VTechWorks Repository :: Browsing by Author "Long, Timothy E."

Browsing by Author "Long, Timothy E."

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3D Printing of Specialty Devices for Geochemical Investigations: Real-Time Studies of Goethite and Schwertmannite Formation
Kletetschka, Karel (Virginia Tech, 2018-06-29)
New types of laboratory reactors that are highly customizable, low-cost and easy to produce are needed to investigate low-temperature geochemical processes. We recently showed that desktop 3D printing stereolithography (SLA) can be used to efficiently fabricate a mixed flow reactor (MFR) with high dimensional accuracy comparable to traditional machining methods (Michel et al., 2018). We also showed that the SLA method allowed for the addition of complex features that are often beyond the capabilities of traditional methods. However, the stability of 3D printed parts at low-temperature geochemical conditions has not been fully evaluated. The objectives of this work were twofold: 1) to provide a framework for assessing the stability and compatibility of SLA printed materials at geochemically relevant conditions, and 2) to show how 3D printed specialty devices can enable new laboratory geochemical experiments. Part 1 of this Master's thesis presents findings for enhancing mechanical and solvent resistance properties of a commercial 3D printing material (Formlabs Clear) by UV post-curing procedures and also provide data showing its stability in aqueous solutions at pH 0, 5.7, and 12 for periods of up to 18 days. Thermal degradation patterns, mechanical analysis, and leachable fraction data are provided. Part 2 shows experiments coupling 3D printed reactors and flow devices for in situ small-angle x-ray scattering (SAXS). Schwertmannite (pH 2.7) and goethite (6.2) are precipitated from solution using various setups and observed differences in growth rates are discussed. The data show the potential of 3D printing for enabling novel laboratory geochemical experiments.
Adhesion Studies of Polymers: (I) Autohesion of Ethylene/1-Octene Copolymers; (II) Method Development and Adhesive Characterization of Pressure Sensitive Adhesive in Paper Laminates for Postage Stamps
Yang, Hailing (Virginia Tech, 2006-04-21)
Autohesion is defined as the resistance to separation of two bonded identical films that have been joined together for a period of time under a given temperature and pressure. Studies on the autohesion phenomenon can provide fundamental insights into the physical processes of adhesive bond and failure, as well as the practical engineering issues such as crack healing, elastomer tack, polymer fusion, self-healing, and polymer welding. In the first part of this dissertation work, four ethylene/1-octene (EO) copolymers were used in the present study consisting of molecules with linear polyethylene backbone to which hexyl groups are attached at random intervals. These copolymers have similar number-average molecular weight (Mn) and polydispersity, but different 1-octene content. These hexyl groups act as the short branches and hinder the crystallization, reduce density to some extent in the solid state, lower the melting temperature, and decrease the stiffness of the bulk materials. A full understanding of the autohesion behavior of the ethylene/1-octene copolymers involves investigations at three different length scales: 1) the molecular scale which controls the interfacial structure; 2) the mesoscopic or microscopic scale which can provide information on the formation of interfaces and on how the energy is dissipated during a fracture process; and 3) the macroscopic scale at which the mechanical properties such as fracture energy can be obtained for a particular test geometry. In the present study, the effects of the branch content on the formation and fracture of the interface of these ethylene/1-octene assemblies were evaluated at the bonding temperatures (Tb) and bonding times (tb). The correlation among these three length scales was also investigated and modeled. The adhesion strength of these symmetric interfaces of EO copolymers was investigated by T-peel fracture tests. The fracture of the interface is an irreversible entropy creating process which involved a substantial amount of energy dissipation. The results of such mechanical tests with respect to the bonding temperature (Tb), bonding time (tb) and peel rate indicated this energy dissipation is the result of a complicated interplay between the ability of the interface to transfer stress and its plastic and viscoelastic deformation properties. When Tb is much higher than the characteristic temperature (Tc), the interfaces were completely healed and cohesive failure was observed in T-peel tests. In this case, the fracture strength decreased with increasing branch content. In contrast, when Tb is very close to Tc, the fracture strength showed an increase with the branch content with either interfacial failure or cohesive failure being observed depending on the branch content and Tb. At higher peel rates, it is observed that higher peel energies are required to fracture the surfaces. Transmission electron microscopy (TEM) showed that the interfacial/interphase structure changed from amorphous to crystalline with an increase in the Tb. The results from the bonding time effect studies showed that the peel energy is proportional to tb1/2 regardless of Tb. But the branch content and the Tb play an important role on the seal rate. Thus, higher seal rate was found for higher Tb and higher branch content. These results also suggest that the autohesion of ethylene/1-octene copolymers are strongly associated with the interactions of melted chains. The chain compositions of these Zeigler-Natta EO copolymers are highly heterogeneous with the branches concentrated in the lower molecular weight portion. Long linear chain segments could form large, well-ordered crystals that provide strong anchors for the tie molecules and therefore determine the density of inter-crystalline links. Short chains with lots of branches could behave as protrusions along the chain to obstruct chain disentanglement and limit a chain from sliding through a crystal. Due to these reasons, the short chains with branches would contribute much less than the long linear chains to the full peel strength after complete sealing. However, higher peel strengths could be obtained only at the higher temperatures or longer bonding times at which the long linear chains begin to melt and diffuse across the interface. On the other hand, the higher branch content samples have the lower crystallinity and could obtain the higher chain mobility at the lower bonding temperatures and with shorter bonding times. Therefore, higher seal strength was observed for the higher branch content samples at lower Tb. Following T-peel fracture tests of ethylene/1-octene copolymer assemblies which showed interfacial failures, the fractured surfaces were investigated by using Atomic Force Microscopy (AFM) and characterized by fractal analysis together with the original films. The AFM images showed strong dependence on the peel rate and branch content. Quantitatively, the fractal analyses demonstrated fractal characteristics at the different finite scales. Two regimes showing fractal features were identified for each surface. In regime I (low magnifications) the fracture test did not change the fractal dimensions much. But there were significant changes in regime II before welding and after T-peel fracture tests. The length scale that separated these two regimes is very close to the size of lamellar structures. The characteristic sizes at which the fractal characteristics emerge were shown to appear at larger scales for surfaces fractured at higher peel rates. This suggests that the appearance of fractal behavior at larger scales requires higher fracture energies. The characteristic sizes and fractal dimensions were shown to depend on the molecular structure. Because the fractal analysis suggests at least some crystalline lamellae on the surfaces still existed during T-peel fracture tests, a "Stitch-welding" has been therefore proposed as the autohesion mechanism in which only chains in the amorphous portions could inter-diffuse. In the second part of this dissertation work, a multi-layer lap-shear geometry has been designed and proven as a reliable testing method in evaluation of the dynamical mechanical properties of polyacrylic pressure sensitive adhesive (PSA) in paper lamination for postage stamp applications. In-situ testing of four different PSA stamp laminates constructed by laminating water-based polyacrylic PSAs to the stamp face papers were carried out using a dynamic mechanical analyzer (DMA) in the temperature range from -50 to 60 oC at frequencies 0.1, 1, 10, and 100 Hz. This geometry requires the tension mode on the DMA, but the results which were recorded as tensile properties were converted to shearing properties of the PSA layers in the laminate. The effect of the thickness (layers of laminates) on the dynamical mechanical properties has been studied and the results suggested that a multi-layer geometry with 5-10 layers could be an appropriate structure to produce enhanced responses. Therefore, the geometry with 8-layer laminates was used for frequency sweep/isothermal temperature and frequency sweep/temperature step tests. The results showed three relaxation responses that is, glassy, transition, and flow regions with respect to the frequencies and temperatures. These results also implied the viscoelastic characteristics of these PSA products. The tensile properties of the face papers were also tested using the same parameters as those of the multi-layer geometry. Significant differences were found between the shearing behaviors of the multi-layer geometry and the tensile behaviors of the elastic face paper. This suggests that the tensile deformation of the face paper in the multi-layer geometry could be ignored and the elastic paper did not contribute to the shearing properties of the PSA layers. Time-temperature superposition curves have been produced with reference temperature set at 23 oC, which can be used to predict the long term and short term performances of these samples at this temperature. This method can be utilized as a standard testing method on the PSA adhesives in the laminate form. In addition to the dynamic mechanical properties, it can also be developed to be a general standard method on testing the rheological properties of adhesives, polymer melts and other viscous materials.
