In today’s energy sector, it has been observed a revolutionary increase in shale gas recovery induced by reservoir fracking. So-called unconventional reservoirs became profitable after introducing a well stimulation technique. Some of the analysts expect that shale gas is going to expand worldwide energy supply. However, there is still a lack of an efficient as well as accurate modeling techniques, which can provide a good recovery and production estimates. Gas transports in shale reservoir is a complex process, consisting of slippage effect, gas diffusion along the wall, viscous flow due to the pressure gradient. Conventional industrial simulators are unable to model the flow as the flow doesn’t follow Darcy’s formulation. It is significant to build a unified model considering all given mechanisms for shale reservoir production study and analyze the importance of each mechanism in varied conditions. In this work, a unified mathematical model is proposed for shale gas reservoirs. The proposed model was build based on the dual porosity continuum media model; mass conservation equations for both matrix and fracture systems were build using the dusty gas model. In the matrix, gas desorption, Knudsen diffusion and viscous flow were taken into account. The model was also developed by implementing thermodynamic calculations to correct for the gas compressibility, or to obtain accurate treatment of the multicomponent gas. Previously, the model was built on the idealization of the gas, considering every molecule identical without any interaction. Moreover, the compositional variety of shale gas requires to consider impurities in the gas due to very high variety. Peng-Robinson equation of state was used to com- pute and correct for the gas density to pressure relation by solving the cubic equation to improve the model. The results show that considering the compressibility of the gas will noticeably increase gas production under given reservoir conditions and slow down the production decline curve. Therefore, for a more accurate prediction of shale gas production, it is crucial to consider compressibility behavior of the gas.

No description available.

Recently laser cooling of semiconductors has received renewed attention, with the hope that a semiconductor cooler might be able to achieve cryogenic temperatures. In order to study semiconductor laser cooling at cryogenic temperatures, it is crucial that the theory include both the effects of excitons and the electron-hole plasma. In this dissertation, I present a theoreticalanalysis of laser cooling of bulk GaAs based on a microscopic many-particle theory of absorptionand luminescence of a partially ionized electron-hole plasma.This theory has been analyzed from a temperature 10K to 500K. It is shown that at high temperatures (above 300K), cooling can be modeled using older models with a few parameter changes. Below 200K, band filling effects dominate over Auger recombination. Below 30K excitonic effects are essential for laser cooling. In all cases, excitonic effects make cooling easier then predicted by a free carrier model.The initial cooling model is based on the assumption of a homogeneous undoped semiconductor. This model has been systematically modified to include effects that are present in real laser cooling experiments. The following modifications have been performed. 1) Propagation and polariton effects have been included. 2) The effect of p-doping has been included. (n-doping can be modeled in a similar fashion.) 3) In experiments, a passivation layer is required to minimize non-radiative recombination. The passivation results in a npn heterostructure. The effect of the npn heterostructure on cooling has been analyzed. 4) The effect of a Gaussian pump beam was analyzed and 5) Some of the parameters in the cooling model have a large uncertainty. The effect of modifying these parameters has been analyzed.Most of the extensions to the original theory have only had a modest effect on the overall results. However we find that the current passivation technique may not be sufficient to allow cooling. The passivation technique currently used appears to be very good at low densities, but loses some of it's effectiveness at the moderately high densities required for laser cooling. We suggest one possible solution that might enable laser cooling. If the sample can be properly passivated, then we expect laser cooling to be possible.

No description available.

