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Current thinking on the best propulsion system for a next-generation supersonic cruising (Mach 2 to Mach 4) aircraft is a mixed-flow turbofan engine with afterburner. This study investigates the performance increase of a turbofan engine through the use of isothermal combustion inside the high-pressure turbine (High-Pressure Turburner, HPTB) as an alternative form of thrust augmentation. A cycle analysis computer program is developed for accurate prediction of the engine performance and a supersonic transport cruising at Mach 2 at 60,000 ft is used to demonstrate the merit of using a turburner. When assuming no increase in turbine cooling flow is needed, the engine with HPTB could provide either 7.7% increase in cruise range or a 41% reduction in engine mass flow when compared to a traditional turbofan engine providing the sane thrust. If the required cooling flow in the turbine is almost doubled, the new engine with HPTB could still provide a 4.6% increase in range or 33% reduction in engine mass flow. In fact, the results also show that the degradation of engine performance because of increased cooling flow in a turburner is less than half of the degradation of engine performance because of increased cooling flow in a regular turbine. Therefore, a turbofan engine with HPTB will still easily out-perform a traditional turbofan when even more cooling than currently assumed is introduced. Closer examination of the simulation results in off-design regimes also shows that the new engine not only satisfies the thrust and efficiency requirement at the design cruise point, but also provides enough thrust and comparable or better efficiency in all other flight regimes such as transonic acceleration and take-off. Another finding is that the off-design bypass ratio of the new engine increases slower than a regular turbofan as the aircraft flies higher and faster. This behavior enables the new engine to maintain higher thrust over a larger flight envelope, crucial in developing faster air-breathing aircraft for the future. As a result, an engine with HPTB provides significant benefit both at the design point and in the off-design regimes, allowing smaller and more efficient engines for supersonic aircraft to be realized. / Ph. D.

This thesis broadly addresses the issue of materials sustainability in the production of Portland cement concrete. Two methods are presented, both aimed at achieving more sustainable concrete through the use of waste and recycled materials. The first method involves utilizing reclaimed asphalt pavement (RAP) as an aggregate in structural concrete, and the second method involves utilizing waste quarry fines as partial replacement of Portland cement in concrete mixes. Many efforts have been made in recent years to justify the use of RAP aggregates in concrete. All previous efforts appear to unanimously report a reduction in concrete performance with varying proportions of RAP usage. The poor performance of RAP aggregates in concrete is attributed mainly to a larger, more porous interfacial transition zone (ITZ) and to the cohesive failure of the asphalt. It is hypothesized that the detrimental impact on the ITZ is attributable to organic compounds leached from the asphalt in the high pH pore solution. This study proves the presence of organic compounds in the pore solution and demonstrates that there is an apparent retardation of cement hydration. This study also attempted to pretreat the RAP in a sodium hydroxide (NaOH) solution to pre-leach the organic compounds. The pretreatment demonstrated that organic compounds were leached and that NaOH modified the asphalt surface chemistry. However, only a marginal improvement in compressive strength was observed by completing the pretreatment. Replacement of Portland cement by filler products is a practice aimed at reducing the carbon footprint of concrete, such as is common with Type IL Portland limestone cement. This study investigates the impact of replacing cement with seven different quarry fines materials. The quarry fines were used to replace cement at 5% to 20% by volume in either cement paste or mortar samples that were then analyzed for various physicochemical properties. It was found that all the quarry fines had detrimental impact on the hydration kinetics of cement pastes. The inclusion of quarry fines was also found to cause varying degrees of reduction in mortar compressive strength. While further analyses of the quarry fines are required, quarry fines 2, 5 and 7 did display encouraging signs to suggest the potential for use as a filler material in blended cements. / Master of Science / This thesis broadly addresses the issue of sustainability in the cement and concrete industry. Sustainability is a significant problem for the cement and concrete industry due to the large amount of carbon emissions produced in the manufacturing process of Portland cement. One method to reduce the carbon footprint of concrete is to use recycled aggregates, and reclaimed asphalt pavement (RAP) is investigated in this thesis as a recycled aggregate option. Previous studies have shown that the use of RAP in concrete results in poor mechanical performance when compared to conventional concrete. In this thesis, the RAP was pretreated by soaking it in sodium hydroxide (NaOH) to see if any improvement is noted. It was determined that the pretreatment resulted in marginal improvements in concrete performance. Another method to reduce the carbon footprint of concrete is through the use of substitutions of Portland cement. In this thesis, quarry fines from around Virginia were investigated for potential as substitutive material. Quarry fines are a by-product from quarrying operations and are often considered a waste material because they have limited applications. This study analyzed the performance of cementitious materials prepared with various substitutive percentages of quarry fines and found that, in general, the inclusion of quarry fines resulted in a decrease of mechanical performance. In total, seven quarry fines were tested and only two showed potential for use as a substitution in Portland cement concrete. These two investigations are essential in reaching the goal of reducing the carbon footprint of the cement and concrete industry.