Advancing Elastomers to Additive Manufacturing Through Tailored Photochemistry and Latex Design
Scott, Philip Jonathan (Virginia Tech, 2020-07-08)
Additive manufacturing (AM) fabricates complex geometries inaccessible through other manufacturing techniques. However, each AM platform imposes unique process-induced constraints which are not addressed by traditional polymeric materials. Vat photopolymerization (VP) represents a leading AM platform which yields high geometric resolution, surface finish, and isotropic mechanical properties. However, this process requires low viscosity (<20 Pa·s) photocurable liquids, which generally restricts the molecular weight of suitable VP precursors. This obstacle, in concert with the inability to polymerize high molecular weight polymers in the printer vat, effectively limits the molecular weight of linear network strands between crosslink points (Mc) and diminishes the mechanical and elastic performance of VP printed objects. Polymer colloids (latex) effectively decouple the relationship between viscosity and molecular weight by sequestering large polymer chains within discrete, non-continuous particles dispersed in water, thereby mitigating long-range entanglements throughout the colloid. Incorporation of photocrosslinking chemistry into the continuous, aqueous phase of latex combined photocurability with the rheological advantages of latex and yielded a high molecular weight precursor suitable for VP. Continuous-phase photocrosslinking generated a hydrogel scaffold network which surrounded the particles and yielded a solid "green body" structure. Photorheology elucidated rapid photocuring behavior and tunable green body storage moduli based on scaffold composition. Subsequent water removal and annealing promoted particle coalescence by penetration through the scaffold, demonstrating a novel approach to semiinterpenetrating network (sIPN) formation. The sIPN's retained the geometric shape of the photocured green body yet exhibited mechanical properties dominated by the high molecular weight latex polymer. Dynamic mechanical analysis (DMA) revealed shifting of the latex polymer and photocrosslinked scaffold T_g's to a common value, a well-established phenomenon due phasemixing in (s)IPN's. Tensile analysis confirmed elastic behavior and ultimate strains above 500% for printed styrene-butadiene rubber (SBR) latexes which confirmed the efficacy of this approach to print high performance elastomers. Further investigations probed the versatility of this approach to other polymer compositions and a broader range of latex thermal properties. Semibatch emulsion polymerization generated a systematic series of random copolymer latexes with varied compositional ratios of hexyl methacrylate (HMA) and methyl methacrylate (MMA), and thus established a platform for investigating the effect of latex particle thermal properties on this newly discovered latex photoprocessing approach. Incorporation of scaffold monomer, N-vinyl pyrrolidone (NVP), and crosslinker, N,N'-methylene bisacrylamide (MBAm), into the continuous, aqueous phase of each latex afforded tunable photocurability. Photorheology revealed higher storage moduli for green bodies embedded with glassy latex particles, suggesting a reinforcing effect. Post-cure processing elucidated the necessity to anneal the green bodies above the T_g of the polymer particles to promote flow and particle coalescence, which was evidenced by an optical transition from opaque to transparent upon loss of the light-scattering particle domains. Differential scanning calorimetry (DSC) provided a comparison of the thermal properties of each neat latex polymer with the corresponding sIPN. Another direction investigated the modularity of this approach to 3D print mixtures of dissimilar particles (hybrid colloids). Polymer-inorganic hybrid colloids containing SBR and silica nanoparticles provided a highly tunable route to printing elastomeric nanocomposite sIPN's. The bimodal particle size distribution introduced by the mixture of SBR (150 nm) and silica (12 nm) nanoparticles enabled tuning of colloid behavior to introduce yield-stress behavior at high particle concentrations. High-silica hybrid colloids therefore exhibited both a shear-induced reversible liquid-solid transition (indicated by a modulus crossover) and irreversible photocrosslinking, which established a unique processing window for UV-assisted direct ink write (UV-DIW) AM. Concentric cylinder rheology probed the yield-stress behavior of hybrid colloids at high particle concentrations which facilitated both the extrusion of these materials through the UV-DIW nozzle and the retention of their as-deposited shaped during printing. Photorheology confirmed rapid photocuring of all hybrid colloids to yield increased moduli capable of supporting subsequent layers. Scanning electron microscopy (SEM) confirmed well-dispersed silica aggregates in the nanocomposite sIPN's. DMA and tensile confirmed significant reinforcement of (thermo)mechanical properties as a result of silica incorporation. sIPN's with relative weight ratio of 30:70 silica:SBR achieved maximum strains above 300% and maximum strengths over 10 MPa. In a different approach to enhancing VP part mechanical properties, thiol-ene chemistry provided simultaneous linear chain extension and crosslinking in oligomeric diacrylate systems, providing tunable increases to Mc of the photocured networks. Hydrogenated polybutadiene diacrylate (HPBDA) oligomers provided the first example of hydrocarbon elastomer photopolymers for VP. 1,6-hexanedithiol provided a miscible dithiol chain extender which introduced linear thiol-ene chain extension to compete with acrylate crosslinking. DMA and tensile confirmed a decrease in T_g and increased strain-at-break with decreased crosslink density. Other work investigated the synthesis and characterization of first-ever phosphonium polyzwitterions. Free radical polymerization synthesized air-stable triarylphosphine-containing polymers and random copolymers from the monomer 4-(diphenylphosphino) styrene (DPPS). ³¹P NMR spectroscopy confirmed quantitative post-polymerization alkylation of pendant triarylphosphines to yield phosphonium ionomers and polyzwitterions. Systematic comparison of neutral, ionomer, and polyzwitterions elucidated significant (thermo)mechanical reinforcement by interactions between large phosphonium sulfobetaine dipoles. Broadband dielectric spectroscopy (BDS) confirmed the presence of these dipoles through significant increases in static dielectric content. Small-angle X-ray scattering (SAX) illustrated ionic domain formation for all charged polymers.
