>Magister Scientiae - MSc / Fly ash is the most abundant of the waste materials generated from coal combustion in coal-fired power stations. South Africa uses more than 100 million tonnes of low grade bituminous coal annually to produce cheap electricity thereby generating huge amounts of fly ash each year. The disposal of fly ash has been a major concern to the world because of its potential environmental impact due to the possible leaching of the toxic elements contained in fly ash. This study centres on the chemical characterization and leaching behaviour of the fly ashes generated from SASOL Synfuels and ESKOM power station at Secunda and Tutuka in South Africa respectively. The aim is to understand the composition of the fly ashes and to determine the leachability of species from the ashes in order to predict the environmental effect of the different ash handling system of the coalfired stations (wet disposal system in Secunda and dry disposal system in Tutuka). Several leaching methods were employed in this study in order to develop a methodology for evaluating and modelling ash system and were able to discriminate between ash types and model ash handling system. Fly ashes from the two South African coal-fired stations were subjected to total acid-digestion and XRF analyses in order to determine the total amounts of major and minor species contained in the fly ashes. The total acid-digestion test and the XRF analysis revealed that the major species such as Al, Si, Ca, Na, Mg, K, Sr, Ba and S04, and minor species such as Fe, Ti, V, Mn, Cr, Ni and Cu were present in both fly ashes in fairly similar concentrations. The mineralogical characterization by XRD of Secunda and Tutuka fly ashes revealed mullite and quartz as the major mineral phases with minor peaks of CaO and calcite. Several leaching tests and different leaching conditions were employed in this study in order to develop a standardized replicable methodology for environmental impact assessment and for modelling the impact of different ash handling scenarios. The fly ashes were exposed to these different leaf leachant of different pHs on the leachability of species from the fly ashes. To achieve this, DIN-S4, TCLP and ANC tests were employed. The natural pH of the fly ash leachates were very high ranging between 12.56 and 13.08. The DIN-S4 leaching test revealed that the easily soluble species of the fly ashes include Ca, Mg, Na, K and S04 and various toxic elements. The leachates from the TCLP test recorded higher concentrations of Ca, Mg, Na, K and S04 which was attributed to the slight decrease in the pH due to the addition of a acidic leachant with a pH of 2.88. Comparison of the amount leached (DIN-S4) from the fly ashes with the total concentrations of each of the components of the fly ashes (determined by the total acid-digestion), the percentage of each of the readily soluble species ranged from 15-24.23% for Ca, 0.23-0.45% for K, 0.58-0.82% for Na, 0.0047-0.007% for Mg, 0.96-3.33% for Ba and 0.012-1.51 % for S04 per dry mass of each component in the fly ash. The ANC test revealed the effect of a leachant of specified pH on the release of species from the fly ashes with concentrations of the major and minor species leached out of the fly ashes found to be higher than the concentrations released into the leachates when DIN-S4 and TCLP test were considered at specific pH and showed the pH dependence of the solubility and release of species. These tests also showed the effect of the liquid to solid ratio upon leachability of species. In addition to the batch leaching tests mentioned above, dissolution kinetics and up-flow percolation tests were carried out on the fly ashes to determine the leaching behaviours of the fly ashes over time and the factors controlling the release of species from the fly ashes in the long term. The dissolution kinetics test was done for an extended period of 60 days with recycle of the leachant and the up-flow percolation test was carried out with constant leachant renewal until a liquid/solid ratio of 20 was attained (:::::;9d0ays). The geochemical computer code PHREEQC and MINTEQ database was used for geochemical modelling of the leachates at various reaction times and LIS ratios. The geochemical modelling results revealed that the release of the species from the fly ashes is controlled by the solubility of mineral phases in many case except for Na. The release of Ca, S04, Mg, Ba and Sr in the leachates of the fly ashes were predicted to be controlled by portlandite, gypsum, brucite, barite and celestite respectively while birnessite, magnetite, BaCr04, CaMo04 and Ba(As04h were predicted to be the mineral phases controlling the release of Mn, Fe, Cr, Mo and As respectively. The pH of the leachates plays a significant role in the leaching of both major and minor species from the fly ashes. The concentrations of species leached into solution at low pH (ANC and TCLP) were