In order to simulate cellular blood, a coarse-grained spectrin-link (SL) red blood cell (RBC) membrane model is coupled with a lattice-Boltzmann (LB) based suspension solver. The LB method resolves the hydrodynamics governed by the Navier--Stokes equations while the SL method accurately models the deformation of RBCs under numerous configurations. This method has been parallelized using Message Passing Interface (MPI) protocols for the simulation of dense suspensions of RBCs characteristic of whole blood on world-class computing resources. Simulations were performed to study rheological effects in unbounded shear using the Lees-Edwards boundary condition with good agreement with rotational viscometer results from literature. The particle-phase normal-stress tensor was analyzed and demonstrated a change in sign of the particle-phase pressure from low to high shear rates due to RBCs transitioning from a compressive state to a tensile state in the flow direction. Non-Newtonian effects such as viscosity shear thinning were observed for shear rates ranging from 14-440 inverse seconds as well as the strong dependence on hematocrit at low shear rates. An increase in membrane bending energy was shown to be an important factor for determining the average orientation of RBCs, which ultimately affects the suspension viscosity. The shear stress on platelets was observed to be higher than the average shear stress in blood, which emphasizes the importance of modeling platelets as finite particles. Hagen-Poiseuille flow simulations were performed in rigid vessels for investigating the change in cell-depleted layer thickness with shear rate, the Fåhraeus-Linqvist effect, and the process of platelet margination. The process of platelet margination was shown to be sensitive to platelet shape. Specifically, it is shown that lower aspect ratio particles migrate more rapidly than thin disks. Margination rate is shown to increase with hematocrit, due to the larger number of RBC-platelet interactions, and with the increase in suspending fluid viscosity.

The presented research report deals with the investigation of magnesium aluminum based layered double hydroxide (LDH) as a potential nanofiller and flame-retardant for polymers with special reference to polyethylene. LDH is a mixed hydroxide of di- and trivalent metal ions that crystallizes in the form of mineral brucite. The basic reason for selecting LDH or more specifically magnesium-aluminum based LDH (Mg-Al LDH) is their typical metal hydroxide-like chemistry and conventional clay-like layered crystalline structure. The former is helpful in the direct participation in flame inhibition through endothermic decomposition and stable char formation. On the other hand, the later makes LDH suitable for polymer nanocomposite preparation, which can address the poor dispersibility problem associated with conventional metal hydroxide type fillers in polyolefin matrix. Besides, unlike layered silicate type clays (often reported for their capability to improve flame retardancy of polymers), LDH being reactive during combustion has higher efficiency to reduce the heat released during combustion of the composites. LDH clay with fixed Al:Mg ratio was synthesized using urea hydrolysis method and characterized. The organic modification of Mg-Al LDH using anionic surfactants has been studied in details. The main purpose of such modification is to enlarge the interlayer distance and to render it more organophilic. The surfactants were selected based on their functionality, chain length, etc and the modification was carried out by regeneration method. In the modified LDHs, the surfactants anions are arranged as a monolayer in the interlayer region and expand the interlayer distance according to their tail size. PE/LDH nanocomposites were prepared by melt-compounding method using a co-rotating tightly intermeshed twin-screw extruder and the morphological, mechanical and flammability properties of the nanocomposites were investigated in details. The X-ray diffraction analysis and electron microscopic analysis show a complex LDH particle morphology with hierarchy of particle size and shape starting from exfoliated particles fragments to particle aggregates over few hundred nm size. The exfoliated LDH platelets are distributed both in the vicinity of large particles and also in the bulk matrix. The melt rheological characterization of the nanocomposites also reflects the similar complex particle morphology. The dynamic oscillatory shear experiments showed that with increasing LDH concentration, the rheological behavior of the nanocomposite melts deviates strongly from that of the unfilled polyethylene. Thermogravimetric analysis (TGA) shows that LDH significantly improves the thermal stability of the polymer matrix in comparison to the unfilled polymer. The flammability studies of the PE/LDH nanocomposites have been reported in terms of various standard methods, like limited oxygen index (LOI), cone-calorimetry and UL-94 vertical and horizontal burn tests. The cone-calorimetric investigation shows that the nanocomposites have significantly lower burning rate and heat released during combustion. With increasing concentration of LDH though the LOI value of the nanocomposite increases marginally, the burning behavior, like dripping, rate of burning, etc are significantly improved. The flammability performance of LDH in combination with other commonly used flame-retardant (magnesium hydroxide) was also investigated. It has been observed that in polyethylene, a 50 wt% combination filler (4:1 weight ratio of magnesium hydroxide and LDH) can provide similar flammability ratings (like V0 rating in UL94 test, no dripping, etc) as that observed with 60 wt% magnesium hydroxide alone.

