On the statistics of transverse permeability of randomly distributed fibers

An RVE–based stochastic numerical model is used to calculate the permeability of randomly generated porous media at different values of the fiber volume fraction for the case of transverse flow in a unidirectional ply. Analysis of the numerical results shows that the permeability is not normally distributed. With the aim of proposing a new understanding on this particular topic, permeability data are fitted using both a mixture model and a unimodal distribution. Our findings suggest that permeability can be fitted well using a mixture model based on the lognormal and power law distributions. In case of a unimodal distribution, it is found, using the maximum-likelihood estimation method (MLE), that the generalized extreme value (GEV) distribution represents the best fit. Finally, an expression of the permeability as a function of the fiber volume fraction based on the GEV distribution is discussed in light of the previous results.

Effect of the processing conditions on the microstructure and properties of rotational molded polyamide 11

Rotomolded containers for solvents and hydrocarbons require the use of high-permeability resins such as polyamide (PA). The published studies with this material are very scarce. In this work, a commercial grade of PA11 was rotational-molded using different processing temperatures and characterized with a range of techniques. The study aims at investigating the influence of the processing conditions on the microstructure and properties of molded parts. The results showed that the spherulitic morphology and the mechanical properties are affected by the processing temperature, the optimum processing range being between 220°C and 240°C. Overheating causes a decrease of the impact strength and a severe increase in the formation of pinholes at the outer surface due to polymer degradation and formation of volatile products. The thermo-oxidation reactions occurring at the inner surface of the samples result in the formation of products that absorb in the UV and visible light regions and cause the microhardness and the melt viscosity of the material to increase. The extent and severity of the degradation at the inner surface may be easily assessed by fluorescence microscopy. © 2008 Wiley Periodicals, Inc.

Crystallization on the Mesoscale : Self-Assembly of Iron Oxide Nanocubes into Mesocrystals

Self-assembly of nanoparticles is a promising route to form complex, nanostructured materials with functional properties. Nanoparticle assemblies characterized by a crystallographic alignment of the nanoparticles on the atomic scale, i.e. mesocrystals, are commonly found in nature with outstanding functional and mechanical properties. This thesis aims to investigate and understand the formation mechanisms of mesocrystals formed by self-assembling iron oxide nanocubes. We have used the thermal decomposition method to synthesize monodisperse, oleate-capped iron oxide nanocubes with average edge lengths between 7 nm and 12 nm and studied the evaporation-induced self-assembly in dilute toluene-based nanocube dispersions. The influence of packing constraints on the alignment of the nanocubes in nanofluidic containers has been investigated with small and wide angle X-ray scattering (SAXS and WAXS, respectively). We found that the nanocubes preferentially orient one of their {100} faces with the confining channel wall and display mesocrystalline alignment irrespective of the channel widths.  We manipulated the solvent evaporation rate of drop-cast dispersions on fluorosilane-functionalized silica substrates in a custom-designed cell. The growth stages of the assembly process were investigated using light microscopy and quartz crystal microbalance with dissipation monitoring (QCM-D). We found that particle transport phenomena, e.g. the coffee ring effect and Marangoni flow, result in complex-shaped arrays near the three-phase contact line of a drying colloidal drop when the nitrogen flow rate is high. Diffusion-driven nanoparticle assembly into large mesocrystals with a well-defined morphology dominates at much lower nitrogen flow rates. Analysis of the time-resolved video microscopy data was used to quantify the mesocrystal growth and establish a particle diffusion-based, three-dimensional growth model. The dissipation obtained from the QCM-D signal reached its maximum value when the microscopy-observed lateral growth of the mesocrystals ceased, which we address to the fluid-like behavior of the mesocrystals and their weak binding to the substrate. Analysis of electron microscopy images and diffraction patterns showed that the formed arrays display significant nanoparticle ordering, regardless of the distinctive formation process.  We followed the two-stage formation mechanism of mesocrystals in levitating colloidal drops with real-time SAXS. Modelling of the SAXS data with the square-well potential together with calculations of van der Waals interactions suggests that the nanocubes initially form disordered clusters, which quickly transform into an ordered phase.

