Electrostatic self-assembly was used to fabricate several samples of polymers known to have non-linear optical behavior. These samples characteristics were measured with interferometry and their electro-optic coefficients determined to be on the order that of LiNbO3. The self-assembled samples are shown to have an enhanced polar order compared to that of more traditional poled polymers. Furthermore, this polar order is intrinsic and thus doesn't require electric field poling and does not decay with time. The self-assembly process is therefore shown to possess great potential for the fabrication of high-speed electro-optic modulators for commercial and military applications. / Master of Science

Nanocomposites of multilayer structures of zirconia/polymer thin-film coatings have been fabricated on quartz and single-crystal silicon substrates by the Ionically Self-Assembled Monolayer (ISAM) technique. Particle size distribution was measured to calculate the grain diameter of the zirconia particles. UV/Vis spectroscopy and ellipsometry were used to characterize the ISAM technique. SEM and AFM were used to observe the microscopic structure of the multilayer structures. Some mechanical properties were characterized by adhesion, abrasion, and nano-hardness tests. It was shown that an important distinction of this novel technique over conventional coating processes is the fabrication of excellent molecular-level uniform films with precise control of film thickness at the à ngström-level at ambient temperature and pressure conditions. It was also shown the maximum Vickers microhardness of ZrO2/polymer nanocomposite thin-film coatings prepared by this method was greater than 25 GPa. / Master of Science

The research work presented in this dissertation relates to lot streaming in two-stage flow shops and assembly shops. Lot streaming refers to the process of splitting a production lot into sublots, and then, processing the sublots on different machines simultaneously in an overlapping manner. Such a strategy allows finished material at each stage to be transferred downstream sooner than if production and transfer batches were restricted to be the same size. In the case when each sublot consists of just one item, a single-piece-flow is obtained. Such a continuous flow is a key element of the Toyota Production System. However, single-piece-flow increases the number of transfers and the total transportation cost (time). As a result, it may not be economically justifiable in many cases, and therefore, material may have to be transferred in batches (called transfer batches, or sublots). Lot streaming addresses the problems of determining optimal sublot sizes for use in various machine environments and optimizes different performance measures.Given this relationship between lot streaming and the Toyota Production System, lot streaming can be considered a generalization of lean principles. In this dissertation, we first provide a comprehensive review of the existing literature related to lot streaming. We show that two-stage flow shop problems have been studied more frequently than other machine environments. In particular, single-lot two-machine flow shops have been very well researched and efficient solution techniques have been discovered for a large variety of problems. While two-stage flow shop lot streaming problems have been studied extensively, we find that the existing literature assumes that production rates at each stage remain constant. Such an assumption is not valid when processing rates change, for example, due to learning. Learning here, refers to the improvements in processing rates achieved due to experience gained from processing units. We consider the case when the phenomenon of learning affects processing and setup times in a two-stage flow shop processing a single lot, and when, sublot-attached setup times exist. The decrease in unit-processing time, or sublot-attached setup time, is given by Wright's learning curve. We find closed-form expressions or simple search techniques to obtain optimal sublot sizes that minimize the makespan when the effect of learning reduces processing times, sublot-attached setup times, or, both. Then, we provide a general method to transform a large family of scheduling problems related to lot streaming in the presence of learning, to their equivalent counterparts that are not influenced by learning. This transformation is valid for all integrable learning functions (including the Wright's learning curve). As a result, a large variety of new problems involving learning can be solved using existing solution techniques. We then consider lot streaming in stochastic environments in the context of sourcing material. Such problems have been well studied in the literature related to lot streaming for cost-based objective functions when demand is continuous, and when processing times are deterministic, or, for material sourcing problems when the time required to procure a lot is stochastic but is independent of the lot size. We extend this study to the case when the time required to produce a given quantity of products is stochastic and dependent on the number of units produced. We consider the case when two sublots are used, and also compare the performance of lot streaming to the case when each sublot is sourced from an independent supplier. Next, we address a new problem related to lot streaming in a two-stage assembly shop, where we minimize a weighted sum of material handling costs and makespan. We consider the case when several suppliers provide material to a single manufacturer, who then assembles units from different suppliers into a single item. We assume deterministic, but not necessarily constant, lead times for each supplier, who may use lot streaming to provide material to the manufacturer. Lead times are defined as the length of the time interval between a supplier beginning to process material and the time when the first sublot is delivered to the manufacturer; Subsequent sublots must be transported early enough so that the manufacturer is not starved of material. The supplier may reduce this lead time by using lot streaming, but at an increased material handling cost. The decrease in lead time is also affected by other factors such as lot attached/detached setup times, transportation times etc. We allow these factors to be different for each supplier, and each lot processed by the same supplier. We refer to this problem as the Assembly Lot Streaming Problem (ALSP). We show that the ALSP can be solved using two steps. The first step consists of solution to several two-stage, single-lot, flow shop, makespan minimization problems. The solution to these problems generate prospective sublot sizes. Solution methods outlined in the existing literature can be used to complete this step. The second step obtains optimal number of sublots and production sequence. For a given production sequence, this step can be executed in polynomial-time; otherwise, the second step problem is NP-hard and integer programming formulations and decomposition-based methodologies are investigated for their solution. We make very limited assumptions regarding the handling cost and the relationship between the supplier lead time and number of sublots used. As a result, our solution methodology has a wide scope. / Ph. D.

