Enhanced Biocompatibility of NiTi (Nitinol) Via Surface Treatment and Alloying

It is projected that by 2020, there will be 138 million Americans over 45, the age at which the increased incidence of heart diseases is documented. Many will require stents. This multi-billion dollar industry, with over 2 million patients worldwide, 15% of whom use Nitinol stents have experienced a decline in sales recently, due in part to thrombosis. It is a sudden blood clot that forms inside stents. As a result, the Food and Drug Administration and American Heart Association are calling for a new generation of stents, new designs and different alloys that are more adaptable to the arteries. The future of Nitinol therefore depends on a better understanding of the mechanisms by which Nitinol surfaces can be rendered stable and inert. In this investigation, binary and ternary Nitinol alloys were prepared and subjected to various surface treatments such as electropolishing (EP), magnetoelectropolishing (MEP) and water boiling & passivation (W&P). In vitro corrosion tests were conducted on Nitinol alloys in accordance with ASTM F 2129-08. The metal ions released into the electrolyte during corrosion tests were measured by Inductively Coupled Plasma Mass Spectroscopy (ICP-MS). Biocompatibility was assessed by observing the growth of human umbilical vein endothelial cells (HUVEC) on the surface of Nitinol alloys. Static and dynamic immersion tests were performed by immersing the Nitinol alloys in cell culture media and measuring the amount of metal ions released in solution. Sulforhodamine B (SRB) assays were performed to elucidate the effect of metal ions on the growth of HUVEC cells. The surfaces of the alloys were studied using Scanning Electron Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS) respectively. Finally, wettability and surface energy were measured by Contact Angle Meter, whereas surface roughness was measured by Atomic Force Microscopy (AFM). All the surface treated alloys exhibited high resistance to corrosion when compared with untreated alloys. SRB assays revealed that Ni and Cu ions exhibited greater toxicity than Cr, Ta and Ti ions on HUVEC cells. EP and MEP alloys possessed relatively smooth surfaces and some were composed of nickel oxides instead of elemental nickel as determined by XPS. MEP exhibited lowest surface energy and lowest surface roughness.

Last Interglacial synthesis of high-latitude temperature: temperature anomalies and associated errors for 4 time slices

The Last Interglacial (LIG, 129-116 thousand of years BP, ka) represents a test bed for climate model feedbacks in warmer-than-present high latitude regions. However, mainly because aligning different palaeoclimatic archives and from different parts of the world is not trivial, a spatio-temporal picture of LIG temperature changes is difficult to obtain. Here, we have selected 47 polar ice core and sub-polar marine sediment records and developed a strategy to align them onto the recent AICC2012 ice core chronology. We provide the first compilation of high-latitude temperature changes across the LIG associated with a coherent temporal framework built between ice core and marine sediment records. Our new data synthesis highlights non-synchronous maximum temperature changes between the two hemispheres with the Southern Ocean and Antarctica records showing an early warming compared to North Atlantic records. We also observe warmer than present-day conditions that occur for a longer time period in southern high latitudes than in northern high latitudes. Finally, the amplitude of temperature changes at high northern latitudes is larger compared to high southern latitude temperature changes recorded at the onset and the demise of the LIG. We have also compiled four data-based time slices with temperature anomalies (compared to present-day conditions) at 115 ka, 120 ka, 125 ka and 130 ka and quantitatively estimated temperature uncertainties that include relative dating errors. This provides an improved benchmark for performing more robust model-data comparison. The surface temperature simulated by two General Circulation Models (CCSM3 and HadCM3) for 130 ka and 125 ka is compared to the corresponding time slice data synthesis. This comparison shows that the models predict warmer than present conditions earlier than documented in the North Atlantic, while neither model is able to produce the reconstructed early Southern Ocean and Antarctic warming. Our results highlight the importance of producing a sequence of time slices rather than one single time slice averaging the LIG climate conditions.