The exploitation of the relationship between the chemical and physical properties of materials is the hallmark of advancing science throughout the world. The basic understanding of how and why molecules react and interact with each other in different environments allows for the discovery and implementation of new materials and devices that not only advance the state of human life but continually change the planet. The work described in this dissertation generally falls under three diverse categories: functionalization of fullerenes, investigation of host/guest interactions in solution, and the synthesis and characterization of ion containing polymers. The separation and functionalization of fullerenes is a recent and exciting area of research. The separation methods outlined are intended to increase the availability of endohedral metallofullerenes by decreasing their cost of production. Functionalized fullerene species were achieved through Bingel and Prato reactions to provide materials with novel functional groups. These materials may be further utilized in photovoltaic or other organic electronic devices. The characterization of noncovalent interactions between different molecules in solution is the focus of supramolecular chemistry. Isothermal Titration Calorimetry stands out as one of the best, among the many methods used to elucidate the characteristics of these systems. The binding of bis- imidazolium and paraquat guests with macrocyclic host molecules has been explored in this work. The measurements of the association constants for these systems will aid in the ongoing synthesis of new host/guest systems. Ion containing polymers were synthesized and characterized for their use in electroactive devices. Imidazolium containing polymers with bulky anions were synthesized on low glass transition polymer chains. These materials had enhanced ion conductivity and may eventually be used in electronic actuator materials. / Ph. D.

Advanced analytical techniques were utilized to investigate the intermolecular forces in several nanostructured materials. Techniques including, but not limited to, isothermal titration calorimetry (ITC), variable temperature Fourier transform infrared (FTIR) spectroscopy, and ultraviolet-visible (UV-Vis) thermal curves were used to study the fundamental interactions present in various nanomaterials, and to further probe the influence of these interactions on the overall behavior of the material. The areas of focus included self-assembly of surfactant micelles, polycation complexation of DNA, and temperature-dependent hydrogen bonding in polymeric systems. ITC was successfully used to determine the low critical micelle concentration (CMC) for a novel gemini surfactant with limited water solubility. CMCs were measured at decreasing methanol molar fractions (xMeOH) in water and the resulting linear relationship between CMC and methanol concentration was used to mathematically extrapolate to a predicted CMC at xMeOH = 0. Using this technique, the CMC value for the novel gemini surfactant was predicted to be 0.037 ± 0.004 mM. This extrapolation technique was also validated with surfactant standards. ITC was also used to investigate the binding thermodynamics of polyplex formation with polycations and DNA. The imidazolium-containing and trehalose-based polycations were both found to have endothermic, entropically driven binding with DNA, while the adenine-containing polycation exhibited exothermic DNA binding. In addition, ITC was also used to confirm the stoichiometric binding ratio of linear polyethylenimine and DNA polyplexes as determined by a novel NMR method. Dynamic light scattering (DLS) and zeta potential measurements were also performed to determine the size and surface charge of polyplexes. Circular dichroism (CD) and FTIR spectroscopies provided information regarding the structural changes that may occur in the DNA upon complexation with polymers. UV-Vis thermal curves indicated that polyplexes exhibit a greater thermal stability than DNA by itself. Variable temperature FTIR spectroscopy was used to quantitatively compare the hydrogen bonding behavior of multi-walled carbon nanotube (MWCNT)-polyurethane composites. Spectra were collected from 35 to 185 deg C for samples containing various weight percent loadings of MWCNTs with different hydrogen bonding surface functionalities. Peak fitting analysis was performed in the carbonyl-stretching region for each sample, and the hydrogen-bonding index (Rindex) was reported. Rindex values were used to quantitatively compare all of the composite samples in regards to temperature effects, weight percent loadings of MWCNTs, and the different functionalizations. In general, higher weight percent loadings of the MWCNTs resulted in greater Rindex values and increased hydrogen bond dissociation temperatures. In addition, at 5 and 10 wt% loadings the initial Rindex values displayed a trend that tracked well with the increasing hydrogen bonding capacity of the various surface functionalities. / Ph. D.