No / The reversible in situ formation of a self-assembly building block (naphthalenediimide (NDI)–dipeptide conjugate) by enzymatic condensation of NDI-functionalized tyrosine (NDI-Y) and phenylalanine-amide (F-NH2) to form NDI-YF-NH2 is described. This coupled biocatalytic condensation/assembly approach is thermodynamically driven and gives rise to nanostructures with optimized supramolecular interactions as evidenced by substantial aggregation induced emission upon assembly. Furthermore, in the presence of di-hydroxy/alkoxy naphthalene donors, efficient charge-transfer complexes are produced. The dynamic formation of NDI-YF-NH2 and electronic and H-bonding interactions are analyzed and characterized by different methods. Microscopy (TEM and AFM) and rheology are used to characterize the formed nanostructures. Dynamic nanostructures, whose formation and function are driven by free-energy minimization, are inherently self-healing and provide opportunities for the development of aqueous adaptive nanotechnology.

No / We report on a supramolecular self-assembly system that displays coupled light switching, biocatalytic condensation/hydrolysis and gelation. The equilibrium state of this system can be regulated by light, favouring in situ formation, by protease catalysed peptide synthesis, of self-assembling trans-Azo-YF-NH2 in ambient light; however, irradiation with UV light gives rise to the cis-isomer, which readily hydrolyzes to its amino acid derivatives (cis-Azo-Y + F-NH2) with consequent gel dissolution.

No / Coupling of peptide self-assembly to dynamic sequence exchange provides a useful approach for the discovery of self-assembling materials. In here, we demonstrate the discovery and optimization of aqueous, gel-phase nanostructures based on dynamically exchanging peptide sequences that self-select to maximize charge transfer of n-type semiconducting naphthalenediimide (NDI)-dipeptide bioconjugates with various π-electron-rich donors (dialkoxy/hydroxy/amino-naphthalene or pyrene derivatives). These gel-phase peptide libraries are characterized by spectroscopy (UV–vis and fluorescence), microscopy (TEM), HPLC, and oscillatory rheology and it is found that, of the various peptide sequences explored (tyrosine Y-NDI with tyrosine Y, phenylalanine F, leucine L, valine V, alanine A or glycine G-NH2), the optimum sequence is tyrosine-phenylalanine in each case; however, both its absolute and relative yield amplification is dictated by the properties of the donor component, indicating cooperativity of peptide sequence and donor/acceptor pairs in assembly. The methodology provides an in situ discovery tool for nanostructures that enable dynamic interfacing of supramolecular electronics with aqueous (biological) systems.