Advancing Step-Growth Polymers: Novel Macromolecular Design and Electrostatic Interactions in Polyesters and Polyurethanes
Zhang, Musan (Virginia Tech, 2013-06-17)
Conventional melt transesterification successfully synthesized high molecular weight segmented copolyesters. The cycloaliphatic monomers 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO) and dimethyl-1,4-cyclohexane dicarboxylate (DMCD) afforded sterically hindered, ester carbonyls in high-Tg polyester precursors. Reaction between the polyester polyol precursor and a primary or secondary alcohol at melt polymerization temperatures revealed reduced transesterification of the polyester hard segment as a result of enhanced steric hindrance adjacent to the ester linkages. Subsequent polymerization of a 4,000 g/mol polyol with monomers comprising the low-Tg block yielded high molecular weight polymers that exhibited enhanced mechanical properties compared to a non-segmented copolyester control. Atomic force microscopy uncovered unique needle-like, interconnected, microphase separated surface morphologies, and small-angle X-ray scattering confirmed the presence of bulk microphase separation. This new synthetic strategy enabled selective control of ionic charge placement into the hard segment or soft segment block of segmented copolyesters using melt transesterification. The ionic placement impacted the microphase-separated morphology, which influenced its thermomechanical properties and resulting mechanical performance. Melt transesterification of low-Tg, sodium sulfonated copolyesters achieved up to 15 mol% ionic content. The 10 and 15 mol% sodium sulfonated copolyesters exhibited water-dispersibility, which enabled cation dialysis exchanges to divalent metal cations. The sulfonated copolyesters containing divalent metal cations exhibited enhanced rubbery plateau moduli to higher temperatures. Novel trialkylphosphonium ionic liquids chain extenders enabled the successful synthesis of poly(ethylene glycol)-based, cationic polyurethanes with pendant phosphoniums in the hard segments (HS). Aqueous size exclusion chromatography (SEC) confirmed the charged polyurethanes, which varied the phosphonium alkyl substituent length (ethyl and butyl) and cationic HS content (25, 50, 75 mol%), achieved high absolute molecular weights. Dynamic mechanical analysis (DMA) demonstrated the triethylphosphonium (TEP) and tributylphosphonium (TBP) polyurethanes displayed similar thermomechanical properties, including increased rubbery plateau moduli and flow temperatures. Fourier transform infrared spectroscopy (FTIR) emphasized the significance of ion-dipole interaction on hydrogen bonding. Atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), and wide-angle X-ray diffraction (WAXD) supported microphase separated morphologies in the trialkylphosphonium polyurethanes, despite the presence of ionic interactions. Sorption isotherm experiments revealed TBP polyurethanes displayed similar water sorption profiles to the noncharged analogue and lower water absorptivity compared to TEP. The phosphonium polyurethanes displayed significantly improved tensile strain; however, lower tensile stress of the TEP polyurethane was presumably due to absorbed water. In addition, we also explored applications of the trialkylphosphonium polyurethanes as nucleic acid delivery vectors and demonstrated their abilities to form colloidally stable polyplexes in salt-containing media.
Anionic synthesis and characterization of alkyl methacrylate containing polymeric systems
Long, Timothy E. (Virginia Polytechnic Institute and State University, 1987)
The anionic synthesis of alkyl methacrylates has received sparse attention in comparison to the synthesis of nonpolar hydrocarbon monomers such as styrene or the dienes. The two major reasons for the sluggish synthetic development of this class of polar monomers are the protic impurities present in most commercially available grades of monomer and the inherent side reactions associated with the ester functionality during anionic polymerization. However, by very carefully controlling various synthetic parameters and utilizing rigorously purified monomers, one can take advantage of the "living" nature of this polymerization to synthesize a variety of well-defined polymeric materials. Small variations in polymerization conditions drastically affect the properties of the polymers obtained. However, the effects depend largely upon the size of the ester alkyl group involved. The subtle relationships among such variables as ester alkyl group size, polymerization temperature, polymerization solvent and initiator have been explored and are discussed. Extensive thermal, microstructural and mechanical characterization reveal very interesting effects on the resulting polymer properties. Styrene-acrylic, acrylic-acrylic and diene-acrylic block copolymers have been synthesized demonstrating predictable molecular weights, narrow molecular weight distributions and controlled composition. These novel block copolymers preparation selective also serve as of acid- and hydrolysis excellent precursors for the ion- containing polymers. By of certain labile poly(alkyl methacrylate) esters and subsequent neutralization, metal carboxylates were introduced into a variety of block copolymers. In addition to the preparation of surfactant-like macromolecules and blend compatibilizers, novel ion-containing block copolymers were synthesized.
Anisotropic Morphologies and Properties in Perfluorosulfonate Ionomer-Based Materials
Park, Jong Keun (Virginia Tech, 2009-12-09)
The overall goal of this investigation was to elucidate specific structure-property relationships in perfluorosulfonate ionomers (PFSIs)-related materials. The project can be broken into two primary foci. First, we explored the current state of understanding related to morphology-property relationships in PFSIs with specific attention to the nano-scale organization of the ionic and crystalline domains. Specifically, the effect of uniaxial orientation on the structure and transport properties of Nafion® membranes was examined. Small angle X-ray scattering (SAXS) experiments on dry membranes that were uniaxially elongated showed a strong anisotropic morphology which was shown to persist over the swelling process without a significant relaxation. Herman's order parameters for the ionomer peak were strongly influenced by uniaxial deformation, which supports the presence of cylindrical rather than spherical morphology for ionic domains. Comparison of the water diffusion coefficients between unoriented and oriented samples revealed that uniaxial deformation of Nafion® membranes essentially enhances transport ability in one direction (i.e., the parallel to draw direction) and suppresses in the other two directions (i.e., two orthogonal directions relative to the stretching direction). Based on 1-dimensional analyses of oriented SAXS patterns at the azimuthal angle 90o, three recent models (lamellar model, semicrystalline rod-like model and fringed-micelle model) for the morphology of PFSIs were critically evaluated. The loss of meridional scattering, different orientation behavior of the crystalline and ionic domains, and inherent chain stiffness precludes the possibility of a chain-folded lamellar morphology. While the inter-aggregate dimensions remain constant at high draw ratios, the inter-crystalline spacings decrease significantly. Coupled with the distinctly different orientation behavior, these observations preclude the existence of crystallites solely within rod-like aggregates. While the worm-like ionic channel model was able to explain the behavior of SAXS and wide angle X-ray scattering (WAXS) relatively well, this model also had limitations such as (1) crystalline domains directly linked to the ionic domain (and thus a lack of amorphous domains) and (2) a presence of only a single ionic channel between two neighboring crystallites. Second, electroactive materials, specifically ionic polymer-metal composites (IPMCs) that undergo bending motions with the stimulus of a relatively weak electric field were fabricated. To understand the role of the nanoscale morphology of the membrane matrix in affecting the actuation behavior of IPMC systems, we evaluated actuation performance of IPMCs subjected to uniaxial orientation. The PFSI nanostructure altered by uniaxial orientation mimicked the fibrillar structure of biological muscle tissue and yielded a new anisotropic actuation response. It was evident that IPMCs cut from films oriented perpendicular to the draw direction yielded displacement values that were significantly greater than that of unoriented IPMCs. In contrast, IPMCs cut from films oriented parallel to the draw direction appeared to resist bending and yield displacement values that were much less than that of the unoriented IPMC. This anisotropic actuation behavior was attributed to the contribution of the nanoscale morphology to the bulk bending modulus. Overall, this study clearly demonstrated, for the first time, the importance of the nanoscale morphology in affecting/controlling the actuation behavior in IPMC systems.
Assembly of Conductive Colloidal Gold Electrodes on Flexible Polymeric Substrates using Solution-Based Methods
Supriya, Lakshmi (Virginia Tech, 2005-10-19)
This work describes the techniques of assembling colloidal gold on flexible polymeric substrates from solution. The process takes advantage of the strong affinity of gold to thiol and amino groups. Polymeric substrates were modified with silanes having these functional groups prior to Au attachment or in the case of poly(urethane urea) (PUU), no surface functionalization was required. This polymer has terminal amine and N-H groups on the polymer chain, which can act as coordination points for gold. Immersion in the colloidal gold solution led to the formation of a monolayer. Increased coverage was obtained by two methods. The first was a reduction or "seeding" process, where Au was reduced onto the attached particles on the surface. The second was using different linker molecules and creating a multilayered film by a layer-by-layer assembly. Three linker molecules of different lengths were used. Films fabricated using the smallest molecule had the least resistance whereas films fabricated with the longest molecule were not conductive. The resistance of these films may be varied easily by heating. Heating the films at temperatures as low as 120 °C caused a dramatic decrease in the resistance of over six orders in magnitude. Successful attachment of gold to PUU with very good adhesion properties was also demonstrated. The attachment of gold was stable in different solvents. Upon stretching the PUU-Au films, it was observed that there is a reversible resistance increase with strain and at a certain strain, the film becomes non-conductive. This sharp transition from conductive to insulating has potential applications in flexible switches and sensors. A hysteresis in the strain-resistance curves, analogous to the hysteresis in the stress-strain curves of the polymer was also observed. Using PUU as an adhesive agent, gold electrodes were successfully assembled on Nafion-based polymer transducers. These materials showed comparable actuation behavior to the electrodes made by the Pt-reduction method, with the added advantage of the ability to form patterned electrodes for distributed transducers. Patterning techniques were developed to form colloid-polymer multilayers for use in photonic crystal materials using selective deposition on patterned silane monolayers. Patterns of gold electrodes were also made on flexible polymers using a photoresist-based method.
