During the last few years the scientific interest in chalcogenides glasses has been provoked on account of their properties and new application possibilities. These materials exhibit electrical and optical properties, which make them useful for several potential applications. Specifically the threshold and memory switching behavior and the infrared transmission of many of these glasses make the materials to be well suitable for use in memory devices and in fiber optics. Multicomponent glasses have been found to be more useful for many of these applications since the properties could be tailored for the specific uses. On account of this there has been great deal of interest in recent years in understanding the composition dependent variations of physical properties in these glasses. Models based on network topology and chemical ordering have been proposed to explain the composition dependence of physical properties. The Chemically Ordered Covalent Network (COCN) model is one of the best efforts put forth in this subject. This model predicts distinctive physical properties of these glasses for compositions at which there is a maximum number of heteropolar bonds. A physical model based on changes in network topology with composition has been proposed recently. This model predicts the rigidity to percolate in the network at the mean coordination number <r> = 2.40. This critical value of <r> at which the rigidity percolates is called the mechanical threshold or the rigidity percolation threshold. One more argument based on medium range interactions, existing in these glassy networks, suggests that the mechanical threshold should occur at <r> = 2.67. A general lack of consensus in the existing experimental reports on the mechanical threshold in some chalcogenides glasses prevents one from identifying the correct threshold value of <r>. A systematic study of the composition dependence of glasses with a large glass-forming region is necessary to resolve this controversy. The correct threshold value of <r> and the reason for the departure from this value in the other cases is the first step towards verifying the applicability of this model to chalcogenide glasses. Glasses belonging to IV — V — VI groups are natural candidates for this study because of their large glass forming region. It also seems possible to isolate the chemical threshold from interfering with the mechanical threshold in some of these glasses. In device applications of any semiconductor the optical and the electrical band gaps need to be varied and this is commonly done by doping. The large density of valence alteration pairs and intrinsic disorder of amorphous semiconductors counter-balances the effects of external additives. As a result, it is hard to electrically dope these materials. Non-equilibrium experimental techniques have been used to some extent, but one of the limitations is that they are confined to the thin film state. The finding that p to n type conduction sign changes can be induced by Bi and Pb in bulk Ge-M (M= S, Se and Te) glasses has therefore created special interest. This thesis deals with Ge-Se glass matrix doped with Te, Bi and Pb. The optical, thermal and electrical properties have been studied. The present thesis work is arranged in several chapters. The basic introduction of chalcogenide glasses is given in chapter one. This includes an introduction to chalcogenide glasses followed by a brief discussion on the important structural models, the possible defects in chalcogenide glasses and the electrical, optical and thermal properties of chalcogenide glasses. The second chapter discusses the experimental techniques used in the present investigations. The basic principles and theory behind the experiments, the experimental setup and the experimental procedure leading to the determination of the physical properties are given here. These include information about Differential Scanning Calorimetry (DSC), Photo acoustic (PA) spectroscopy and Photoluminescence studies. In the third chapter the experimental investigations on Ge-Se-Te glasses are presented. The chapter starts with the preparation and characterization of these glasses. It then gives an account of the earlier studies on Ge-Se-Te glasses that are relevant to the present work. The results of the DSC and PA studies are discussed in the following two sections. In the systems with Gex Se80-x Te20 and Gex Se75.x Te25, glasses with less than 20 at. % of Ge do not show any crystallization peak due to Se rich content. But Te and Ge-rich glasses show strong crystallization tendency. The composition dependence of Tg of this glassy system gives an evidence for the occurrence of the topological threshold or mechanical threshold at <r> = 2.40 and chemical threshold at <r> = 2.67. These can be explained on the basis of COCN model. The optical band gap and thermal diffusivity studies also show anomalous behavior at <r> = 2.40 and <r> = 2.67. The experimental results on Ge-Se-Te glasses are summarized in the last section of this chapter. The investigations on Bi doped Ge-Se and Ge-Se-Te glasses are given in the fourth chapter. The chapter starts with a brief introduction of preparation, characterization and a short review of earlier work. In PA studies the anomalous behavior is observed in thermal diffusivity and thermal diffusion length plot at 8-9 at. % of Bi doping of the Ge-Se and Ge-Se-Te glasses where the conduction changes from p to n type. These results are explained on the basis of percolation model and the formation of Bi2Se3 microcrystalline phase. Finally these results are summarized at the end of the chapter. The fifth chapter is devoted to the investigations on Pb doped Ge-Se glasses. It is arranged in five sections; preparation and characterization, earlier work, Photo acoustic and Photoluminescence studies. In PA studies the composition dependence of thermal diffusivity show anomalous behavior at x =F 9 at % of Pb in Pbx Ge42-x Sesg glasses and y = 21 at. % of Ge in Pb2o Gey Seso-y glasses where the conduction changes from p to n type. After that it reaches the maximum. After the conduction sign changes the conductivity increases with addition of respective Pb and Ge concentration in both series of glasses, which is reflected in thermal diffusivity value also. The results have been explained on the basis of COCN model. From PL studies, the PL intensity is high in un-doped Ge42 Scss glasses. With the addition of Pb into Ge-Se system the PL intensity goes down drastically up to 9 at. % of Pb, beyond 9 at. % the PL intensity is approximately the same up to 15 at. %. In the last section the results are summarized. Chapter six summarizes the essential features of the work reported in the thesis. These conclusions are drawn from the present and the earlier reported studies on Ge-Se-Te glasses, Bi doped Ge-Se and Ge-Se-Te glasses and Pb doped Ge-Se glasses. Finally based on the present experimental results, some future work has been suggested which could throw some light on a better understanding of/? to n transition and defects state of these glasses. It is worth extending the microscopic phase separation studies in these glasses. Highly sensitive experimental techniques are needed in this regard. Also some simulation work like Monte-Carlo simulation and Molecular dynamics simulation needs to be undertaken for understanding the microscopic phase separation and the role of defects in carrier type reversal in these glassy materials. All the references cited in the thesis are collected and listed at the end of the thesis.