higher than the concentrations released at high pH (DIN-S4, dissolution kinetics and up-flow percolation tests). The amounts of the toxic elements such as As, Se, Cd, Cr and Pb that leached out of the fly ashes when in contact with demineralized water (DIN-S4) were very low and below the target water quality range (TWQR) of South African Department of Water Affairs and Forestry (DWAF), but the amounts of As and Se leached out by acidic leachant applied in the TCLP test and at lower pH ranging between 8 and 10 the case of the ANC test were slightly higher than the TWQR, which is an indication that the pH of the leaching solution and the contact time playa significant role on the leaching of species out of the fly ashes. This study revealed that the leaching of species from the fly ashes depends on various factors which include: physical and chemical characteristics and mineralogical composition of the fly ashes, the total concentrations of species in the ash, the rate of flow through the ash system and more importantly the pH of the leachant to which the ash system is exposed to. The results of different experiments and analysis carried out on the two South African fly ashes (Secunda and Tutuka fly ashes) showed that, despite the high concentrations of soluble species or leachable elements in the fly ashes, the leaching of major, minor and trace elements into the soils and the groundwater could be minimized if certain conditions such as avoiding acidic precipitation that could reduce the pH of the ash system are adhered to. The leaching trends of the species and the geochemical modelling data also showed that the formation of secondary mineral phases could reduce the release of toxic elements, the release of which would require aggressive low pH leachants, high flow rate, high recharge and long-term leaching for the dissolution of the formed mineral phases. In conclusion, the combination of the leaching tests employed in this study gives information on the leaching behaviour of the Secunda and Tutuka fly ashes and the factors controlling the leaching of the elements from the fly ashes. This study has been able to show that elements are leached out of the fly ashes at both alkaline and acidic pH. It is also revealed in the study that the disposal techniques employed by the coal-fired stations which were simulated by using the dissolution kinetics and up-flow percolation tests are adequate methods for modelling of the ash disposal scenario. These two methods show that the dry disposal system at Tutuka will encourage equilibration of the ash/water system thereby facilitating the precipitation of mineral phases that could control the release of both major and minor species from the fly ash, whereas the wet ashing system at Secunda may expose the ash to sufficient flow to rapidly leach species out into the environment.

<div>The interplay between network topology and traffic dynamics in road networks impacts various performance measures. There are extensive existing researches focusing on link-level fundamental diagrams, traffic assignments under route choice assumptions. However, the underlying coupling of structure and dynamic makes network-level traffic not fully investigated. In this thesis, we build structural and dynamic models to deal with three challenges: 1) describing road network topology and understanding the difference between cities; 2) quantifying network congestion considering both road network topology and traffic flow information; 3) allocating transportation management resources to optimize the road network connectivity.</div><div><br></div><div>The first part of the thesis focuses on structural models for complex road networks. Online road map data platforms, like OpenStreetMap, provide us with reliable road network data of the world. To solve the duplicate node problem, an O(n) time complexity node merging algorithm is designed to pre-process the raw road network with n nodes. Hereafter, we define unweighted and weighted node degree distribution for</div><div>road networks. Numerical experiments present the heterogeneity in node degree distribution for Beijing and Shanghai road network. Additionally, we find that the power law distribution fits the weighted road network under certain parameter settings, extending the current knowledge that degree distribution for the primal road network is not power law.</div><div><br></div><div>In the second part, we develop a road network congestion analysis and management framework. Different from previous methods, our framework incorporates both network structure and dynamics. Moreover, it relies on link speed data only, which is more accessible than previously used link density data. Specifically, we start from the existing traffic percolation theory and critical relative speed to describe network-level traffic congestion level. Based on traffic component curves, we construct Aij for two road segments i and j to quantify the necessity of considering the two road segments in the same traffic zone. Finally, we apply the Louvain algorithm on defined road segment networks to generate road network partition candidates. These candidate partitions will help transportation engineers to control regional traffic.