Bibenzoate copolyesters and methods to produce them
(United States Patent and Trademark Office, 2020-09-08)
Bibenzoate copolyesters are based on (4,4′-biphenyl dicarboxylic acid-co-3,4′-biphenyl dicarboxylic acid) as the diacid component, and on an alicyclic diol compound such as 1,4-cyclohexanedimethanol as a portion of the diol component. Copolyesters are based on 4,4′-biphenyl dicarboxylic acid, and/or 3,4′-biphenyl dicarboxylic acid as the diacid component and may include a multifunctional acid. Copolymers may optionally base an essentially amorphous morphology, high glass transition temperature, high elongation at break, and/or high melting temperature. A method to make the copolymers controls the characteristics of the copolyester selected from one or a combination of amorphous morphology or degree of crystallinity, Tg, Tm, tensile modulus, flexural modulus, elongation at break, and so on, by selecting the proportions of the 4,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof, 3,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof, and/or the proportion of the 1,4-cyclohexanedimethanol in the diol component.
Bio-inspired Design and Self-Assembly of Nucleobase- and Ion-Containing Polymers
Zhang, Keren (Virginia Tech, 2016-06-24)
Bio-inspired monomers functionalized with nucleobase or ionic group allowed synthesis of supramolecular polymers using free radical polymerization and controlled radical polymerization techniques. Comprehensive investigations for the structure-property-morphology relationships of these supramolecular polymers elucidated the effect of noncovalent interactions on polymer physical properties and self-assembly behaviors. Reverse addition-fragmentation chain transfer (RAFT) polymerization afforded acrylic ABC and ABA triblock copolymers with nucleobase-functionalized external blocks and a low-Tg central block. The hard-soft-hard triblock polymer architecture drove microphase-separation into a physically crosslinked hard phase in a low Tg matrix. Hydrogen bonding in the hard phase enhanced the mechanical strength and maintained processability of microphase-separated copolymers for thermoplastics and elastomers. A thermodynamically favored one-to-one stoichiometry of adenine and thymine yielded the optimal thermomechanical performance. Intermolecular hydrogen bonding of two thymine units and one adenine unit allowed the formation of base triplets and directed self-assembly of ABC triblock copolymers into remarkably well-defined lamellae with long-range ordering. Acetyl protected cytosine and guanine-containing random copolymers exhibited tunable cohesive strength and peel strength as pressure sensitive adhesives. Post-functionalization converted unprotected cytosine pendent groups in acrylic random copolymers to ureido-cytosine units that formed quadruple self-hydrogen bonding. Ureido-cytosine containing random copolymers self-assembled into nano-fibrillar hard domains in a soft acrylic matrix, and exhibited enhanced cohesive strength, wide service temperature window, and low moisture uptake as soft adhesives. A library of styrenic DABCO salt-containing monomers allowed the synthesis of random ionomers with two quaternized nitrogen cations on each ionic pendant group. Thermomechanical, morphological, and rheological analyses revealed that doubly-charged DABCO salts formed stronger ionic association and promoted more well-defined microphase-separation compared to singly-charged analogs with the same charge density. Bulkier counterions led to enhanced thermal stability, increased phase-mixing, and reduced water uptake for DABCO salt-containing copolymers, while alkyl substituent lengths only significantly affected water uptake of DABCO salt-containing copolymers. Step growth polymerization of plant oil-based AB monomer and diamines enabled the synthesis of unprecedented isocyanate-free poly(amide hydroxyurethane)s, the first examples of film-forming, linear isocyanate-free polyurethanes with mechanical integrity and processability. Successful electrospinning of segmented PAHUs afforded randomly orientated, semicrystalline fibers that formed stretchable, free-standing fiber mats with superior cell adhesion and biocompatibility.
Block Copolymer-derived Porous Polyimides and Carbon for High-Performance Energy Storage
Guo, Dong (Virginia Tech, 2022-05-12)
Block copolymer-derived nanoporous materials are featured with microstructures defined by the microphase separation of constituent blocks, enabling various applications in energy storage. Dictated by the molecular weights and volume fractions of constituent blocks, the microphase separation forms nanoscale microstructures of 1-100 nm. Selective removal of a sacrificial phase produces nanopores with tailored pore width, continuity, and tortuosity. The remaining phase customizes the properties of resulting nanoporous materials, including specific surface area, electrical conductivity/insulation, and mechanical performance. Therefore, block copolymer-derived porous materials are felicitous for use in high-performance energy storage. This dissertation presents the utilization of block copolymers to derive nanoporous materials: i) high-modulus polyimide separators for lithium-metal batteries, and ii) high-surface-area carbon electrodes for fast-charging zinc-ion batteries. In lithium-metal batteries, the dendritic growth of lithium leads to deteriorating performance and severe safety concerns. Suppressing lithium dendrites is imperative to guarantee both high performance and safe cycling. Mesoporous polyimide separators are promising for dendrite suppression: i) the mesopores are smaller than the width of lithium dendrites, preventing lithium dendrites from penetrating the separator. ii) The high-modulus polyimide ceases the growth of lithium dendrites. Herein, this dissertation reports a mesoporous polyimide separator produced by thermalizing polylactide-b-polyimide-b-polylactide at 280 °C. The mesoporous polyimide separator exhibits a median pore width of 21 nm and a storage modulus of 1.8 GPa. When serving as a dendrite-suppressing separator in lithium-metal batteries, the mesoporous polyimide separator enables safe cycling for 500 hours at a current density of 4 mA/cm2. In zinc-ion batteries, developing cathodes compatible with fast charging remains a challenge. Conventional MnO2 gravel cathodes suffer from low electrical conductivity and slow ion (de-)insertion, resulting in poor recharging performance. In this dissertation, porous carbon fiber (PCF) supported MnO2 (PCF@MnO2), comprising nanometer-thick MnO2 deposited on block copolymer-derived PCF, serves as a fast-charging cathode. The high electrical conductivity of PCF and fast ion (de-)insertion in nanometer-thick MnO2 both contribute to a high rate capability. The PCF@MnO2 cathode, with a MnO2 loading of 59.1 wt%, achieves a MnO2-based specific capacity of 326 and 184 mAh/g at a current density of 0.1 and 1.0 A/g, respectively. This dissertation investigates approaches to utilizing block copolymers-derived nanoporous materials for high-performance energy storage. Those approaches are envisaged to inspire the design of block copolymer-derived nanoporous materials, and advance the development of "beyond Li-ion" energy storage.
