A one-dimensional model of a heterogeneous material consisting of a matrix with embedded separated particles is considered, and the melting or solidification of the particles is investigated. The matrix is in imperfect contact with the particles, and the lumped capacity approximation applies to each individual particle. Heat is generated inside the particles or is transferred from the matrix to the particles coupled through a contact conductance. The matrix is not allowed to change phase and energy is either generated inside the matrix or transferred from the boundaries, which is initially conducted through the matrix material. The physical model of this coupled, two-step heat transfer process is solved using the energy method. The investigation is conducted in several phases using a building block approach. First, a lumped capacity system during phase transition is studied, then a one-dimensional homogeneous material during phase change is investigated, and finally the one-dimensional heterogeneous material is analyzed. A numerical solution based on the finite difference method is used to solve the model equations. This method allows for any kind of boundary conditions, any combination of material properties, particle sizes and contact conductance. In addition, computer programs, using Mathematica, are developed for the lumped capacity system, homogeneous material, and heterogeneous material. Results show the effects of control volume thickness, time step, contact conductance, material properties, internal sources, and external sources. / Master of Science

Current fire induced burnthrough models of aluminum typically rely solely on temperature thresholds and cannot accurately capture either the occurrence or the time to burnthrough. This research experimentally explores the fire induced burnthrough phenomenon of AA6061-T651 plates under multiple sized exposures and introduces a new burnthrough model based on the near melting creep rupture properties of the material. Fire experiments to induce burnthrough on aluminum plates were conducted using localized exposure from a propane jet burner and broader exposure from a propane sand burner. A material melting mechanism was observed for all localized exposures while a material rupture mechanism was observed for horizontally oriented plates exposed to the broader heat flux. Numerical burnthrough models were developed for each of the observed burnthrough mechanisms. Material melting was captured using a temperature threshold model of 633 deg C. Material rupture was captured using a Larson-Miller based creep rupture model. To implement the material rupture model, a characterization of the creep rupture properties was conducted at temperatures between 500 and 590 deg C. The Larson-Miller curve was subsequently developed to capture rupture behavior. Additionally, the secondary and tertiary creep behavior of the material was modeled using a modified Kachanov-Rabotnov creep model. Thermal finite element model accuracy was increased by adapting a methodology for using infrared thermography to measure spatially and temporally varying full-field heat flux maps. Once validated and implemented, thermal models of the aluminum burnthrough experiments were accurate to 20 deg C in the transient and 10 deg C in the steady state regions. Using thermo-mechanical finite element analyses, the burnthrough models were benchmarked against experimental data. Utilizing the melting and rupture mechanism models, burnthrough occurrence was accurately modeled for over 90% of experiments and modeled burnthrough times were within 20% for the melting mechanism and 50% for the rupture mechanism. Simplified burnthrough equations were also developed to facilitate the use of the burnthrough models in a design setting. Equations were benchmarked against models of flat and stiffened plates and the burnthrough experiments. Melting mechanism burnthrough time results were within 25% of benchmark values suggesting accurate capture of the mechanism. Rupture mechanism burnthrough results were within 60% of benchmark values. / Ph. D.

No / We report a numerical calculation of the melting point of NaCl. The solid-liquid transition was located by determining the point where the chemical potentials of the solid and liquid phases intersect. To compute these chemical potentials, we made use of free energy calculations. For the solid phase the free energy was determined by thermodynamic integration from the Einstein crystal. For the liquid phase two distinct approaches were employed: one based on particle insertion and growth using the Kirkwood coupling parameter, and the other involving thermodynamic integration of the NaCl liquid to a Lennard-Jones fluid. The latter approach was found to be significantly more accurate. The coexistence point at 1074 K was characterized by a pressure of -30+/-40 MPa and a chemical potential of -97.9+/-0.2kßT. This result is remarkably good as the error bounds on the pressure enclose the expected coexistence pressure of about 0.1 MPa (ambient). Using the Clausius-Clapyron relation, we estimate that dP/dT~3 MPa/K. This yields a melting point of 1064+/-14 K at ambient pressure, which encompasses the quoted range for the experimental melting point (1072.45-1074.4 K). The good agreement with the experimental melting-point data provides additional evidence that the Tosi-Fumi model for NaCl is quite accurate. Our study illustrates that the melting point of an ionic system can be calculated accurately by employing a judicious combination of free energy techniques. The techniques used in this work can be directly extended to more complex, charged systems.

