addition of polar solvent, or heating. During the course of studying the effect of heating on the micelles, I developed a new approach to generate cylindrical micelles with controllable and uniform length, a one-dimensional analogue of self-seeding of crystalline polymers. I carried out a systematic study to investigate the self-seeding behavior of PFS block copolymers.

My Ph.D. thesis is presented in two parts. In the first part, I describe the preparation of organic-inorganic hybrid micelles formed from poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) block copolymers and CdSe quantum dots (QDs). Several distinct morphologies were observed including, spheres, finite-sized wormlike networks and clusters of hollow vesicles. A series of experiments were carried out to explore whether these hybrid colloids were thermodynamically stable or formed under kinetic control. Upon addition of 2-propanol (2-PrOH) to a chloroform solution containing a mixture of PS404-b-P4VP76 plus CdSe QDs (2-PrOH is a good solvent for P4VP block and a precipitant for PS block and QDs), uniform spherical micelles formed almost instantly, with a PS core and a thin P4VP corona to which the QDs were attached. Vigorous stirring of this solution for two days led to the formation of three-dimensional wormlike networks consisted of Y-junctions and cylindrical struts, terminated by bulbous spherical end-caps. Even more profound structural changes occurred when the solution was subjected to prolonged magnetic stirring (e.g. 1 month). ii In contrast, manipulating the chemical composition of the initial block copolymer could trigger a spontaneous structural transition from sphere to network of wormlike micelles over 2 h without the need of stirring. The second part of the thesis begins by describing a modular approach for preparing polyferrocenyldimethylsilane (PFS) block copolymers via a Cu-catalyzed alkyne/azide coupling reaction to covalently combine two homopolymers synthesized separately. This strategy opens the door to a broad library of novel functional PFS block copolymers, for example, poly(ferrocenyldimethylsilane-b-N-isopropyl acrylamide) (PFS-b-PNIPAM). In an attempt to expand our understanding of PFS block copolymer self-assembly in polar solvents, I investigated the self-assembly of a new polymer (PFS26-b-PNIPAM105) in alcohol solvents. When the block polymer was dissolved in methanol, ethanol and 2-propanol, it formed long fiber-like micelles with uniform width. I also showed that micelles of this polymer underwent seeded growth in methanol, leading to cylindrical micelles that were nearly mono- dispersed in length.

My Ph.D. thesis is presented in two parts. In the first part, I describe the preparation of organic-inorganic hybrid micelles formed from poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) block copolymers and CdSe quantum dots (QDs). Several distinct morphologies were observed including, spheres, finite-sized wormlike networks and clusters of hollow vesicles. A series of experiments were carried out to explore whether these hybrid colloids were thermodynamically stable or formed under kinetic control. Upon addition of 2-propanol (2-PrOH) to a chloroform solution containing a mixture of PS404-b-P4VP76 plus CdSe QDs (2-PrOH is a good solvent for P4VP block and a precipitant for PS block and QDs), uniform spherical micelles formed almost instantly, with a PS core and a thin P4VP corona to which the QDs were attached. Vigorous stirring of this solution for two days led to the formation of three-dimensional wormlike networks consisted of Y-junctions and cylindrical struts, terminated by bulbous spherical end-caps. Even more profound structural changes occurred when the solution was subjected to prolonged magnetic stirring (e.g. 1 month). ii In contrast, manipulating the chemical composition of the initial block copolymer could trigger a spontaneous structural transition from sphere to network of wormlike micelles over 2 h without the need of stirring. The second part of the thesis begins by describing a modular approach for preparing polyferrocenyldimethylsilane (PFS) block copolymers via a Cu-catalyzed alkyne/azide coupling reaction to covalently combine two homopolymers synthesized separately. This strategy opens the door to a broad library of novel functional PFS block copolymers, for example, poly(ferrocenyldimethylsilane-b-N-isopropyl acrylamide) (PFS-b-PNIPAM). In an attempt to expand our understanding of PFS block copolymer self-assembly in polar solvents, I investigated the self-assembly of a new polymer (PFS26-b-PNIPAM105) in alcohol solvents. When the block polymer was dissolved in methanol, ethanol and 2-propanol, it formed long fiber-like micelles with uniform width. I also showed that micelles of this polymer underwent seeded growth in methanol, leading to cylindrical micelles that were nearly mono- dispersed in length.