Half-degree gridded nitrogen and phosphorus fertilizer use for global agriculture production during 1900-2013

In addition to enhance agricultural productivity, synthetic nitrogen (N) and phosphorous (P) fertilizer application in croplands dramatically altered global nutrient budget, water quality, greenhouse gas balance, and their feedbacks to the climate system. However, due to the lack of geospatial fertilizer input data, current Earth system/land surface modeling studies have to ignore or use over-simplified data (e.g., static, spatially uniform fertilizer use) to characterize agricultural N and P input over decadal or century-long period. We therefore develop a global time-series gridded data of annual synthetic N and P fertilizer use rate in croplands, matched with HYDE 3,2 historical land use maps, at a resolution of 0.5º latitude by longitude during 1900-2013. Our data indicate N and P fertilizer use rates increased by approximately 8 times and 3 times, respectively, since the year 1961, when IFA (International Fertilizer Industry Association) and FAO (Food and Agricultural Organization) survey of country-level fertilizer input were available. Considering cropland expansion, increase of total fertilizer consumption amount is even larger. Hotspots of agricultural N fertilizer use shifted from the U.S. and Western Europe in the 1960s to East Asia in the early 21st century. P fertilizer input show the similar pattern with additional hotspot in Brazil. We find a global increase of fertilizer N/P ratio by 0.8 g N/g P per decade (p< 0.05) during 1961-2013, which may have important global implication of human impacts on agroecosystem functions in the long run. Our data can serve as one of critical input drivers for regional and global assessment on agricultural productivity, crop yield, agriculture-derived greenhouse gas balance, global nutrient budget, land-to-aquatic nutrient loss, and ecosystem feedback to the climate system.

Longitudinal Clinical Evaluation of Undercut Areas and Rest Seats of Abutment Teeth in Removable Partial Denture Treatment

PURPOSE: Adequate preparation of abutment teeth for removable partial denture (RPD) rest seats allows appropriate masticatory force transmission, retention, and stability of supporting structures. It follows that careful preparation will be important for the longevity of the rehabilitation. The present study aimed to clinically evaluate rest seats and undercut areas of abutment teeth in RPD wearers after 2 years of use. MATERIALS AND METHODS: A total of 193 occlusal, incisal, and cingulum rest seats were evaluated in terms of shape, rest adaptation, wear, caries, fractures, and surface type (enamel, composite resin, or amalgam). Two hundred and fourteen undercut areas were evaluated in terms of surface type (enamel or restoration) and integrity. This study was approved by the Research Ethics Committee of the Federal University of Rio Grande do Norte, resolution 196/1996, protocol number 11/05. RESULTS: Intact preparations accounted for 92.2% of the total. Application of the Pearson test (p= 0.289) found no statistically significant differences among the materials on which the rest seats were prepared. For the undercut areas, 20.7% of those obtained on restorative material were nonintact. In addition, Fisher's exact test showed a statistically significant difference (p= 0.001) in surface type; enamel surfaces were shown to be 14 times more stable than restored surfaces. CONCLUSIONS: The results of this study suggest that rest seats are stable, regardless of the material on which they are prepared. Retentive areas were shown to be more stable when they were located in enamel.

Longitudinal Clinical Evaluation of Undercut Areas and Rest Seats of Abutment Teeth in Removable Partial Denture Treatment

PURPOSE: Adequate preparation of abutment teeth for removable partial denture (RPD) rest seats allows appropriate masticatory force transmission, retention, and stability of supporting structures. It follows that careful preparation will be important for the longevity of the rehabilitation. The present study aimed to clinically evaluate rest seats and undercut areas of abutment teeth in RPD wearers after 2 years of use. MATERIALS AND METHODS: A total of 193 occlusal, incisal, and cingulum rest seats were evaluated in terms of shape, rest adaptation, wear, caries, fractures, and surface type (enamel, composite resin, or amalgam). Two hundred and fourteen undercut areas were evaluated in terms of surface type (enamel or restoration) and integrity. This study was approved by the Research Ethics Committee of the Federal University of Rio Grande do Norte, resolution 196/1996, protocol number 11/05. RESULTS: Intact preparations accounted for 92.2% of the total. Application of the Pearson test (p= 0.289) found no statistically significant differences among the materials on which the rest seats were prepared. For the undercut areas, 20.7% of those obtained on restorative material were nonintact. In addition, Fisher's exact test showed a statistically significant difference (p= 0.001) in surface type; enamel surfaces were shown to be 14 times more stable than restored surfaces. CONCLUSIONS: The results of this study suggest that rest seats are stable, regardless of the material on which they are prepared. Retentive areas were shown to be more stable when they were located in enamel.