</div><div><br></div><div>The last part formulates and solves a road network management resource allocation optimization. The objective is to maximize critical relative speed, which is defined from traffic component curves and is closely related to personal driving comfort. Budget upper bound serves as one of the constraints. To solve the simulation-based nonlinear optimization problem, we propose a simple allocation and a meta-heuristic method based on the genetic algorithm. Three applications demonstrate that the meta-heuristic method finds better solutions than simple allocation. The results will inform the optimal allocation of resources at each road segment in metropolitan cities to enhance the connectivity of road networks.</div>

This work presents a numerical investigation of self-avoiding walks (SAWs) on percolation clusters, a canonical model for polymers in disordered media. A new algorithm has been developed allowing exact enumeration of over ten thousand steps. This is an increase of several orders of magnitude compared to previously existing enumeration methods, which allow for barely more than forty steps. Such an increase is achieved by exploiting the fractal structure of critical percolation clusters: they are hierarchically organized into a tree of loosely connected nested regions in which the walks segments are enumerated separately. After the enumeration process, a region is \"decimated\" and behaves in the following effectively as a single point. Since this method only works efficiently near the percolation threshold, a chain-growth Monte Carlo algorithm has also been used. Main focus of the investigations was the asymptotic scaling behavior of the average end-to-end distance as function of the number of steps on critical clusters in different dimensions. Thanks the highly efficient new method, existing estimates of the scaling exponents could be improved substantially. Also investigated were the number of possible chain conformation and the average entropy, which were found to follow an unusual scaling behavior. For concentrations above the percolation threshold the exponent describing the growth of the end-to-end distance turned out to differ from that on regular lattices, defying the prediction of the accepted theory. Finally, SAWs with short range attractions on percolation clusters are discussed. Here, it emerged that there seems to be no temperature-driven collapse transition as the asymptotic scaling behavior of the end-to-end distance even at zero temperature is the same as for athermal SAWs. / Die vorliegenden Arbeit präsentiert eine numerische Studie von selbstvermeidenden Zufallswegen (SAWs) auf Perkolationsclustern, ein kanonisches Modell für Polymere in stark ungeordneten Medien. Hierfür wurde ein neuer Algorithmus entwickelt, welcher es ermöglicht SAWs von mehr als zehntausend Schritten exakt auszuzählen. Dies bedeutet eine Steigerung von mehreren Größenordnungen gegenüber der zuvor existierenden Methode, welche kaum mehr als vierzig Schritte zulässt. Solch eine Steigerung wird erreicht, indem die fraktale Struktur der Perkolationscluster geziehlt ausgenutzt wird: Die Cluster werden hierarchisch in lose verbundene Gebiete unterteilt, innerhalb welcher Wegstücke separat ausgezählt werden können. Nach dem Auszählen wird ein Gebiet \"dezimiert\" und verhält sich während der Behandlung größerer Gebiete effektiv wie ein Gitterpunkt. Da diese neue Methode nur nahe der Perkolationsschwelle funktioniert, wurde zum Erzielen der Ergebnisse zudem ein Kettenwachstums-Monte-Carlo-Algorithmus (PERM) eingesetzt. Untersucht wurde zunächst das asymptotische Skalenverhalten des Abstands der beiden Kettenenden als Funktion der Schrittzahl auf kritischen Clustern in verschiedenen Dimensionen. Dank der neuen hochperformanten Methode konnten die bisherigen Schätzer für den dies beschreibenden Exponenten signifikant verbessert werden. Neben dem Abstand wurde zudem die Anzahl der möglichen Konformationen und die mittlere Entropie angeschaut, für welche ein ungewöhnliches Skalenverhalten gefunden wurde. Für Konzentrationen oberhalb der Perkolationsschwelle wurde festgestellt, dass der Exponent, welcher das Wachstum des Endabstands beschreibt, nicht dem für freie SAWs entspricht, was nach gängiger Lehrmeinung der Fall sein sollte. Schlussendlich wurden SAWs mit Anziehung zwischen benachbarten Monomeren untersucht. Hier zeigte sich, dass es auf kritischen Perkolationsclustern keinen Phasenübergang zu geben scheint, an welchem die Ketten kollabieren, sondern dass das Skalenverhalten des Endabstands selbst am absoluten Nullpunkt der Temperatur unverändert ist.

