The goal of this project was to study some unexplored optical and magneto-optical properties of the newest member of III-V ferromagnetic structures, InMnSb, as well as InSb films and InSb/AlInSb quantum wells. The emphasis was on dynamical aspects such as charge and spin dynamics in order to address several important issues of the spin-related phenomena. The objectives in this project were to: 1) understand charge/spin dynamics in NGS with different confinement potentials, 2) study phenomena such as interband photo-galvanic effects, in order to generate spin polarized current, 3) probe the effect of magnetic impurities on the spin/charge dynamics. This thesis describes three experiments: detection and measurement of spin polarized photocurrents in InSb films and quantum wells arising from the circular photogalvanic effect, and measurements of the carrier and spin relaxation in InSb and InMnSb structures by magneto-optical Kerr effect and differential transmission. The samples for our studies have been provided by Prof. Heremans at Virginia Tech, Prof. Santos at the University of Oklahoma, and Prof. Furdyna at the University of Notre Dame. / Ph. D.

Water chemistry and fluid velocity are factors that can perpetuate certain types of non-uniform pitting corrosion in copper tube, specifically in waters with high chlorine and a high pH. These two parameters can further act synergistically to alter pitting propensities in copper pipes subjected to this type of water. A preliminary short-term experiment considered pitting propensity in copper pipe as a function of water chemistry. This study used a water chemistry that had been documented to promote and sustain pitting in copper tube that further developed into fully penetrating pinhole leaks. Modifications to this base water chemistry found that dosing a chloramine disinfect (rather than free chlorine) or the addition of silica greatly reduced corrosion activity and pitting propensity on copper pipes. In another short-term experiment, copper pitting propensity was considered as a function of fluid velocity. A number of different fluid velocities were tested in several different pipe diameters using the same documented pitting water. Velocity was observed to significantly increase pitting propensity in all pipe diameters considered. At the highest fluid velocity tested (11.2 fps) a pinhole leak formed in ¼â tubing after only 2 months of testing. Larger pipe diameters were also found to increase the likelihood of forming deeper pits on the pipe surface at the same fluid velocity. Chlorine was a driving factor in corrosion for preliminary tests conducted using this pitting water. The reduction of chlorine to chloride is believed to be the primary cathodic reaction limiting the overall rate of corrosion in this type of water. As such, a subsequent study considered the relationship between the rate of chlorine reduction and corresponding corrosion activity. Chlorine reduction or demand rates were found to be good indicators for pitting propensity and corrosion activity for this particular type of water. All preceding work led to the development and design of a large scale, long-term, copper pitting study. A matrix of 21 unique conditions tested various water chemistries, flow conditions, corrosion inhibitors, and galvanic connections of copper pipes to other metallic plumbing materials. The severity of pitting corrosion was observed to be dramatically decreased by lower free chlorine residual concentrations, high alkalinity, and sufficient doses of copper corrosion inhibitors such as natural organic matter, silica, and orthophosphate. Pitting severity was consequently observed to increase at a low alkalinity, indicating that this parameter has a significant effect on corrosion reactions. Furthermore, the addition of aluminum solids to the base pitting water chemistry dramatically increased the formation of tubercle mounds on the inside of the copper pipes in contact with the waster. Aluminum solids have been observed to be a vital constituent for sustaining pit growth in this specific water at lower pHs, however, the role of this constituent at the high pH levels tested in this study was previously unknown. From simple visual observation, aluminum solids appear to increase the aggressiveness of this water even at higher pHs. / Master of Science

