Thesis (MScEng)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: See item for full text / AFRIKAANSE OPSOMMING: Sien item vir volteks

The surface response of a polymer substrate to external stimuli such as initial wetting is controlled by the outermost molecular layer. Thus, changes on the nanoscale may be engaged to control macroscale wetting behavior. Our work has predominantly focused on surface modification of conventional polyurethane coatings (HMDI-BD-PTMO). Studies on network constrained phase separation and facile polydimethylsiloxane surface functionalization led to the discovery of a simpler one-step and more general approach to functional polymer surfaces that we have designated as “Bottle-Brush Nanoglass” (BB-NG) after the two principle components: (a) a polyoxetane soft block “spine” with side chain “A” bristles and triethoxysilyl chain ends and (b) an alkoxysilane that together with BB chain ends comprise precursors to a “nanoglass”, NG phase. This paper focuses on the extent of modification for a conventional aliphatic polyurethane using a range of fluoropolyoxetane (poly(trifluoroethoxymethyl-methyl oxetane) diol) or 3F diol based modifier concentrations. Upon generating a blend of the polyurethane with the modifier, the BB-NG which is a minor constituent of the blend, phase separates to provide the topmost layer of the coating. Initial results demonstrate that the modified polymer coatings exhibit an expected increase in contact angles with water. Wetting behavior was characterized using the sessile drop technique as well as Dynamic Contact Analysis (DCA, Wilhelmy Plate). Surface composition as well as near surface topology and morphology are characterized by X-ray Photoelectron Spectroscopy (XPS) and Tapping Mode Atomic Force Microscopy (TM-AFM) respectively. Contrast in phase images reflect the surface modulus and viscoelasticity, from which physical form or compositional differences may be deduced. These characteristics have also been explored in our study by hardness tests via nanoindentation.

The objective of this research work was to develop a methodology for experimentally estimating the interfacial properties at slag-metal interfaces. From previous experiments carried out in the division, it was decided to use surface active elements like sulfur or oxygen to trace any motion at the interface. For this purpose the following experimental investigations were carried out. Firstly the density of slag was estimated using the Archimedes Principle and the Sessile Drop technique. The density of the slag would give the molten slag height required for the surface active element to travel before reaching the slag-metal interface. Diffusivity measurements were uniquely designed in order to estimate the sulfur diffusion through slag media. It was for the first time that the chemical diffusivity was estimated from the concentration in the metal phase. Experiments carried out validated the models developed earlier. The density and diffusivity value of sulfur in the slag was used to accurately capture the time for sulfur to reach the slag-metal interface. The oscillations were identified by calculating the contact angle variations and the interfacial velocity was estimated from the change in the surface area of the liquid iron drop. The interfacial tension was estimated from the contact angles and the interfacial dilatational modulus was calculated. Based on cold model experiments using water as well as mercury, an equation of the dependence of the interfacial shear viscosity on the interfacial velocity and interfacial tension was established. This paved way for the estimation of the interfacial shear viscosity at the slag-metal interface. The present study is expected to have a strong impact on refining reactions in pyometallurgical industries where slag/metal interfaces play an important role. From a fundamental view point, this provides a deeper insight into interfacial phenomena and presents an experimental technique to quantify the same. / QC 20101130

Le chêne sessile (Quercus petraea) est une essence majeure de la sylviculture française. Sa ramification, phénomène de mise en place des rameaux, a pour origine unique les bourgeons proventifs axillaires mis en place lors de l'élongation des pousses annuelles (PA). On distingue la ramification séquentielle (les branches séquentielles) et la ramification épicormique. L'ontogénèse des épicormiques, c'est-à-dire le passage d'un bourgeon épicormique à un rameau épicormique plus complexe tel qu'un gourmand, picot ou broussin est encore peu connue. Les rameaux laissent dans le bois des marques, les traces raméales, qui peuvent fortement déprécier la qualité du bois. Etudier l'ontogénèse des rameaux épicormiques du chêne passe par un suivi longitudinal ou une analyse rétrospective des PA, ou par une dissection de l'arbre et une observation des traces raméales. Pour s'affranchir de ces méthodologies fastidieuses nous avons utilisé la tomographie à rayons X qui permet une étude exhaustive de toutes les traces raméales d'un billon, de leur ontogénèse ainsi que la reconstruction du billon en 3D. Les études menées au cours de cette thèse ont permis de mettre en évidence un important effet de l'arbre qui confère à chacun d'entre eux sa propre capacité à mettre en place et maintenir des épicormiques. Plus un arbre présente d'épicormiques dans son jeune âge, plus il en présentera quelques années plus tard. Cette tendance est modulée par la sylviculture actuelle, comme le maintien d'une végétation d'accompagnement qui joue sur les réserves en eau et carbohydrates de l'arbre, et la sylviculture passée, notamment les éclaircies fortes ayant favorisé les émissions de gourmands. Cependant la sélection précoce des arbres objectifs présentant le moins de formations épicormiques est une recommandation sylvicole de première importance dans le but de produire davantage de bois d'œuvre de la meilleure qualité possible. Une stratégie d'intégration de ces résultats dans le simulateur de croissance Fagacée est proposée.