<p>The use of atomistic level simulations like molecular dynamics are becoming a key part in the process of materials discovery, optimization and development since they can provide complete description of a material and contribute to understand the response of materials under certain conditions or to elucidate the mechanisms involved in the materials behavior.</p> <p>We will discuss to cases in which molecular dynamics simulations are used to characterize and understand the behavior of materials: i) prediction of properties of small organic crystals in order to be implemented in a multiscale modeling framework which objective is to predict mechanically induced amorphization without experimental input other than</p> <p>the molecular structure and ii) characterization of temperature dependent spatio-temporal domains of high mobility torsions in several bulk polymers, thin slab and isolated chains; strikingly we observe universality in the percolation of these domains across the glass transition.</p> <p>However, as in any model, validation of the predicted results against appropriate experiments is a critical stage, especially if the predicted results are to be used in decision making. Various sources of uncertainties alter both modeling and experimental results and therefore the validation process. We will present molecular dynamics simulations to assess uncertainties associated with the prediction of several important properties of thermoplastic polymers; in which we independently quantify how the predictions are affected by several sources. Interestingly, we nd that all sources of uncertainties studied influence predictions, but their relative importance depends on the specific quantity of interest.</p>

<p>Prema postojećem tumačenju Ziegler-Natta polimerizacije, smatra se da se prekursor prelaznog metala (Mt) aktivira pomoću alkila metala, a da se rast polimernog lanca ostvaruje umetanjem monomera između Mt i rastućeg polimernog lanca. Postoje mnoga neslaganja eksperimentalnih činjenica sa tumačenjem polimerizacije mehanizmom insertacije. U ovom radu predložen je novi mehanizam polimerizacije olefina pomoću jedinjenja prelaznih metala perkolacijom naelektrisanja (CPM): makromolekulski lanac nastaje polimerizacijorm grozda monomera (nM) koji je adsorbovan na nosaču (S) između dva adsorbovana prelazna metala, jednog u vi&scaron;em (Mt⁺⁴), a drugog u nižem oksidacionom stanju (Mt⁺²):</p><p style="text-align: center;">( Mt^n+1...nM^...Mtⁿ⁺¹)/S&nbsp;&rarr;(MtⁿMtⁿ)/S + polimer.</p><p>Novi&nbsp;mehanizam polimerizacije perkoracijom naelektrisanja potvrđen je eksperimentalnim podacima, matematičkim proračunima i kompjuterskim simulacijama. U radu je prvo ukazano na značaj dosada&scaron;njih istraživanja i dat je prikaz pojedinih eksperimentalnih činjenica koje potvrđuju perkolacioni model polimerizacije. Po principu Monte-Carlo simulacija, napravljen je novi specijalni kompjuterski program &quot;Lattice&quot; koji omogućuje simulaciju polimerizacije olefina pomoću CPM. U radu je dat detaljan opis kompjuterskog programa &quot;Lattice&quot; i oja&scaron;njeno je na koji način se eksperimentalni parametri prevode u parametre perkolacionog modela polimerizacije. Na osnovu matematičkog proračuna i kompjuterske simulacije (primenom teorije Kobozeva) predviđen je uticaj sadržaja prelaznog metala na nosaču na produktivnost metala i nosača, &scaron;to je potvrđeno eksperimentalnim podacima. U radu je prikazano na koji način promene: tipa nosača, početne povr&scaron;inske koncentracije monomera, koncentracije prelaznim metala redosledu dodavanja reagujućih komponenti, utiču na grafiku brzina polimerizacije - vreme. Primenom perkolacionog modela polimerizacije obja&scaron;njene su eksperimentalne činjenice koje do sad nisu mogle biti potpuno obja&scaron;njene primenom mehanizma insertacije.</p> / <p>According the current explanation of Ziegler-Natta polymerization, transition metal (Mt)<br />is activated by alkyl group and vacant orbital are formed. It is belived that polymer<br />chain propagates by monomer insertion between Mt and growing polymer chain. It has also been known that by using existing insertion mechanism of the polymerization,<br />some experimentally proved facts cannot be explained completely. In this paper new<br />charge percolation mechanism (CPM) of olefin polymeiization by supported Mt<br />complexes is presented: a macromolecular chain is formed polymerization of<br />monomer cluster (nM) adsorbed at the support (S) between two immobilised Mt ions,<br />one in the higher (Mt⁺⁴) and the other in the lower (Mt⁺²) oxidation state:</p><p style="text-align: center;">( Mtn+1...nM...Mtn+1)/S &rarr;(MtnMtn)/S + polymer.