Les plaines de laves de Cerberus sur Mars présentent des morphologies volcaniques, fluviatiles et tectoniques. Une étude détaillée de cette région a permis de compiler diverses observations dans une carte géologique dont les morphologies fluviatiles et volcaniques. Les plaines de laves sont datées au plus de 250 millions d'années, et présentent des relations stratigraphiques complexes entre les volcans boucliers et les grosses coulées de lave. Les volumes de laves ont été contraints, à l'aide d'une modélisation originale de bassin, à un maximum de 17.104 km3. La cartographie des plaines de laves à permis de développer deux axes de recherche : (1) L'étude des dépôts volcaniques éoliens. L'étude de la tâche de faible albédo de Cerberus, suggère qu'il s'agit d'une strate de cendres ou de téphras mise à jour par la formation de Grjota' Vallis, distribuée par les vents vers le sud ouest de la zone. Cette tâche est finalement un témoin possible de l'activité explosive de Cerberus. (2) l'étude des dépôts effusifs. L'étude de la rhéologie des coulées de laves met en évidence deux types de viscosités indépendantes des taux d'émission, dont une se situe dans les valeurs de viscosité trouvées sur d'autres édifices martiens (105 Pa.s), et une autre qui présente les plus faibles valeurs de viscosité sur Mars (<103 Pa.s). L'absence d'édifice majeur fait des plaines de Cerberus une province volcanique unique sur Mars, dont l'évolution future reste incertaine.

An increase in environmental awareness and energy concerns had recently prompted efforts to make pavement construction cheaper and more environmentally friendly. Warm mix asphalt (WMA) is an asphalt mixture production technology that promises to reduce production costs and greenhouse gas emissions. Foamed asphalt binder is increasingly being used to produce WMA. This dissertation addresses several issues related to the use of foamed asphalt binder for WMA applications. The first objective of the research presented in this dissertation is to develop a method and metrics to precisely quantify the characteristics of asphalt binder foams. Laboratory measurements were obtained using the newly developed method to evaluate the extent and stability of foams produced using different asphalt binders at different water contents and laboratory foaming devices. Results demonstrate that the method developed is promising in terms of its ability to provide a detailed history of the behavior of foamed asphalt binder as the foam collapses. In addition, results indicate that the method is sensitive to distinguish between foaming characteristics of different asphalt binders as well as different water contents and foaming devices. The second objective of this study was to relate intrinsic properties of the asphalt binder to its foaming characteristics. A physical model was developed for expansion of asphalt binder foam based on foam physics and fluid mechanics of micro-droplets. The model relates foamant water and asphalt binder mixing efficiency with the surface tension of the asphalt binder. The model can be used to predict which binder can be effectively foamed and used, and whether any chemical modification to the binder is necessary to achieve the same. Results indicate that only a small percentage of water is effective in foaming the asphalt binder. The last objective of this research was to evaluate the influence of foaming on asphalt binder residues and mixture workability and coatability. The influence of foaming process on the rheological properties of asphalt binder residue was investigated. In addition, the significance of foamed asphalt binder characteristics on mixture workability and coatability was evaluated. Results from this last part of the study can be used to optimize binder foaming such that the resulting mixture is coated and compacted without compromising performance. / text