With the emergence of Matrix Assisted Laser Desorption/Ionization-Time-of-flight as a tool for diagnosis of diseases via proteomics, there is an increasing need for greater sensitivity. Analysis of peptides by MALDI-TOF-MS is affected by sample formulation and spotting onto a MALDI target. This dissertation investigates a novel MALDI sample preparation technique, Induction Based Fluidics (IBF), for depositing precise volumes (pL to nL) of samples onto the target. We have seen that while using IBF, the induced electric field accompanying deposition enhances matrix crystallization yielding smaller crystals with more homogeneity, as compared to conventional manual micropipette (MP) depositions. An investigation of the signal-to-noise (S/N) for IBF deposition of tryptic digested Bovine Serum Albumin (BSA) showed a significant improvement in the signal-to-noise ratio for 0.5 and 0.25 pmol/µL BSA sample compared to equivalent MP depositions. The S/N enhancement for IBF and MP depositions of BSA were studied using à-cyano-4-hydroycinnamic acid (CHCA) and 2,5-dihydroxybenzoic acid (DHB) matrices, and CHCA showed better results than DHB . The exciting results obtained by IBF prompted us to probe sample morphology more fully and to relate morphology to the detections level and hopefully, to increase the utility of MALDI-TOF-MS for detection of a larger range of peptides. Morphology results were correlated to sensitivity limits using both dispensing techniques. Because of dissimilar rates of evaporation, different or uneven deposition thickness, or crystal lattice morphology, discontinuous crystallization patterns were observed for MP depositions. However, IBF deposited samples occupied less planar area with uniform distribution of crystals, thereby reducing sample crystal heterogeneity and laborious hunt for a "sweet" or "hot" spot to produce high quality spectra. The application of IBF was extended to the tryptic digested BSA protein using peptide mass fingerprinting. IBF deposition resulted in a larger number of detectable peptides as well as higher sequence coverage as compared to equivalent MP depositions. In last few decades, advanced research and potential applications in the field of microelectronics have spurred interest in the development of reticulated doped polymer films. Bis (ethylenedioxy) tetrathiafulvalene (BEDO-TTF)/Polycarbonate (PC) films were synthesized and characterized for use in hand-held real time explosives sensors, capable of detecting nitro-based compounds (nitroaromatics, nitoamines and nitroesters), which are the main components of Improvised Explosive Devices or IEDs. Reticulated doped polymer films were prepared by exposing solid solutions of BEDO-TTF in PC to iodine to form conductive charge transfer complexes. The resulting films exhibited room temperature conductivities ranging from 6.33-90.4*10-5 S cm-1. The colored iodine complexes in the film were reduced by cyclic voltammetry yielding conductive, colorless, transparent films. Dielectric analysis (DEA) was used to probe relaxations in neat PC and BEDO-TTF/PC showed that BEDO-TTF plasticized the PC and decreased the glass transition temperature. Two secondary relaxations appeared in PC films, whereas the transitions merged in the doped film. DEA also revealed conductivity relaxations above 180°C, which were characterized by the electric modulus formalism and showed that BEDO-TTF increased the alternating current, (AC) conductivity in PC.

