The objective of this work is to examine the effect of cement chemistry and physical properties on activation energy. Research efforts indicated that time dependent concrete properties such as strength, heat evolution, and thermal cracking are predictable through the concept of activation energy. Equivalent age concept, which uses the activation energy is key to such predictions. Furthermore, research has shown that Portland cement concrete properties are affected by particles size distribution, Blaine fineness, mineralogy and chemical composition. In this study, four Portland cements were used to evaluate different methods of activation energy determination based on strength and heat of hydration of paste and mortar mixtures. Moreover, equivalency of activation energy determined through strength and heat of hydration is addressed. The findings indicate that activation energy determined through strength measurements cannot be used for heat of hydration prediction. Additionally, models were proposed that are capable of predicting the activation energy for heat of hydration and strength. The proposed models incorporated the effect of cement chemistry, mineralogy, and particle size distribution in predicting activation energy.

This thesis focus on the analysis of spin-lattice NMRD relaxation profilesmeasured in various complex systems such as proteins, zeolites and ionicliquids. Proton, deuterium and fluoride T1-NMRD relaxation profiles wereobtained from a fast-field cycling (FFC) instrument. It is found that alsopossible to obtain NMRD profiles from the molecular dynamics (MD)simulation trajectories. NMRD Profiles were analyzed by using differentrelaxation models, such as the Solomon-Bloembergen-Morgan (SBM) theoryand the Stochastic Liouville (SL) theory. Paper I described the hydration of protein PrxV obtained from a MDsimulation, and compared with the picture emerges from an analysis byusing a generally accepted relaxation model [appendix C]. The result showsthat the information from NMRD analysis is an averaged picture of watermolecules with similar relaxation times; and the MD simulations containsinformation of all types of interested water molecules with differentresidence times. In paper II NMRD profiles have been used to characterize the hydration ofthe oxygen-evolving complex in state S1 of photosystem II. NMRDexperiments were performed on both intact protein samples and Mndepletedsamples, and characteristic dispersion difference were foundbetween 0.03 MHz to 1 MHz; approximately. Both the SBM theory and theSL theory have been used to explain this dispersion difference, and it isfound that this is due to a paramagnetic enhancement of 1-2 water moleculesnearby ~10 Å from the spin center of the Mn4CaO5 cluster. The result showsthe reorientation of the molecular cluster is in μs time interval. Whencompare these two theories, the SL theory presented a better interpretationbecause parameters obtained from the SBM theory shows they didn’t fulfilthe presupposed perturbation criterion (the Kubo term). Paper III deals with the water dynamics in the restricted/confined spaces inthe zeolite samples (H-ZSM-5 and NH4-ZSM-5) and obtained by proton anddeuterium spin-lattice NMRD profiles. The results show that the spin-latticeNMRD can be used to characterize various zeolites. The temperature has aweak effect on the relaxation rate R1, but the change of different counter ionsmay change the hydration and the translational diffusion pores and givedifferent R1. Proton and fluoride NMRD profiles and MD simulations were both used tostudy the dynamics of BMIM[PF6] in paper IV. Results indicate the reorientation of the molecules are in the ns time regime, and the effectivecorrelation time obtained from 1H and 19F are the same. From the MDsimulation it is found the reorientation of [PF6]- ions is much faster (in ps)compare with BMIM+ ion which moves in the ns time range. With previous results, the FFC NMRD profiles are indeed very informativetools to study the molecular dynamics of complex systems. The MDsimulation can be used as a complementary method to obtain detailedinformation. By combine these two methods, it provide a more colorfulpicture in the study of protein hydration and liquid molecular dynamics.

Raman spectroscopic observations of the characteristics and dissociation of methane hydrate were carried out on hydrates synthesized in silica sands with particle sizes of 53-75 μm, 90-106 μm, 106-150 μm, and 150-180 μm. The results obtained indicate that methane hydrates formed in silica sands had similar characteristics regarding cage occupancy and hydration number (5.99) to bulk hydrate, indicative of no influence of particle size on hydrate composition. During hydrate dissociation, the change in average intensity ratio of large to small cages were generally consistent with that of bulk hydrate but dropped dramatically after a certain time, and this turning point seems to be related to the particle size of silica sands.