Šiame moksliniame darbe nagrinėjama paprastojo (Quercus robur L.) ir bekočio (Q. petraea [Matt.] Liebl.) ąžuolų hibridizacija Trako miške (Alytaus raj.), bei su ja susiję ąžuolų pomiškio plitimo, lapijos nuokritų biocheminės sudėties bei įtakos dirvožemio mikrobiotai procesai. Šis darbas nuo kitų Europoje atliktų tyrimų išsiskiria savo specifika, kadangi tyrimų objektas apima bekočio ąžuolo arealo pakraštį. Nustatyta, kad tarprūšiniai hibridai Trako miške plito greičiau nei bekočiai. Trako miško motinmedžių ir jų palikuonių palyginamoji taksonominė analizė parodė, kad tarprūšinių paprastojo ir bekočio ąžuolų hibridų morfologinių lapų požymių variacija juvenaliniame amžiuje buvo didesnė nei vienos kurios tėvinių rūšių. Molekulinė-genetinė analizė patvirtino rūšinės priklausomybės nustatymo pagal morfologinius lapų požymius tinkamumą ir efektyvumą. Įrodyta, kad hibridizacijos procesams būdingas asimetrinio kryžminimosi pobūdis ir introgresijos procese dalyvauja ribotas individų skaičius. Vyrauja grįžtamasis kryžminimasis su viena iš tėvinių rūšių, šiuo atveju su bekočiu ąžuolu. Didesnė lignino koncentracija paprastojo ąžuolo lapuose sąlygojo mažesnį bakterijų ir mikroorganizmų, ypač mikromicetų, aktyvumą šio ąžuolo rizosferoje. Palyginus su paprastuoju ąžuolu, bekočio ir hibridinių ąžuolų lapų nuokritos ir rizosferos organinės medžiagos buvo intensyviau skaidomos. Todėl šių ąžuolų aplinkoje sąlygos plisti pomiškiui yra palankesnės negu po paprastaisiais ąžuolais. / This study analyzes hybridization of pedunculate (Quercus robur L.) and sessile (Q. petraea [Matt.] Liebl.) oak in forest Trakas (Alytus district), including the following processes related to hybridization: the prevalence of oak undergrowth, leaf litter fall and its biochemical composition, impact on soil microbiota. This study differs from other studies carried out in Europe by its specifics, since the research object is situated at the edge of the natural distribution of sessile oak. It was found the increase of the number of hybrid oaks in the undergrowth. A comparative taxonomic analysis of the parental trees of the Trakas forest showed that the variation of morphological traits of leaves of interspecific hybrids of pedunculate and sessile oaks was higher at juvenile age if compared with any paternal species. Molecular-genetic analysis confirmed suitability and effectiveness of the use of leaf morphological traits for species discrimination. Studies confirmed that hybridization process had a character of asymmetric crossings, a limited number of individuals participate in the introgression process. Backcross with one of the parental species – sessile oak prevails. The leaves litter fall of pedunculate oak was distinguished for a higher content of lignin, which determines decreased activeness of bacteria and, especially, micromicetes in the rhizosphere. The decomposition rate of leaves litter fall and organic compounds in rhizosphere under sessile and hybrid oaks were... [to full text]

