The construction industry is increasingly turning to the use of environmentally friendly materials in order to meet the sustainable aspect required by modern infrastructures. Consequently, for the last two decades, the expansion of this concept, and the increasing global warming have raised concerns on the extensive use of Portland cement due to the high amount of carbon dioxide gas associated with its production. The development of geopolymer concretes offers promising signs for a change in the way of producing concrete. However, to seriously consider geopolymer binders as an alternative to ordinary Portland cement, the durability of this new material should be evaluated in any comparative analysis. The main purpose of this study was to evaluate the durability characteristics of low calcium fly ash-based geopolymer concretes subjected to the marine environment, compared to ordinary Portland cement concrete with similar exposure. To achieve this goal, 8 molar geopolymer, 14 molar geopolymer and ordinary Portland cement concrete mixes were prepared and tested for exposure in seawater. Compressive strengths in the range of 2900 to 8700 psi (20-60 MPa) were obtained. The corrosion resistance performance of steel-reinforced concrete beams, made of these mixes, was also studied, using an accelerated electrochemical method, with submergence in salt water. The test results indicated that the geopolymer concrete showed excellent resistance to chloride attack, with longer time to corrosion cracking, compared to ordinary Portland cement concrete. / by Jean-Baptiste Edouard. / Thesis (M.S.C.S.)--Florida Atlantic University, 2011. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2011. Mode of access: World Wide Web.

The increasing integration of digital information with our daily lives has led to the rise of big data, cloud computing, and the internet of things. The growth in these categories will lead to an exponential increase in the required capacity for data centers and high performance computation. Meanwhile, due to bottlenecks in data access caused by the limited energy and bandwidth scalability of electrical interconnects, computational speedup can no longer scale with demand. A better solution is necessary in order to increase computational performance and reduce the carbon footprint of our digital future. People have long thought of photonic interconnects, which can offer higher bandwidth, greater energy efficiency, and orders-of-magnitude distance scalability compared to electrical interconnects, as a solution to the data access bottleneck in chip, board, and datacenter scale networks. Over the past three decades we have seen impressive growth of photonic technology from theoretical predictions to high-performance commercially available devices. However, the dream of an all-optical interconnection network for use in CPU, Memory, and rack-to-rack datacenter interconnects is not yet realized. Many challenges and obstacles still have to be addressed. This work investigates these challenges and describe some of the ways to overcome them. First we will first examine the pattern sensitivity of microring modulators, which are likely to be found as the first element in an optical interconnect. My work will illustrate the advantage of using depletion mode modulators compared to injection mode modulators as the number of consecutive symbols in the data pattern increases. Next we will look at the problem of thermal initialization for microring demultiplexers near the output of the optical interconnect. My work demonstrates the fastest achieved initialization speed to-date for a microring based demultiplexer. I will also explore an thermal initialization and control method for microrings based on temperature measurement using a pn-junction. Finally, we will look at how to control and initialize microring and MZI based optical switch fabrics, which is the second element found in a optical interconnect. Work here will show the possibility of switching high-speed WDM datastreams through microring based switches, as well as methods to deal with the complexities inherent in control and initialization of high-radix switch topologies. Through these demonstrations I hope to show that the challenges facing optical interconnects, although very real, are surmountable using reasonable engineering efforts.