Yes / Triplexes formed from oligonucleic acids are key to a number of biological processes. They have attracted attention as molecular biology tools and as a result of their relevance in novel therapeutic strategies. The recognition properties of single-stranded nucleic acids are also relevant in third-strand binding. Thus, there has been considerable activity in generating such moieties, referred to as triplex forming oligonucleotides (TFOs). Triplexes, composed of Watson–Crick (W–C) base-paired DNA duplexes and a Hoogsteen base-paired RNA strand, are reported to be more thermodynamically stable than those in which the third strand is DNA. Consequently, synthetic efforts have been focused on developing TFOs with RNA-like structural properties. Here, the structural and stability studies of such a TFO, composed of deoxynucleic acids, but with 3′-S-phosphorothiolate (3′-SP) linkages at two sites is described. The modification results in an increase in triplex melting temperature as determined by UV absorption measurements. 1H NMR analysis and structure generation for the (hairpin) duplex component and the native and modified triplexes revealed that the double helix is not significantly altered by the major groove binding of either TFO. However, the triplex involving the 3′-SP modifications is more compact. The 3′-SP modification was previously shown to stabilise G-quadruplex and i-motif structures and therefore is now proposed as a generic solution to stabilising multi-stranded DNA structures.

Yes / In this study, a comparison of different methods to predict drug−polymer solubility was carried out on binary systems consisting of five model drugs (paracetamol, chloramphenicol, celecoxib, indomethacin, and felodipine) and polyvinylpyrrolidone/vinyl acetate copolymers (PVP/VA) of different monomer weight ratios. The drug−polymer solubility at 25 °C was predicted using the Flory−Huggins model, from data obtained at elevated temperature using thermal analysis methods based on the recrystallization of a supersaturated amorphous solid dispersion and two variations of the melting point depression method. These predictions were compared with the solubility in the low molecular weight liquid analogues of the PVP/VA copolymer (N-vinylpyrrolidone and vinyl acetate). The predicted solubilities at 25 °C varied considerably depending on the method used. However, the three thermal analysis methods ranked the predicted solubilities in the same order, except for the felodipine−PVP system. Furthermore, the magnitude of the predicted solubilities from the recrystallization method and melting point depression method correlated well with the estimates based on the solubility in the liquid analogues, which suggests that this method can be used as an initial screening tool if a liquid analogue is available. The learnings of this important comparative study provided general guidance for the selection of the most suitable method(s) for the screening of drug−polymer solubility. / The Irish Research Council and Eli Lilly S.A. through an Irish Research Council Enterprise Partnership Scholarship for C.M.B., in part by The Royal Society in the form of Industrial Fellowship awarded to G.A., and in part by a research grant from Science Foundation Ireland (SFI) under Grant Number SFI/12/RC/2275 (for A.M.H., L.T., K.P., and A.K.).

With the increasing research on advanced reactors, molten salt reactors have been recognized for their potential. As with any advanced reactor concept, each component and material must be thoroughly investigated before any reactors of that type are created. One of the most pressing issues in MSR research is that of the salts themselves. Though there are a multitude of salts to choose from when designing such a reactor, many of these salts lack the extensive research required to fully understand them. Across the decades there have been many studies that have investigated select molten salts, but there are a few problems with many of those studies. Those problems are the following: prior papers use obsolete and less reliable methods for their measurements, the papers don't investigate the salts across a wide enough range of temperatures nor at varying compositions, and finally many of the salts that are seen as candidates today were not given as much attention when molten salt reactors were first conceptualized which has resulted in a lack of research on them. Indeed, the research into these salts is lacking in many ways. This study seeks to investigate a collection of promising coolant salts in depth with acknowledgment to those past studies. LiF-NaF-KF (46.5-11.5-42.0 mol%) will be used as a calibration standard and for the purpose of verifying our methodology. Specifically, FLiNaK was used in the development of volume-height curves as calibration for density measurements. NaOH-KOH of four different compositions ( 0.5-0.5mol%, 0.55-0.45mol%, 0.6-0.4mol%, and 0.65-0.35 mol%) will be evaluated for their densities and heat capacities. And finally, BeF2-NaF(43-57mol%) will be evaluated within the question of if the properties are desirable enough that the dangers posed by beryllium are an acceptable risk. BeF2-NaF will have melting point, heat capacity, density, and vapor pressure measurements performed. Additionally, extensive impurity analysis and removal (via an HF gas system) was done to our BeF2-NaF samples. The melting point and heat capacity were evaluated using dynamic scanning calorimetry (DSC), the vapor pressure was evaluated using thermogravimetric analysis (TGA), and the density was measured using a system similar to the Arrhenius method that measures height. / Master of Science / Decades have passed since the discussion of nuclear energy began. Although great progress has been made in the field, the nuclear reactors in use today consist mainly of boiling water reactors (BWRs) or pressurized water reactors (PWRs). As reliable as these reactors have become, one can no longer ignore the fact that there is a multitude of other options for how a reactor can be built and operated. Options that provide greater safety and more energy output. Many reactor concepts of the past were discounted for the extensive research that would be required to make use of them. However, as time has passed and technology has improved, that research has become more and more possible. Many advanced reactors are the result of that attention to the reactor concepts and materials of the past that couldn't be given the attention that they deserve until now. Molten salt reactors (MSRs) are one of those promising concepts. However, before they can be built every part of the reactor, from the structure to the materials, must be entirely understood. One of the most pressing issues in MSR research is the properties of the salts in consideration for use. Though there are a multitude of salts to choose from when designing such a reactor, many of these salts lack the extensive research required to fully understand them. Across the decades there have been many studies that have investigated select molten salts, but there are a few problems with many of those studies. Those problems are the following: the papers are so old that the methods that were used are now obsolete, the papers don't investigate the salts across a wide enough range of temperatures nor at varying compositions, and finally many of the salts that are seen as candidates today were not given as much attention when molten salt reactors were first conceptualized which has resulted in a lack of research on them. Indeed, the research into these salts is lacking in many ways. This study seeks to investigate a collection of promising coolant salts in depth with acknowledgment to those past studies. LiF-NaF-KF will be used as a calibration standard and for the purpose of verifying our methodology. A multitude of different compositions of NaOH-KOH will be evaluated for their densities and heat capacities. And finally, BeF2-NaF will be evaluated within the question of if the properties are desirable enough that the dangers posed by beryllium are an acceptable risk. BeF2-NaF will have melting point, heat capacity, density, and vapor pressure measurements performed. Additionally, extensive impurity analysis and removal was done to our BeF2-NaF samples.