The dedicated gas hydrate coring/drilling program was carried out under National Gas Hydrate Program (NGHP) in four Indian offshore areas (Kerala-Konkan, Krishna- Godavari, Mahanadi and Andman) during 28th April to 19th August, 2006. During NGHP Expedition 01, 2006, total of 39 holes were drilled/cored at 21 sites in these areas. The gas hydrates have been found to be present in large quantities in Indian offshore areas particularly in KG basin. More than 130 confirmed solid gas hydrate samples were recovered during this hydrate coring/drilling program. The laboratory analysis was carried out on the 34 natural gas hydrate samples recovered from offshore India. The gas hydrate characterization was carried out using the microscopic techniques such as Raman, 13C NMR and XRD for its structure, cavity occupancy and hydration number. The gas hydrates occur in grayish green fine sediments, gray medium sands and white volcanic ash as pore-filling hydrate and massive hydrates in fractured shale/clay. The visible massive gas hydrates developed especially at Site NGHP 1-10B, 10C, 10D and 21A in K G area. The structures of the gas hydrates in the studied samples are all sI, with methane as the dominant guest molecule. The occupancy of methane in large cage is almost complete, while it is variable in the small cage (0.75 to 0.99). The hydration number is 6.10 ± 0.15 for most of the hydrates in the samples studied. This paper presents the results of the laboratory analysis on the structural characterization of natural gas hydrates in core samples from offshore India.

This research is part of an ongoing project to create gypsum wallboards with enhanced fire resistance. The main goal of this research is to better understand the dehydration properties of calcium sulfate dihydrate, and the hydration of calcium sulfate hemihydrate as well as anhydrous calcium sulfate. The lab-scale kinetics of these processes were studied using thermogravimetric analysis and sorption analysis. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were used to characterize the products from different processes. In addition to the instrumental studies, small batches were handled in ovens and liquid slurries to better mimic the real world processing of these materials. The effects of temperature, time and humidity were investigated to determine their influence on the kinetics of dehydration/hydration of different hydration forms of calcium sulfate.

Fluorescence techniques are being considered for the detection and identification of bacterial spores. This thesis sets out to empirically characterize the detailed autofluorescence spectroscopic properties of spores and their target molecules. The multiwavelength fluorescence studies from a unique endogenous biomarker, dipicolinic acid (DPA) and its calcium salt (CaDPA) in bacterial spores are found to be useful for fluorescence characterization of spores. A systematic determination of the fluorescence profile of the major chemical components of Bacillus spores and the effect of UV irradiation on them has been performed in dry samples, wet paste and in aqueous solution. The thesis applies reliable tools for accurately describing complex nature of spectral profile from bacterial spores, and for interpreting and identifying their spectral properties. We show that multiwavelength fluorescence technique combined with Principal Component Analysis (PCA) clearly indicates identifiable grouping among dry and wet Bacillus spore species. Differences are also observed between dried, wet and redried spores, indicating the stark effect of hydration on fluorescence fingerprints. The study revealed that changes in fluorescence of spores due to hydration/drying were reversible and supports a recent model of a dynamic and dormant spore structure. The spectra were analysed with PCA, revealing several spectroscopically characteristic features enabling spore species separation. The identified spectral features could be attributed to specific spore chemical components by comparing the spore sample signals with spectra obtained from the target molecules. PCA indicated underlying spectral patterns strongly related to species and the derived components were correlated with the chemical composition of the spore samples. More importantly, we examined and compared the fluorescence of normal spores with a mutant of the same strain whose spores lack DPA. We discovered that the dramatic fluorescence enhancement of Bacillus spores can be caused by UV irradiation in the spectral region of this unique biomarker without any pre treatment. Differences between spectra of spores, spore strains and other biological samples are very marked and are due to the dominance of the dipicolinate features in the spore spectra. This could lead to a cheap, more sensitive, faster and reagentless bacterial spore detector.