Polyethylene (PE) is produced in a huge scale globally and has plenty of desirable properties. It is used in coating, packaging, and artificial joint replacements. The growing need for high performance polyethylene led to the development of new catalysts, monomers and polymerizations. The synthesis of polymethylene (equivalent to polyethylene) by living polyhomologation opened the way to well-defined polymethylenes-based polymeric materials with controlled structure, molecular weight and narrow polydispersity. Such model polymers are substantial to study the structure-properties relationships. This research presents a new strategy based on the in situ formation of B-thexyl-silaboracyclic serving as initiating sites for the polyhomologation of dimethylsulfoxonium methylide. Combination with metal-free ring-opening polymerization (ROP) of ɛ-caprolactone (CL) and atom transfer radical polymerization (ATRP) of styrene led to three polymethylene-based 3-miktoarm stars copolymers PCL(PM-OH)2, Br-PCL(PM-OH)2 and PS(PM-OH)2.

Shallow marine gas hydrates occurring above the Sulfate-Methane-Interface (SMI) often contain small amounts of H2S beside methane and other hydrocarbons, but the distribution of H2S in these natural samples is not always homogeneous. To learn more about the formation of H2Scontaining hydrates, gas hydrates with different ratios of H2S/CH4 were synthesized under various conditions. The samples were synthesized from ice and water phases, with constant feed gas compositions or controlled changes in feed gas compositions. It turns out that the detailed nature of the synthetic hydrate samples depends on the method of sample preparation. The sample prepared with gas containing small amounts of H2S (1% H2S and 99% CH4) appeared homogeneous in composition, while that prepared in a water-H2S-CH4 system with higher H2S contents was heterogeneous. The samples were analysed with Raman spectroscopy, and differential scanning calorimetry (DSC).

The avoidance of hydrate blockages in deepwater subsea tiebacks presents a major technical challenge with severe implications for production, safety and cost. The successful prediction of when and where hydrate plugs form could lead to substantial reductions in the use of chemical inhibitors, and to corresponding savings in operational expenditure. The diffusivity of the gas hydrate former (methane) or the host molecule (water), through a hydrate film is a key property for such predictions of hydrate plug formation. In this paper, a novel application of Differential Scanning Calorimetry is described in which a hydrate film was allowed to grow at a hydrocarbon-water interface for different hold-times. By determining the change in mass of the hydrate film as a function of hold-time, an effective diffusivity could be inferred. The effect of the subcooling, and of the addition of a liquid hydrocarbon layer were also investigated. Finally, the transferability of these results to hydrate growth from water-in-oil emulsions is discussed.

A HP micro DSC-VII from SETARAM was used to study the efficiency and mechanism of action of commercial kinetic inhibitors for gas-hydrate formation in drilling fluids (OBM). The main objective was to find a suitable and reliable method of screening for these chemicals. The DSC technique consists in monitoring the heat exchanges, due to phase changes (here hydrate formation or dissociation), either versus time at constant temperature or versus temperature during a heating or cooling program. All products showed a gas hydrate dissociation temperature (at a given pressure) that matched with theoretical and previously published data. Nevertheless, for some additives two thermal signals were observed on the thermograms, one that corresponds to the theoretical value and another at a higher temperature (about +4°C). This second peak is insensitive to the heating rate applied for the dissociation, but the areas ratio (1stpeak/2nd peak) changes with the additive concentration and with the driving force applied during the hydrate formation. Additionally, additive/water and additive/water/THF systems were tested. In each case, two dissociation peaks were also measured. The results allow us to disregard any kinetic effects bonded to this thermal phenomenon, and lead us to infer that some additives may induce non-classical crystalline structures of gas hydrates. To verify these results, crystallographic and spectroscopic experiments must be performed. The stabilities of these new compounds are under study.

Universiẗat, Diss., 2003--Dortmund.