Polymer Nanocomposites (PNC) are a new class of materials characterized by their large interfacial areas between the host polymer and nanofiller. This unique feature, due to the size of the nanofiller, is understood to be the cause of enhanced mechanical, electrical, optical, and barrier properties observed of PNCs, relative to the properties of the unfilled polymer. This interface can determine the miscibility of the nanofiller in the polymer, which, in turn, influences the PNC's properties. In addition, this interface alters the polymer's structure near the surface of the nanofiller resulting in heterogeneity of local properties that can be expressed at the macroscopic level. Considering the polymer-nanoparticle interface significantly influences PNC properties, it is apparent that some atomistic level of detail is required to accurately predict the behavior of PNCs. Though an all-atom simulation of a PNC would be able to accomplish the latter, it is an impractical approach to pursue even with the most advanced computational resources currently available. In this contribution, we develop (1) an equilibrium coarse-graining method to predict nanoparticle dispersion in a polymer melt, (2) a dynamic coarse-graining method to predict rheological properties of polymer-nanoparticle melt mixtures, and (3) a numerical approach that includes interfacial layer effects and polymer rigidity when predicting barrier properties of PNCs. In addition to the above, we study how particle and polymer characteristics affect the interfacial layer thickness as well as how the polymer-nanoparticle interface may influence the entanglement network in a polymer melt. More specifically, we use a mean-field theory approach to discern how the concentration of a semiflexible polymer, its rigidity and the particle's size determine the interfacial layer thickness, and the scaling laws to describe this dependency. We also utilize molecular dynamics and simulation techniques on a model PNC to determine if the polymer-nanoparticle interaction can influence the entanglement network of a polymer melt. / text

No description available.

Polypropylene (PP) and ethylene-co-octene copolymer (EOC) blends were prepared at various component ratios and reinforced with silica nanoparticles (SiO2). Strategies to improve filler dispersion involved the grafting of a silane coupling agent on the PP matrix, the addition of a maleated PP (PP-g-MA) as a compatibilizer and the use of hydrophobic silica nanoparticles. These approaches resulted in a fine dispersion of the nanoparticles within the PP phase and induced a reduction of the size of the EOC domains, due to a barrier effect. Tensile and flexural properties were significantly increased, whereas ductility and impact properties were not affected. These enhancements are attributed to the favourable microstructure of the blends, featuring a segregated microstructure, and to the improved interfacial adhesion between the functionalized polymer matrix and the surface of the nanoparticles. The microstructure and rheology of model melt compounded EOC-based nanocomposites were investigated. Functionalization of the polyolefin matrix was accomplished through silane grafting, or addition of a maleated EOC (EOC-g-MA) compatibilizer. Various grades of unmodified SiO2 having different specific surface areas (SSA), as well as a surface-modified grade were added to the EOC matrix at various loadings. The formation of covalent and hydrogen bonds between the silanol groups and the functionalized polymer generated strong polymer/filler (P/F) interactions, resulting in improved filler dispersion. Bound polymer characterization revealed that in the compatibilized materials, the amount of polymer physically attached to the nanoparticles was higher than in the non-compatibilized samples. In the absence of a compatibilizer, larger SiO2 aggregates formed upon increasing SSA because of increased probability of hydrogen bonding between the particles. The increased propensity for aggregation was revealed by time sweeps as well as by the increased strain sensitivity in stress sweeps. On the contrary, the compatibilized composites exhibited a stable response and a higher critical strain for the onset of non-linearity, indicative of stronger adhesion between the fillers and the matrix. Superposition of oscillatory and creep/recovery experiments revealed that the viscoelastic properties in the terminal region were influenced substantially by the state of dispersion of the nanoparticles. In the absence of a compatibilizer, substantial enhancements in the linear viscoelastic (LVE) functions were noted and an increasing SSA resulted in more significant deviations from terminal flow. On the contrary, the SSA of the particles had no effect on the viscoelastic and mechanical properties of the compatibilized composites. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2011-04-18 15:17:52.471