Orientador: Edson Seizo Mori / Coorientador: Mário Tomazello Filho / Banca: Mário Luiz Teixeira de Moraes / Banca: José de Castro Silva / Resumo: Em melhoramento genético florestal, ensaios de campo baseados em progênies de polinização aberta são muito utilizados. Tais ensaios constituem importante estratégia na seleção de plantas e contribuem para o progresso do melhoramento no Brasil. Dessa forma, a presente pesquisa, objetiva formar um pomar de hibridação de Eucalyptus urophylla, para subsidiar a introgressão de genes de interesse na qualidade da madeira. Para isto, foram estimados os parâmetros genéticos em um teste de progênies de Eucalyptus urophylla S. T. Blake, nas idades de um, dois, três, cinco, e sete anos. Avaliaram-se quatro caracteres de interesse no melhoramento florestal: altura (m), diâmetro a altura do peito (DAP) (cm), volume individual das arvores (m³) e densidade aparente do lenho das árvores por densitometria de raios X (g cm-3). O delineamento experimental do teste, foi o de blocos casualizados com 77 tratamentos, seis repetições e seis plantas por parcela linear. O teste da razão de verossimilhança (LRT), revelou diferenças altamente significativas em nível de 1% de probabilidade (p<0,01) entre os caracteres avaliados, exceto para DAP a um ano, que foi significativa em nível de 5% de probabilidade (p<0,05) e não significativa, para densidade aparente, também a um ano. Os coeficientes de variação experimental (CVe), foram da ordem de 5% a 8% para altura e DAP, 12% a 13% para densidade aparente do lenho e 15% a 19% para volume. A herdabilidade média de progênies ( 2mhˆ ) foi superior a 0,83 para altura, 0,67 para DAP, 0,72 para volume e entre 0,65 e 0,84 para densidade aparente. A seleção, para volume aos sete anos de idade, entre tratamentos e dentro de parcelas, pelo indice multi efeito (IME), possibilitou a obtenção de 39 progênies para formação de: (i) um pomar de hibridação, com somente... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In forest genetic improvement, field trials based on pollinated progenies are widely used. These tests are an important strategy in the selection of plants and contribute to the progress of genetic improvement in Brazil. This research aims to create a hybridization orchard of Eucalyptus urophylla to support the introgression of genes that influence timber quality. For this, the genetic parameters in a progeny test of Eucalyptus urophylla S. T. Blake were estimated at the ages of one, two, three, five and seven years. Four forest genetic improvement traits were assessed: Height (m), Diameter at breast height (DBH) (cm), volume (m³) and wood density through X-ray densitometry (g cm-3). The trial was set out in randomized blocks (77 treatments, six repetitions and six plants per linear plot). The LRT test revealed significant differences at (p<0.01) level, between the evaluated characteristics, except for DBH at one year (p<0.05) and was not significant for wood density; the magnitude of the experimental variation coefficients (CVe) were in the order of 5 to 8% for height and DBH, and 15 to 19% for volume. The average heritability of the progenies ( 2 m h ˆ ) was greater than 0.83 for height, 0.67 and 0.72, for DBH and volume, respectively and between 0.65 and 0.84 for density. The selection based on Multi-Effect Index (MEI) within treatments and plots allowed to obtain 39 progenies to form: (i) a hybridization orchard, with one tree per progeny and a Genetic Gain (Gs) of 35.34%; (ii) recombination... (Complete abstract click electronic access below) / Mestre

M-Tech: Chemistry (Vaal University of Technology) / ABSTRACT The research was aimed to study the causes of excessive foaming in a waste water treatment plant. Although the activated sludge process has been adopted to treat this industrial waste water , lots of problems were experienced by the inhibitory effects of toxic compounds that are found in industrial effluents and the foaming stability that was very high. Industrial waste water treatment using sludge processes was found to be more challenging than the normal municipal waste water treatment although the principle is the same; the foaming tendencies were found to be more in industrial waste water. In this study the composition of influents to the waste water treatment plant and operating parameter’s effects on foaming tendencies were examined. The foaming potential in the plant was found to be chemically related due to high contamination of compounds such as phenols, which played a major role in formation of stable foam. It was recommended that there must be pretreatment of the incoming influents to minimize their impact to waste water treatment.

Conventional contact ultrasonic methods suffer from large variability, which is known to originate from a number of sources such as coupling variability, and the surface roughness at the transducer/specimen interface. The inherently small higherharmonic signals can be significantly influenced by the changes in contact conditions, especially in nonlinear ultrasonic measurements. For this reason, the noncontact generation and detection techniques are very attractive. This research first focuses on the optical generation of tone-burst surface acoustic waves in a metallic specimen. Two methods that use laser light as an optical source are compared for generating surface acoustics waves in the 5 MHz range. Both the shadow mask and diffraction grating are used to convert a laser pulse to a tone-burst signal pattern on the specimen. The generated signals are detected by a wedge transducer at a fixed location and then the harmonic contents in the generated signals and the repeatability of the methods are evaluated. Finally, the developed method is used to characterize the material nonlinearity of aluminum (Al 6061) and steel (A36). The results showed repeatable measurements for ablative signal excitation on aluminum.