Bridging Mesoscale Phenomena and Macroscopic Properties in Block Copolymers Containing Ionic Interactions and Hydrogen Bonding
Chen, Mingtao (Virginia Tech, 2018-08-08)
Anionic polymerization and controlled radical polymerization enabled the synthesis of novel block copolymers with non-covalent interactions (electrostatic interaction and/or hydrogen bonding) to examine the relationships between mesoscale phenomenon and macroscopic physical properties. Non-covalent interactions offer extra intra- and inter-molecular interactions to achieve stimuli-responsive materials in various applications, such as artificial muscles, thermoplastic elastomers, and reversible biomacromolecule binding. The relationship between non-covalent interaction promoted mesoscale phenomenon (such as morphology) and consequent macroscopic physical properties is the key to optimize material design and improve end-use performance for emerging applications. Pendant hydrogen bonding in ABA block copolymers promoted microphase separation and delayed the order-disorder transition, resulting in tunable morphologies (through composition changes) and extended rubbery plateaus. Reversible addition-fragmentation chain transfer (RAFT) polymerization afforded a facile synthesis of ABA triblock copolymers with hydrogen bonding (urea sites) and electrostatic interactions (pyridinium groups). Pyridine groups facilitated hydrogen bonding through a preorganization effect, leading to highly ordered, long-range lamellar morphology and a significant increase of flow temperature (Tf) 80 °C above the hard block Tg. After quaternization of pyridine groups, electrostatic interaction, as a second physical crosslinking mechanism, disrupted ordered lamellar morphology and decreased Tf. Yet, extra physical crosslinking from electrostatic interactions pertained ordered hydrogen bonding at high temperature and exhibited improved stress-relaxation properties. Both conventional free radical polymerization and RAFT polymerization generated a library of poly(ionic liquid) (PIL) homopolymers with imidazolium groups as bond charge moieties. A long chain alkyl spacer between imidazolium groups and the polymer backbones ensured a low glass transition temperature (Tg), which is beneficial to ion conductivity. Four different counter anions enabled readily tunable Tgs all below room temperature and showed promising ion conductivities as high as 2.45 × 10⁻⁵ S/cm at 30 °C. For the first time, the influence of counter anions on radical polymerization kinetics was observed and investigated thoroughly using in situ FTIR, NMR diffusometry, and simulation. Monomer diffusion and aggregation barely contributed to the kinetic differences, and the Marcus theory was applied to explain the polymerization kinetic differences which showed promising simulation results. RAFT polymerization readily prepared AB diblock, ABA triblock and (AB)3 3-arm diblock copolymers using the ionic liquid (IL) monomers discussed above and deuterated/hydrogenated styrene. We demonstrated the first example of in situ morphology studies during an actuation process, and counter anions with varied electrostatic interactions showed different mesoscale mechanisms, which accounted for macroscopic actuation. The long chain alkyl spacer between imidazolium groups and polymer backbones decoupled ion dynamics and structural relaxation. For the first time, composition changes of block copolymers achieved tunable viscoelastic properties without altering ion conductivity, which provided an ideal example for actuation materials, solid electrolytes, and ion exchange membranes.
Carbohydrate Mediation of Aqueous Polymerizations: Cyclodextrin Mediation of Aqueous Polymerizations of Methacrylates
Madison, Phillip Holland IV (Virginia Tech, 2001-06-14)
Cyclodextrin mediation offers a unique mechanism with the potential for interesting control of reaction parameters. Cyclodextrin mediation of hydrophobic monomers may offer desirable kinetics over conventional free radical polymerizations, and it has been shown in this work that cyclodextrin mediation facilitates polymerization of hydrophobic monomers in aqueous solution and in ethylene glycol. It also may be a facile method for controlling relative reactivity of comonomer mixtures. In addition, complexation of cyclodextrin with guest molecules has been utilized in selective synthesis where the host cyclodextrin has been utilized to sterically hinder the attack of certain reactive sites contained within the host cavity. This aspect of inclusion complexation could also be utilized in free radical polymerizations of monomers with multiple reactive double bonds to preferentially reduce the reactivity of the hindered reactive sites. This thesis involves the use of methylated(1.8)-beta-cyclodextrin (MeCD) as a mediator for polymerizations in solvents that would not facilitate polymerization of the pure monomer in the absence of cyclodextrin. This study focuses on the carbohydrate mediation of a series of methacrylic monomers. t-Butyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate were complexed with methylated(1.8)-beta-cyclodextrin and subsequently dissolved in either water or ethylene glycol. The complexes were studied by 1H and 13C NMR spectroscopy, thin layer chromatography, CPK modeling, and thermogravimetric analysis, and were found to have molar ratios of cyclodextrin to monomer as high as 1.0 to 0.72. These complexes were then free radically polymerized in either water or ethylene glycol and resulted in high molecular weight polymers that precipitated out of solution, allowing for facile polymer isolation through filtration. Isolated yields were found to be as high as 86 %. The majority of the cyclodextrin remained in solution after polymerization. It was also recovered and found to be recyclable. Heterogeneous polymerizations were also performed with 2-ethylhexyl methacrylate in which linear dextrin and methylated (1.8)-beta-cyclodextrin were used in emulsifier quantities. It was found that linear dextrin, at concentrations of 3.0 wt% produced a stable latex product with high molecular weight and an isolated yield of >90%. MeCD on the other hand failed to produce a stable emulsion at concentrations between 0.9-3.0 wt%, but remarkably MeCD at 3.0 wt% gave high molecular weight coagulated polymer with a yield of >90%. It is proposed that a heterogeneous mechanism inconsistent with the four major types discussed by Arshady is taking place. Unlike typical suspension or emulsion polymerizations, the cyclodextrin mediated polymerizations are completely homogeneous at the onset, making them more like a dispersion or precipitation polymerization. However, in dispersion and precipitation polymerizations the pure monomer is soluble in the reaction media. In the absence of cyclodextrin, the monomers utilized in this study possessed no appreciable solubility in the reaction media. Therefore, it is proposed that cyclodextrin acts as a phase transfer agent, effectively solublizing the hydrophobic monomer and allowing for the aqueous dispersion or precipitation type polymerization to occur, depending on the relative solubility of the components. Bulk polymerizations of t-butyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate and their subsequent use in the preparation of carbohydrate/poly(alkyl methacrylate) blends was also performed in this project. Bulk polymers were utilized as references for physical properties for the polymers produced through polymerization of the MeCD/monomer complexes in either aqueous solution or in ethylene glycol. 1H NMR analysis of the polymers from both the cyclodextrin mediation and bulk polymerizations indicated that the tacticity of the polymers produced in both cases were identical. The bulk polymers were also used in the preparation of carbohydrate/methacrylic blends with potential applications in the areas of selective barriers, biodegradable films. Inclusion of drug molecules or antioxidants into these cyclodextrin containing films also may have potential in drug delivery, or food packaging applications. In addition, the side chain liquid crystalline monomer, 6-(4-hexyloxy-biphenyl-4-yloxy)hexyl methacrylate was synthesized in high purity via a three-step procedure and confirmed by a combination of mass spectrometry, thin layer chromatography, and 1H and 13C NMR. This hydrophobic liquid crystalline monomer was subsequently complexed with 1.0-3.0 equivalents of methylated(1.8)-beta-cyclodextrin in an attempt to alter the water solubility of the monomer. Complexes of this side-chain liquid crystalline monomer have not been studied previously and it is proposed that complexation with cyclodextrin will lead not only to novel polymerizations routes for this monomer, but also to novel smectic phases for this thermotropic liquid crystalline polymer.