Modern construction practices require proper knowledge to predict concrete pumping pressure, especially in high-volume and high-rise applications. Despite the progress made over the last decades, the spread of concrete pumping to high-rise construction has been hampered by the lack of standardized operating procedures and performance criteria. By and large, the guidelines available today focus predominantly on pumping Conventional Vibrated Concrete (CVC), while ambiguity still surrounds pumping Self-Consolidating Concrete (SCC) and other types of Highly-Workable Concrete (HWC). This PhD dissertation focuses on the fundamental principles relevant to the flow of high-strength SCC in pumping pipes, and it aims to develop methods to predict and reduce the required pumping pressure. The flow pattern of SCC in pipes is analytically investigated, providing a numerical approach to predict the pumping pressure based on the properties of both concrete and the lubrication layer, the pipe diameter, and the flow rate. The analytical results are further validated through full-scale pumping tests executed at the laboratory of the Université de Sherbrooke. Through this phase 26 optimal concrete mixtures were pumped in a 30-m pumping circuit to investigate the interactions between the concrete properties and pressure loss. The same tests are also employed to empirically correlate pressure loss with rheological and tribological properties of concrete at different flow rates. The resulting correlations furnish instrumental models capable of computing pressure loss for a wide range of concrete properties. In another application, the experimental results are analyzed to identify the influence of pumping on concrete properties with time. Full-scale pumping results are statistically analyzed in order to establish a quantitative description of the most influential parameters governing the concrete flow in pipes. As a result, concrete pipe flow is statically modeled, allowing the computation of pressure loss at different flow rates based on the the rheological and tribological properties of the concrete and the pipe diameter. Another statistical model is derived to calculate the pressure loss as a function of the V-funnel flow time, granting the advantage of predicting the pressure loss on job sites without the need for complex rheological and tribological measurements. In light of the research findings of the previous phases, a new simple test method called the pipe flow test (PFT) is developed in the context of this research, specifically for predicting pipe flow pressure loss. With preceding research phases as insights, the final stage of this project is directed toward mix design optimization faced with the challenge of reducing the pumping pressure and meeting the strength requirements of high-strength SCC. Ultimately, the research findings emanating from this investigation provide practical guidelines and conclusive models to predict and reduce pumping pressure for a wide scope of concrete mixtures and pipe diameters.