No description available.

Durant la phase de construction des puits pétrolier, le ciment est coulé dans l'espace annulaire entre le cuvelage et la roche environnante. La gaine de ciment a pour but de tenir le cuvelage, garantir l'étanchéité des puits pétroliers, ou des réservoirs de stockage de CO2, et de protéger le cuvelage de la corrosion. Au cours de la vie du puits, cette gaine de ciment est soumise tout le long du puits à des sollicitations thermiques et mécaniques qui varient au cours du temps et qui peuvent modifier ses propriétés et altérer son étanchéité. L'objet de cette thèse est d'étudier l'effet de la température et des contraintes sur les propriétés mécaniques de la pâte de ciment en cours de prise et de la pâte de ciment durcie. L'approche est basée sur une étude expérimentale qui combine des essais calorimétriques, des mesures de vitesse des ondes et des essais oedométriques avec le système des cellules STCA (Slurry To Cement Analyzer) sur le ciment en cours de prise ainsi que des essais de compression uniaxiale et triaxiale sur la pâte de ciment durcie. Les résultats expérimentaux ont montré que la température et la pression accélèrent la cinétique d'hydratation et que la température affecte significativement les propriétés élastiques du matériau tandis que la pression ne les influence pas pour une gamme de pression limitée à 20MPa. Une modélisation de la cinétique d'hydratation associée à une technique d'homogénéisation est proposée afin d'interpréter les essais. On a mis aussi en évidence que lorsque la prise se fait sous contraintes mécaniques, des déformations irréversibles peuvent se développer dans la pâte de ciment, ce qui peut conduire à la formation d'un micro-annulaire entre la gaine ciment, le cuvelage et la formation géologique. Le comportement différé de la pâte de ciment durcie a été étudié à partir d'essais de fluage uniaxiaux et d'essais de compression isotrope. Les essais ont mis en évidence que le fluage sous chargement uniaxial est plus important pour un ciment hydraté à une température plus élevée, ce qui est attribué à une microstructure plus hétérogène. Un modèle visco-endommageable permettant de reproduire les phases de fluage primaire et tertiaire a été développé. Les essais de compression isotrope drainés et non-drainé isothermes sous forte contrainte ont montré un comportement différé avec hystérésis lors de cycles décharge-recharge. Ces essais ont été analysés à partir d'un modèle de comportement poro-visco-plastique. Le comportement élastoplastique à court terme a été abordé à l'aide des essais triaxiaux sous chargement déviatorique drainé. Ces essais ont mis en évidence que la température d'essai affecte fortement la surface de charge initiale et les déformations tandis qu'elle ne modifie pas significativement la surface de rupture. Un modèle de plasticité avec une surface de charge fermée et un écrouissage dépendant des déformations plastiques accumulées a été développé pour décrire ces essais. Enfin, une étude préliminaire sur les effets des cycles mécaniques et thermiques a été menée. Des cycles thermiques ne dépassant pas la température d'hydratation ne semblent pas affecter les propriétés mécaniques du matériau. Cependant, une dégradation très rapide avec le nombre de cycles mécaniques a été mise en évidence lorsque la contrainte dépasse 60% de la résistance en compression simple

