Temperature sensing in harsh environment is desired in many areas, such as coal gasification, aerospace, etc. Single crystal sapphire is an excellent candidate for construction of harsh environment sensors due to its superior mechanical and optical properties even at temperature beyond 1600°C. The temperature inside a coal gasifier can be as high as 1200°C. And there is dramatic temperature gradient between the inner and outer layers of the gasifier refractory. Previous work has been done at Virginia Tech's Center for Photonics Technology to design and fabricate a sapphire wafer based Fabry-Perot interferometer (FPI) sensor for temperature sensing in coal gasifiers. The sensor head is based on the use of sapphire wafer which is attached to a lead-in sapphire fiber to be applied in the ultrahigh temperature region; and the sapphire fiber is spliced to a multi-mode fused silica fiber for quality signal transmission in lower temperature areas. One of the challenges encountered by this approach is the shear force to the sapphire fiber, which is caused by the differential thermal expansion between the inner and outer layers of the gasifier refractory. This shear force may be so significant to break the sensor probe. This thesis proposed a free space based interrogation sensing system to address that problem. In this free space based interrogation sensing system, only the sensor head is placed in the inner refractory wall, while all the other parts of the system are placed in the outer refractory or outside the gasifier at the ambient room temperature. An optical frequency domain reflectometry (OFDR) based multiplexed technique is applied in the sensor design to realize temperature measurement at multiple locations along the optical path. In this work, three sapphire wafers based multiplexed temperature sensor is fabricated and calibrated in laboratory. This multiplexed high temperature sensor shows linear response in the range of 20°C ~ 1000°C, with a sensitivity of 1.602?10??/°C and a resolution of 1.3°C. / Master of Science

Polymeric diphenylmethane diisocyanate, pMDI, is a wood adhesive that provides excellent composite board properties. Much is unknown about the specific mechanism of pMDI/wood adhesion under conditions that are typical of wood gluing operations. The present research describes the use of ¹⁵N cross-polarization, magic-angle spinning (CP/MAS) NMR as a technique for probing the cure chemistry and bondline morphology of pMDI-bonded wood composites. A 99% ¹⁵N-enriched pMDI resin with desirable adhesive properties was synthesized. A series of model cellulose/¹⁵N-pMDI composites, cured as a function of cellulose precure moisture content, were tested prior to solid wood composites in order to test the feasibility of this technique. Solid wood/¹⁵N-pMDI composites were then cured as a function of wood precure moisture content, cure temperature, and cure time. The ¹⁵N CP/MAS NMR spectra clearly show the dominance of the isocyanate/water reaction on the cure chemistry of all composites tested, both cellulose and solid wood. Four prominent resonances are observed in each spectrum: residual isocyanate, polyurea, and the amide and imide nitrogens of biuret type structures. Different trends in the relative intensities of these resonances are observed as a function of the press variables. Significant amounts of urethane formation are not detected; however, low amounts could be obscured by signal overlap. Relaxation studies using variable contact time experiments were complicated by excessively long cross-polarization rates for nonprotonated nitrogens. However, experiments using variable spin lock times prior to fixed contact periods indicate that the cured resin in these composites is probably a homogeneous continuum. The utility of ¹⁵N CP/MAS NMR for elucidating fine structural and morphological information from complex isocyanate-cured wood composites is clearly demonstrated. / Master of Science