Dynamic fault tree analysis with PEWMA modeling of event rates and Bayesian updating of material balance parameters using MCMC

This research explores Bayesian updating as a tool for estimating parameters probabilistically by dynamic analysis of data sequences. Two distinct Bayesian updating methodologies are assessed. The first approach focuses on Bayesian updating of failure rates for primary events in fault trees. A Poisson Exponentially Moving Average (PEWMA) model is implemnented to carry out Bayesian updating of failure rates for individual primary events in the fault tree. To provide a basis for testing of the PEWMA model, a fault tree is developed based on the Texas City Refinery incident which occurred in 2005. A qualitative fault tree analysis is then carried out to obtain a logical expression for the top event. A dynamic Fault Tree analysis is carried out by evaluating the top event probability at each Bayesian updating step by Monte Carlo sampling from posterior failure rate distributions. It is demonstrated that PEWMA modeling is advantageous over conventional conjugate Poisson-Gamma updating techniques when failure data is collected over long time spans. The second approach focuses on Bayesian updating of parameters in non-linear forward models. Specifically, the technique is applied to the hydrocarbon material balance equation. In order to test the accuracy of the implemented Bayesian updating models, a synthetic data set is developed using the Eclipse reservoir simulator. Both structured grid and MCMC sampling based solution techniques are implemented and are shown to model the synthetic data set with good accuracy. Furthermore, a graphical analysis shows that the implemented MCMC model displays good convergence properties. A case study demonstrates that Likelihood variance affects the rate at which the posterior assimilates information from the measured data sequence. Error in the measured data significantly affects the accuracy of the posterior parameter distributions. Increasing the likelihood variance mitigates random measurement errors, but casuses the overall variance of the posterior to increase. Bayesian updating is shown to be advantageous over deterministic regression techniques as it allows for incorporation of prior belief and full modeling uncertainty over the parameter ranges. As such, the Bayesian approach to estimation of parameters in the material balance equation shows utility for incorporation into reservoir engineering workflows.

Alkenones and alkenes in surface waters and sediments of the Southern Ocean

The concentration of C37-C39 long-chain alkenones and alkenes were determined in surface water and surface sediment samples from the subpolar waters of the Southern Ocean. Distributions of these compounds were similar in both sample sets indicating little differential degradation between or within compound classes. The relative amounts of the tri- to tetra-unsaturated C37 alkenones increased with increasing temperature for temperatures below 6°C similar to the di- and tri-unsaturated C37 alkenones. The C37 di-, tri-, and tetra-unsaturated methyl alkenones are used in paleotemperature calculations via the U37K and the U37K ratios. In these datasets, the relative abundances of the C37:2 and the C37.3 alkenones as a proportion of the total C37 alkenones were opposite and strongly related to temperature (the latter with more scatter), but the abundance of the C37:4 alkenone showed no relationship with temperature. The original definition of U37K includes the abundance of 37:4 in both the numerator and denominator, and thus it is perhaps not surprising that there is considerable scatter in the values obtained for U37K at low temperatures. Of the two, we suggest that U37K' is the better parameter for use in paleotemperature estimations, even in cold locations. U37K' values in the sediments fall on virtually the same regression line obtained for the water column samples of Sikes and Volkman (1993, doi:10.1016/0016-7037(93)90120-L), indicating that their calibration is suitable for use in Southern Ocean sediments. The comparison of water column data with sedimentary temperature estimates suggests that the alkenone distributions are dominated by contributions from the summer when the biomass of Emiliania huxleyi and presumably flux to the sediment, is expected to be high.

Description and composition iron-manganese concretions from the Pacific

One the most interesting features of ocean sedimentation is the manganese formations on the surface of the ocean floor in some areas. These are especially widespread in the Pacific Ocean as concretions, grains, and crusts on rock fragments and bedrock outcrops. Iron-manganese concretions are the most abundant as they completely cover about 10% of the bottom of the Pacific Ocean where there are ore concentrations. The concretions occupy from 20-50% of the bottom and up to 80-90% on separate submarine rises. Such concretions are found in different types of bottom deposits, from abyssal red clays to terrigenous muds, but they occur most widely in red clays and quite often in carbonate muds. Their shape and their dimensions are very diverse and change from place to place, from station to station, varying from 0.5-20 cm. They may be oval, globular, reniform, or slaggy and often they are fiat or isometric concretions of an indefinite shape. The concretions generally have nuclei of pumice, basalt fragments, clayey and tuffaceous material, sharks' teeth, whale ossicles, and fossil sponges. Most concretions have concentric layers, combined with dendritic ramifications of iron and manganese oxides.