Cationic Glycopolymers for DNA Delivery: Cellular Internalization Mechanisms and Biological Characterization
McLendon, Patrick Michael (Virginia Tech, 2009-10-20)
Understanding the biological mechanisms of polymeric DNA delivery is essential to develop vehicles that perform optimally. In this work, the cellular internalization mechanisms of poly(glycoamidoamine) (PGAA) DNA delivery polymers were investigated. Polymer:DNA complexes interact with cell-surface glycosaminoglycans (GAGs) in a manner independent of electrostatic interactions. Desulfation and GAG removal leads to decreased uptake. Individual polyplexes appear to have differing affinities for specific GAGs, as polyplex dissociation occurs in a charge-independent manner, and may influence binding. Internalization occurs through close interactions with GAGs, as GAGs accumulate on polyplex surfaces, resulting in negatively-charged polyplexes and decompaction of intact polyplexes is observed upon interaction with GAG. PGAA polyplexes enter cells via a complex, multifaceted internalization route. Pharmacological inhibition of endocytosis and visualization by confocal microscopy reveal that internalization occurs primarily through an actin and dynamin-dependent mechanism. Caveolae/raft-mediated endocytosis appears to be the predominant internalization mechanism, with clathrin-mediated endocytosis also significantly involved. Internalization occurs to a smaller degree via macropinocytosis and direct membrane penetration. Caveolae-mediated, but not clathrin-mediated, internalization leads to transgene expression, suggesting a targeting opportunity based on uptake mechanisms. PEGylation of PGAA polyplexes was achieved to minimize polyplex aggregation in serum. Polyplex size increased in serum, but PEGylation prevented further polyplex growth over time compared to non-PEGylated polymers. Specific targeting of hepatocytes through end-modification of PEG with galactose was unsuccessful, likely due to inaccessibility of targeting groups. Further hepatocyte targeting efforts focused on malonate-based polymers with clickable linkages for facile linkage of targeting groups. Despite favorable surface presentation of galactose, receptor-specific internalization of polyplexes was unsuccessful, as competitive inhibition in HepG2 cells resulted in significant polyplex internalization derived from nonspecific membrane interactions. Chemical modification of vehicles allows systematic study of structure-function properties leading to efficient intracellular delivery. Increasing G4 molecular weight generally increases toxicity and decreases transgene expression in HeLa cells. Incorporating galactose into a lanthanide-chelating polymer facilitated efficient cellular internalization that was visualized by two-photon microscopy. Increased gene expression was observed that correlated to increasing galactose, suggesting that polymer degradation increases gene expression. Also studied were branched peptides targeted to HIV-1 TAR, which displayed high biocompatibility and favorable internalization profiles in mammalian cells.
Characterization and Modeling of the Ionomer-Conductor Interface in Ionic Polymer Transducers
Akle, Barbar Jawad (Virginia Tech, 2005-07-29)
Ionomeric polymer transducers consist of an ion-exchange membrane plated with conductive metal layers on its outer surfaces. Such materials are known to exhibit electromechanical coupling under the application of electric fields and imposed deformation (Oguro et al., 1992; Shahinpoor et al., 1998). Compared to other types of electromechanical transducers, such as piezoelectric materials, ionomeric transducers have the advantage of high-strain output (> 9% is possible), low-voltage operation (typically less than 5 V), and high sensitivity in the charge-sensing mode. A series of experiments on actuators with various ionic polymers such as Nafion and novel poly(Arylene ether disulphonate) systems (BPS and PATS) and electrode composition demonstrated the existence of a linear correlation between the strain response and the capacitance of the material. This correlation was shown to be independent of the polymer composition and the plating parameters. Due to the fact that the low-frequency capacitance of an ionomer is strongly related to charge accumulation at the electrodes, this correlation suggests a strong relationship between the surface charge accumulation and the mechanical deformation in ionomeric actuators. The strain response of water-hydrated transducers varies from 50 μstrain/V to 750 μstrain/V at 1Hz while the strain-to-charge response is between 9 ^μstrain_{^c_m²} and 15 ^μstrain_{^c_m²}. This contribution suggests a strong correlation between cationic motion and the strain in the polymer at the ionomer-conductor interface. A novel fabrication technique for ionic polymer transducers was developed for this dissertation for the purpose of quantifying the relationship between electrode composition and transducer performance. It consists of mixing an ionic polymer dispersion (or solution) with a fine conducting powder and attaching it to the membrane as an electrode. The Direct Assembly Process (DAP) allows the use of any type of ionomer, diluent, conducting powder, and counter ion in the transducer, and permits the exploration of any novel polymeric design. Several conducting powders have been incorporated in the electrode including single-walled carbon nanotubes (SWNT), polyaniline (PANI) powders, high surface area RuO2, and carbon black electrodes. The DAP provided the tool which enabled us to study the effect of electrode architecture on performance of ionic polymer transducers. The DAP allows the variation in the electrode architecture which enabled us to fabricate dry transducers with 50x better performance compared to transducers made using the state of the art impregnation-reduction technique. DAP fabricated transducers achieved a strain of 9.4% at a strain rate of 1%/s. Each electrode material had an optimal concentration in the electrode. For RuO2, the optimal loading was approximately 45% by volume. This study also demonstrated that carbon nanotubes electrodes have an optimal performance at loadings around 30 vol%, while PANI electrodes are optimized at 95 vol%. Extensional actuation in ionic polymer transducers was first reported and characterized in this dissertation. An electromechanical coupling model presented by Leo et al. (2005) defined the strain in the active areas as a function of the charge. This model assumed a linear and a quadratic term that produces a nonlinear response for a sine wave actuation input. The quadratic term in the strain generates a zero net bending moment for ionic polymer transducers with symmetric electrodes, while the linear term is canceled in extensional actuation for symmetric electrodes. Experimental results demonstrated strains on the order of 110 μstrain in the thickness direction compared to 1700 μstrain peak to peak on the external fibers for the same transducer, could be achieved when it is allowed to bend under +/-2V potential at 0.5 Hz. Extensional and bending actuation in ionic polymer transducers were explained using a bimorph active area model. Several experiments were performed to compare the bending actuation with the extensional actuation capability. The active area in the model was assumed to be the high surface area electrode. Electric double layer theory states that ions accumulate in a thin boundary layer close to the metal-polymer interface. Since the metal powders are evenly dispersed in the electrode area of the transducer, this area is expected to actuate evenly upon voltage application. This active area model emphasizes the importance the boundary layer on the conductor-ionomer interfacial area. Computing model parameters based on experimental results demonstrated that the active areas model collapses the bending data from a maximum variation of 200% for the strain per charge, to less than 68% for the model linear term. Furthermore, the model successfully predicted bending response from parameters computed using thickness experimental results. The prediction was particularly precise in estimating the trends of non-linearity as a function of the amount of asymmetry between the two electrodes.
Characterization and structure-property relationships of an injectable thiol-Michael addition hydrogel toward compatibility with glioblastoma therapy
Khan, Zerin Mahzabin; Wilts, Emily; Vlaisavljevich, Eli; Long, Timothy E.; Verbridge, Scott S. (Elsevier, 2022-05-01)
Glioblastoma multiforme (GBM) is an aggressive primary brain cancer and although patients undergo surgery and chemoradiotherapy, residual cancer cells still migrate to healthy brain tissue and lead to tumor relapse after treatment. New therapeutic strategies are therefore urgently needed to better mitigate this tumor recurrence. To address this need, we envision after surgical removal of the tumor, implantable biomaterials in the resection cavity can treat or collect residual GBM cells for their subsequent eradication. To this end, we systematically characterized a poly(ethylene glycol)-based injectable hydrogel crosslinked via a thiol-Michael addition reaction by tuning its hydration level and aqueous NaHCO3 concentration. The physical and chemical properties of the different formulations were investigated by assessing the strength and stability of the polymer networks and their swelling behavior. The hydrogel biocompatibility was assessed by performing in vitro cytotoxicity assays, immunoassays, and immunocytochemistry to monitor the reactivity of astrocytes cultured on the hydrogel surface over time. These characterization studies revealed key structure-property relationships. Furthermore, the results indicated hydrogels synthesized with 0.175 M NaHCO3 and 50 wt% water content swelled the least, possessed a storage modulus that can withstand high intracranial pressures while avoiding a mechanical mismatch, had a sufficiently crosslinked polymer network, and did not degrade rapidly. This formulation was not cytotoxic to astrocytes and produced minimal immunogenic responses in vitro. These properties suggest this hydrogel formulation is the most optimal for implantation in the resection cavity and compatible toward GBM therapy. Statement of significance: Survival times for glioblastoma patients have not improved significantly over the last several decades, as cancer cells remain after conventional therapies and form secondary tumors. We characterized a biodegradable, injectable hydrogel to reveal structure-property relationships that can be tuned to conform the hydrogel toward glioblastoma therapy. Nine formulations were systematically characterized to optimize the hydrogel based on physical, chemical, and biological compatibility with the glioblastoma microenvironment. This hydrogel can potentially be used for adjuvant therapy to glioblastoma treatment, such as by providing a source of molecular release for therapeutic agents, which will be investigated in future work. The optimized formulation will be developed further to capture and eradicate glioblastoma cells with chemical and physical stimuli in future research.