Hydroxyakyl lignin derivatives were reacted with polymeric methylene diphenyl diisocyanate (PMDI) and hexamethoxy-methyl-melamine (HMMM) to form polyurethane and polyether wood adhesives respectively. Adhesive performance in shear block tests indicated: (a) that the combination of lignin and PHDI reduced the adhesive strength shown by neat PMDI. The HMMM failed to produce an acceptable wood adhesive in the absence of lignin, requiring 50-60% lignin derivative co-substrate for peak performance; (b) adhesive performance was related to molecular weight, if an organic solvent was the carrier, or solubility if the formulation was emulsified; (c) adhesive performance for the lignin based adhesives was better than a urea formaldehyde reference. Structure property relationships were determined by correlating data obtained by the analysis of (in vivo) cured adhesive films and (in vitro) adhesive strength data resulting from shear block testing. The results indicated that: (a) glass transition temperatures of the in vivo cured adhesives were inversely related to the strength of the adhesives cured in vitro; (b) variations in infrared analysis of the in vivo cured adhesives were used to determine the levels of products from the cross linking reaction. In vitro adhesive strength was directly related to the level of reaction products determined to be present in the in vivo wood adhesives; (c) the relationships between the analysis of in vivo and in vitro cured adhesives indicated that the lignin component may act as a soft segment blocks or domains in a more rigid polymer matrix. Particle board was produced with the lignin adhesives with: (a) properties equal to those produced with commercial OF resins; (b) spray application greatly reducing the effects of carrier compatibility; (c) none of the lignin based adhesives were water resistant. / Master of Science

A surface pretreatment for aluminum and titanium involving the reaction of phosphonic acid (RPO(OH)2), R=butyl or vinyl for aluminum and R=vinyl for titanium, has been investigated. The durability of phosphonic acid-pretreated samples was compared with that for P2-etched (ferric sulfate-sulfuric acid) adherends. Samples were bonded with LaRC-IA adhesive in a wedge test geometry. Environmental testing consisted of static and cyclical exposure for 240 hours in three atmospheres: 1) 170°C, 2 torr; 2) -20°C; 3) 60°C, 70% relative humidity. Crack propagation arrested within 48 hours. The order of durability in static environmental tests for aluminum was vinyl phosphonic acid > P2 > butyl phosphonic acid. The durability performance was reversed for cyclic testing. The durability of specimens using P2-etched titanium was superior to that for vinyl phosphonic acid-treated titanium in all environmental tests. / Master of Science

The bonding of plastic sheeting to metal is a recent development of the surface coating industry. The product, a pre-finished material, has the strength of the base metal and exterior finish of the plastic. It is used in making radio and television cabinets, furniture, and chemical containers. In order to improve the bonding practice, it is necessary for the engineer to be well informed of the fundamental principles involved. A knowledge of the theory of bonding, the nature of the bond, and the factors affecting the bond strength would be helpful in attaining this goal. The purpose of this investigation was to study the factors affecting the bond strength between polyvinyl chloride sheeting and metal. The metals used in this investigation were aluminum, brass, copper, nickel, low carbon steel, and stainless steel. The plastic sheeting was bonded to the metal by means of synthetic adhesive. Five different commercial adhesives were used. These were vinyl chloride-acetate resin, VYNW, modified vinyl chloride-acetate resin, VMCH, vinyl acetate resin, A-70, vinyl alcohol-acetate resin, T-24-9, and vinyl alcohol-acetate resin, MA-28-18. The specimens of metal were treated as follows. Three sets of specimens were prepared. The first set was degreased with solvent only, the second one was polished and degreased, and the third one was degreased and etched. Semi-rigid polyvinyl chloride sheeting was bonded to the metal at a temperature of 70°, 150°, 250°, and 350°F under a pressure of 200 pounds per square inch. A series of the bonded specimens was stretched to 10, 20, and 30 percent elongation. A series of steel-steel laminates was prepared. They were bonded by different adhesives at 250°F under 200 pounds per square inch. The specimens of this series were tested for shear strength. The effect of surface conditions, of bonding temperatures, of nature of metals, of types of adhesives, and of amount of plasticizer in the adhesive upon the bond strength between polyvinyl chloride sheet and metal was determined and the following conclusions were reached: 1. The bond strength was affected by surface conditions. Etched specimens had higher bond strength than polished ones except low carbon steel. 2. The bonding temperature had no definite influence on the bond strengths of aluminum, nickel, low carbon steel, and stainless steel laminates. 3. The bond strengths of brass and copper laminates increased with the bonding temperature. 4. The average bond strengths of polished specimens of low carbon steel, aluminum, stainless steel, nickel, copper, and brass were 19.6, 15.5, 14.2, 8.5, 5.5, and 2.5 pounds per inch respectively. The strengths of these metal laminates followed the order of these metals in the galvanic series except aluminum. 5. The adhesion between adhesive and metal varied directly with the polarity of the adhesive. 6. The bond strength was also affected by the amount of plasticizer in the adhesive. When the laminates were subjected to stretching, the rate of decrease in strength was inversely proportional to the amount of plasticizer in the adhesive. / Master of Science