Corrosion of drinking water distribution systems can cost water utilities and homeowners tens of billions of dollars each year in infrastructure damage, adversely impacting public health and causing water loss through leaks. Often, seemingly innocuous choices made by utilities, plumbers, and consumers can have a dramatic impacts on corrosion and pipeline longevity. This work demonstrated that brass pipe connectors used in partial lead service line replacements (PLSLR) can significantly influence galvanic corrosion between lead and copper pipes. Galvanic crevice corrosion was implicated in a fourfold increase in lead compared to a traditional direct connection, which was previously assumed to be a worst-case connection method. In field sampling conducted in two cities, a new sampling method designed to detect particulate lead risks demonstrated that the choice of flow rate has a substantial impact on lead-in-water hazards. On average, lead concentrations detected in water at high flow without stagnation were at least 3X-4X higher than in traditional regulatory samples with stagnation, demonstrating a new 'worst case' lead release scenario due to detachment of lead particulates. Although galvanized steel was previously considered a minor lead source, it can contain up to 2% lead on the surface, and elevated lead-in-water samples from several cities were traced to galvanized pipe, including the home of a child with elevated blood lead. Furthermore, if both galvanized and copper pipe are present, as occurs in large buildings, deposition corrosion is possible, leading to both increased lead exposure and pipe failures in as little as two years. Systematic laboratory studies of deposition corrosion identified key factors that increase or decrease its likelihood; soluble copper concentration and flow pattern were identified as controlling factors. Because of the high copper concentrations and continuous flow associated with mixed-metal hot water recirculating systems, these systems were identified as a worst-case scenario for galvanic corrosion. Deposition corrosion was also confirmed as a contributing mechanism to increased lead release, if copper pipe is placed before a lead pipe as occurs in partial service line replacements. Dump-and-fill tests confirmed copper solubility as a key factor in deposition corrosion impacts, and a detailed analysis of lead pipes from both laboratory studies and field tests was consistent with pure metallic copper deposits on the pipe surface, especially near the galvanic junction with copper. Finally, preliminary experiments were conducted to determine whether nanoparticles from novel water treatment techniques could have a negative impact on downstream drinking water pipeline infrastructure. Although increases in the corrosion of iron, copper, and stainless steel pipes in the presence of silver and carbon nanomaterials were generally small or non-existent, in one case the presence of silver nanoparticles increased iron release from stainless steel by more than 30X via a localized corrosion mechanism, with pitting rates as high as 1.2 mm/y, implying serious corrosion consequences are possible for stainless steel pipes if nanoparticles are present. / Ph. D.

Dyslexic children are probably not a homogeneous group in terms of important characteristics assumed to be involved in reading; disability since underlying causes may vary widely. Such characteristics as arousal and performance on a vigilance task would differ not only from a control group, but also within the RD sample. It was hypothesized that HBD symptoms would be associated with lowered arousal and poorer vigilance performance whereas children experiencing reading difficulties presumably because of specific language dysfunction would resemble controls in arousal and performance. The results supported vigilance predictions for omissions, but not commissions. Poorer performance was associated with HBD symptoms. Age, however, proved to have an even greater effect on vigilance performance. Arousal results, for the most part, were not in the predicted direction. Arousal, measured by skin conductance, increased over time for children in this sample, rather than decreased as we expected from adult data. This indicated that vigilance and arousal cannot be equated in the same sense that has been suggested for adults. / Master of Science