Cobalt is a commonly known sensitiser in industrial settings and has been classified by the IARC as a possible group (2B) human carcinogen. Workers at a South African base metal refinery are potentially exposed to cobalt in the cobalt packaging area. The respiratory and dermal exposure to cobalt is a possible health risk. Quantifying the exposures levels assists in determining the degree of the risk as well as the management thereof. The objectives of this study were to assess dermal and respiratory exposure of workers at a cobalt packaging area and to assess their skin condition by measuring transepidermal water loss (TEWL) and skin hydration indices. The skin hydration index was measured on the back of the hand, forehead, wrist and palm at the start, during and end of the shift. The TEWL index was measured at the start and end of the shift on the same areas as the hydration index. Ghostwipes was chosen as preferred wipe sampling media to collect dermal and surface samples. Wipe samples were also taken on suspected contaminated workplace surfaces. Respiratory samples were taken by using the Institute of Occupational Medicine (IOM) inhalable aerosol sampler at a flow rate of 2 l/min. Wipes and respiratory samples were analysed for cobalt according to NIOSH method 9102 using inductively coupled plasma–atomic emission spectrometry (ICP–AES). The hydration indices indicated that worker’s skin are slightly dry to normal at the beginning of the shift. Hydration on the wrist increased significantly during the shift. TEWL indices increased significantly on the back of the hand, wrist and forehead during the shift. TEWL indices of the palm showed a low barrier function before the shift and deteriorated further to a very low barrier function at the end of the shift. Significant dermal cobalt loading occurred on the back of the hand, forehead, wrist and palm during the shift. The palm was the most exposed and the forehead least. The barrier function of the skin is most likely to be affected by exposure to cobalt. The skin condition of workers put them at greater risk to develop adverse health effects of cobalt. Workplace surfaces were contaminated with cobalt. Airborne cobalt was visible at different working stations. Cobalt exposure is due to numerous sources in the packaging area, thus contributing to the dermal exposure. Respiratory exposure exceeded the 8 hour occupational exposure limit for most of the workers. The guidance limit for short term exposure was exceeded by half of the workers. It is important to minimise the exposure to cobalt in packaging area. Manifestation of the adverse health effects are usually not visible in the short term, the necessary precautions have to be taken to protect the workers. / Thesis (M.Sc. (Occupational Hygiene))--North-West University, Potchefstroom Campus, 2011.

Cobalt is a commonly known sensitiser in industrial settings and has been classified by the IARC as a possible group (2B) human carcinogen. Workers at a South African base metal refinery are potentially exposed to cobalt in the cobalt packaging area. The respiratory and dermal exposure to cobalt is a possible health risk. Quantifying the exposures levels assists in determining the degree of the risk as well as the management thereof. The objectives of this study were to assess dermal and respiratory exposure of workers at a cobalt packaging area and to assess their skin condition by measuring transepidermal water loss (TEWL) and skin hydration indices. The skin hydration index was measured on the back of the hand, forehead, wrist and palm at the start, during and end of the shift. The TEWL index was measured at the start and end of the shift on the same areas as the hydration index. Ghostwipes was chosen as preferred wipe sampling media to collect dermal and surface samples. Wipe samples were also taken on suspected contaminated workplace surfaces. Respiratory samples were taken by using the Institute of Occupational Medicine (IOM) inhalable aerosol sampler at a flow rate of 2 l/min. Wipes and respiratory samples were analysed for cobalt according to NIOSH method 9102 using inductively coupled plasma–atomic emission spectrometry (ICP–AES). The hydration indices indicated that worker’s skin are slightly dry to normal at the beginning of the shift. Hydration on the wrist increased significantly during the shift. TEWL indices increased significantly on the back of the hand, wrist and forehead during the shift. TEWL indices of the palm showed a low barrier function before the shift and deteriorated further to a very low barrier function at the end of the shift. Significant dermal cobalt loading occurred on the back of the hand, forehead, wrist and palm during the shift. The palm was the most exposed and the forehead least. The barrier function of the skin is most likely to be affected by exposure to cobalt. The skin condition of workers put them at greater risk to develop adverse health effects of cobalt. Workplace surfaces were contaminated with cobalt. Airborne cobalt was visible at different working stations. Cobalt exposure is due to numerous sources in the packaging area, thus contributing to the dermal exposure. Respiratory exposure exceeded the 8 hour occupational exposure limit for most of the workers. The guidance limit for short term exposure was exceeded by half of the workers. It is important to minimise the exposure to cobalt in packaging area. Manifestation of the adverse health effects are usually not visible in the short term, the necessary precautions have to be taken to protect the workers. / Thesis (M.Sc. (Occupational Hygiene))--North-West University, Potchefstroom Campus, 2011.