Lecithin wird unter anderem zur Steuerung der rheologischen Eigenschaften von Lebensmittelsuspensionen wie zum Beispiel Schokolade eingesetzt. In erster Linie findet dabei Sojalecithin Verwendung, wogegen die Wirkungen von Lecithinen aus Sonnenblumen oder Raps unzureichend dokumentiert sind. Anhand von Untersuchungen an Modellsuspensionen werden Wirkungsbeziehungen von Lecithin auf mikrostruktureller Ebene beleuchtet, um Ursachen für dessen Funktionalität in ölbasierten Suspensionen abzuleiten. Darüber hinaus erfolgt ein Vergleich der Wirkung von Soja-, Raps- und Sonnenblumenlecithin auf rheologische, sensorische und morphologische Eigenschaften von Schokolade. Rheologische Untersuchungen an Zucker/Öl- und Glaskugel/Öl-Suspensionen verdeutlichen den Einfluss der Suspensionsbestandteile auf die Wirkung von Lecithin in ölbasierten Suspensionen. Sedimentationsanalysen an Zucker/Öl-Suspensionen zeigen, dass die Reduktion der rheologischen Parameter mit der Senkung des Sedimentvolumens und einer verstärkt polydispersen Sedimentation einhergeht. Glaskugel/Öl-Suspensionen bilden im Vergleich zu Zucker/Öl-Suspensionen ein deutlich kompakteres Sediment, was auf geringer ausgeprägte Interaktionen zwischen den Glaspartikeln hindeutet und durch Untersuchungen mittels Rasterkraftmikroskop bestätigt wird. Die Anreicherung des Dispersionsmediums mit Lecithin führt zur Adsorption von grenzflächenaktiven Molekülen an der fest/flüssig-Grenzfläche und reduziert die adhäsiven Kräfte zwischen Zuckeroberflächen. In Zucker/Sojaöl-Suspensionen zeigen die Phospholipide Phosphatidsäure, Phosphatidylcholin und Phosphatidylethanolamin im Vergleich zu Sojalecithin eine geringer ausgeprägte Funktionalität bei kleinen Phospholipidkonzentrationen. Soja-, Raps- und Sonnenblumenlecithine besitzen in dunkler und in milchhaltiger Schokoladenmasse lediglich hinsichtlich ihrer Wirkung auf die Fließgrenze leichte Unterschiede. Die Präparate zeigen keine verallgemeinerbaren Wirkunterschiede auf die Fettkristallmorphologie und die Textur von gelagerter dunkler und milchhaltiger Schokolade. Des Weiteren lassen sensorische Untersuchungen keine signifikant ausgeprägte Präferenz für dunkle oder milchhaltige Schokolade erkennen, wenn die Probe mit Soja-, Raps- oder Sonnenblumenlecithin versetzt wird. Die Ergebnisse zeigen, dass die Reduktion der adhäsiven Kräfte zwischen Zuckerpartikeln eine Ursache für die Senkung der rheologischen Parameter und des Sedimentvolumens von Zucker/Öl-Suspensionen darstellt. Außerdem ist zu erkennen, dass bei geringen Phospholipidkonzentrationen synergetische Effekte zwischen unterschiedlichen grenzflächenaktiven Substanzen zu einem Anstieg der Funktionalität des eingesetzten Präparates führen können. Darüber hinaus ist festzustellen, dass Soja-, Raps- und Sonnenblumenlecithin die rheologischen, sensorischen und morphologischen Eigenschaften von Schokolade in gleichem Maß beeinflussen. / Lecithin is used in the food industry, for example to control the rheological properties of oil-based suspensions, such as chocolate. First and foremost, soybean lecithin is used, whereas the effects of possible alternatives, such as lecithin from sunflower or canola, are still insufficient documented. On the basis of model suspensions the effect of lecithin on the microstructural level will be investigated to derive causes of the functionality of the surfactant in oil-based suspensions. Additionally, a comparison is made regarding the effects of soybean lecithin, canola lecithin and sunflower lecithin on the rheological and morphological properties as well as on sensory characteristics of chocolate. Rheological studies illustrate the influence of the suspension components to the action of lecithin in oil-based suspensions. While, in sugar/oil-suspensions, lecithin reduces apparent viscosity and yield stress, the effect of the surfactant in glass sphere/oil-suspensions depends on the dispersion medium. Sedimentation analyses of sugar/oil-suspensions show that the reduction of the rheological parameters coincides with the reduction of the sediment volume and an increased polydisperse sedimentation. The sediment of glass sphere/oil-suspensions is more compact in comparison to sugar/oil-suspensions, indicating less pronounced interactions between glass spheres. Investigations using atomic force microscopy show the less pronounced interactions between glass spheres. While interactions (adhesive forces) are detectable between sugar surfaces dispersed in oil, no interactions can be determined between glass surfaces. The enrichment of the dispersion medium with lecithin results in the adsorption of the surfactants at the sugar surface and reduces the adhesive forces. In sugar/soybean oil suspensions and at low phospholipid concentrations the results indicate a less pronounced functionality of the individual phospholipids, phosphatidylcholine, phosphatidylethanolamine and phosphatidic acid in comparison to soybean lecithin. In dark chocolate and milk chocolate soybean lecithin, canola lecithin and sunflower lecithin reduces apparent viscosity at low to medium shear rate in the same way. In contrast, small differences in terms of their effect on the yield stress are observed. The lecithins do not show differences regarding their impact on fat crystal morphology and texture of stored dark chocolate and milk chocolate. Furthermore, in sensory studies, no significant preference differences were detectable in case of dark chocolate or milk chocolate containing soybean lecithin, canola lecithin or sunflower lecithin. The results show that the reduction of the adhesive forces between sugar particles causes the reduction of rheological parameters and the sediment volume of sugar/oil-suspensions. Furthermore, at low phospholipid concentrations possible synergistic effects between different surfactants can lead to an increase of the functionality of suractants. Additionally it can be concluded that soybean lecithin, canola lecithin and sunflower lecithin affect the rheological and morphological properties as well as the sensory characteristics of chocolate in equal measure.

Telechelic associating polymer networks consist of polymer chains terminated by endgroups that have a different chemical composition than the polymer backbone. When dissolved in a solution, the endgroups cluster together to form aggregates. At low temperature, a strongly connected reversible network is formed and the system behaves like a gel. Telechelic networks are of interest since they are representative for biopolymer networks (e.g. F-actin) and are widely used in medical applications (e.g. hydrogels for tissue engineering, wound dressings) and consumer products (e.g. contact lenses, paint thickeners). In this thesis such systems are studied by means of a molecular dynamics/Monte Carlo simulation. At first, the system in rest is studied by means of graph theory. The changes in network topology upon cooling to the gel state, are characterized. Hereto an extensive study of the eigenvalue spectrum of the gel network is performed. As a result, an in-depth investigation of the eigenvalue spectra for spatial ER, scale-free, and small-world networks is carried out. Next, the gel under the application of a constant shear is studied, with a focus on shear banding and the changes in topology under shear. Finally, the relation between the gel transition and percolation is discussed.