Polymer synthesis and functionalization enabled the tailoring of polymer functionality for additive manufacturing (AM), elastomer, and biological applications. Inspiration from academic and patent literature prompted an emphasis on polymer functionality and its implications on diverse applications. Critical analysis of existing elastomers for AM aided the synthesis and characterization of novel photopolymer systems for lithography-based 3D printing. Emphasis on structure-processing-property relationships facilitated the attainment of success in proposed applications and prompted further fundamental understanding for systems that leveraged poly(dimethyl siloxane)s (PDMS), aliphatic polyesters, polyamides, and polyethers for emerging applications. The thiol-ene reaction possesses many desirable traits for vat photopolymerization (VP) AM, namely that it proceeds rapidly to high yield, does not undergo significant side reactions, remains tolerant of the presence of water or oxygen, and remains regiospecific. Leveraging these traits, a novel PDMS-based photopolymer system was synthesized and designed that underwent simultaneous chain extension and crosslinking, affording relatively low viscosity prior to photocuring but the modulus and tensile strain at break properties of higher molecular weight precursors upon photocuring. A monomeric competition study confirmed chemical preference for the chain-extension reaction in the absence of diffusion. Photocalorimetry, photorheology, and soxhlet extraction measured photocuring kinetics and demonstrated high gel fractions upon photocuring. A further improvement on the low-temperature elastomeric behavior occurred via introduction of a small amount of diphenylsiloxane or diethylsiloxane repeating units, which successfully suppressed crystallization and extended the rubbery plateau close to the glass transition temperature (Tg) for these elastomers. Finally, a melt polymerization of PDMS diamines in the presence of a disiloxane diamine chain extender and urea afforded isocyanate-free polyureas in the absence of solvent and catalyst. Dynamic mechanical analysis (DMA) measured multiple, distinct α-relaxations that suggested microphase separation. This work leverages the unique properties of PDMS and provides multiple chemistries that achieve elastomeric properties for a variety of applications. Similar work of new polymers for VP AM was performed that leveraged the low Tg poly(propylene glycol) (PPG) and poly(tri(ethylene glycol) adipate) (PTEGA) for use in tissue scaffolding, footwear, and improved glove grip performance applications. The double endcapping of a PPG diamine with a diisocyanate and then hydroxyethyl acrylate provided a urethane/urea-containing, photocurable oligomer. Supercritical fluid chromatography with evaporative light scattering detection elucidated oligomer molecular weight distributions with repeat unit resolution, while the combination of these PPG-containing oligomers with various reactive diluents prior to photocuring yielded highly tunable and efficiently crosslinked networks with wide-ranging thermomechanical properties. Functionalization of the PTEGA diol with isocyanatoethyl methacrylate yielded a photocurable polyester for tissue scaffolding applications without the production of acidic byproducts that might induce polymer backbone scission. Initial VP AM, cell viability experiments, and modulus measurements indicate promise for use of these PTEGA oligomers for the 3D production of vascularized tissue scaffolds. Similar review of powder bed fusion (PBF) patent literature revealed a polyamide 12 (PA12) composition that remained melt stable during PBF processing, unlike alternative commercial products. Further investigation revealed a fundamental difference in polymer backbone and endgroup chemical structure between these products, yielding profound differences for powder recyclability after printing. An anionic dispersion polymerization of laurolactam in the presence of a steric stabilizer and initiator yielded PA12 microparticles with high sphericity directly from the polymerization without significant post-processing requirements. Steric stabilizer concentration and stirring rate remained the most important variables for the control of PA12 powder particle size and melt viscosity. Finally, preliminary fusion of single-layered PA12 structures demonstrated promise and provided insight into powder particle size and melt viscosity requirements. / PHD / Additive manufacturing (AM) enables the creation of unique geometries not accessible with alternative manufacturing techniques such as injection molding, while also reducing the waste associated with subtractive manufacturing (e.g. machining). However, AM currently suffers from a lack of commercially-available polymers that provide elastomeric properties after processing. Poly(dimethyl siloxane)s (PDMS) possess distinctive properties due to their organosilicon polymer backbone that include chemical inertness, non-flammability, high gas permeability, and low surface energy. For these reasons, siloxanes enjoy wide-ranging applications from personal care products, contact lenses, elastomeric sealants, and medical devices. This dissertation focuses on the synthesis and functionalization of novel PDMS-, polyether-, polyester-, and polyamide-containing photopolymers or powders for improved performance in diverse applications that employ processing via vat photopolymerization (VP) or powder bed fusion (PBF) AM. Examples from this work include a novel photopolymer composition that undergoes simultaneous chain extension and crosslinking, affording low molecular weight and low viscosity precursors prior to VP-AM but the properties of higher molecular weight precursors, once photocured. Related work involved the characterization and VP-AM of siloxane terpolymers that suppress crystallization normally observed in PDMS, resulting in 3D printed objects that retain their elastomeric properties close to the glass transition temperature (Tg). Separate work leveraged the unique PDMS backbone for the melt polymerization of PDMS diamines in the presence of a chain extender and urea, yielding isocyanate-free PDMS polyureas in the absence of solvent or catalyst. This reaction creates ammonia as the only by-product and avoids the use of isocyanates, as well as their highly toxic precursors, phosgene. Finally, another research direction facilitates the understanding of observed differences in melt stability between commercially-available grades of polyamide 12 (PA12) powders for powder bed fusion. An anionic dispersion polymerization based in the patent literature facilitated further understanding of the polymerization process and produced melt-stable PA12 microparticles directly from the polymerization process, without requiring additional post-processing grinding or precipitation steps for powder production.