Shape from photographs:a multi-view stereo pipeline

Acquiring 3D shape from images is a classic problem in Computer Vision occupying researchers for at least 20 years. Only recently however have these ideas matured enough to provide highly accurate results. We present a complete algorithm to reconstruct 3D objects from images using the stereo correspondence cue. The technique can be described as a pipeline of four basic building blocks: camera calibration, image segmentation, photo-consistency estimation from images, and surface extraction from photo-consistency. In this Chapter we will put more emphasis on the latter two: namely how to extract geometric information from a set of photographs without explicit camera visibility, and how to combine different geometry estimates in an optimal way. © 2010 Springer-Verlag Berlin Heidelberg.

Influence of cutting parameters and tool wear on martensitic stainless steel surface integrity after a face milling process

Surface finish is one of the most relevant aspects of machining operations, since it is one of the principle methods to assess quality. Also, surface finish influences mechanical properties such as fatigue behavior, wear, corrosion, etc. The feed, the cutting speed, the cutting tool material, the workpiece material and the cutting tool wear are some of the most important factors that affects the surface roughness of the machined surface. Due to the importance of the martensitic 416 stainless steel in the petroleum industry, especially in valve parts and pump shafts, this material was selected to study the influence of the feed per tooth and cutting speed on tool wear and surface integrity. Also the influence of tool wear on surface roughness is analyzed. Results showed that high values of roughness are obtained when using low cutting speed and feed per tooth and by using these conditions tool wear decreases prolonging tool life. Copyright © 2009 by ASME.

Nanostructured copper oxides and phosphates from a new solid-state route

Nanostructured copper containing materials of CuO, Cu3(PO4)3 and Cu2P2O7 have been prepared by solid-state pyrolysis of molecular CuCl2·NC5H4OH (I), CuCl2·CNCH2C6H4OH (II), oligomeric [Cu(PPh3)Cl]4 (III), N3P3[OC6H4CH2CN·CuCl]6[PF6] (IV), N3P3[OC6H5]5[OC5H4N·Cu][PF6] (V), polymeric chitosan·(CuCl2)n (VI) and polystyrene-co-4-vinylpyridine PS-b-4-PVP·(CuCl2) (VII) precursors. The products strongly depend on the precursor used. The pyrolytic products from phosphorus-containing precursors (III), (IV) and (V) are Cu phosphates or pyrophosphates, while non-phosphorous-containing precursors (VI) and (VII), result in mainly CuO. The use of chitosan as a solid-state template/stabilizer induces the formation of CuO and Cu2O nanoparticles. Copper pyrophosphate (Cu2P2O7) deposited on Si using (IV) as the precursor exhibits single-crystal dots of average diameter 100 nm and heights equivalent to twice the unit cell b-axis (1.5–1.7 nm) and an areal density of 5.1–7.7 Gigadots/in.2. Cu2P2O7 deposited from precursor (VI) exhibits unique labyrinthine high surface area deposits. The morphology of CuO deposited on Si from pyrolysis of (VI) depends on the polymer/Cu meta ratio. Magnetic measurements performed using SQUID on CuO nanoparticle networks suggest superparamagnetic behavior. The results give insights into compositional, shape and morphological control of the as-formed nanostructures through the structure of the precursors.