Epoxy resin is an important engineering material in many industries such as electronics, automotive, aerospace, etc not only because it is an excellent adhesive but also because the materials based on it provide outstanding mechanical, thermal, and electrical properties. Epoxy resin has been proved to be an excellent matrix material for the nanocomposites when including another phase such as inorganic nanofillers. The properties of a nanocomposite material, in general, are a hybrid between the properties of matrix material and the nanofillers. In this sense, the thermal, mechanical, and electrical properties of a nanocomposite may be affected by the corresponding properties of matrix material. When the sonication is used to disperse the nanofillers in the polymer matrix, with the dispersal of the nanofillers, there comes some modification in the matrix as well and it finally affects the properties of nanocomposites. In this regard, we attempted to study the thermal, mechanical, and dynamic properties of EPON 862 epoxy resin where ultrasonic processing was taken as the effect causing variable. Uncured epoxy was subjected to thermal behavior studies before and after ultrasonic treatment and the cured epoxies with amine hardener EPICURE 3223 (diethylenetriamine) after sonications were tested for mechanical and dynamic properties. We monitored the ultrasonic processing effect in fictive temperature, enthalpy, and specific heat capacity using differential scanning calorimetry. Fictive temperature decreased whereas enthalpy and specific heat capacity were found to increase with the increased ultrasonic processing time. Cured epoxy rectangular solid strips were used to study the mechanical and dynamic properties. Flexural strength at 3% strain value measured with Dillon universal testing machine under 3-point bending method was found to degrade with the ultrasonic processing. The storage modulus and damping properties were studied for the two samples sonicated for 60 minutes and 120 minutes. Our study showed that the 60 minutes sonicated sample has higher damping or loss modulus than 120 minutes sonicated sample.

The structural adhesives widely used in structural strengthening applications are thermoset ambient cure adhesive polymers. At ambient temperatures, these polymers are in a relatively hard and inflexible state. At higher temperatures, the material becomes soft and flexible. The region where the molecular mobility changes dramatically is known as the glass transition temperature Tg and often is presented as a single value. Epoxy polymers exhibit a significant reduction in mechanical properties near glass transition temperature Tg when they are exposed to elevated temperatures. Glass transition temperature Tg is used to characterise the change in epoxy adhesive properties with changing temperature. The mechanical properties of epoxies tend to improve with curing temperature. This is because the crosslink density between the adhesive molecular structures increases during the curing process consequently the Tg improves. The aims of this work are first to demonstrate the importance of curing temperature. Second, to investigate the influence of glass transition temperature !! improvement on the performance of EB-FRP strengthened steel structures in flexure at ambient and elevated temperatures. Third, to compare analytical results with experimental results from the flexure tests results. Finally, to compare the current design guideline recommendations with the flexure tests results. The most commonly used methods to evaluate Tg Dynamic Mechanical Analysis (DMA) and Differential Scanning Calorimetry (DSC) were used to study Tg. Two off-shelf structural adhesives were investigated to understand their property variation with temperature. Epoxy coupons were cured at different elevated temperature and humidity environments up to 28 days. A combination of two extreme relative humidity of 0 and 100% and variable curing temperatures between 15 to 80°C were considered. From a test matrix of 300 DMA and over 250 DSC coupons these conclusions were drawn. First, ambient cured thermosets have a linear relationship between Tg and curing temperature, but Tg is reduced if a certain temperature is reached. Second, a fully cured adhesive requires heating treatment. Without a curing regime, designed Tg may never be achieved. Finally, curing time is crucial at the low curing temperatures while it is less significant at the higher curing temperature. The results of Tg investigation were used to select appropriate curing temperature that the adhesives resistance to temperature can be maximised without damaging the mechanical properties. The study helps designs to understand and assess the behaviour of these two adhesives when they are exposed to extreme temperatures. The study increases the awareness that a fully cured adhesive may never be achieved at ambient or low temperatures. It is important to find the mechanical properties and Tg when the coupons are exposed to the same curing temperature. To investigate the influence of glass transition temperature Tg improvement on the performance of EB-FRP strengthened steel structures in flexure at ambient and elevated temperature, nine three metre length beams were designed to behave as a concrete-steel composite bridge deck. The beams were tested in four-point bending. Lap shear, DMA test, and pull-off adhesion samples were prepared and cured at the same conditions and tested at ambient temperature. Six beams were tested under only mechanically loading at ambient temperature, including the control specimen. Five beams were tested at ambient temperature to show the effects of adhesive curing on FRP strengthened sections. A significant increase of load capacity of the adhesive joints was achieved due to the curing of the joints at elevated temperature. The failure occurred was in the same manner. An increase in the load capacity was observed with increasing curing temperature. An increase of approximately 25% was noticed in the ultimate load capacity of the specimens cured at 50°C compared to the specimens cured at 30°C. The load capacity of lap-shear specimens cured at 50°C was 28% higher than the specimens cured at 30°C. Three specimens were tested under mechanical and thermal loading. A bespoke thermal chamber was designed and fabricated to apply a controlled thermal loading. The beams were loaded mechanically up to 350kN, first. The temperature of the specimens was then increased at a rate of 0.8°C/min. The sustained load 350kN remained constant during the heating phase. Digital Image Correlation (DIC) technique was used to detect the slippage of the tip of the FRP plates. The only specimen cured at 30°C showed relatively poor performance compared to the two specimens cured at 50°C. The plate ends started to slip when the adhesive storage modulus from the DMA runs reduced approximately by 15 and 18% for the beams cured at 30 and 50°C respectively. Pull-off adhesion tests confirmed that adequate surface preparation of over 25 MPa was achieved The flexural model for the composite steel section represented to predicate load-deflection behaviour of the specimens using semi-experimental constitutive material law. The model successfully predicts the load-deflection behaviour of specimens, considering the strain hardening contribution. A bond stress analysis is also presented, which counts for the effect of FRP plate moment effect. The experimental and theoretical FRP plate slippage assuming only adhesive degradation with temperature are compared. The analytical bond models cannot predict the experimental failure because the linear elastic material properties were assumed and the failure was adhesion.