Wide literature precedence exists for polymers containing electrostatic interactions and polymers containing hydrogen bonding motifs, however the combination of electrostatic and hydrogen bonding interactions is not widely investigated in current literature. Polyelectrolytes containing hydrogen bonding groups are expected to exhibit properties of both classes of supramolecular interactions. A series of adenine- and thyminecontaining PDMAEMA and tert-butyl acrylate copolymers were synthesized to investigate the effect of incorporating hydrogen bonding groups into a polyelectrolyte. Incorporation of the styrenic nucleobases significantly affected the solubility of these copolymers on aqueous solutions and showed salt-triggerability with higher contents of these groups. Polyelectrolytes are capable of binding and condensing DNA through electrostatic interactions with the negatively charged phosphate groups of the DNA backbone; however a high degree of cytotoxicity is also often observed for these gene delivery systems. The high level of cytotoxicity is attributed to high degree of cationic character for the polyplexes formed with these systems according to the proton-sponge hypothesis. One method of reducing the overall cationic character for these systems is incorporation of non-electrostatic binding mechanisms such as hydrogen bonding. A series of nucleobase-containing PDMAEMA copolymers were utilized in order to investigate the effect of incorporation of these groups on the cell viability, binding efficiency, and transfection efficiency of PDMAEMA. / Master of Science