The study presented in this dissertation concerns the evaporation, in normal ambient conditions, of sessile droplets (pinned and freely receding) of various HFE liquids (instead of the widely used water), which are considered so far as environmentally friendly and are often used as heat-transfer fluids in thermal management applications. They are pure perfectly-wetting and volatile liquids with low thermal conductivity and high vapor density. These properties affect in their own way many aspects concerning droplet evaporation such as the evaporation-induced contact angles, evaporation rate of a droplet, contact line pinning and Marangoni flow, all of which are treated in the present dissertation.<p>In general, the thesis starts with a general introduction including but not limited to sessile droplets (Chapter 1). In Chapter 2 we provide a general overview of capillarity-related concepts. Then, in Chapter 3 we present the interferometric setup, along with the liquids and the substrate that is used in the experiments, and also explain the reasons why this particular method is chosen. In Chapter 4 we address, among others, the issue of evaporation-induced contact angles under complete wetting conditions. The behavior of the global evaporation rate is also examined here, whereas in Chapter 5 we discuss the influence of thermocapillary stresses on the shape of strongly evaporating droplets. Finally, before concluding in Chapter 7, we address in Chapter 6 the still open question of the influence of non-equilibrium effects, such as evaporation, on the contact-line pinning at a sharp edge, a phenomenon usually described in the framework of equilibrium thermodynamics. The experimental results obtained are also compared with the predictions of existing theoretical models giving rise to interesting conclusions and promising perspectives for future research.<p> / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

The odorous house ant (<i>Tapinoma sessile</i>) is an adaptive and widespread pest ant species found in North America. Despite the economic and ecological impact of pest ants, effective management still faces many challenges and control failures with liquid spray insecticides in urban and natural environments. In many insects such as bed bugs and cockroaches, chemical control measures have resulted in insecticide resistance. However, in contrast to non-social insects, insecticide resistance has never been documented in social insects. The current study had three main goals. The first objective was to examine regional variation in <i>T. sessile</i> insecticide susceptibility to three classes of insecticides commonly used in urban ant control. The second objective was to compare insecticide susceptibility in <i>T. sessile</i> colonies collected in natural vs. urban areas. The final objective was to determine if insecticide susceptibility varies in workers vs. queens. A total of 30 <i>T. sessile</i> colonies were collected within a 50-mile radius of Purdue University campus, Tippecanoe County, Indiana. Fifteen colonies were collected in natural areas and 15 in urban areas. Insecticide susceptibility of all 30 colonies was tested using residual exposure assays. Urban and natural colonies showed no significant differences in tests with lambda-cyhalothrin and fipronil. In tests with dinotefuran, urban colonies were significantly more tolerant relative to natural colonies. These results suggest that habitat type does not reliably predict susceptibility levels in individual populations. Queens were found to be significantly more tolerant relative to their worker counterparts across all three insecticides. Lower insecticide susceptibility in the queens may explain why <i>T. sessile</i> is such a persistent pest in urban environments. This 15 study’s results can in part provide a foundation for the development of more effective and efficient control methods for <i>T. sessile</i>.

Serratierte Läsionen im Kolorektum stellen eine Problemzone für Kliniker und Pathologen dar; dies liegt zum einen an der noch nicht allgemein bekannten Nomenklatur, zum anderen an dem noch nicht abschließend geklärten Progressionsrisiko der verschiedenen serratierten Polypen. Mittlerweile gilt als akzeptiert, dass neben der klassischen Adenom-Karzinom-Sequenz ein alternativer serratierter und ein sogenannter gemischter Karzinogeneseweg existiert; diese Karzinogenesewege sind in Bezug auf die präinvasiven Vorstufen, die molekularen Pfade und die Prognose der Karzinome heterogen. Bei den serratierten Adenokarzinomen lassen sich ein Niedrigrisiko-Subtyp (Häufigkeit <20%, mit meist proximaler Lokalisation, dem sessilen serratierten Adenom als Vorläuferläsion, BRAF-Mutation, hoher Mikrosatelliteninstabilität, CpG-Methylierung/hMLH1-Ausfall und einer 5-Jahres-Überlebensrate von >70%) sowie ein Hochrisiko-Subtyp (Häufigkeit >80%, mit meist distaler Lokalisation, dem traditionellen serratierten Adenom als Vorläuferläsion, KRAS-Mutation, niedriger Mikrosatelliteninstabilität/mikrosatellitenstabil, CpG-Methylierung/ p53-Akkumulation und einer 5-Jahres-Überlebens-Rate von <30%) unterscheiden. Eine molekular pathologische Bestimmung des Mikrosatellitenstatus und einer BRAF-oder KRAS-Mutation in Verbindung mit einer hMLH1-und p53-Immunhistochemie lässt eine bessere Unterscheidung dieser beiden Typen zu und wird klinisch zunehmend relevant. / Serrated Lesions of the Colorectum – a Pathological or a Pathologist’s Problem? The classification and treatment of serrated lesions in the lower gastrointestinal tract remains a difficult task for clinicians and surgical pathologists; on the one hand, due to the inconsistent nomenclature of serrated lesions in the lower gastrointestinal tract and, on the other hand, due to the poor understanding of the underlying mechanisms and risk factors for progression of these lesions. It is widely accepted that in addition to the classic adenoma-carcinoma sequence a recently discovered serrated or mixed pathway is important in colorectal carcinogenesis. These two pathways are heterogeneous with regard to precursor lesions, molecular mechanisms and prognosis. Depending on their molecular signature, serrated colorectal adenocarcinomas, for instance, can be subdivided into a low-risk (frequency <20%, often with proximal location, the sessile serrated adenoma as a precursor lesion, BRAF mutation, high microsatellite instability, CpG methylation/hMLH1 loss and a 5-year survival rate of >70%) and a high-risk subtype (frequency >80%, often with distal location, the traditional serrated adenoma as a precursor lesion, KRAS mutation, low microsatellite instability/microsatellite stable, CpG methylation/ p53 accumulation and a 5-year survival rate of <30%). The evaluation of the microsatellite status as well as the detection of BRAF or KRAS mutations together with immunohistochemistry for hMLH1 and p53 will allow a discrimination between these two subtypes and will become increasingly important in the future. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