In many source waters across the United States (US), chloride levels are increasing and this change could be problematic for galvanized iron pipe (GIP) installed in consumers' homes and buildings. The higher levels of chloride might increase the rate of galvanic corrosion between the sacrificial zinc coating and the underlying iron (steel) pipe. There are also concerns that the iron in GIP can accumulate lead on its surface from upstream lead service lines, occasionally causing high lead in water from GIP during scale sloughing and associated red water events. The role of high chloride and potential mitigation strategies by orthophosphate and alkalinity on galvanic iron-zinc corrosion in GIP were examined by using new iron and zinc wires, and complementary studies with 85-year-old harvested GIP coupons from the Washington Suburban Sanitary Commission (WSSC). Sequential samplings on a constructed pilot-scale test rig with copper – lead – GIP ¬– brass meter configuration were used to evaluate lead source fingerprinting methods (metal co-occurrence, correlating the plumbing configuration to sample profiling data, and evaluation of lead isotope ratios) and role of flow rate. As chloride concentration increased from 2.6 to 554 mg/L, galvanic current and weight loss of sacrificial zinc increased by about an order of magnitude. Iron leaching also increased by 4.4 times as chloride levels increased by a factor of 12 in WSSC modified water to simulate actual road salt runoff events. Increased orthophosphate or alkalinity could at least partly counter the adverse effects of chloride, as the average iron concentration decreased by 43% as orthophosphate level increased from 3.8 to 11.2 mg/L as P, and average iron concentrations decreased by 32% as alkalinity increased from 50 to 90 mg/L as CaCO3. Applying fingerprinting methods on sequential samples has the potential to determine whether premise plumbing contains GIP and/or lead pipe. Specifically, the metal co-occurrence fingerprinting technique was successful in identifying the location of GIP by the detection of low-level cadmium, and the lead isotope ratio fingerprinting technique was fairly successful in identifying lead pipe. Additionally, our study found that GIP was not contaminated by an upstream lead pipe after five months of conditioning; hence, water discoloration (iron level > 400 ppb) does not always indicate lead problems from GIP. However, with longer exposure of GIP to lead pipe, the magnitude of the problem might increase. As flow rate increased from 0.9 to 2.4 GPM, the median particulate iron release increased by 3.3 times, and the median particulate lead release (>83% particulate lead) increased by 4.9 times. / Master of Science / In many source waters across the United States (US), chloride levels are increasing and this change could be problematic for galvanized iron pipe (GIP) installed in consumers' homes and buildings. The higher levels of chloride might increase the rate of galvanic corrosion in GIP. There are also concerns that the iron in GIP can accumulate lead on its surface from upstream lead service lines, occasionally causing high lead in water from GIP during scale sloughing and associated red water events. The role of high chloride and potential mitigation strategies for GIP by adjusting orthophosphate and alkalinity were examined by conducting bench scale testing. Sequential samplings on a constructed pilot-scale test rig with different lead source pipe sections were used to evaluate lead source fingerprinting methods and role of flow rate. Higher chloride in water increased galvanic current and weight loss of zinc coating as chloride concentration increased from 2.6 to 554 mg/L in the fundamental experiments. Iron leaching also increased as chloride levels increased in the GIP coupon testing. Increasing orthophosphate or alkalinity proved to counter the adverse effects of chloride as the average iron concentration decreased. Sampling profiles can be useful in determining whether premise plumbing contains GIP or lead pipe by using fingerprinting methods. Iron and lead leaching from GIP increased as the water flow rate increased.

<p>In view of the important applications of carbides and carbo-nitrides of transition metals in the heat-resistant and hard materials industries, the thermodynamic activities of Cr and Mn in the Cr-C, Fe-Cr-C, Mn-Ni-C and Mn-Ni-C-N systems have been studied in the present work by the use of the galvanic cell technique. CaF₂single crystals were used as the solid electrolyte. The phase relationships in selected regions of the systems in question were investigated by the use of the equilibration technique. The phase compositions and microstructures of the alloys were analysed by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM).</p><p>In the Cr-C system, the Gibbs energy of formation of Cr3C2 were obtained from ElectroMotive Force (EMF) measurements conducted in the temperature range 950-1150 K. The values of the enthalpy of formation of Cr₃C₂ were evaluated by the third-law method. The ground-state energy of the hypothetic end-member compound CrC3, in the bcc structure at 0 K, was calculated by use of the Ab-initio method. Based on the obtained results the Cr-C system was reassessed by use of the CALPHAD approach.