Topic I An empirical potential for calculating hydrogen bonding energies is developed for systems of the type A-H--B, where A and/or B is oxygen or nitrogen. Point charge and van der Waals interaction are included in the potential. The parameters of the potential were optimized by means of a simplex algorithm within a range of A-B distances from 2.8 A through 5.0 A. The root mean square deviation between the empirical potential and the ab initio results of 216 configurations of (H₂O)₂, (NH₃)₂ and NH₃•H₂O is 0.9 kcal/mol and 0.5 kcal/mol for 61 configurations of methanol dimers. Applications of the potential to water dimers, ammonia dimers, their mixed dimers, water oligomers and ice-h as well as the β form of the methanol crystal show that the potential yields reasonable results compared to those computed by "ab initio" methods using 6-31G* basis sets. The potential is compatible with MM2 program. It is simpler than earlier potentials in that neither dipoles nor Morse potentials are involved. It should be superior to the empirical potentials developed by Jorgensen that used STO-3G ab initio calculated results as the standards. The potential might be useful for estimation of hydrogen bond energies in a local part of a large molecule to avoid the prohibitive expense of ab initio calculation. Topic II The monoclinic anthracene crystal is used as an example to demonstrate the feasibility of optimizing the orientation of molecules in the unit cell by matching calculated and experimental refractivity ellipsoids using a simplex algorithm. The calculated refractivity ellipsoid is determined by use of an empirical formula using bond directional polarizabilities. Optimization of the molecular orientations to provide the best fit to the experimental ellipsoid starting from several assumed orientations results in fits for which the maximum deviation from the experimental molecular orientation was no more than 10 degrees. The method can be applied to other monoclinic molecular crystals directly and could be extended to other crystal systems with anisotropic optical properties. Topic III Three mechanisms (Walden inversion, addition-rearrangement-elimination and proton 1,3 shift mechanisms) of the following reaction were suggested by Jay et al. and Andrade et al. respectively. CH₃CN + C⃰N- = CH₃C⃰N + CN-. The mechanism of Walden inversion was determined to be the least likely one based on Andrade's MNDO results. Our calculations, based on 3-21G and 4-31G results, show the contrary result that the Walden inversion is the most likely mechanism among the three considered. However, solvation effects were neglected in the calculations and these effects could play a major role in the choice of mechanisms. Simple calculations based on Boltzmann distribution of precursor concentrations and the Arrhenius law show that Walden inversion predominates over Jay's addition-elimination-rearrangement mechanism even when MNDO energy levels were used. Estimated orders of magnitude for the rate ratios were determined. / Ph. D.

Yes / Nanocrystalline hydroxyapatite (nanoHA) is the main hard component of bone and has potential to be used to promote osseointegration of implants and to treat bone defects. Here, using active pharmaceutical ingredients (APIs) like ibuprofen, we report on the prospects of combining nanoHA with biologically active compounds to improve the clinical performance of these treatments. In this study we designed and investigated the possibility of API attachment to the surface of nano-HA crystals via the formation of a hydrogen-bonded complex. The mechanistic studies of an ibuprofen/nanoHA complex formation have been performed using a holistic approach encompassing spectroscopic (FT-IR and Raman) and X-ray diffraction techniques as well as quantum chemistry calculations (DFT), while comparing the behaviour of the ibuprofen/nanoHA complex with that of a physical mixture of the two components. Whereas ibuprofen exists in dimeric form both in solid and liquid state, our study showed that the formation of the ibuprofen/nanoHA complex most likely occurs via the dissociation of the ibuprofen dimer into monomeric species promoted by ethanol, with subsequent attachment of a monomer to the HA surface. An adsorption mode for this process is proposed; this includes hydrogen bonding of the hydroxyl group of ibuprofen to the hydroxyl group of the apatite, together with the interaction of the ibuprofen carbonyl group to an HA calcium centre. Overall, this mechanistic study provides new insights into the molecular interactions between APIs and the surfaces of bioactive inorganic solids and sheds light on the relation between the non-covalent bonding and drug release properties. / Authors would like to acknowledge funding support from EPSRC (EP/L027011/1, EP/K029592/1). This research was performed in part at the MIDAS Facility, at the University of Sheffield, which was established with support from the Department of Energy and Climate Change.

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