Green chemistry principles have been applied to the enhancement of two industrial chemistry problems. An industrially used reaction to form alcohols from aldehydes and ketones, the Meerwein-Ponndorf-Verley reduction, was improved by introducing a new catalyst Al(OtBu)₃. Due to the lower state of aggregation of this catalyst versus the conventional Al(OiPr)₃ catalyst, reduction rates were found to be faster in both pure iPrOH and mixed solvent systems for three model compounds: benzaldehyde, acetophenone, and a complex, chiral ketone, (S)-CMK. This allowed for the successful implementation of two important milestones; lowering the amount of catalyst needed necessary to complete the reactions (an economic benefit and lower waste) and the conversion from traditional batch reactions to continuous flow (a processing benefit) whereby reactions can be scaled-out rather than scaled-up. Another industrially important field of research that was focused on was CO₂ capture. High energy demands from current CO₂ capture methods such as aqueous amine solvents, specifically from coal-fired power plant flue gas, led to the development of non-aqueous reversible ionic liquids based on silylated amines. Structural modifications of the substitution around the silicon atom, the length of the alkyl chain bonding the silicon and amine, branching along the alkyl backbone, and investigating secondary and primary amines within this class of silylated amines were completed. These amines were reacted with CO₂ and the CO₂ capacity, the ionic liquid viscosity, reversal temperature and reaction enthalpy were all considered as a function of structure. In all cases the capacity was found to be not only greater than that of monethanolamine, an industrial standard, but higher than theoretical predictions through the formation of carbamic acid. Viscosity, reversal temperature, and reaction enthalpy were all found to be tunable through structure. These modifications gave significant insight into the necessary direction for optimization of these solvents as energy-efficient replacements of current CO₂ capture technology.

Homogenous acid catalysts are prevalent throughout the chemical industry but all have the drawback of requiring post reaction neutralization and subsequent downstream removal of the product salt. The use of a base to neutralize the acid and the processing of the salt are ancillary to the process and the disposal of the salt is an environmental concern. The work presented here shows the use of alkylcarbonic acids, which form in situ with CO₂ pressure and neutralize on loss of CO₂ pressure rather than requiring a base. Thus CO₂ can be used to "switch" the acid on and off. The properties of alkylcarbonic acids are explored to gain understanding of the mechanisms by which they act. The acids are also used to catalyze the synthesis of α-pinene, methyl yellow, and benzyl iodide. These reactions are examples of common acid catalyzed reactions where this technology could be implemented. The second half of the work explores two other "switches". The first is using temperature to break an emulsion with a novel thermally cleavable surfactant. This technology has potential applications in a wide range of fields where surfactants are used including polymerization, oil recovery, and biosynthesis. The second is using CO₂ to liquefy a solid ionic compound to allow its use as a solvent. This would greatly increase the number of ionic species available for use in ionic liquid-CO₂ biphasic systems.

This study considered the potential use of lignin as possible renewable fuel and chemical feedstock source. Among the various polymers present in lignocellulosic biomass, the polyaromatic lignin is the one component that is most chemically similar to petroleum. However, it still contains a much larger amount of oxygen compared to crude oil. As such, two strategies were employed in this study: (1) studying the lignin depolymerization in the presence of high temperature and base catalysts; and, (2) employing hydrodeoxygenation as a means to decrease the O/C ratio in lignin-derived model compounds. The base-catalyzed depolymerization (BCD) of organosolv lignin was done in a 500-mL Monel Parr reactor at temperatures ranging from 165°C to 350°C. Complete solubilization of lignin derivatives was possible in the presence of NaOH and KOH, except at 350°C. NMR experiments revealed formation of oxidized groups (carboxylic and hydroxyl groups) as well as alkyl groups. On the other hand, the use of NH4OH showed N incorporation. Identified and quantified DCM-soluble monomeric compounds were at most 6% of the starting material and are mainly phenolic. This study revealed the apparent susceptibility of syringyl units over guaiacyl units in BCD. This could in turn guide the choice of substrate on which base-catalyzed depolymerization could be applied. Syringaldehyde was used as the starting material to study batch hydrodeoxygenation (HDO) using several non-cobalt/molybdenum based catalysts. A 50-ml Parr reactor was used, pressurized by 1000 psig of H2 and heated to 300°C. Nickel based catalysts (nickel phosphide, nickel oxide and nickel phosphate) as well as supported precious metals (Pt and Pd) were tested as HDO catalysts. Of the three O-containing functional groups of syringaldehyde, the aldehydic group was found to be the most susceptible. In the presence of the Al2O3-supported catalysts, the methyl groups liberated were found to be incorporated back into the aromatic ring, forming alkylated compounds. In the last section of this dissertation, hydrothermally synthesized supported Ni on mesoporous silica (MCF) and acid catalysts (HY and H-Al-MCF) were used for probing the effect of bifunctional metal-acid catalysis on phenol hydrodeoxygenation/hydrogenation. Catalyst configurations were varied from the previously studied wet-impregnated Pt/HY catalyst. Based on a hypothesis that coking catalyzed by the acidic zeolite in the wet impregnated Pt/HY catalyst was the main cause of catalyst deactivation and decreased phenol conversion, separately synthesized metal and acid catalyst systems were tested. Complete phenol conversion was sustained for at least three times longer in a continuous flow reactor operated at 200°C and 0.79 MPa of flowing H2. The separation of the metal and acid sites generated a tunable system capable of producing cyclohexanol, cyclohexane or cyclohexene at very high selectivities, even achieving 99% selectivities for cyclohexane.