Doctor of Philosophy / Department of Grain Science and Industry / X. Susan Sun / Biobased polymers derived from renewable resources are increasingly important due to acute concerns about the environmental issues and limited petroleum resources. Poly(lactic acid) (PLA) is such a polymer that has shown great potential to produce biodegradable plastics. However, low glass transition temperature (Tg), low thermal stability, slow biodegradation rate, and high cost limit its broad applications. This dissertation seeks to overcome these limitations by reinforcing PLA with inorganic nanoparticles and low-cost agricultural residues. We first synthesized PLA nanocomposites by in situ melt polycondensation of L-lactic acid and surface-hydroxylized nanoparticles (MgO nanocrystals and TiO2 nanowires) and investigated the structure-property relationships. PLA grafted nanoparticles (PLA-g-MgO, PLA-g-TiO2) were isolated from the bulk nanocomposites via repeated dispersion/centrifugation processes. The covalent grafting of PLA chains onto nanoparticle surface was confirmed by Fourier transform infrared spectroscopy and thermalgravimetric analysis (TGA). Transmission electron microscopy and differential scanning calorimetry (DSC) results also sustained the presence of the third phase. Morphological images showed uniform dispersion of nanoparticles in the PLA matrix and demonstrated a strong interfacial interaction between them. Calculation based on TGA revealed that more than 42.5% PLA was successfully grafted into PLA-g-MgO and more than 30% was grafted into PLA-g-TiO2. Those grafted PLA chains exhibited significantly increased thermal stability. The Tg of PLA-g-TiO2 was improved by 7 °C compared with that of pure PLA. We also reinforced PLA with low-value agricultural residues, including wood flour (WF), soy flour (SF), and distillers dried grains with solubles (DDGS) by thermal blending. Tensile measurements and morphological images indicated that methylene diphenyl diisocyanate (MDI) was an effective coupling agent for PLA/WF and PLA/DDGS systems. MDI compatibilized PLA/WF and PLA/DDGS composites showed comparable tensile strength and elongation at break as pure PLA, with obviously increased Young’s modulus. Increased crystallinity was observed for PLA composites with SF and DDGS. Such PLA composites have similar or superior properties compared with pure PLA, especially at a lower cost and higher biodegradation rate than pure PLA. The results from this study are promising. These novel PLA thermoplastic composites with enhanced properties have potential for many applications, such as packaging materials, textiles, appliance components, autoparts, and medical implants.

Master of Science / Department of Grain Science and Industry / Xiuzhi Susan Sun / Plant oil-based raw materials have become more attractive alternatives in polymer industry as fossil resources depletion and environmental concerns continue to arise. Camelina (camelina sativa L.) seed contains about 45% of oil and about 90% of the oil is unsaturated fatty acids such as linoleic acid, α-linolenic acid, and erucic acids. It also provides the advantages of low cost and low fertilizer demand. Functionalized oils such as epoxidized camelina oil (ECO) and di-hydroxyl camelina oil (DCO) can be used for resins, adhesives, coatings, etc. The objectives of this work were to synthesize and characterize ECO and DCO from camelina oil. The epoxidation reaction of camelina oil was completed with formic acid and hydrogen peroxide. Catalyst ratio, reaction time, and temperature effects on the epoxidation reaction were studied. The optimum epoxy content of 7.52 wt% with a conversion rate of 76.34% was obtained from camelina oil using excess hydrogen peroxide and a molar ratio of formic acid of less than 1 for 5 hours in 50 °C. Camelina oil yields higher epoxy content (7.52 wt%) than soybean oil (6.53 wt%); however, soybean oil had a higher conversion rate of 80.16% compared to camelina oil because of uniform fatty acids distribution. In this study, we found that epoxidation efficiency is significantly affected by fatty acids composition, structure, and distribution. DCO was synthesized from ECO with different reaction parameters. The ring opening of ECO was performed with water, perchloric acid, and THF as proton donor, catalyst, and solvent respectively. Hydroxyl value of DCO was measured, and the maximal hydroxyl value was 369.24 mg KOH/g. physical properties of DCO were characterized by acid value and moisture content; thermal properties of DCO were obtained using different scanning calorimeter (DSC), thermalgravimetric analysis (TGA). Amount of solvent and acid catalyst addition affected the hydroxyl value and residual acid in DCO. Heat capacity, phase transition temperatures, and thermal stability of DCO were obtained and showed higher values than ECO’s. The DCO showed higher peel adhesion when it was formulated with epoxidized soybean oils through UV curing because camelina oil allows higher epoxy content, which results in higher hydroxyl values.