The purpose of this work was to develop a steel tempering model that is useful to the commercial heat treater. Most of the tempering models reported address isothermal conditions which are not typical of most heating methods used to perform the tempering heat treatment. In this work, a non-isothermal tempering model was developed based on the tempering response of four steel alloys. This tempering model employs the quantity resulting from the numerical integration of the time-temperature profiles of both the heating and cooling portions of the tempering cycle. The model provided a very good agreement between experimental and predicted hardness when secondary hardening did not occur. The developed tempering model was then used as the basis for a process simulation model of a large indirect gas-fired furnace. Unlike the small-scale laboratory experiments performed in the development stage of this work, the temperature variation in this furnace was significant. Recording the temperature with time at 29 locations within the furnace allowed for suitable characterization of the temperature variation. The thermal data was used as inputs in a finite element method model and the time – temperature profiles of three production heavy truck side rails were then simulated. The tempering model provided a good prediction of the tempered hardness compared to experimental measurements. Finally, conclusions are drawn and suggestions are made for future work. / Ph. D.

This work is an experimental study on heat transfer from a human arm and a model cylinder. Heat transfer from a human forearm to a large jet, representative of a building HVAC vent/outlet was studied using both an IR camera and a heat flux sensor. The isothermal jet was discharged horizontally from a wind tunnel, at the same temperature as the ambient air. The model cylinder was used to validate the heat transfer results with results from previous studies, using both the IR camera and heat flux sensors. Further, a study on heat transfer to impingement jets from a human forearm at various Reynolds numbers (Re = 9500-41000) and impinging distances of four and eight jet diameters was done. Heat transfer from a human arm to such impingement jets were then compared with heat transfer due to natural convection under both open and controlled environments. A significant increase in convection heat transfer with Reynolds number and distance from the jet outlet was observed. A nearly four-fold increase in convection heat transfer coefficient was obtained when a jet with Reynolds number of 9500 was impinged on a human arm when compared to that obtained under natural convection in an open environment. Empirical correlations for predicting the stagnation and average Nusselt number from a human arm were also developed with high values of correlation coefficients for future studies. Impingement jets were found to be an effective means to transfer heat from human bodies and could potentially be used for creating thermally conditioned microenvironments. / M. S.

This thesis is concerned with the development of methods and models to aid in optimization and development of new materials for Fused Filament Fabrication (FFF). We demonstrate a novel FFF nozzle design to enable the first measurements of in-situ rheology inside FFF nozzles, which is critical for part performance by ensuring that the polymer extrudate is flowing at an appropriate temperature and flow rate during the part build process. Testing was performed using Acrylonitrile butadiene styrene filament and a modified Monoprice Maker Select 3D printer. Tests using the default temperature control settings of the printer showed an 11 °C drop in temperature and significant fluctuations in pressure, during printing and while idle, of ± 2 °C and +/-14 kPa. These deviations were eliminated at lower flow rates with a properly calibrated proportional–integral–derivative (PID) system. At high flow rates, drops in temperature as high as 6.5 °C were observed even with a properly calibrated PID, providing critical input to the impact of flow rate and PID calibration on polymer melt temperature inside FFF nozzles. Pressure readings ranging from 140-6900 kPa were measured over the range of filament feed rates and corresponding extrusion flow rates. Theoretical predictions of pressure profiles, assuming a powerlaw fluid model, matched well with experimental results. Our nozzle prototype succeeded in measuring internal conditions of FFF nozzles for the first time, thereby providing several important insights into the printing process which are vital for monitoring and improving FFF printed parts. Furthermore, finite difference simulations based on first principles analysis are presented which are capable of quantifying the effect of processing conditions on the properties of semicrystalline parts made by FFF. Each layer was modelled as a rectangular cross section which was broken down into smaller elements for modelling. Crystallinity of each element was calculated using a parallel Avrami model which accounts for changes in crystallization rate due to temperature and