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This thesis describes the synthesis of ruthenium based molecular clusters and their characterisation. Chapter 2 introduces the concept that the very large zero-field splitting (D = 2.9 cm–1) in the S = 5/2 ground state of [Ru2Mn(μ3-O)(tBuCO2)6(py)3] can be modelled by antisymmetric exchange effects. This is supported by measurement of the single ion D values from the Fe2Mn analogue. The same model is applied to the Ru2Ni analogue to describe the zero-field splitting in the S = 1 ground state, (DGS = +8.0 cm–1 from DNi = -4.0 cm–1) in Chapter 3.Chapters 3 and 4 give the full characterisation of each of the two families, [MIII2MII(μ3-O)(tBuCO2)6(py)3] (MIII = Ru or Fe, MII = Mn, Co, Ni or Zn), through IR, electronic absorption and NMR spectroscopy and are structurally characterised by X-ray diffraction. The total spin ground states and zero-field splitting of those ground states have been ascertained by SQUID magnetometry and EPR spectroscopy. Due to the redox activity of the Ru2M complexes chemical oxidations led to the isolation of [RuIII2CoIIIO(tBuCO2)6(py)3]+ (5) and [RuIIIRuIVNiIIO(tBuCO2)6(py)3]+ (6); the locus of their oxidation was determined with the aid of X-ray absorption spectroscopy (XAS).Chapter 5 shows that due to the ease of the substitution of the terminal ligand in Ru2M they can be linked to other molecular clusters with N-donor ligands, in this case [Cr7NiF8(tBuCO2)15(O2CC5H4N)][NH2Pr2] in order to synthesise [Ru2NiO(tBuCO2)6(py)(Cr7NiF8(tBuCO2)15(O2CC5H4N))2][NH2Pr2]2. In situ oxidation experiments have also been carried out to assess the switchabilty of the redox active linker. Chapter 6 demonstrates a new structural archetype for tetranuclear ruthenium mixed-metal complexes, with the formula, [Ru2M2(µ3-OH)2(tBuCO2)7(py)4], where M is either Co (1) or Ni (2). SQUID magnetometry and EPR spectroscopy have determined the spin ground states as, Seff = 1/2 in 1 and S = 3/2 in 2. The magnetic anisotropy in 2 has been determined as +2.02 cm–1 for the S = 3/2 ground state.

No description available.

Sustainability requires a new pathway and our industry must evolve to be a contributor to finding the right answer, rather than delivering the trusted solutions that have served us well in an industry of unconstrained resources. Aspiration of initiating a dialogue about our professional responsibility: the dialogue must engage with matters beyond engineering and find relevance in the disparate academic research, to drive the pragmatic decision making required by industry. / Dissertation (MArch(Prof))--University of Pretoria, 2009. / Architecture / unrestricted

Master of Science / Department of Statistics / Christopher Vahl / Among the most used statistical concepts and techniques, seen even in the most cursory of introductory courses, are the confidence interval, binomial distribution, and sample size estimation. This paper investigates a particular case of generating a confidence interval from a binomial experiment in the case where zero successes are expected. Several current methods of generating a binomial proportion confidence interval are examined by means of large-scale simulations and compared in order to determine an ad-hoc method for generating a confidence interval with coverage as close as possible to nominal while minimizing width. This is then used to construct a formula which allows for the estimation of a sample size necessary to obtain a sufficiently narrow confidence interval (with some predetermined probability of success) using the ad-hoc method given a prior estimate of the probability of success for a single trial. With this formula, binomial experiments could potentially be planned more efficiently, allowing researchers to plan only for the amount of precision they deem necessary, rather than trying to work with methods of producing confidence intervals that result in inefficient or, at worst, meaningless bounds.