Chemical and Physical Modifications of Semicrystalline Gels to Achieve Controlled Heterogeneity
Anderson, Lindsey J. (Virginia Tech, 2019-02-07)
Sulfonated polyaromatic hydrocarbon membranes have emerged as desirable candidates for proton exchange membranes (PEMs) due to their excellent mechanical properties, high thermal and chemical stability, and low cost. Specifically, sulfonated multiblock copolymers are attractive because their phase-separated morphologies aide in facile proton transport. In this work, the functionalization of semicrystalline gels of poly(ether ether ketone) (PEEK) is explored as a novel post-polymerization method to prepared blocky copolymers, and the effect of copolymer architecture on membrane physical properties, structure, and performance is extensively investigated. First, the blocky sulfonation of PEEK was explored to prepare blocky copolymers (SPEEK) with densely sulfonated domains and unfunctionalized, crystallizable domains. Compared to random SPEEK ionomers at similar ion content, blocky SPEEK exhibited enhanced crystallizability, decreased melting point depression, and faster crystallization kinetics. Phase separation between the hydrophilic sulfonated blocks and hydrophobic PEEK blocks, aided by polymer crystallization, resulted in enhanced water uptake, superior proton conductivity, and more closely associated ionic domains than random SPEEK. Furthermore, the random and blocky bromination of PEEK was investigated to prepare PEEK derivatives (BrPEEK) with reactive aryl-bromides. Spectroscopic evidence revealed long domains of unfunctionalized homopolymer for blocky BrPEEK, and this translated to an increased degree of crystallinity, higher melting temperature, and more rapid crystallization kinetics than random BrPEEK at similar degrees of bromination. The subsequent sulfonation of blocky BrPEEK resulted in a hydrophilic-hydrophobic blocky copolymer with clear multi-phase behavior. The phase-separated morphology contributed to decreased water uptake and areal swelling compared to random SPEEK and resulted in considerably higher proton conductivity at much lower hydration levels. Moreover, Ullmann coupling introduced superacidic perfluorosulfonic acid side chains to the BrPEEK backbone, which yielded membranes with less water content and less dimensional swelling than random SPEEK. Superior proton transport than random SPEEK was observed due to the superacid side chain and wider hydrophilic channels within the membranes, resulting in more continuous pathways for proton transport. Overall, this work provided a novel platform for the preparation of functionalized PEEK membranes using a simple post-polymerization functionalization procedure. The established methods produced blocky-type copolymers with properties reminiscent of multiblock copolymers prepared by direct polymerization from monomers/oligomers.
Chemical Modification of Cellulose Esters for Oral Drug Delivery
Meng, Xiangtao (Virginia Tech, 2016-06-20)
Polymer functional groups have critical impacts upon physical, chemical and mechanical properties, and thus affect the specific applications of the polymer. Functionalization of cellulose esters and ethers has been under extensive investigation for applications including drug delivery, cosmetics, food ingredients, and automobile coating. In oral delivery of poorly water-soluble drugs, amorphous solid dispersion (ASD) formulations have been used, prepared by forming miscible blends of polymers and drugs to inhibit crystallization and enhance bioavailability of the drug. The Edgar and Taylor groups have revealed that some cellulose omega-carboxyalkanoates were highly effective as ASD polymers, with the pendant carboxylic acid groups providing both specific polymer-drug interactions and pH-triggered release through swelling of the ionized polymer matrix. While a variety of functional groups such as hydroxyl and amide groups are also of interest, cellulose functionalization has relied heavily on classical methods such as esterification and etherification for appending functional groups. These methods, although they have been very useful, are limited in two respects. First, they typically employ harsh reaction conditions. Secondly, each synthetic pathway is only applicable for one or a narrow group of functionalities due to restrictions imposed by the required reaction conditions. To this end, there is a great impetus to identify novel reactions in cellulose modification that are mild, efficient and ideally modular. In the initial effort to design and synthesize cellulose esters for oral drug delivery, we developed several new methods in cellulose functionalization, which can overcome drawbacks of conventional synthetic pathways, provide novel cellulose derivatives that are otherwise inaccessible, and present a platform for structure-property relationship study. Cellulose omega-hydroxyalkanoates were previously difficult to access as the hydroxyl groups, if not protected, react with carboxylic acid/carbonyl during a typical esterification reaction or ring opening of lactones, producing cellulose-g-polyester and homopolyester. We demonstrated the viability of chemoselective olefin hydroboration-oxidation in the synthesis of cellulose omega]-hydroxyesters in the presence of ester groups. Cellulose esters with terminally olefinic side chains were transformed to the target products by two-step, one-pot hydroboration-oxidation reactions, using 9-borabicyclo[3.3.1]nonane (9-BBN) as hydroboration agent, followed by oxidizing the organoborane intermediate to a primary alcohol using mildly alkaline H2O2. The use of 9-BBN as hydroboration agent and sodium acetate as base catalyst in oxidation successfully avoided cleavage of ester linkages by borane reduction and base catalyzed hydrolysis. With the impetus of modular and efficient synthesis, we introduced olefin cross-metathesis (CM) in polysaccharide functionalization. Using Grubbs type catalyst, cellulose esters with terminally olefinic side chains were reacted with various CM partners including acrylic acid, acrylates and acrylamides to afford families of functionalized cellulose esters. Molar excesses of CM partners were used in order to suppress potential crosslinking caused by self-metathesis between terminally olefinic side chains. Amide CM partners can chelate with the ruthenium catalyst and cause low conversions in conventional solvents such as THF. While the inherent reactivity toward CM and tendency of acrylamides to chelate Ru is influenced by the acrylamide N-substituents, employing acetic acid as a solvent significantly improved the conversion of certain acrylamides. We observed that the CM products are prone to crosslinking during storage, and found that the crosslinking is likely caused by free radical abstraction of gamma-hydrogen of the alpha, beta-unsaturation and subsequent recombination. We further demonstrated successful hydrogenation of these alpha, beta-unsaturated acids, esters, and amides, thereby eliminating the potential for radical-induced crosslinking during storage. The alpha, beta-unsaturation on CM products can cause crosslinking due to gamma-H abstraction and recombination if not reduced immediately after reaction. Instead of eliminating the double bond by hydrogenation, we described a method to make use of these reactive conjugated olefins by post-CM thiol-Michael addition. Under amine catalysis, different CM products and thiols were combined and reacted. Using proper thiols and catalyst, complete conversion can be achieved under mild reaction conditions. The combination of the two modular reactions creates versatile access to multi-functionalized cellulose derivatives. Compared with conventional reactions, these reactions enable click or click-like conjugation of functional groups onto cellulose backbone. The modular profile of the reactions enables clean and informative structure-property relationship studies for ASD. These approaches also provide opportunities for the synthesis of chemically and architecturally diverse cellulosic polymers that are otherwise difficult to access, opening doors for many other applications such as antimicrobial, antifouling, in vivo drug delivery, and bioconjugation. We believe that the cellulose functionalization approaches we pioneered can be expanded to the modification of other polysaccharides and polymers, and that these reactions will become useful tools in the toolbox of polymer/polysaccharide chemists.