Impact of Rapid Transit on the Residential Market in Hudson County, New Jersey

The New York Metropolitan region is one of the most populous urban agglomerations in the world, and the single largest in North America.[1] It is also one of the most prominent economic centers, with New York City at the epicenter of its growth. With the entire region growing rapidly over the last decade, it is essential to analyze the socio-economic changes in order to understand the impact it has on commercial real estate. With its focus on housing rentals, this study aims to highlight housing costs as a function of rapid transit over time.

The influence of photon excitation and proton irradiation on the luminescence properties of yttria stabilized zirconia doped with praseodymium ions

Lanthanide doped zirconia based materials are promising phosphors for lighting applications. Transparent yttria stabilized zirconia fibres, in situ doped with Pr3+ ions, were grown by the laser floating zone method. The single crystalline doped fibres were found to be homogeneous in composition and provide an intense red luminescence at room temperature. The stability of this luminescence due to transitions between the 1D2 → 3H4 multiplets of the Pr3+ ions (intra-4f2 configuration) was studied by photo- and iono-luminescence. The evolution of the red integrated photoluminescence intensity with temperature indicates that the overall luminescence decreases to ca. 40% of the initial intensity at 14 K when heated to room temperature (RT). RT analysis of the iono-luminescence dependence on irradiation fluence reveals a decrease of the intensity (to slightly more than ∼60% of the initial intensity after 25 min of proton irradiation exposure). Nevertheless the luminescence intensity saturates at non-zero values for higher irradiation fluences revealing good potential for the use of this material in radiation environments.

Positive Encounters: An Investigative Study on the Effects of Interactions between Cations and Quantum Dots

Thesis (Ph.D.)--University of Washington, 2016-06

Sediment Budget for Cane Land on the Lower Herbert River Floodplain, North Queensland, Australia

Land use in the river catchments of tropical North Queensland appears to have increased the export of sediment and nutrients to the coast. Although evidence of harmful effect of sediment on coastal and riverine ecosystems is limited, there is a growing concern about its possible negative impacts. Sugarcane cultivation on the floodplains of the tropical North Queensland river catchments is thought to be an important source of excess sediment in the river drainage systems. Minimum-tillage, trash blanket harvesting has been shown to reduce erosion from sloping sugarcane fields, but in the strongly modified floodplain landscape other elements (e.g. drains, water furrows and headlands) could still be important sediment sources. The main objectives of this thesis are to quantify the amount of sediment coming from low-lying cane land and identify the important sediment sources in the landscape. The results of this thesis enable sugarcane farmers to take targeted measures for further reduction of the export of sediment and nutrients. Sediment budgets provide a useful approach to identify and quantify potential sediment sources. For this study a sediment budget is calculated for a part of the Ripple Creek catchment, which is a sub-catchment of the Lower Herbert River. The input of sediment from all potential sources in cane land and the storage of sediment within the catchment have been quantified and compared with the output of sediment from the catchment. Input from, and storage on headlands, main drains, minor drains and water furrows, was estimated from erosion pin and surface profile measurements. Input from forested upland, input from fields and the output at the outlet of the catchment was estimated with discharge data from gauged streams and flumes. Data for the sediment budget were collected during two ‘wet’-seasons: 1999-2000 and 2000-2001. The results of the sediment budget indicate that this tropical floodplain area is a net source of sediment. Plant cane fields, which do not have a protective trash cover, were the largest net source of sediment during the 1999-2000 season. Sediment input from water furrows was higher, but there was also considerable storage of sediment in this landscape element. Headlands tend to act as sinks. The source or sink function of drains is less clear, but seems to depend on their shape and vegetation cover. An important problem in this study is the high uncertainty in the estimates of the sediment budget components and is, for example, likely to be the cause of the imbalance in the sediment budget. High uncertainties have particularly affected the results from the 20002001 season. The main source of uncertainty is spatial variation in the erosion and deposition processes. Uncertainty has to be taken into consideration when interpreting the budget results. The observation of a floodplain as sediment source contradicts the general understanding that floodplains are areas of sediment storage within river catchments. A second objective of this thesis was therefore to provide an answer to the question: how can floodplains in the tropical North Queensland catchments can be a source of sediment? In geomorphic literature various factors have been pointed out, that could control floodplain erosion processes. However, their importance is not 'uniquely identified'. Among the most apparent factors are the stream power of the floodwater and the resistance of the floodplain surface both through its sedimentary composition and the vegetation cover. If the cultivated floodplains of the North Queensland catchments are considered in the light of these factors, there is a justified reason to expect them to be a sediment source. Cultivation has lowered the resistance of their surface; increased drainage has increased the drainage velocity and flood control structures have altered flooding patterns. For the Ripple Creek floodplain four qualitative scenarios have been developed that describe erosion and deposition under different flow conditions. Two of these scenarios were experienced during the budget study, involving runoff from local hillslopes and heavy rainfall, which caused floodplain erosion. In the longer term larger flood events, involving floodwater from the Herbert River, may lead to different erosion and deposition processes. The present study has shown that the tropical floodplain of the Herbert River catchment can be a source of sediment under particular flow conditions. It has also shown which elements in the sugarcane landscape are the most important sediment sources under these conditions. This understanding will enable sugarcane farmers to further reduce sediment export from cane land and prevent the negative impact this may have on the North Queensland coastal ecosystems.