Yes / Co-crystallization of polymers with different configurations/tacticities provides access to materials with enhanced performance. The stereocomplexation of isotactic poly(L-lactide) and poly(D-lactide) has led to improved properties compared with each homochiral material. Herein, we report the preparation of stereocomplex micelles from a mixture of poly(L-lactide)-b-poly(acrylic acid) and poly(D-lactide)-b-poly(acrylic acid) diblock copolymers in water via crystallization-driven self-assembly. During the formation of these stereocomplex micelles, an unexpected morphological transition results in the formation of dense crystalline spherical micelles rather than cylinders. Furthermore, mixture of cylinders with opposite homochirality in either THF/H2O mixtures or in pure water at 65 °C leads to disassembly into stereocomplexed spherical micelles. Similarly, a transition is also observed in a related PEO-b-PLLA/PEO-b-PDLA system, demonstrating wider applicability. This new mechanism for morphological reorganization, through competitive crystallization and stereocomplexation and without the requirement for an external stimulus, allows for new opportunities in controlled release and delivery applications. / University of Warwick, Swiss National Science Foundation and the EPSRC. The Royal Society - an Industry Fellowship to A.P.D. The Engineering and Physical Sciences Research Council (EP/G004897/1) - funding to support postdoctoral fellowships for A.P.B. as well as funding for J.S. and M.A.D. through the Warwick Centre for Analytical Science (EP/F034210/1). The Science City Research Alliance and the HEFCE Strategic Development Fund - funding support. Some items of equipment that were used in this research were funded by Birmingham Science City, with support from Advantage West Midlands and part-funded by the European Regional Development Fund.

Yes / We report the crystallization-driven self-assembly of diblock copolymers bearing a poly(L-lactide) block into cylindrical micelles. Three different hydrophilic corona-forming blocks have been employed: poly(4-acryloyl morpholine) (P4AM), poly(ethylene oxide) (PEO) and poly(N,N-dimethylacrylamide) (PDMA). Optimization of the experimental conditions to improve the dispersities of the resultant cylinders through variation of the solvent ratio, the polymer concentration, and the addition speed of the selective solvent is reported. The last parameter has been shown to play a crucial role in the homogeneity of the initial solution, which leads to a pure cylindrical phase with a narrow distribution of length. The hydrophilic characters of the polymers have been shown to direct the length of the resultant cylinders, with the most hydrophilic corona block leading to the shortest cylinders. / EPSRC and the University of Warwick, the Swiss National Science Foundation - Early Postdoc Mobility fellowship (Grant no PBNEP2-142949 to A.P.B.). The Warwick Research Development Fund. Some items of equipment funded by Birmingham Science City: Innovative Uses for Advanced Materials in the Modern World (West Midlands Centre for Advanced Materials Project 2), with support from Advantage West Midlands (AWM) and part funded by the European Regional Development Fund (ERDF).

Yes / Polymer self-assembly in solution is a simple strategy for the preparation of elegant yet complex nanomaterials. However, exhaustive synthesis of the copolymer synthons is often required to access specific assemblies. In this work we show that the blending of just two diblock copolymers with identical block lengths but varying hydrophobic monomer incorporations can be used to access a range of assemblies of intermediate hydrophobic composition. Indeed, the nanostructures produced from blending are identical to those formed with the directly synthesized copolymer of the same composition. This new approach presents researchers with a more efficient and accessible methodology to access precision self-assembled nanostructures, and we highlight its potential by applying it to a demonstrator catalytically active system. / European Science Foundation (ESF), Engineering and Physical Sciences Research Council (EPSRC), United States. Air Force. Office of Scientific Research (AFOSR)

Yes / Amphiphilic nucleobase-containing block copolymers with poly(oligo(ethylene glycol) methyl ether methacrylate) as the hydrophilic block and nucleobase-containing blocks as the hydrophobic segments were successfully synthesized using RAFT polymerization and then self-assembled via solvent switch in aqueous solutions. Effects of the common solvent on the resultant morphologies of the adenine (A) and thymine (T) homopolymers, and A/T copolymer blocks and blends were investigated. These studies highlighted that depending on the identity of the common solvent, DMF or DMSO, spherical micelles or bicontinuous micelles were obtained. We propose that this is due to the presence of A–T interactions playing a key role in the morphology and stability of the resultant nanoparticles, which resulted in a distinct system compared to individual adenine or thymine polymers. Finally, the effects of annealing on the self-assemblies were explored. It was found that annealing could lead to better-defined spherical micelles and induce a morphology transition from bicontinuous micelles to onion-like vesicles, which was considered to occur due to a structural rearrangement of complementary nucleobase interactions resulting from the annealing process. / European Research Council (ERC), University of Warwick, Engineering and Physical Sciences Research Council (EPSRC), National Science Foundation (U.S.) (NSF)