The word piezo in greek means \to compress". Piezoelectric sensors work on the principle of direct piezoelectric effect, where a mechanical input generates a corresponding electric charge. The advantages of these sensors are wide fre-quency range of operation, high stiffness and small size. The main limitation of a piezoelectric sensor is that it cannot be used in measurements that are truly static. When a piezoelectric sensor is subjected to a static force, a fixed amount of charge is developed which would eventually decay at a rate dependent on the external impedance of the sensor circuitry. Operating sensors at resonance have been one of the methods to overcome the limitation of using piezoelectric sensors for static measurements. However, since both actuation and sensing are done by the same piezoelectric element, this results in a cross-talk of input and output signals. The drawback of using single piezoelectric element for actuation and sensing is overcome in this work by using two identical elements|one for actuation and one for sensing. The operating frequency is about 10 % of the natural frequency of the sensor, thus enabling to operate the sensor in non resonant mode. Since the actuation and sensing mechanisms are separated, static measurement can be carried out. The output signal from the sensing element is monitored by a Lock-in amplifier which works on the principle of phase sensitive detection. The advantage of this sensor design is high sensitivity along with narrow band detection. It can be shown that the voltage output of the sensor Vout / a1 + m(b1 + b2F + b3K) + c1F + d1K, where m and K are the external mass and interaction stiffness, respectively, F is the force acting on it. By maintaining any two of these three quantities constant, the remaining one can be measured without any difficulty. The non resonant mode of operation makes it possible to explore the potential of this sensor in investigating mechanics of solid-liquid (viscous), solid-solid (inelastic) and solid-tissue(viscoelastic) interactions. High sensitivity, wide range of measurement (1 g{1 g) and high resolutio(0.1 g) of the non resonant mass sensor makes it possible to use it in measure-ment of very small masses of the order 1 g. Typically, resonant sensors such as quartz crystal microbalance (QCM) are used for mass measurements at that range. However, since the performance of resonant sensors is controlled by damp-ing, a phenomenon known as `missing mass effect' arises. Operating a sensor in non resonant mode (stiffness controlled mode) is a way to overcome this problem, especially when the mass is viscous and/or viscoelastic in nature. Drosophila fly, egg and larvae are the viscoelastic masses that are measured using this non res-onant sensor. Evaporating sessile drops of water and Cetyl trimethylammonium bromide (CTAB) surfactant solution from nominally flat surfaces are monitored to characterize the sensor for viscous mass measurement. Evaporation rate per unit surface area remains more or less constant, during the initial stages of evap-oration. When the surfactant concentration is varied, evaporation rate per unit surface area is highest for solutions around critical miscelle concentration (CMC). A study is carried out to understand the effect of concentrations on spreading of ink over inkjet printing paper. It is found that the spreading is least around CMC, since spreading is dependent on the rate of evaporation. The non resonant piezoelectric sensor which has high stiffness and quick re-sponse is also capable of measuring very small frictional forces. This sensor is configured to work as an inertial slider. Friction measurement at micro scales is important for designing microsystems such as stick-slip actuators. At such length scales, experiments have to performed at low loads and high excitation frequencies. The support stiffness of such systems should be high and the force of friction generated during slipping, when displacements are smaller than the contact radius, are of the order of few N. The displacement during slipping (S) is dependent on the amplitude of the input voltage to the actuation element. The frictional force measured during slipping by the sensor element indicates that the co-efficient of friction ( ) is independent of the sliding velocity. The developed non resonant sensor in this work under small amplitude exci-tation, can measure force gradient (i.e. stiffness). The total force generated when a needle is inserted into a viscoelastic material is a sum of force due to stiffness of the material, friction and the cutting force at the tip. The force due to stiffness is dominant when the needle is bending the tissue before the puncture occurs. Use of the non resonant sensor in tandem with strain gauge force sensor enables distinguishing the three components of the total force. The slope of the force-displacement (F -d) curve during the initial stages of needle penetration into the viscoelastic material, before puncture, is indicative of the stiffness of the mate-rial. The peak force measured during penetration is higher for needles with larger diameters and lower insertion velocities. The viscoelastic response (relaxation) of the material remains independent of the insertion velocity, for a given thickness of the material and a constant needle diameter. In summary, the sensor designed and developed in this work operates in stiffness controlled mode to eliminate the `missing mass effect' encountered dur-ing resonant mode of operation, has been clearly highlighted. Mass, force and stiffness measurements are possible over a wide range just by varying the ampli-tude of the input signal to the actuator element. The advantages such as high stiffness, small size and high response makes it advantageous to carry out in-situ micro scale studies in scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