A Study on the liquefaction risk in seismic design of foundations

A fully coupled non-linear effective stress response finite difference (FD) model is built to survey the counter-intuitive recent findings on the reliance of pore water pressure ratio on foundation contact pressure. Two alternative design scenarios for a benchmark problem are explored and contrasted in the light of construction emission rates using the EFFC-DFI methodology. A strain-hardening effective stress plasticity model is adopted to simulate the dynamic loading. A combination of input motions, contact pressure, initial vertical total pressure and distance to foundation centreline are employed, as model variables, to further investigate the control of permanent and variable actions on the residual pore pressure ratio. The model is verified against the Ghosh and Madabhushi high acceleration field test database. The outputs of this work is aimed to improve the current computer-aided seismic foundation design that relies on ground’s packing state and consistency. The results confirm that on seismic excitation of shallow foundations, the likelihood of effective stress loss is greater in deeper depths and across free field. For the benchmark problem, adopting a shallow foundation system instead of piled foundation benefitted in a 75% less emission rate, a marked proportion of which is owed to reduced materials and haulage carbon cost.

The Effect of Mark Enhancement Techniques on the Subsequent Detection of Saliva

There appears to be a limited but growing body of research on the sequential analysis/treatment of multiple types of evidence. The development of an integrated forensic approach is necessary to maximise evidence recovery and to ensure that a particular treatment is not detrimental to other types of evidence. This study aims to assess the effect of latent and blood mark enhancement techniques (e.g. fluorescence, ninhydrin, acid violet 17, black iron-oxide powder suspension) on the subsequent detection of saliva. Saliva detection was performed by means of a presumptive test (Phadebas®) in addition to analysis by a rapid stain identification (RSID) kit test and confirmatory DNA testing. Additional variables included a saliva depletion series and a number of different substrates with varying porosities as well as different ageing periods. Examination and photography under white light and fluorescence was carried out prior to and after chemical enhancement All enhancement techniques (except Bluestar® Forensic Magnum luminol) employed in this study resulted in an improved visualisation of the saliva stains, although the inherent fluorescence of saliva was sometimes blocked after chemical treatment. The use of protein stains was, in general, detrimental to the detection of saliva. Positive results were less pronounced after the use of black iron-oxide powder suspension, cyanoacrylate fuming followed by BY40 and ninhydrin when compared to the respective positive controls. The application of Bluestar® Forensic Magnum luminol and black magnetic powder proved to be the least detrimental, with no significant difference between the test results and the positive controls. The use of non-destructive fluorescence examination provided good visualisation; however, only the first few marks in the depletion were observed. Of the samples selected for DNA analysis only depletion 1 samples contained sufficient DNA quantity for further processing using standard methodology. The 28 day delay between sample deposition and collection resulted in a 5-fold reduction in the amount of useable DNA. When sufficient DNA quantities were recovered, enhancement techniques did not have a detrimental effect on the ability to generate DNA profiles. This study aims to contribute to a strategy for maximising evidence recovery and efficiency for the detection of latent marks and saliva. The results demonstrate that most of the enhancement techniques employed in this study were not detrimental to the subsequent detection of saliva by means of presumptive, confirmative and DNA tests.