multiple crystallization mechanisms. The amount of polymer diffusion, also referred to as the degree of healing, was calculated using a novel incremental diffusion model which accounted for not only changes in reptation time due to temperature but also restrictions to healing due to crystallinity. To the authors knowledge, this is the first healing model capable of accounting for the effect of crystallinity on healing and is relevant to any process involving healing of crystalline interfaces; not just FFF. Cumulative shear stresses between each layer and at the bottom of the part were also calculated for the first time using a force balance model by assuming constant shear strain throughout each layer. Simulations were performed using typical printing conditions for polyether ether ketone. In the first layer of a 24 layer part, the average degree of crystallinity, healing, and shear stress were 25.0%, 53.8% and 19.4 MPa respectively. The degree of crystallinity and healing at layer 22 (which represented the steady state values) were 18.4-25.0% and 51.4% respectively. When crystallinity was not accounted for, varying the printing parameters and material properties supported the use of high temperatures and specific heat in addition to a low printing speed, heat transfer coefficient, and thermal conductivity to maximize part properties. These conditions also supported crystallization, however, which led to a simultaneous reduction in the part properties when crystallinity was taken into account. These contradictory effects will need to be considered when optimizing the printing parameters, though the optimal balance will be highly dependent on the material used and the limitations of the printer. Experimental validation of the accuracy of the heat transfer and polymer diffusion models was performed using an amorphous polymer (polyether imide). Single road wide parts were printed at various nozzle temperatures, bed temperatures, and printing speeds and the results were compared to the simulated results. The predicted shear stress in the bottom of the part ranged from 2.3-3.8 MPa and correlated to warpages at the corners of each part of 1.2-2.4 mm. A linear increase in warpage with predicted shear stress was observed supporting the shear stress model. Predicted degrees of healing ranged from 2-90% but the experimental results ranged from 15-36%. Results of the healing model underpredicted strength at low printing speeds and over predicted strength at high printing speeds. The experimental validations showed the capabilities of the models, but the effect of printing speed will need to be investigated further to improve the accuracy of the healing model. / MS / This thesis is concerned with the development of methods and models to aid in optimizing a type of 3D printing known as Fused Filament Fabrication (FFF). We demonstrate a novel FFF nozzle design to enable the first measurements of the temperature and pressure within FFF nozzles, which is critical for ensuring that the printer is printing at the appropriate temperature and flow rate. Testing was performed using a material known as Acrylonitrile butadiene styrene and a modified Monoprice Maker Select 3D printer. Tests using the default temperature control settings of the printer showed an 11 °C drop in temperature and significant fluctuations in pressure, during printing and while idle, of ± 2 °C and +/-14 kPa. These deviations were eliminated at lower flow rates with a properly calibrated temperature control system. At high flow rates, drops in temperature as high as 6.5 °C were observed even with a properly calibrated temperature control system, providing critical input to the impact of flow rate and temperature control calibration on the temperature of the polymer melt inside FFF nozzles. Pressure readings ranging from 140-6900 kPa were measured over the range of extrusion flow rates tested. Theoretical predictions of the pressure within the nozzles matched well with the experimental results. Our nozzle prototype succeeded in measuring internal conditions of FFF nozzles for the first time, thereby providing several important insights into the printing process which are vital for monitoring and improving FFF printed parts. Furthermore, simulations of the FFF process are presented which can quantify the effect of processing conditions on the properties of FFF parts made from materials which can crystallize. Each layer was modelled as a rectangular cross section which was broken down into smaller elements for modelling. Crystallinity of each element was calculated using a model which can account for changes in the rate of crystallization due to temperature as well as multiple types of crystallization. The strength of the interlayer bonds was calculated using a novel model which accounts for the effects of temperature and crystallinity. To the authors knowledge, this is the first bonding model capable of accounting for the effect of crystallinity on bonding and is relevant to any process involving bonding of crystalline materials; not just FFF. The shear stress between each layer and at the