The first step on the way to understanding the complicated dynamics of spray is to study the behavior of isolated droplets. In many industrial and natural processes such as turbulent combustion, agricultural sprays, spray cooler, falling raindrops and cloud evolution the droplet is subjected to a chaotic unsteady external flow field. The interaction between the liquid and gaseous phases results in very intricate droplet dynamics like capillary instabilities, atomization, droplet collision and coalescence and vaporization, to name a few. In this dissertation, the focus is on shape oscillations, atomization and vaporization dynamics of pendant and sessile droplets. A droplet residing on a substrate which vibrates vertically at ultrasonic frequency will exhibit different modes of shape oscillation. The competition between capillary forces and inertia forces is basically responsible for these oscillations. However, when an acoustic force field is introduced asymmetrically around the droplet, we discover with the help of ultra high-speed imaging, a new droplet spreading phase. This new method of droplet manipulation could nd application in micro fluidics and lab-on-a-chip systems. By lading the droplet with nanoparticles, the spreading rate can be easily controlled. The spreading phase is followed by an atomization phase where surface ligaments grow to disintegrate into daughter droplets; the intensity of atomization is found to decrease with increase in fluid viscosity. The ability to control atomization characteristics of droplets by lading them with nanoparticles is a powerful technique that may be implemented in spray coolers and combustors to control the spray characteristics or combustion efficiency. Both the spreading and ligament dynamics have been theoretically simulated and the physics behind the observed trends is explained. The growth rate of the ligaments is found to be governed by Weber number modified to include the acoustic pressure level of the standing wave. The frequency of ligament breakup is found to decrease with fluid viscosity and this observation is adequately supported by a theory developed based on the evolution crater on the droplet surface. Turning now to the pendant droplets, by decomposing the droplet shape into Legendre modes, the shape oscillations exhibited by a droplet hanging from the junction of cross-wire placed at the center of an air jet is studied. Both high-speed imaging and hot-wire anemometry are employed. The driving force of oscillation of droplets subjected to the air jet is proved to be the inherent pressure fluctuations in the jet. The effect of surface tension, viscosity and Reynolds number on the shape oscillation level has been examined. The first experimental evidence of viscous attenuation of lower frequencies in a particular mode in glycerol/water mixture is reported. A theoretical model was developed to simulate the droplet shape oscillations induced by different ambient flow fields like pulsatile flow, vortical flow and flow with broadband energy spectrum. The time of interaction of the droplet with an eddy in the flow is found to be very crucial in determining the amplitude of oscillation of the droplet. The shorter the interaction time, the higher are the chances of the droplet oscillation being pushed into resonance. Finally, the heat transfer and droplet regression dynamics of pendant droplets in a hot air stream of various chemical compositions (like conventional fuels, alternative fuels and nanosuspensions) have been experimentally analyzed using high speed imaging. The droplet is deployed at the junction of cross-wire at the centre of a vertical air jet. A hybrid timescale has been proposed which incorporates the effects of latent heat of vaporization, saturation vapor pressure and thermal diffusivity. This timescale in essence encapsulates the different parameters that influence the droplet vaporization rate. The analysis further permitted the evaluation of the effect of various parameters such as surrounding temperature, Reynolds number, far-field vapor presence, impurity content and agglomeration dynamics (nanosuspensions) in the droplet.