The transdermal delivery of drugs has a lot of advantages above other routes of delivery, such as the avoidance of first-pass hepatic and intestinal metabolism, the non-invasive infusion of drugs, etc. However, the transdermal delivery of drugs, especially hydrophilic drugs, is limited due to the lipophilic nature of the stratum corneum. Methotrexate is a folic acid antagonist with antineoplastic activity and is used for the treatment of psoriasis and Kaposi's sarcoma. The permeation of methotrexate through the skin for systemic use is however limited due to its high molecular weight, the fact that it is mainty dissociated at physiological pH and its hydrophilic nature (Alvarez-Figueroa et al.. 2001). Thus the aim of my study was to enhance the permeation of methotrexate with the use of terpene. Terpenes are lipophilic in nature and have Log P values of around 2-4 (Godwin & Michniak, 1999). These characteristics make them excellent candidates as penetration enhancers. Terpenes are not only used for penetration enhancers, but in a huge number of other products, such as aromatherapeutic oils. For this reason the permeation of the terpenes through human skin and the effect of methotrexate on this permeation were also determined. The following enhancers were used in this study: menthol, menthone. isomenthol, limonene, B-myrcene, a-pinene and 1,8-cineole Five different sets of experiments were done in this study: a) a control experiment with methotrexate in the absence of the terpenes without ethanol; b) a control experiment with methotrexate in the absence of the terpenes with ethanol: c) experiments with methotrexate in the presence of the terpenes; d) control experiments with the terpenes in the absence of methotrexate and e) experiments with tile terpenes in the presence of methotrexate. For this study only human female abdominal skin was used. A saturated solution of methotrexate in water:propylene glycol (50:50) with a pH between 4 and 5 (Vaidyanathan et al., 1985) was used as the model drug and the receptor phase was PBS-buffer (pH=74) and water:ethanol (50:50) for HPLC and GC analysis respectively. The dilfusion apparatus used consisted of Vertical Franz diffusion cells with a capacity of 2 ml and a diffusion area of 1.075 cm2. The cells were placed in a water bath (+- 37 "C) on magnetic stirrers for the duration of the experiment. After the receptor phase was placed in the receptor compartment the cells were equilibrated for an hour before putting 25 ul of a 5% terpene solution in absolute ethanol on the skin in the donor compartment. This was left for half and hour to allow evaporation of the ethanol. The saturated solution of the methotrexate was now placed on the skin in the donor compartment. The experiments for methotrexate stretched over a period of 12 hours and samples were collected every 2 hours. The terpene experiments were performed over a 24-hour period and samples were taken at 2,4,6,12 and 24 hours. The concentration methotrexate permeated was determined by using HPLC-analysis and terpenes by using GC-analysis. The flux (ug/cm2/h), kp(cm/h), lag time (h) and enhancement ratio were calculated to compare the methotrexate permeation in the control and actual experiments. The results showed that a-pinene, B-myrcene and isomenthol enhanced the permeation of methotrexate most, although all the terpenes had an enhancing effect. They produced a 4- fold increase in the flux values of methotrexate. Due to the fact that the terpene experiments were only a semi-quantitative evaluation only the percentage terpenes that permeated was calculated. The experiments were done on all the terpenes except apinene. All the terpenes permeated the skin with menthol having the highest permeation. The results also showed that methotrexate did have an effect on the terpene permeation. Menthone and menthol's permeation was higher in the presence of methotrexate, while the other terpenes had a higher permeation in the absence of methotrexate. The reason for this is not clear. In conclusion, the study revealed that the enhancers used did have an enhancing effect on methotrexate permeation. This could be due to the extraction or disruption of lipids by the terpenes (Zhoa & Singh, 2000) or an increase in diffusivity and partitioning. The terpene experiments also showed that the terpenes do permeate the skin and that methotrexate does have an effect on this permeation. / Thesis (M.Sc.)--North-West University, Potchefstroom Campus, 2004.

Previous studies have attempted to probe the structure of ultra-thin Nickel silicide films as they evolve in the manufacturing process with limited success. These studies have used ultra-thin Nickel silicide films that were quenched during the manufacturer's annealing process at select temperatures. This study aims to determine the structure of quenched ultra-thin Ni-Si films using Grazing Incidence X-Ray Absorption Near Edge Spectroscopy (GI-XANES) and ab-initio calculations (FDMNES). Successful calculations were prepared for the δ and θ Ni2Si phases, as well as the Ni3Si2, NiSi and NiSi2 phases. The GI-XANES experimental data was taken at the Canadian Light Source, at the Hard X-Ray Microanalysis Beamline (HXMA). XANES and FDMNES are used to identify two phases of the ultra-thin films: the as-deposited phase as a low-ordered Ni3Si2 phase, and the epitaxial NiSi2 phase was found in samples annealed past 400˚C.

No description available.