</p><p>In the Fe-Cr-C system, 16 different alloys were quenched at 1223 K and their equilibrium phases identified by XRD. The experimental results show that the substitution of Cr by Fe in the (Cr,Fe)₇C₃ carbide changes the lattice parameters of the phase. A slight decrease of the lattice parameters with an increase in the Fe content was established. The lattice parameters of the γ-phase in the Fe-Cr solid solution did also show a decrease with an increase of the Fe content. The activities of chromium in Fe-Cr-C alloys were investigated in the temperature range 940-1155 K. The activity of chromium decreases with an increase in the Fe content when the ratio of C/(Cr+C) was constant. It was also established that the activity of chromium decreases with an increase of the carbon content when the iron content was constant. The experimental results obtained were compared with the data calculated by use of the Thermo-Calc software. </p><p>In the Mn-Ni-C system the phase relationships were investigated at 1073 K as well as at 1223 K. The experimental results obtained showed that the site fraction of Ni in the metallic sublattice of the carbides M₂₃C₆, M₇C₃ and M₅C₂ (M=Mn and Ni) was quite low (approximately 2~3 percent). The activities of manganese in Mn-Ni-C alloys were investigated in the temperature range 940-1165 K. The three-phase region γ/M₇C₃/graphite was partly constructed at 1073 K. </p><p>In the Mn-Ni-C-N system, nitrogen was introduced into Mn-Ni-C alloys by equilibrating with N2 gas. It was established that the solubility of nitrogen in the investigated alloys was effected by the carbon content, and that a (Mn,Ni)₄(N,C) compound was formed in the nitrided alloys. EMF measurements were performed on Mn-Ni-C-N alloys in the temperature interval 940-1127 K. The addition of nitrogen to Mn-Ni-C alloys was found to decrease the activity of manganese. The negative effect of nitrogen on the activity of manganese was found to decrease as the carbon content increased.</p><p><b>Keywords:</b> Thermodynamic activity; Galvanic cell technique; Transition metal carbides; Transition metal nitrides; Phase equilibrium; Thermodynamics; Differential thermal analysis; Scanning electron microscopy; Transmission electron microscopy; Ab-initio calculations; CALPHAD approach;</p>

A dissertation submitted in fulfilment of the requirements for the degree Master of Science in Engineering, in the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg. January 2017 Johannesburg / It is well known that emotional stress has a negative impact on people’s health and physical, emotional and mental performance. Previous research has investigated the effects of stress on various aspects of physiology such as respiration, heart rate, heart rate variability (HRV), skin conductance, skin temperature and electrical activity in the brain. Essentially, HRV, Electroencephalography (EEG), skin conductance and skin temperature appear to reflect a stress response or state of arousal. Whilst the relationship between respiration rate, respiration rhythm and HRV is well documented, less is known about the relationship between respiration rate, EEG, skin conductance and skin temperature, whilst HRV is maximum (when there is resonance between HRV and respiration i.e. in phase with one another). This research project aims to investigate the impact that one session of slow paced breathing has on EEG, heart rate variability (HRV), skin conductance and skin temperature. Twenty male participants were randomly assigned to either a control or intervention group. Physiological data were recorded for the intervention and control group during one breathing session, over a short initial baseline (B1), a main session of 12 minutes, and a final baseline (B2). The only difference between the control and intervention groups was that during the main session, the intervention group practiced slow paced breathing (at 6 breaths per minute), while the control group breathed spontaneously. Wavelet transformation was used to analyse EEG data while Fourier transformation was used to analyse HRV. The study shows that slow-paced breathing significantly increases the low frequency and total power of the HRV but does not change the high frequency power of HRV. Furthermore, skin temperature significantly increased for the control group from B1 to Main, and was significantly higher for the control group when compared to the intervention group during the main session. There were