The effect of ionic Co presence on the structural, optical and photocatalytic properties of modified cobalt–titanate nanotubes

With the aim of producing materials with enhanced optical and photocatalytic properties, titanate nanotubes (TNTs) modified by cobalt doping (Co-TNT) and by Na+ -> Co ion-exchange (TNT/Co) were successfully prepared by a hydrothermal method. The influence of the doping level and of the cobalt position in the TNT crystalline structure was studied. Although no perceptible influence of the cobalt ion position on the morphology of the prepared titanate nanotubes was observed, the optical behaviour of the cobalt modified samples is clearly dependent on the cobalt ions either substituting the Ti4+ ions in the TiO6 octahedra building blocks of the TNT structure (doped samples) or replacing the Na+ ions between the TiO6 interlayers (ion-exchange samples). The catalytic ability of these materials on pollutant photodegradation was investigated. First, the evaluation of hydroxyl radical formation using the terephthalic acid as a probe was performed. Afterwards, phenol, naphthol yellow S and brilliant green were used as model pollutants. Anticipating real world situations, photocatalytic experiments were performed using solutions combining these pollutants. The results show that the Co modified TNT materials (Co-TNT and TNT/Co) are good catalysts, the photocatalytic performance being dependent on the Co/Ti ratio and on the structural metal location. The Co(1%)-TNT doped sample was the best photocatalyst for all the degradation processes studied.

Remarks on the morphology and distribution of some rare centric diatoms in southern Brazilian continental shelf and slope waters

This paper provides information on the morphology and occurrence of extant diatoms of the family Asterolampraceae and Azpeitia species of the southernmost Brazilian continental shelf and slope waters in the Southwestern Atlantic Ocean (28 - 34°S), under the influence of Tropical, Subtropical, Subantarctic Waters, terrestrial discharges from La Plata River and Lagoa dos Patos lagoon. Plankton was sampled (20 µm net; vertical hauls) at the same 27 stations in winter 2005 and summer 2007. Among Asterolampraceae, Asteromphalus flabellatus was the most frequent species (57% of samples) observed mainly in winter samples (92%) in Subtropical Shelf Water but also under the influence of La Plata River plume (salinity <35). Lower frequencies were observed for Asterolampra marylandica, Asteromphalus elegans, Asteromphalus heptactis and Spatangidium arachne. Four species of Azpeitia were observed: A. barronii and A. neocrenulata for the first time in the South Atlantic Ocean while A. africana and A. nodulifer had already been registered in equatorial and southern areas of Brazil. All Azpeitia species were rare (19%) in offshore samples (100-200 m depth. Remarks on the morphology based on light and scanning electron microcopy observations are provided along with their distribution in the study area.

Translating Wordplay: A case study on the translation of wordplay in Terry Pratchett’s Soul Music

Wordplay and the translation of wordplay is a complex subject that has been addressed by various studies. The combination of a single form and multiple meanings created by wordplay makes it challenging to translate. Translating wordplay has even been considered impossible. This thesis explores wordplay and the translation of wordplay through an analysis of wordplay found in an English novel and its Finnish translation. The purpose is to shed light on the problems and solutions found in the data. The study consists of a quantitative analysis and a subsequent discussion on the findings. The findings from the study indicate that cultural aspects such as idioms and allusions are especially problematic when it comes to translating wordplay. Also, the communicative functions of wordplay were found to be central for a successful translation. It is concluded that these aspects require further study.

Effects of unilateral visual deprivation on the developing avian brain

The effect of varying states of visual deprivation on the development of the optic lobes and cerebral hemispheres has been studied in the chick where the visual pathways are totally crossed over. Unilateral eye extirpation of the new hatched chick resulted in arrested development of the contralateral but not ipsilateral lobe, as measured by weight, protein content and acetylcholinesterase activity. Similar effects but of smaller magnitude were observed in the cerebral hemispheres. Histologic and enzymic evidence revealed the absence of significant degeneration in the optic lobe contralateral to an eye removed 17 days previously. These results were observed in the optic lobes of operated animals maintained either in light of in darkness between 3 and 17 days after hatch. However, in the inpaired cerebral hemispheres, differences could only be detected in birds kept the light. The effects of unilateral eyelid suturing on the development of chick brain regions were also examined. In this group, all asymmetrical differences observed within paired brain regions were totally light dependent and confined to the cerebral hemispheres. The hemisphere contralateral to the sutured eye weighed less and had less acetylcholinesterase activity than its paired hemisphere. The cerebral hemispheres of monocularly treated birds manifested effects of similar magnitude whether the treatment was enucleation or suturing. This suggests that the complete development of the associative centers in avian cerebral hemispheres is dependent on both intact innervation and on the information content of the visual input. © 1969.