In this work differential scanning calorimetry, dynamic mechanical analysis, Fourier-Transformed Infrared Spectroscopy [FT-IR] and polarized light microscopy will be employed to characterize polymeric systems. The first chapter broadly covers polymer synthesis and important characterization methods. In the second chapter, a polyamide (PA12) will be sintered via a novel additive manufacturing (AM) technology developed here at USF termed LAPS (Large Area Projection Sintering). LAPS uses extended sintering timespans to ensure complete melting and densification of the polymer powder over the entire two-dimensional area of the part’s footprint. Further, it allows for the printed layer to crystallize and shrink in its entirety as the temperature falls below the crystallization temperature prior to the next layer being added. The printed parts (termed coupons) will be assayed by DSC and polarized light microscopy to determine sintering efficacy. Additionally, the parts will be compared to coupons printed with conventional methods to show that the USF AM technology shows superior elongation at break (EaB), with comparable ultimate tensile strength (UTS) and Young’s Modulus to laser sintered coupons. This is notable as conventional AM methods produce parts which usually compromise between EaB and modulus. The EaB of LAPS-printed parts is comparable to injection molding (IM) grade PA12, which is remarkable as IM grade PA12 powder normally has higher molecular weight and limited crystallinity. The reduced crystallinity of IM grade PA12 parts is thought to be due to the high shear rates during injection and fast cooling rates post-fabrication. Further, the USF LAPS parts show minimal or no detectable porosity. Porosity is an artifact of the sintering process which conventional techniques like laser sintering (LS) have little ability to mitigate, as higher energy wattages simply burn and degrade the polymer surface with insufficient time available for heat transfer and bulk melt flow. Porosity is documented as one of the leading causes of part failure and decreased mechanical properties in the literature, and as such the USF AM technology is in the process of being patented as of March, 2018. Chapters three through six will explore a phenomenon first noticed by clinicians at the James A. Haley Veterans Hospital. They observed that starch-thickened drinks for patients suffering from dysphagia became dangerously thinned down upon addition of the osmotic drug polyethylene glycol (PEG) 3350, marketed as Miralax®. Starch-based hydrocolloids are common thickeners used for patients with dysphagia, and so any incompatibility with such a ubiquitous drug as PEG 3350 poses an immediate danger. Patients with the disorder can suffer increased rates of aspiration-related pneumonia, incurring up to nearly a 60% fatality rate within a year. Chances for aspiration greatly increase for food items which are too inviscid to safely swallow. Rheology and FT-IR spectroscopy will be used to show that the breakdown of the starch network in aqueous solution is dependent upon the molecular weight of PEG. As the molecular weight of PEG is reduced to that of a small molecule (~300MW) from its large drug form (3350MW), the structure stabilizes and can resist shearing forces in a steady shear rheological experiment. Spectroscopy will show that PEG molecular weight also influences syneresis and the crystallinity of the starch hydrocolloid solutions. It is postulated that the molecular weight of PEG influences its miscibility in starch solutions, and its ability to interrupt the hydrogen bonding and entanglements which maintain the elastic framework which allow starch thickeners to impart viscosity and resist shearing forces. When this framework collapses, absorbed water is expelled as evidenced as a biphasic separation where water collects on top of the starch suspension. This was the phenomenon observed by the clinicians at the Veterans’ Hospital.