no significant skin temperature changes between sessions for the intervention group. Skin conductance increased significantly from Main to B2 for the control group. No significant changes were found between sessions for the intervention group and between groups. EEG theta power at Cz decreased significantly from Main to B2 for the control group only, while theta power decreased at F4 from Main to B2 for both groups. Lastly, beta power at Cz decreased from B1 to B2 for the control group only. This significant effect that slow-paced breathing has on HRV suggests the hypothesis that with frequent practice, basal HRV would increase, and with it, potential benefits such as a reduction in anxiety and improved performance in specific tasks. Slow-paced breathing biofeedback thus shows promise as a simple, cheap, measurable and effective method to reduce the impact of stress on some physiological signals, suggesting a direction for future research. / MT2017

In view of the important applications of carbides and carbo-nitrides of transition metals in the heat-resistant and hard materials industries, the thermodynamic activities of Cr and Mn in the Cr-C, Fe-Cr-C, Mn-Ni-C and Mn-Ni-C-N systems have been studied in the present work by the use of the galvanic cell technique. CaF2single crystals were used as the solid electrolyte. The phase relationships in selected regions of the systems in question were investigated by the use of the equilibration technique. The phase compositions and microstructures of the alloys were analysed by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). In the Cr-C system, the Gibbs energy of formation of Cr3C2 were obtained from ElectroMotive Force (EMF) measurements conducted in the temperature range 950-1150 K. The values of the enthalpy of formation of Cr3C2 were evaluated by the third-law method. The ground-state energy of the hypothetic end-member compound CrC3, in the bcc structure at 0 K, was calculated by use of the Ab-initio method. Based on the obtained results the Cr-C system was reassessed by use of the CALPHAD approach. In the Fe-Cr-C system, 16 different alloys were quenched at 1223 K and their equilibrium phases identified by XRD. The experimental results show that the substitution of Cr by Fe in the (Cr,Fe)7C3 carbide changes the lattice parameters of the phase. A slight decrease of the lattice parameters with an increase in the Fe content was established. The lattice parameters of the γ-phase in the Fe-Cr solid solution did also show a decrease with an increase of the Fe content. The activities of chromium in Fe-Cr-C alloys were investigated in the temperature range 940-1155 K. The activity of chromium decreases with an increase in the Fe content when the ratio of C/(Cr+C) was constant. It was also established that the activity of chromium decreases with an increase of the carbon content when the iron content was constant. The experimental results obtained were compared with the data calculated by use of the Thermo-Calc software. In the Mn-Ni-C system the phase relationships were investigated at 1073 K as well as at 1223 K. The experimental results obtained showed that the site fraction of Ni in the metallic sublattice of the carbides M23C6, M7C3 and M5C2 (M=Mn and Ni) was quite low (approximately 2~3 percent). The activities of manganese in Mn-Ni-C alloys were investigated in the temperature range 940-1165 K. The three-phase region γ/M7C3/graphite was partly constructed at 1073 K. In the Mn-Ni-C-N system, nitrogen was introduced into Mn-Ni-C alloys by equilibrating with N2 gas. It was established that the solubility of nitrogen in the investigated alloys was effected by the carbon content, and that a (Mn,Ni)4(N,C) compound was formed in the nitrided alloys. EMF measurements were performed on Mn-Ni-C-N alloys in the temperature interval 940-1127 K. The addition of nitrogen to Mn-Ni-C alloys was found to decrease the activity of manganese. The negative effect of nitrogen on the activity of manganese was found to decrease as the carbon content increased. Keywords: Thermodynamic activity; Galvanic cell technique; Transition metal carbides; Transition metal nitrides; Phase equilibrium; Thermodynamics; Differential thermal analysis; Scanning electron microscopy; Transmission electron microscopy; Ab-initio calculations; CALPHAD approach;