We consider real zero-crossing analysis of the real/imaginary parts of the spectrum, namely, spectral zero-crossings (SZCs). The two major contributions are to show that: (i) SZCs provide enable temporal localization of transients; and (b) SZCs are suitable for modeling transient signals. We develop a spectral dual of Kedem’s result linking temporal zero-crossing rate (ZCR) to the spectral centroid. The key requirement is stationarity, which we achieve through random-phase modulations of the time-domain signal. Transient signals are not amenable to modelling in the time domain since they are bursts of energy localized in time and lack structure. We show that the spectrum of transient signals have a rich modulation structure, which leads to an amplitude-modulation – frequency-modulation (AM-FM) model of the spectrum. We generalize Kedem’s arc-cosine formula for lags greater than one. For the specific case of a sinusoid in white Gaussian noise, He and Kedem devised an iterative filtering algorithm, which leads to a contraction mapping. An autoregressive filter of order one is employed and the location of the pole is the parameter that is updated based on the filtered output. We use the higher-order property, which relates the autocorrelation to the expected ZCR of the filtered process, between lagged ZCR and higher-lag autocorrelation to develop an iterative higher-order autoregressive-filtering scheme, which stabilizes the ZCR and consequently provides robust estimates of the autocorrelation at higher lags. Next, we investigate ZC properties of critically sampled outputs of a maximally decimated M-channel power complementary analysis filterbank (PCAF) and derive the relationship between the ZCR of the input Gaussian process at lags that are integer multiples of M in terms of the subband ZCRs. Based on this result, we propose a robust autocorrelation estimator for a signal consisting of a sum of sinusoids of fixed amplitudes and uniformly distributed random phases. Robust subband ZCRs are obtained through iterative filtering and the subband variances are estimated using the method-of-moments estimator. We compare the performance of the proposed estimator with the sample auto-correlation estimate in terms of bias, variance, and mean-squared error, and show through simulations that the performance of the proposed estimator is better than the sample auto- correlation for medium to low SNR. We then consider the ZC statistics of the real/imaginary parts of the discrete Fourier spectrum. We introduce the notion of the spectral zero-crossing rate (SZCR) and show that, for transients, it gives information regarding the location of the transient. We also demonstrate the utility of SZCR to estimate interaural time delay between the left and right head-related impulse responses. The accuracy of interaural time delay plays a vital role in binaural synthesis and a comparison of the performance of the SZCR estimates with that of the cross-correlation estimates illustrate that spectral zeros alone contain enough information for accurately estimating interaural time delay. We provide a mathematical formalism for establishing the dual of the link between zero-crossing rate and spectral centroid. Specifically, we show that the expected SZCR of a stationary spectrum is a temporal centroid. For a deterministic sequence, we obtain the stationary spectrum by modulating the sequence with a random phase unit amplitude sequence and then computing the spectrum. The notion of a stationary spectrum is necessary for deriving counterparts of the results available in temporal zero-crossings literature. The robustness of location information embedded in SZCR is analyzed in presence of a second transient within the observation window, and also in the presence of additive white Gaussian noise. A spectral-domain iterative filtering scheme based on autoregressive filters is presented and improvement in the robustness of the location estimates is demonstrated. As an application, we consider epoch estimation in voiced speech signals and show that the location information is accurately estimated using spectral zeros than other techniques. The relationship between temporal centroid and SZCR also finds applications in frequency-domain linear prediction (FDLP), which is used in audio compression. The prediction coefficients are estimated by solving the Yule-Walker equations constructed from the spectral autocorrelation. We use the relationship between the spectral autocorrelation and temporal centroid to obtain the spectral autocorrelation directly by time-domain windowing without explicitly computing the spectrum. The proposed method leads to identical results as the standard FDLP method but with reduced computational load. We then develop a SZCs-based spectral-envelope and group-delay (SEGD) model, which finds applications in modelling of non-stationary signals such as Castanets. Taking into account the modulation structure and spectral continuity, local polynomial regression is performed to estimate the GD from the real spectral zeros. The SE is estimated based on the phase function computed from the estimated GD. Since the GD estimate is parametric, the degree of smoothness can be controlled directly. Simulation results based on synthetic transient signals are presented to analyze the noise-robustness of the SE-GD model. Applications to castanet modeling, transient compression, and estimation of the glottal closure instants in speech are shown.

Underground mining produces a huge amount of voids and an even larger quantity of mine waste. Overlooking these voids could lead to the possibility of ground subsidence, as well as safety issues during mining operation; while ignoring the waste, could cause environmental pollution and significant suffering. One solution to remedy both (the voids and the waste) is cemented paste backfill (CPB), which is gaining increased recognition in both the mining industry and academic research. Transforming tailings into cemented paste, and transporting this back to underground stopes, not only negates these safety issues to a large degree, but also makes it possible to put waste to good use.However, most studies involving CPB have been conducted at temperatures above 0°C; knowledge of CPB in sub-zero environments is still lacking. For this reason, this thesis investigates the mechanical behaviour of CPB in a the latter type of environment.Uniaxial compressive strength tests were carried out on a series of frozen CPB (FCPB) samples to evaluate the mechanical behaviour (e.g. compressive strengths, geotechnical features, and the stress-strain relationships) of FCPB. It has been discovered in this thesis that FCPB exhibits remarkable strength compared to CPB and, has a great resemblance to frozen soil. Factors which may affect the behaviour of FCPB were thoroughly examined. Binder contents and types were found to be irrelevant; water content, in contrast, plays a dominant role, with an optimum value of around 26% by weight. Sulphate was confirmed to have an adverse effect on the strength of FCPB due to the increasing unfrozen water content and the formation of legible ice lenses. Hydraulic conductivity tests, scanning electron microscope observations, thermal gravimetric analyses, and mercury intrusion porosimetry were also performed as subsidiary experiments to understand the geotechnical features of FCPB. This information will be of significant value for numerous practical applications.

In this PhD thesis, seawater desalination by Membrane Distillation (MD) has been explored from the perspective of process and membrane. Regarding the process, an innovative, energy efficient, and environmentally friendly Zero Thermal Input Membrane Distillation (ZTIMD) process was proposed. ZTIMD uses thermal energy stored in seawater, which makes the process sustainable by being independent of the external sources of thermal energy, which is one of the major contributors to the cost and energy consumption of conventional MD desalination processes. Economic feasibility study was carried out for the ZTIMD process, and it was demonstrated that drinking water could be produced with a cost of $0.28/m3, which is approximately half of the cost of conventional desalination processes. Regarding the membrane, novel MD membranes were developed through incorporation of nanomaterials in polyvinylidene fluoride (PVDF). Different nanomaterials including superhydrophobic SiO2, amine modified hydrophilic SiO2, CuO, and CaCO3 were used for this purpose. It was shown that membrane structure and consequently its performance could be affected by the nanoparticle properties, concentration, presence of backing material, PVDF blend ratio, and penetration time. In a best membrane developed in this work, almost 2500% increase was observed in the Vacuum Membrane Distillation (VMD) flux over that of the neat PVDF membrane at a feed temperature of 27.5 °C and vacuum pressure of 1.2 kPa, when 7.0 wt.% hydrophilic SiO2 nanoparticles were added into a PVDF membrane supported with Non-Woven Fabric (NWF) polyester. The membrane possessed near perfect selectivity.