Master of Science / Department of Mechanical and Nuclear Engineering / Youqi Wang / Electrospinning is one of the most versatile methods used to fabricate nanofibers. Sub micron and nano level fibers can be continuously produced with the help of an external electric field induced on the polymer melt. These nanofibers can be used in a large variety of applications such as biosensors, three dimensional tissue scaffolds, composites, electronic devices, etc. A unique feature of electrospinning is its ability to work with different fiber assemblies. This helps in making application specific changes and also increases the quality and performance of the fibers. PEO (polyethylene oxide) and electrostrictive graft elastomer (an electroactive polymer developed by NASA) were used in our experiments which focus on controlling the shape and alignment of the fibers. Electroactive polymers (EAP’s) are seen as the basis for future artificial muscles because of their ability to deform when external voltage is applied and quickly recover to their original form when the polarity of the applied voltage is reversed. Hence, aligned fibers of the electrostrictive graft elastomer were produced to mimic the alignment in human muscle fibers. Alignment of fibers is the main objective of this research and was facilitated using vacuum technology. The research was basically divided into three phases, starting with checking of the repeatability of the previously developed techniques using polyethylene oxide. Next, the electrostrictive graft elastomer was spun using the electrospinning techniques and was checked for alignment using the Coaxial Electrode method and PLC controlled secondary electric field method. Finally, a vacuum chamber was designed and built with new components and the elastomer was tested for improved alignment in vacuum using the PLC controlled secondary electric field method.

This work describes the results of experimental study of the flow of soft objects (microgels) through microchannels. This work was carried with the intention of building a fundamental biophysical model for the flow of neutrophil cells in microcirculatory system. In Chapter 1 we give a summary of the literature describing the flow of cells and “model cells” in microchannels. Paramount to this we developed methods to modify microchannels fabricated in poly(dimethyl siloxane) (PDMS). Originally, these microchannels could not be used to mimic biological microenvironments because they are hydrophobic and have rectangular cross-sections. We designed a method to create durable protein coatings in PDMS microchannels, as outlined in Chapter 3. Surface modification of the channels was accomplished by a two-step approach which included (i) the site-specific photografting of a layer of poly(acrylamide) (PAAm) to the PDMS surface and (ii) the bioconjugation of PAAm with the desired protein. This method is compatible with different channel geometries and it exhibits excellent longevity under shear stresses up to 1 dyn/cm. The modification was proven to be successful for various proteins of various molecular weights and does not affect protein activity. The microchannels were further modified by modifying the cross-sections in order to replicate cardiovascular flow conditions. In our work, we transformed the rectangular cross-sections into circular corss-sections. Microchannels were modified by polymerizing a liquid silicone oligomer around a gas stream coaxially introduced into the channel, as outlined in Chapter 3. We demonstrated the ability to control the diameter of circular cross-sections of microchannels. The flow behaviour of microgels in microchannels was studied in a series of experiments aimed at studying microgel flow (i) under electrostatic interactions (Chapter 4), (ii) binding of proteins attached to the microgel and the microchannel (Chapter 5) and (iii) under the conditions of varying channel geometry (Chapter 6). This work overall present’s new methods to study the flow of soft objects such as cells, in the confined geometries of microchannels. Using these methods, variables can be independently probed and analyzed.

No description available.

This thesis presented a microfluidic preparation of bubbles-templated micro-size materials. In particular, this thesis focused on the microfluidic formation and dissolution of CO2 bubbles. First, this thesis described pH-regulated behaviours of CO2 bubbles in the microfluidic channel. This method opened a new way to generate small (<10 µm in diameter) with a narrow size distribution (CV<5%). Second, the microfluidic dissolution of CO2 bubbles possessed the important feature: the local change of pH on the bubble surface. This allowed us to encapsulate the bubbles with various colloidal particles. The bubbles coated with particles showed a high stability against coalescences and Ostwald ripening. The dimensions and shapes of bubbles with a shell of colloidal particle were manipulated by the hydrodynamic and chemical means, respectively. Third, we proposed a microfluidic method for the generation of small and stable bubbles coated with a lysozyme-alginate shell. The local pH decrease at the periphery of CO2 bubbles led to the electrostatic attraction between lysozyme on the bubble surface and alginate in the continuous phase. This produced the bubbles with a shell of biopolymers, which gave a long-term stability (up to a month, at least) against the dissolution and coalescence. Fourth, we presented a single-step method to functionalize bubbles with a variety of nanoparticles. The bubbles showed the corresponding properties of nanoparticles on their surface. Further, we explored the potential applications of these bubbles as contrast agents in ultrasound and magnetic resonance imaging.