An experimental investigation of the binary system Co-Cr and the ternary system C-Co-Cr has been carried out in the present thesis. The experimental strategy adopted for the binary system was to measure the thermodynamic activities of Cr, the molar heat capacity as function of time, the phase transformation temperatures with corresponding enthalpies, the Curie transition temperature as well as melting temperatures with corresponding enthalpies. In the ternary system the strategy was to determine the solubility of Co in the Cr7C3 phase as well as the C and Cr contents in the Co rich (fcc) binder phase. The experimental results were compared with atomistic simulations of the solubility of Co in the Cr7C3 phase. Solid state galvanic cell measurements were conducted with both ZrO2-7.5 mol % CaO and CaF2 as the solid electrolyte. In view of possible errors in the measurements with ZrO2-7.5 mol % CaO, as a result of electronic contributions to the conduction of the solid electrolyte, new measurements were conducted with CaF2 as the solid electrolyte. The results indicated that the measured EMF values showed trends which were contrary to the thermodynamic behaviour expected from phase diagram considerations. It was concluded that further detailed experimentation was necessary in order to throw more light on the thermodynamic behaviour of the Co-Cr system. Two different series of DSC measurements were conducted, i.e. one in an atmosphere of pure hydrogen and another in pure argon. In the first investigation, conducted in an atmosphere of pure hydrogen in the temperature interval 318-1660 K, evidence was obtained for the existence of a phase transformation around 900 K in the compositional range 20.7-67.1 wt.% Cr. No indications of such a phase transformation had earlier been seen. In the second investigation, conducted in an atmosphere of pure argon in the temperature interval 298-1823 K, special attention was given to alloys in the Co rich corner of the phase diagram, i.e. 0-10 wt.% Cr. This investigation verified earlier findings of a phase transformations around 900 K in the compositional range 20.7-67.4 wt.% Cr. The magnetic transition temperatures for alloys low in Cr content were also obtained. With the use of the DTA technique the melting temperatures with corresponding enthalpy values for alloys in the compositional range 0.9-7.7 wt.% Cr were obtained. The three-phase triangle fcc+Cr7C3+graphite was investigated at 1373 K, 1423 K and 1473 K. The obtained results showed that the solubility of cobalt in the Cr7C3 phase was significantly higher than previously predicted by thermodynamic calculations. / QC 20100930

Direct methanol fuel cells (DMFC) are being investigated as a portable energy conversion device for military and commercial applications. DMFCs offer the potential to efficiently extract electricity from a dense liquid fuel. However, improvements in materials properties and lowering the cost of the electrocatalysts used in a DMFC are necessary for commercialization of the technology. The cathode electrocatalyst is a critical issue in DMFC because the state-of-the-art catalyst, platinum, is very expensive and rare, and its performance is diminished by methanol that crosses over from the anode to the cathode through the Nafion membrane. This thesis investigates the addition of platinum to a palladium-cobalt nanoalloy electrocatalyst supported on carbon black in order to improve catalyst activity for the oxygen reduction reaction (ORR) and catalyst stability against dissolution in acidic environment without significantly reducing the methanol-tolerance of the catalyst. Platinum was added to the palladium-cobalt nanoalloy catalyst using two synthesis methods. In the first method, platinum was directly alloyed with palladium and cobalt using a polyol reduction method, followed by heat treatment in a reducing atmosphere to form catalysts with 11 and 22 atom % platinum. In the second method, platinum was added to a palladium-cobalt alloy by galvanic displacement reaction to form catalysts with 10 and 22 atom % platinum. The palladium cobalt alloy was synthesized using a polyol method, followed by heat treatment in a reducing atmosphere to alloy the nanoparticles before the Pt displacement. It was found that both methods significantly improve catalyst activity and stability, with the displaced catalysts showing a higher activity than the corresponding alloy catalyst. However the alloy catalysts showed similar resistance to dissolution as the displaced catalysts, and the alloyed catalysts were more tolerant to methanol. The displaced catalyst with 22 atom % platinum (8 wt. % Pt overall) performed similar to a 20 wt. % commercial platinum catalyst in both RDE and single cell DMFC tests. The 10 and 22 atom % Pt displaced catalysts and 22 atom % Pt alloyed all showed higher Pt mass specific activities than a commercial Pt catalyst. / text