bottom of the part was also calculated for the first time by balancing thermal and shear stresses of each layer. Simulations were performed using typical printing conditions for a high performance polymer (polyether ether ketone). In the first layer of a 24 layer part, the average amount of crystallinity, bonding, and shear stress were 25.0%, 53.8% and 19.4 MPa respectively. The degree of crystallinity and healing at layer 22 (which represented the majority of the part) were 18.4-25.0% and 51.4% respectively. When crystallinity was not accounted for, varying the printing parameters and material properties supported the use of high temperatures and specific heat in addition to a low printing speed, heat transfer coefficient, and thermal conductivity to maximize part properties. These conditions also supported crystallization, however, which led to a simultaneous reduction in the part properties when crystallinity was considered. These contradictory effects will need to be considered when optimizing the printing parameters, though the optimal balance will be highly dependent on the material used and the limitations of the printer. Experimental validation of the accuracy of the heat transfer and bonding models was performed using an amorphous polymer (polyether imide). Single road wide parts were printed at various nozzle temperatures, bed temperatures, and printing speeds and the results were compared to the simulated results. The predicted shear stress in the bottom of the part ranged from 2.3-3.8 MPa and correlated to the corners of each part peeling 1.2-2.4 mm from the printer. A linear increase in the experimental peeling with predicted shear stress was observed, supporting the shear stress model. Predicted bonding ranged from 2-90% of the strength of the material, but the experimental results ranged from 15-36%. Results of the bonding model underpredicted strength at low printing speeds and over predicted strength at high printing speeds. The experimental validations showed the capabilities of the models, but the effect of printing speed will need to be investigated further to improve the accuracy of the bonding model.

Four potential new monomers were prepared, all of which were structural analogues of BisGMA (2,2-bis(4-(2-hydroxy-3-methacryloxyprop-1-oxy) phenyl)propane). The synthesis of these tetrafunctional dimethacrylate monomers was based on structural modifications of Bis-GMA in the core and the side chain and required a two-step reaction. The first step was propoxylation or ethoxylation of the bisphenols and the second step was the methacrylation of the resulting products. The core structures are designated by Bis-A for isopropylidene and 6F for hexafluoropropyl. The side chain structures were designated on the basis of the pendant side chains in the glycidyl moiety as -OH, -H, and -CH3 from the epichlorohydrin, ethyleneoxide, and propyleneoxide reaction products with the bisphenols, respectively. Bis-GMA was commercially obtained and used as a standard for comparison of the experimental monomers. All the monomers were prepared by the following general procedure of propoxylation or ethoxylation of the biphenols followed by methacrylation. They were characterized by NMR, FTIR, DSC and Cone and Plate Viscometry. All the experimental monomers exhibited lower viscosities and glass transition temperatures than the control, which was attributed to the elimination of the hydrogen bonding. The monomers were photopolymerized in a differential scanning calorimetry modified with an optics assembly (DPA 7; Double Beam Photocalorimetric Accessory) to study the photo-induced crosslinking reactions. The influence of monomer structure, temperature, light intensity, and initiator concentration on the photopolymerization kinetics of ethoxylated and propoxylated dimethacrylates was investigated by isothermal DSC. The DSC curves showed a rapid increase in rate due to the Trommsdorff effect, and then a decline due to the decrease of monomer concentration and the autodeceleration effect. The monomers with lower viscosities and glass transition temperatures exhibited higher conversions of the double bonds. The final extent of conversion increased with curing temperature, light intensity and initiator concentration. The radiation intensity exponent varied from 0.68 (BisGMA) to 0.74 for the ethoxylated 6F system. The initiator exponent were varied from 0.34 (for BisGMA) to 0.44 for the propoxylated BisA system. The ratio of the reaction rate constant (kt/kp) was calculated for PropBisAdm from both steady-state and non steady-state conditions. The effect of dilution on photopolymerization kinetics of BisGMA/triethyleneglycoldimethacrylate (TEGDMA) mixtures was also studied by isothermal photo-DSC. Dilution with TEGDMA significantly reduced the viscosity and glass transition temperatures of the mixtures due to the increase in the flexibility. The extent of polymerization increased with increasing TEGDMA and curing temperature. The calculation of ratio of rate constants (kt/kp) was also determined and the significance was discussed herein. / Master of Science