Bentonite clays have long been used as additives in animal feed, aiming to improve pellet quality and prevent caking. Certain bentonites are also capable of deactivating aflatoxin B_(1) (AfB_(1)) in feed by adsorption, therefore, detoxifying the feed. However, a 10–fold difference in adsorption capacity has been observed among selected bentonites. The major mineralogical and chemical properties of smectites in determining their adsorption capacities for AfB_(1) are still poorly understood. Improved knowledge of the key controlling factors of aflatoxin adsorption to bentonite clays is needed to guide the selection, modification, and application of the clays as aflatoxin binders. The objective of this study was to test a hypothesis that a smectite's selectivity and adsorption capacity for aflatoxin was mainly determined by the size matching requirement on interlayer surface domains and the aflatoxin molecules. Three approaches were used to vary the size of nanometer-scaled nonpolar domains in the interlayer of smectites: 1) exchanging interlayer cations, 2) selecting natural bentonites with different cation exchange capacities (CEC), and 3) reducing charge density of a high CEC smectite. Six bentonites were fractionated, with their major mineralogical and chemical properties determined. Clay suspensions saturated with different cations were tested for aflatoxin adsorption. Some aflatoxin-smectite complexes were prepared and analyzed with FTIR and XRD. AfB_(1) adsorption isotherms were fitted with Langmuir, modified Langmuir with adsorption dependent affinity, and exponential Langmuir models. Divalent exchange cations with low hydration energy in general resulted in a much higher adsorption capacity and affinity for all six natural bentonite clays. Cations with smaller hydration radii tended to further enhance the adsorption process for aflatoxin on smectites. Charge density of smectite had shown significant effects on the adsorption capacity, affinity, and the isotherm shape. Aflatoxin adsorption isotherms on the six natural smectites and the CEC-reduced 5OK samples by Hofmann and Klemen effects suggested that there is an optimal CEC range between 80~110 cmol(+)/kg for the best aflatoxin binding smectites. When the smectite has a CEC within this range, the mineral has the highest affinity and adsorption capacity for AfB_(1). The aflatoxin adsorption results after cation exchange treatment, selection of different CEC smectites, and the CEC reduction on 5OK confirmed the importance of size and polarity matching on the nanometer scale in smectites’ adsorption for AfB_(1). All clay samples tested in this study were capable of adsorbing aflatoxin into interlayers, and the charge density seemed to have no effect on bonding strength.

No description available.

It is widely accepted that the initial event that significantly influences biocompatibility is the nearly instantaneous adsorption of proteins from biological fluids onto the biomaterial surface. For blood-contacting devices, the complex layer of adsorbed plasma proteins is generally unfavourable and leads to major complications, including thrombus formation, inflammatory tissue responses, and microbial infections. Furthermore, protein interaction with passive films on metallic biomaterial surfaces may contribute to enhanced in vivo corrosion. To gain a better understanding of this phenomenon, the present thesis investigated the fundamental aspects of the interaction of the serum protein fibrinogen with a medical-grade stainless steel 316LVM surface using electrochemical and IR spectroscopy techniques. Aspects of this interaction included the thermodynamics and kinetics of fibrinogen adsorption, the effect of fibrinogen adsorption on the corrosion behavior of 316LVM stainless steel, and the conformational changes of fibrinogen upon its adsorption onto the stainless steel surface. / It was shown that fibrinogen readily adsorbs onto the 316LVM stainless steel surface. Increases in the bulk protein concentration resulted in a corresponding increase of the surface coverage, a dependence that was described by the Langmuir isotherm. Large, negative values of the calculated Gibbs energy of adsorption indicated a highly spontaneous and strong adsorption of fibrinogen onto the 316LVM stainless steel at all investigated temperatures. Although the adsorption process was shown to be endothermic under the applied experimental conditions, the primary driving force for the adsorption process was found to be the positive entropy gain that arises from structural loss and/or rearrangement of the protein upon adsorption, as well as dehydration of the protein and stainless steel surface during the adsorption process. Kinetic measurements indicated that fibrinogen adsorption occurs rapidly. / It was determined that for short contact times (1 hour), the addition of fibrinogen to the electrolyte enhanced the corrosion rate of the 316LVM stainless steel at the open circuit potential. For longer contact times (24 hours), an increase in the polarization resistance values was obtained, indicating an enhanced corrosion resistance of the material. It was postulated that the protein was not capable of complexing the well-stabilized passive film, and instead remained adsorbed to form a protective barrier to diffusion of oxygen-containing species from the electrolyte to the stainless steel surface. / The secondary structure of the surface-adsorbed fibrinogen molecules was investigated by modeling the experimental PM-IRRAS spectra. It was shown that the protein lost a certain extent of its secondary structure upon adsorption to the steel surface. Fibrinogen molecules adsorbed from more dilute solutions were also shown to possess a lower alpha-helical content than those adsorbed from more concentrated solutions, suggesting they laid on the stainless steel surface in a more linear configuration.