Studies on the synthesis of novel PP2A inhibitors and a GPCR detergent

Chapter 1 While targeting kinases in oncology research has been explored extensively, targeting protein phosphatases is currently in its infancy. However, a number of pharmaceutical companies are currently looking to expand their research efforts in this area. PP2A has been shown to down-regulate ERK5, a mitogen-activated protein kinase (MAPK) that has been shown to be important in driving the invasive phenotype of prostate cancer. Fostriecin and its related structural analogues PD 113,270 and 113,271 have been shown to inhibit a mitotic entry checkpoint in cell growth through the potent and selective inhibition of protein phosphatases PP1, PP2A, and PP4 (IC50 of 45 μM, 1.5 nM, and 3 nM respectively). Fostriecin is one of the most selective protein phosphatase inhibitors disclosed to date with a 104 fold selectivity for PP2A/PP4 versus PP1. Unfortunately, fostriecin and its analogues are very unstable, and this instability has effectively prevented them from being used as effective therapeutic leads. The microcystins and nodularins on the other hand, exhibit significant inhibitory activity against PP1 and PP2A (IC50 = 26 pM and 1.8 nM respectively), but their high toxicity has prevented any therapeutic application. Truncation of the ADDA chain from these polypeptides completely attenuates PP inhibitory activity. Simpler analogues incorporating the N-acylated ADDA chain and D-Ala retain moderate activity against PP1 and PP2A (IC50 = 1.0 μM and 0.17 μM respectively). The generation of a new series of fostriecin analogues to further expand its structure-activity relationship is envisaged with a view to creating new more stable PP2A inhibitors. It was hoped that by incorporating some of the more stable structural features of ADDA into fostriecin that stability and activity could be reconciled. With that in mind a series of PP2A inhibitors were synthesised and biologically evaluated. Chapter 2 GPCRs are an important area of research and are the targets of a quarter of the drugs on the market (2005). As a result, GPCRs continue to be at the forefront of research in both small and large drug companies. However one of the difficulties in studying this diverse class of membrane proteins is their tendency to denature in aqueous solution. As a result there is a pressing need to develop new detergents to solubilise, stabilise and crystallise GPCRs in their native form for further study. Cholesterol analogues have been shown to be important for stabilising membrane proteins and preventing their thermal inactivation. In addition the β2-adrenergic receptor, a GPCR membrane protein, has been crystallised in the active state with two cholesterol molecules bound between the I, II, III and IV helices of the protein. This appears to represent a distinct cholesterol binding pocket on the membrane protein that is speculated to be conserved across up to 44% of the rhodopsin class of GPCRs. CHOBIMALT is a cholesterol-based detergent that has been shown to exhibit promising GPCR-stabilising properties. When benchmarked against other cholesterol based detergents it was found to be superior to all others tested except for cholesteryl hemisuccinate.1 CHOBIMALT has an aggregation number of roughly 200 and forms 210 ± 30 kDa micelles, which are significantly larger than those of most detergents used for biological systems which is likely due to the packing constraints associated with CHOBMALT’s large polar headgroup.2 As a result, CHOBIMALT is used mostly as an additive to other commercially available detergents in order to decrease micelle size. A branched dimaltoside motif is common in recently synthesised detergents by Chae and co-workers. These detergents have shown promising detergent properties, for example the maltose neopentyl glycol (MNG) detergent synthesised by Chae. This branched dimaltoside detergent was shown to be able to solubilise and stabilise the very labile light harvesting complex I (LHI) from Rhodopsin capsulatus in its active form for 20 days with little loss of protein conformation.3 A cholesterol-based detergent was envisaged that combines the cholesterol framework of CHOBIMALT but replaces its linear tetrasaccharide with a branched dimaltoside. This detergent would then be investigated to assess its ability to solubilise, stabilise and crystallise GPCR proteins. This cholesterol-based detergent (shown below) was eventually synthesised in 9 linear steps from cholesterol.