The role of the single component instability of surface melt fracture on the interface behavior in stratified bicomponent flow has been examined. First, the factors and conditions leading to the onset of surface melt fracture in linear low-density polyethylene (LLDPE) were identified using fluoro-elastomer (FE) as a blending additive and as a die coating in two visualization dies. A visualization die was constructed so that subsequent experiments examining the joining flow behavior of two stratified flows could be examined. Experiments were conducted in the joining flow die over a range of upstream conditions corresponding to surface melt fracture behavior and the resulting flow birefringence patterns and the interface of the extrudate were examined. It was determined from the: single component studies that the role of FE in eliminating surface melt fracture behavior for LLDPE was to introduce slip at the melt/metal interface in the dies. Additionally, it was determined that the coupling of a critical stress with a critical acceleration of the melt as it exits the die, suggested by Kurtz [19], was an accurate description of the behavior observed experimentally. Under upstream conditions corresponding to surface melt fracture behavior, no irregular distortions were observed in the bicomponent interface. It was therefore concluded that the single component instability of surface melt fracture does not play a role in irregular distortions of the interface. Numerical simulations employing the Phan-Thien Tanner (PTT) constitutive model and the finite element method (FEM) were conducted to examine the influence of relaxation times and extensional viscosity on the developing flow region in joining flow die. Numerical predictions employing material constants fit to the rheological properties of LLDPE were compared with the ex- perimental results to establish the reliability of the numerical method. Qualitative agreement between the predictions and the experimental behavior was observed. However, the magnitude of the stresses predicted by the model were not quantitatively accurate. It was concluded that the numerical method was capable of predicting trends in behavior, but was not quantitatively accurate. Given this limitation, it was suggested by the results of the numerical studies that the relaxation behavior has a pronounced effect on the developing stress field, while the impact of the extensional viscosity is minimal. Simulations were also performed to evaluate the ‘stick-slip’ behavior of LLDPE. The results provided additional support to the supposition of the role of FE in eliminating surface melt fracture behavior in LLDPE. / Ph. D.

This thesis explores the optimization of process parameters for producing single-track thin walls using Laser Powder Bed Fusion (LPBF) additive manufacturing. Using two different coupon designs, the study assesses the feasibility of creating the thinnest possible leak-tight structures within LPBF and evaluating their mechanical properties, including burst pressure and modulus of elasticity under pressure loads. A series of experimental iterations were conducted, varying laser power and laser speed to identify optimal conditions. The findings indicate that a narrow range of process parameters can produce consistently leak-tight thin walls. The results contribute to understanding how to achieve high quality, reliable thin wall structures in the LPBF process, with implications for industrial applications requiring thin, precise, leak tight, and durable walls.

This report aims to investigate the possibility of making roof gutter heating systems more energy efficient while maintaining their performance. With a societal target of becoming climate-neutral, all energy use needs to be minimized and without previous research on the subject, real estate owners may have overused electricity in their efforts. The report assesses available conventional systems, how they work, and their composition. With the help of meteorological data a new system was created that would reduce energy use drastically. The findings state that depending on the earlier system installed by companies the new improved system would only use between 2.5-52% of the energy used by the conventional systems. This is largely because the conventional systems are primitive and has not been updated to a central and internet-connected control system. It is this implementation of online meteorological data and using that data in developed dynamic controlling systems that has led to a decrease in energy use for roof gutter heating systems.