Metal foams are lightweight structures and have large use in many components acting as impact energy absorbers. They have exceptional mechanical, thermal and acoustic properties. The design or selection of foam for packaging is done on the basis of impact loads to be sustained or energy to be absorbed. For transportation of nuclear material, metal foams can be used as a packaging material. It may be noted that apart from other qualification requirements, a package containing nuclear material, has to be certified for drop test. Foam can serve the purpose by providing proper cushioning. Metal foams are still under development and need to be accurately characterized in terms of their mechanical properties as well as cell morphology. The aim of this work is to develop, characterize and model foam using experiments and analysis. Aluminum foam has been developed by powder metallurgy technique and the effect of addition of varying amounts of Mg and Alumina on the strength and energy absorption has been studied. Foams of varying densities have also been developed. The reason for going for higher density is to obtain higher plateau stress. If a package is designed with lower density foam, it may become very bulky and even impractical. The characterization part of the work includes study of porosity distribution, cell wall structure, microscopy, SEM images, etc. Mechanical testing (uniaxial compression) was performed on foam samples to get load deflection curve of foams. Area under a given curve i.e. energy absorbed per unit volume has been compared for various compositions and densities. The analysis part of the work presents effect of specimen size on bulk properties of foam. 2D honeycomb and 3D cases have been discussed. To model the porosities, spherical cavities have been assumed. Uniaxial compression cases with different combinations of porosities have been analyzed. The properties like Young’s modulus, plateau stress, Poisson’s ratio, tangent modulus, etc. have been evaluated. The effect of variation in yield strength and tangent modulus of base material on foam has been studied. It appears that if the model is based on uniform porosity distribution, it may lead to lower bound values of physical properties and give conservative result. Although some of these trends have been observed in published literature, the current numerical study has generated additional information and insight.

Compared to the knowledge base for ordinary portland cement concrete (OPCC), relatively little information exists for calcium aluminate cement concrete (CACC), despite its existence for over 100 years. There is particularly a lack of knowledge related to early-age behavior of CACC, specifically volume change and cracking potential. To assess these early-age properties, two unique pieces of equipment were developed and employed: a rigid cracking frame and free deformation frame which enabled quantification of restrained stress generation and unrestrained autogenous deformation, respectively. These two pieces of equipment employed active temperature control and allowed a wide range of isothermal and realistic temperature conditions to be imposed upon hydrating cementitious samples. Match-cured samples (i.e. identical temperature curing to that in the frames) enabled the quantification of mechanical property development. Samples cured at discrete isothermal temperatures up to 30 °C developed tensile forces in the rigid cracking frame and exhibited shrinkage phenomena in the free deformation frame. At temperatures above 30 °C, the converse was true and significant compressive forces developed in restrained testing and expansion was observed in unrestrained testing. It was found that this was a direct result of microstructural development related to the formation of metastable phases (associated with shrinkage) and stable phases (expansion as a result of conversion from metastable to stable phases). Proper use of this material must take into account behavior associated with both types of hydrate assemblages, metastable and stable. Realistic time-temperature histories were also investigated based on field-scale concrete cast as part of this research project. It was found that volume change at earlyage was dominantly controlled by thermal history. Furthermore, it was not simply the maximum temperature reached, but the rate of temperature rise during hydration and the resulting duration of time spent at high temperature that profoundly influenced volume change and property development. The research described in this dissertation represents a significant advancement of the state-of-knowledge of this unique material and has further elucidated the role of temperature during hydration of CACC. / text