</p><p>New CPM has been confirmed by published experimental data, by calculating and by computer simulation. First it has been clarified the signifigance of the existing<br />experiment and some experimental facts wich are confrlmed by CPM are shown. A special computer program &quot;Lattice&quot; has been developed to simulate olefin<br />polymerization based on CPM using Monte Carlo procedure. In this work it is explanied<br />how the polymerization parametar from real experiments are transfered to percolation<br />and simulation parametars. The effects of thesurface concentration of active centres on<br />metal productivities and support productivites has been predicted by the calculating and computer simulation (using catalytic theory of Kobozev) and confirmed by real<br />experimental data. In this work it is also shown how the polymer structure and tipe of<br />the curve polymerization rate/time depend on reaction conditions (Mt concentration, tipe of the support, Mt/S ratio, sequence of chemical components addition, time). At the end the experimental facts which couldn&#39;t have been explained completaly ty insertion<br />mechanism are explanied using CpM.</p><p style="text-align: center;">&nbsp;</p>

Network connectivity is a fundamental property affecting network performance. Given the reliability of each link, network connectivity determines the probability that a message can be delivered from the source to the destination. In this thesis, we study the directed network connectivity where the message will be forwarded toward the destination hop by hop, so long as the neighbor(s) is (are) closer to the destination. Directed connectivity, closely related to directed percolation, is very complicated to calculate. The existing state-of-the-art can only calculate directed connectivity for a lattice network up-to-the size of 10 × 10. In this thesis, we devise a new approach that is simpler and more scalable and can handle general network topology and heterogeneous links. The proposed approach uses an unambiguous hop count to divide the networks into hops and gives two steps of pre-process to transform hop-count ambiguous networks into unambiguous ones, and derive the end-to-end connectivity. Then, using the Markov property to obtain the state transition probability hop by hop. Second, with tens of thousands of Low Earth Orbit (LEO) satellites covering the Earth, LEO satellite networks can provide coverage and services that are otherwise not possible using terrestrial communication systems. The regular and dense LEO satellite constellation also provides new opportunities and challenges for network protocol design. In this thesis, we apply the directed connectivity analytical model on LEO satellite backbone networks to ensure ultra-reliable and low-latency (URLL) services using LEO networks, and propose a directed percolation routing (DPR) algorithm to lower the cost of transmission without sacrificing speed. Using Starlink constellation (with 1,584 satellites) as an example, the proposed DPR can achieve a few to tens of milliseconds latency reduction for inter-continental transmissions compared to the Internet backbone, while maintaining high reliability without link-layer retransmissions. Finally, considering the link redundancy overhead and delay/reliability tradeoff, DPR can control the size of percolation. In other words, we can choose a part of links to be active links considering the reliability and cost tradeoff. / Graduate

The addition of powered components for active assays into paper-based analytical devices opens new opportunities for medical and environmental analysis in resource-limited applications. Current battery designs within such devices have yet to adopt a ubiquitous circuitry material, necessitating investigation into printed circuitry for scalable platforms. In this study, a microfluidic battery was mated with silver-nanoparticle conductive ink to prototype an all-printed sensing platform. A multi-layer, two-cell device was fabricated, generating 200 μA of direct electrical current at 2.5 V sustained for 16 minutes with a power loss of less than 0.1% through the printed circuitry. Printed circuitry traces exhibited resistivity of 75 to 211 10-5 Ω m. Resistance of the printed traces increased upwards of 200% depending on fold angle and directionality. X-ray diffraction confirmed the presence of face-centered cubic silver after sintering printed traces for 30 minutes at 150°C in air. A conductivity threshold was mapped and an ink concentration of 0.636 μL mm-3 was identified as the lower limit for optimal electrical performance.