Elucidating the Space-Time Structure of Low Level Warm Season Precipitation Processes in the Southern Appalachian Mountains Using Models and Observations

Light rainfall is the baseline input to the annual water budget in mountainous landscapes through the tropics and at mid-latitudes. In the Southern Appalachians, the contribution from light rainfall ranges from 50-60% during wet years to 80-90% during dry years, with convective activity and tropical cyclone input providing most of the interannual variability. The Southern Appalachians is a region characterized by rich biodiversity that is vulnerable to land use/land cover changes due to its proximity to a rapidly growing population. Persistent near surface moisture and associated microclimates observed in this region has been well documented since the colonization of the area in terms of species health, fire frequency, and overall biodiversity. The overarching objective of this research is to elucidate the microphysics of light rainfall and the dynamics of low level moisture in the inner region of the Southern Appalachians during the warm season, with a focus on orographically mediated processes. The overarching research hypothesis is that physical processes leading to and governing the life cycle of orographic fog, low level clouds, and precipitation, and their interactions, are strongly tied to landform, land cover, and the diurnal cycles of flow patterns, radiative forcing, and surface fluxes at the ridge-valley scale. The following science questions will be addressed specifically: 1) How do orographic clouds and fog affect the hydrometeorological regime from event to annual scale and as a function of terrain characteristics and land cover?; 2) What are the source areas, governing processes, and relevant time-scales of near surface moisture convergence patterns in the region?; and 3) What are the four dimensional microphysical and dynamical characteristics, including variability and controlling factors and processes, of fog and light rainfall? The research was conducted with two major components: 1) ground-based high-quality observations using multi-sensor platforms and 2) interpretive numerical modeling guided by the analysis of the in situ data collection. Findings illuminate a high level of spatial – down to the ridge scale - and temporal – from event to annual scale - heterogeneity in observations, and a significant impact on the hydrological regime as a result of seeder-feeder interactions among fog, low level clouds, and stratiform rainfall that enhance coalescence efficiency and lead to significantly higher rainfall rates at the land surface. Specifically, results show that enhancement of an event up to one order of magnitude in short-term accumulation can occur as a result of concurrent fog presence. Results also show that events are modulated strongly by terrain characteristics including elevation, slope, geometry, and land cover. These factors produce interactions between highly localized flows and gradients of temperature and moisture with larger scale circulations. Resulting observations of DSD and rainfall patterns are stratified by region and altitude and exhibit clear diurnal and seasonal cycles.

Spatial Relationships among Hydroacoustic, Hydrographic and Top Predator Patterns: Cetacean Distributions in the Mid-Atlantic Bight

Effective conservation and management of top predators requires a comprehensive understanding of their distributions and of the underlying biological and physical processes that affect these distributions. The Mid-Atlantic Bight shelf break system is a dynamic and productive region where at least 32 species of cetaceans have been recorded through various systematic and opportunistic marine mammal surveys from the 1970s through 2012. My dissertation characterizes the spatial distribution and habitat of cetaceans in the Mid-Atlantic Bight shelf break system by utilizing marine mammal line-transect survey data, synoptic multi-frequency active acoustic data, and fine-scale hydrographic data collected during the 2011 summer Atlantic Marine Assessment Program for Protected Species (AMAPPS) survey. Although studies describing cetacean habitat and distributions have been previously conducted in the Mid-Atlantic Bight, my research specifically focuses on the shelf break region to elucidate both the physical and biological processes that influence cetacean distribution patterns within this cetacean hotspot.

In Chapter One I review biologically important areas for cetaceans in the Atlantic waters of the United States. I describe the study area, the shelf break region of the Mid-Atlantic Bight, in terms of the general oceanography, productivity and biodiversity. According to recent habitat-based cetacean density models, the shelf break region is an area of high cetacean abundance and density, yet little research is directed at understanding the mechanisms that establish this region as a cetacean hotspot.

In Chapter Two I present the basic physical principles of sound in water and describe the methodology used to categorize opportunistically collected multi-frequency active acoustic data using frequency responses techniques. Frequency response classification methods are usually employed in conjunction with net-tow data, but the logistics of the 2011 AMAPPS survey did not allow for appropriate net-tow data to be collected. Biologically meaningful information can be extracted from acoustic scattering regions by comparing the frequency response curves of acoustic regions to theoretical curves of known scattering models. Using the five frequencies on the EK60 system (18, 38, 70, 120, and 200 kHz), three categories of scatterers were defined: fish-like (with swim bladder), nekton-like (e.g., euphausiids), and plankton-like (e.g., copepods). I also employed a multi-frequency acoustic categorization method using three frequencies (18, 38, and 120 kHz) that has been used in the Gulf of Maine and Georges Bank which is based the presence or absence of volume backscatter above a threshold. This method is more objective than the comparison of frequency response curves because it uses an established backscatter value for the threshold. By removing all data below the threshold, only strong scattering information is retained.