Chemically and Photochemically Crosslinked Networks and Acid-Functionalized Mwcnt Composites
Nebipasagil, Ali (Virginia Tech, 2011-05-03)
PTMO-urethane and urea diacrylates (UtDA, UrDA) were synthesized from a two-step reactions of bis (4-isocyanatocyclohexyl) methane (HMDI) with either α,Ï -hydroxy-terminated poly (tetramethylene oxide) (PTMO Mn 250, 1000, 2000 and 2900 g/mol) or α,Ï -aminopropyl-terminated PTMO and 2-hydroxyethyl acrylate (HEA). PTMO-based ester precursors (EtDA) were also synthesized from α,Ï -hydroxy-terminated PTMO (Mn 1000 and 2000 g/mol). Two bis acetoacetates were synthesized from acetoacetylation of 1,4-butanediol and 250 g/mol hydroxy-terminated PTMO with tert-butyl acetoacetate. ¹H NMR spectroscopy confirmed the structure and average molecular weights (Mn)of diacrylates. Mn of these precursors were in the range of 950 to 3670 g/mol by ¹H NMR. The rheological properties of diacrylates were studied and activation energies for flow were calculated. Activation energies increased with increasing Mn and hydrogen-bond segment content. Michael carbon addition was employed to covalently crosslink the precursors resulting in networks with gel fractions better than 90%. DSC and DMA experiments revealed that networks had a broad distribution of glass transition temperatures depending on Mn and degree of hydrogen bonding present in the diacrylates. Their Tg's varied from -61 ºC to 63 ºC depending on the crosslinking density and hydrogen-bonding segment content. TGA revealed that UtDA and UrDA networks had an improved thermal stability compared to their EtDA counterparts. Tensile properties showed a variation depending on the structure and Mn of diacrylate and BisAcAc precursors. The storage moduli of networks precursor change from 25.3 MPa to 2.0 MPa with increasing Mn of the urethane diacrylate Elongation at break increased from 255% to 755 % for the same networks. The Young's moduli increased from 3.27 MPa for EtDA 2000 to 311.1 MPa for UrDA 2000 which was attributed to increasing degree of hydrogen-bonding. Acid functionalization of C70 P Baytubes multiwalled carbon nanotubes (MWCNT) generated acid-functionalized nanotubes (MWCNT-COOH). Suspension of MWCNT-COOH in organic solvents (chloroform, toluene, THF, DMF and 2-propanol) were prepared. DLS indicated average particle diameters of MWCNT-COOH in DMF and in 2-propanol were 139 nm and 162 nm respectively. FESEM of suspensions revealed aggregate free dispersion of MWCNT-COOH in DMF and 2-propanol. MWCNT-COOH containing composite networks were prepared. FESEM images of fracture surfaces of UtDA showed MWCNT-COOH were well-dispersed in the composites. DMA showed an increase in the rubbery plateau modulus which correlated with the MWCNT-COOH content in the networks. Tensile testing also revealed a relationship between MWCNT-COOH content and young's moduli and strain at break of networks. Storage moduli of networks increased from 25 MPa to 211 MPa with increasing MWCNT-COOH content whereas elongation at break decreased from 255 % to 146 %. UtDAs and pentaerythritol tetraacrylate (PETA) were crosslinked under UV radiation (6 passes, 1.42 ± 0.05 W.cm2 for each pass) in the presence of 2,2-dimethoxy-2-phenylacetophenone (DMPA) (1 wt. % of the mixture) UV initiator. DMA demonstrated the presence of broad glass transition regions with a range of Tg's which varied from -60 °C to -30°C. Tensile testing also revealed the relationship between Young's moduli, strain at break and the molecular weight of the diacrylates. The increasing molecular weight of urethane diacrylate precursors caused a drop in the storage moduli of networks from 15.8 MPa to 1.4 MPa and an increase in elongation at break from 76 % to 132 %.
The Chemistry of Dimethacrylate-Styrene Networks and Development of Flame Retardant, Halogen-Free Fiber Reinforced Vinyl Ester Composites
Rosario, Astrid Christa (Virginia Tech, 2004-08-02)
One of the major classes of polymer matrix resins under consideration for structural composite applications in the infrastructure and construction industries is vinyl ester resin. Vinyl ester resin is comprised of low molecular weight poly(hydroxyether) oligomers with methacrylate endgroups diluted with styrene monomer. The methacrylate endgroups cure with styrene via free radical copolymerization to yield thermoset networks. The copolymerization behavior of these networks was monitored by Fourier Transform Infrared Spectroscopy (FTIR) at various cure conditions. Reactions of the carbon-carbon double bonds of the methacrylate (943 cm-1) and styrene (910 cm-1) were followed independently. Oligomers possessing number average molecular weights of 700 g/mole were studied with systematically increasing levels of styrene. The Mortimer-Tidwell reactivity ratios indicated that at low conversion more styrene was incorporated into the network at lower cure temperatures. The experimental vinyl ester-styrene network compositions deviated significantly from those predicted by the Meyer-Lowry integrated copolymer equation at higher conversion, implying that the reactivity ratios for these networks may change with conversion. The kinetic data were used to provide additional insight into the physical and mechanical properties of these materials. In addition to establishing the copolymerization kinetics of these materials, the development of halogen free fiber reinforced vinyl ester composites exhibiting good flame properties was of interest. Flame retardant vinyl ester resins are used by many industries for applications requiring good thermal resistance. The current flame-retardant technology is dependent on brominated vinyl esters, which generate high levels of smoke and carbon monoxide. A series of halogen free binder systems has been developed and dispersed in the vinyl ester to improve flame retardance. The binder approach enables the vinyl ester resin to maintain its low temperature viscosity so that fabrication of composites via Vacuum Assisted Resin Transfer Molding (VARTM) is possible. The first binder system investigated was a polycaprolactone layered silicate nanocomposite, which was prepared via intercalative polymerization. Transmission Electron Microscopy (TEM) and X-ray Diffraction (XRD) data indicated a mixed morphology of exfoliated and intercalated structures. The mechanical properties and the normalized peak heat release rates were comparable to the neat vinyl ester resin. Alternative binder systems possessing inherent flame retardance were also investigated. A series of binders comprised of novolac, bisphenol A diphosphate, and montmorillonite clay were developed and dispersed into the vinyl ester matrix. Cone calorimetry showed reductions in the peak heat release rate comparable to the brominated resin.
Controlled Release of Antioxidants via Biodegradable Polymer Films into Milk and Dry Milk Products
van Aardt, Marleen (Virginia Tech, 2003-11-21)
Residual value is defined as the price for which a used piece of equipment can be sold in the market at a particular time. It is an important element of the owning costs of equipment and needs to be estimated by equipment managers for making investment decisions. The purpose of this study is to gain insights into the residual value of selected groups of heavy construction equipment and to develop a mathematical model for its prediction. Auction sales data were collected from two online databases. Manufacturer publications and an online source provided size parameters and manufacturers suggested retail prices matching the auction records. Macroeconomic indicator values were collected from a variety of sources, including government agencies. The data were brought into the same electronic format and were matched by model name and calendar date, respectively. Data from auctions in the U.S. and in Canada were considered for this study. Equipment from four principal manufacturers of up to 15 years of age at the time of sale was included. A total of 35,542 entries were grouped into 11 different equipment types and 28 categories by size as measured by horse power, standard operating weight, or bucket volume. Equipment types considered were track and wheel excavators, wheel and track loaders, backhoe loaders, integrated toolcarriers, rigid frame and articulated trucks, track dozers, motor graders, and wheel tractor scrapers. Multiple linear regression analyses of the 28 datasets were carried out after outliers had been deleted. Explanatory variables for the regression model were age in years, the indicator variables manufacturer, condition rating, and geographic region, and selected macroeconomic indicators. The response variable was residual value percent, defined as auction price divided by manufacturers suggested retail price. Different first, second, and third-order polynomial models and exponential and logarithmic models of age were examined. A second-order polynomial was selected from these functional forms based on the adjusted coefficient of determination. Coefficients for the 28 models and related statistics were tabulated. A spreadsheet tool incorporating the final regression model and its coefficients was developed. It allows performing the residual value prediction in an interactive and intuitive manner.

Browsing by Author "Long, Timothy E."

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