L'étude expérimentale développée dans ce travail s'articule autour de deux phases principales. La première est la conception d'un système nanocomposite dont les éléments constituants ont été choisis judicieusement en vue d'améliorer ses performances. Le système proposé appartient à la famille des matériaux nanocomposites. Ce système est constitué d'une matrice polymère renforcée par des éléments argileux. Une étude expérimentale a été menée afin d'optimiser le choix de la matrice polymère. En effet, il a été trouvé démontré que lorsque le PDMS est greffé par des radicaux époxydes, sa compatibilité avec la Cloisite C30B devient nettement meilleure. Au niveau de cette même phase, une autre étude expérimentale a été entreprise afin de suivre l'évolution de la structure du mélange en fonction du taux de renfort. En effet, un taux de 2% de la C30B a été jugé approprié pour améliorer les performances du système étudié. Cette première phase du projet a donc abouti à la conception d'un système nanocomposite dit PDMS-Epoxyde/2%C30B. La deuxième phase du présent travail porte sur l'évaluation de l'effet des différents facteurs de cisaillement sur les phénomènes de dispersion-distribution des nanoparticules de Cloisite C30B au sein su polydiméthylsiloxane-epoxyde. Trois facteurs ont été retenus pour cette étude. Le premier étant l'effet du taux de cisaillement "la contrainte de cisaillement" sur l'efficacité du processus d'exfoliation des nanoparticules d'argile dans la matrice polymère. Selon les résultats obtenus, un taux de cisaillement adéquat favorise F intercalation et l'exfoliation mais à un degré assez limité. Cependant, sous l'effet de la déformation, il a été démontré que la qualité de la dispersion /distribution des lamelles d'argile dans la matrice polymère est meilleure que celle obtenue dans le premier cas. Le dernier élément de l'étude expérimentale développée dans le cadre de cette thèse stipule que l'effet de la diffusion moléculaire des chaînes du polymère sur la dispersion-distribution des lamelles d'argile d'une façon individuelle au sein du volume matriciel, sans apport du cisaillement, permet également d'atteindre un niveau avancé d'exfoliation-percolation.

Polymer bonded explosives (PBXs) are composites comprised of energetic crystals with a very high energy density surrounded by a polymer binder. The formation of hotspots within polymer bonded explosives can lead to the thermal decomposition and initiation of the energetic material. A frictional heating model is applied at the mesoscale to assess the potential for the formation of hotspots under low velocity impact loadings. Monitoring of the formation and growth of damage at the mesoscale is considered through the inclusion of a piezoresistive carbon nanotube network within the energetic binder providing embedded strain and damage sensing. A coupled multiphysics thermo-electro-mechanical peridynamics framework is developed to perform computational simulations on an energetic material microstructure subject to these low velocity impact loads. With increase in impact energy, the model predicts larger amounts of sensing and damage thereby supporting the use of carbon nanotubes to assess damage growth and subsequent formation of hotspots. The framework is also applied to assess the combined effects of thermal loading due to prescribed hotspots with inertial effects due to low velocity impact loading. It has been found that the present model is able to detect the presence of hotspot dominated regions within the energetic material through the piezoresistive sensing mechanism. The influence of prescribed hotspots on the thermo-electro-mechanical response of the energetic material under a combination of thermal and inertial loading was observed to dominate the lower velocity impact response via thermal shock damage. In contrast, the higher velocity impact energies demonstrated an inertially dominated damage response. Quantifying the piezoresistive effect derived from embedding carbon nanotubes in polymers remains a challenge since these nanocomposites exhibit significant variation in their electro-mechanical properties depending upon factors such as CNT volume fraction, CNT dispersion, CNT alignment and properties of the polymer. Of interest is electrical percolation where the electrical conductivity of the CNT/polymer nanocomposite increases through orders of magnitude with increase in CNT volume fraction. Estimates and distributions for the electrical conductivity and piezoresistive coefficients of the CNT/polymer nanocomposite are obtained and analyzed with increasing CNT volume fraction and varying barrier potential, which is a parameter that controls the extent of electron tunneling. The effect of CNT alignment is analyzed by comparing the electro-mechanical properties in the alignment direction versus the transverse direction for different