In Chapter Three I analyze the distribution of the categorized acoustic regions of interest during the daytime cross shelf transects. Over all transects, plankton-like acoustic regions of interest were detected most frequently, followed by fish-like acoustic regions and then nekton-like acoustic regions. Plankton-like detections were the only significantly different acoustic detections per kilometer, although nekton-like detections were only slightly not significant. Using the threshold categorization method by Jech and Michaels (2006) provides a more conservative and discrete detection of acoustic scatterers and allows me to retrieve backscatter values along transects in areas that have been categorized. This provides continuous data values that can be integrated at discrete spatial increments for wavelet analysis. Wavelet analysis indicates significant spatial scales of interest for fish-like and nekton-like acoustic backscatter range from one to four kilometers and vary among transects.

In Chapter Four I analyze the fine scale distribution of cetaceans in the shelf break system of the Mid-Atlantic Bight using corrected sightings per trackline region, classification trees, multidimensional scaling, and random forest analysis. I describe habitat for common dolphins, Risso’s dolphins and sperm whales. From the distribution of cetacean sightings, patterns of habitat start to emerge: within the shelf break region of the Mid-Atlantic Bight, common dolphins were sighted more prevalently over the shelf while sperm whales were more frequently found in the deep waters offshore and Risso’s dolphins were most prevalent at the shelf break. Multidimensional scaling presents clear environmental separation among common dolphins and Risso’s dolphins and sperm whales. The sperm whale random forest habitat model had the lowest misclassification error (0.30) and the Risso’s dolphin random forest habitat model had the greatest misclassification error (0.37). Shallow water depth (less than 148 meters) was the primary variable selected in the classification model for common dolphin habitat. Distance to surface density fronts and surface temperature fronts were the primary variables selected in the classification models to describe Risso’s dolphin habitat and sperm whale habitat respectively. When mapped back into geographic space, these three cetacean species occupy different fine-scale habitats within the dynamic Mid-Atlantic Bight shelf break system.

In Chapter Five I present a summary of the previous chapters and present potential analytical steps to address ecological questions pertaining the dynamic shelf break region. Taken together, the results of my dissertation demonstrate the use of opportunistically collected data in ecosystem studies; emphasize the need to incorporate middle trophic level data and oceanographic features into cetacean habitat models; and emphasize the importance of developing more mechanistic understanding of dynamic ecosystems.

Study of the relation between the shape of lacosamide crystals and the composition of crystallization medium

Crystallization is the critical process used by pharmaceutical industries to achieve the desired size, size distribution, shape and polymorphism of a product material. Control of these properties presents a major challenge since they influence considerably downstream processing factors. Experimental work aimed at finding ways to control the crystal shape of Lacosamide, an active pharmaceutical ingredient developed by UCB Pharma, during crystallization was carried out. It was found that the crystal lattice displayed a very strong unidirectional double hydrogen bonding, which was at the origin of the needle shape of the Lacosamide crystals. Two main strategies were followed to hinder the hydrogen bonding and compete with the addition of a Lacosamide molecule along the crystal length axis: changing the crystallization medium or weakening the hydrogen bonding. Various solvents were tested to check whether the solvent used to crystallize Lacosamide had an influence on the final crystal shape. Solvent molecules seemed to slow down the growth in the length axis by hindering the unidirectional hydrogen bonding of Lacosamide crystals, but not enough to promote the crystal growth in the width axis. Additives were also tested. Certain additives have shown to compete in a more efficient way than solvent molecules with the hydrogen bonding of Lacosamide. The additive effect has also shown to be compatible with the solvent effect. In parallel, hydrogen atoms in Lacosamide were changed into deuterium atoms in order to weaken the hydrogen bonds strength. Weakening the hydrogen bonds of Lacosamide allowed to let the crystal grow in the width axis. Deuteration was found to be combinable with solvent effect while being in competition with the additive effect. The Lacosamide molecule was eventually deemed an absolute needle by the terms of Lovette and Doherty. The results of this dissertation are aimed at contributing to this classification.