Polyesters are an attractive class of polymer that can be readily modified with a wide range of different comonomers, during polymerization or with melt blending, to achieve a wide variety of physical properties. This research primarily focuses on polyesters that incorporate rigid aromatic structures that have excellent potential to enhance thermal and mechanical properties. Copolyesters were prepared through melt polycondensation of diesters and diols in the presence of an exchange catalyst. Monomer incorporation was verified with nuclear magnetic resonance (NMR) and molecular weights were obtained by measuring inherent viscosity (ninh). Physical properties were assessed with thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and rheology. Mechanical properties were assessed with tensile and impact testing. Copolyesters of poly(ethylene terephthalate) (PET) were synthesized by substituting dimethyl terephthalate (DMT) with dimethyl 4,4'-biphenyldicarboxylate (4,4'BB) resulting in enhanced glass transition (Tg) temperatures relative to PET while affording melting temperatures (Tm) low enough to allow facile melt processing. Further modification with dimethyl isophthalate (DMI) or dimethyl 3,4'-biphenyldicarboxylate (3,4'BB) slowed crystallization sufficiently to allow biaxial orientation, leading to further studies assessing the permeability of oriented films. Novel amorphous polyesters were synthesized with 3,4'BB or 4,4'BB in combination with neopentyl glycol (NPG), 1,4-cyclohexandimethanol (CHDM) and ethylene glycol (EG). Use of multiple diols produced clear, amorphous copolyesters with Tgs as high at 129 C. A series of novel high temperature(Tm) copolyesters were synthesized from dimethyl 2,6-naphthalenedicarboxylate (DMN) and 4,4'BB combined with CHDM. Studies were performed with standard DSC and thin film calorimetry to show the convergence of multiples melting endotherms in an effort to determine their origin. Preliminary work was performed on the modification of poly(1,4-cyclohexylenedimethylene terephthalate) (PCT), poly(1,4-cyclohexylenedimethylene 2,6-naphthalate) (PCN) and poly(1,4-cyclohexylenedimethylene 4,4'-bibenzoate) (PCB) with dimethyl p-terphenyl-4,4''-dicarboxylate. / PHD / Polyesters have a unique balance of properties that sets them apart from other polymers formed by step growth reactions. The transesterification reaction that forms polyesters occurs continually at reaction temperatures, making it easy to randomly distribute a mixture of different comonomers along the backbone during the polymerization process, or even when blending two different polyesters. Poly(ethylene terephthalate), commonly referred to as PET, is the most important polyester currently in production, and is prized for its transparency, chemical resistance, and recyclability. PET was first made by John Whinfield and James Dickson at Calico Printers’ Association of Mansfield, in 1941 and was eventually licensed to DuPont in the 1970s. It has since become a valuable resource for producing synthetic textiles and replacing heavier materials, such as glass and metal, to produce lightweight containers, especially for food storage. Many of the polyesters, such as PET, that we see on a daily basis are actually copolyesters that contain low levels of additional comonomers that have been added to improve some property of the final polymer or to facilitate processing. In research, modification of polyesters with different comonomers broadens our understanding in how the molecular structure of comonomers affects polyester properties. This makes it possible to tune a copolyester’s physical properties in a way that can enhance its suitability for a wide range of applications. The research described in this dissertation is focused on exploring how rigid monomer structures containing multiple aromatic rings might be used to produce polyesters with improved performance relative to current commercial polyesters. Materials that demonstrate good barrier to gases such as CO₂ and O₂ are important for packaging that can seal in and preserve food and beverages. In our research, we modified PET with bibenzoate structures to produce films that showed improved gas barrier when stretched in a manner that imitates the stretch blow molding process used to produce bottles. These materials showed good promise for packaging capable of preserving food for longer periods of time. Clear, food safe plastics that do not deform at the boiling temperature of water are important for baby bottles and durable dishwasher safe containers, which are commonly sterilized with boiling water. Until recently, such materials were produced from bisphenol-A polycarbonate (BPA PC), which fell out of favor for food safe applications over concerns that BPA, believed to have endocrine disrupting activity, may leach into food and beverages. Bibenzoate monomers, which increases the application temperature of many polyesters, were combined with different combinations of diol monomers to produce transparent copolyesters that are usable at higher temperatures. These materials demonstrated excellent potential as food safe alternatives to BPA containing materials. Crystalline plastics that resist distorting at high temperatures are important for applications in the electronics and automotive industry. Semicrystalline polyesters provide less expensive alternatives to the costly liquid crystalline polymers commonly used for high temperature applications. We explored the properties of a number of semicrystalline copolyester compositions capable of exceeding the application temperature of semicrystalline polyesters currently on the market.