orientation conditions. Estimates of piezoresistive coefficients are converted into gage factors and compared with experimental sources in literature. The methodology for this work uses automated scripts which are used in conjunction with high performance computing to generate several 5 μm ×5 μm realizations for different CNT volume fractions. These realizations are then analyzed using finite elements to obtain volume averaged effective values, which are then subsequently used to generate measures of central tendency (estimated mean) and variability (standard deviation, coefficient of variation, skewness and kurtosis) in a descriptive statistical analysis. / Doctor of Philosophy / Carbon nanotubes or CNTs belong to a class of novel materials known as nanomaterials which are materials with length scales on the order of nanometers. CNTs have been widely studied due to their unique mechanical, electrical and thermal properties in comparison to traditional materials such as metals or plastics. Often times, research and applications concerning the use of CNTs involves embedding the CNTs as a filler within a larger composite material system. In the present work, CNTs are considered to be embedded within a polymer. It is known that the electrical properties of such a CNT/polymer composite change in response to the application of a mechanical force. This change in electrical properties is caused due to the presence of CNTs and is used as a means of sensing the mechanical state of the composite, i.e. real time structural monitoring. The extent of the change in electrical properties, also known as sensing, depends upon a number of different factors such as the amount of CNTs used per unit volume of the polymer, how well dispersed or clumped together the CNTs are within the polymer and the type of polymer material used, among other factors. A statistical analysis is performed with several case studies where these factors are varied and the resulting change in the sensing response is monitored. Several important conclusions were made from the statistical analysis with some of the results providing new insights into the sensing behavior of CNT/polymer composites. For example, it was found that a key parameter known as barrier potential, which directly influences the extent of sensing achieved through a mechanism known as electrical tunneling, needs to be several orders of magnitude lower than previously reported values to accurately capture the sensing effects. Key metrics quantifying the extent of sensing from the analysis were found to be in agreement with previously reported experimental results. The significance of such a statistical study lies in the fact that CNT embedded composites are increasingly being proposed and used for sensing applications. The use of CNT embedded polymers to encase explosive crystalline grains such as HMX or RDX is one such example. These explosive grains are used in a number of different civil and military applications such as fuel rocket propellants, industry explosives, military munitions etc. The grains possess extremely high energy densities and are susceptible to undergo violent chemical reaction if a trigger is provided through thermal or mechanical means. As such, the monitoring of the structural state of these explosives is crucial for their safe handling and processing. In this work, the sensing response of a composite material comprising of explosive grains surrounded by polymer material containing CNTs is studied in response to different types of mechanical loads, ranging from mild stimuli to impact. It was found that the sensing mechanism was capable of tracking mechanical damage as well as the resulting temperature increases interior to the composite. In addition to its application to safety and preventative measures, the use of CNTs in this context also provided insight into the mechanisms related to the sudden release of energy in these explosive grains which is of significant interest since this is an active area of research as well.

A laboratory study was conducted to determine nitrogen removal rates from a land-applied wastewater as a function of the length of time the wastewater remained in the root zone. A digital simulation model was used as an aid in describing soil water (and wastewater) movement through the root zone under wet conditions (i.e. root zone 50- 75% saturated). A procedure was developed to predict the rate and volume of drainage as a function of initial soil moisture content, amount of liquid applied, and time after liquid application. An exact relationship between nitrogen removals and wastewater residence time in the root zone could not be developed. However, removals of up to 95% of applied NH₄-N were demonstrated in an 18-cm deep root zone with residence times as short as 2 hours. The exact nature of these removals was not determined. / Ph. D.