Understanding near Fermi-level electronic structure through x-ray emission spectroscopy

Thesis (Ph.D.)--University of Washington, 2016-08

Optical emission spectroscopy as a process-monitoring tool in PECVD of amorphous carbon coatings

Dans ce projet de recherche, le dépôt des couches minces de carbone amorphe (généralement connu sous le nom de DLC pour Diamond-Like Carbon en anglais) par un procédé de dépôt chimique en phase vapeur assisté par plasma (ou PECVD pour Plasma Enhanced Chemical Vapor deposition en anglais) a été étudié en utilisant la Spectroscopie d’Émission Optique (OES) et l’analyse partielle par régression des moindres carrés (PLSR). L’objectif de ce mémoire est d’établir un modèle statistique pour prévoir les propriétés des revêtements DLC selon les paramètres du procédé de déposition ou selon les données acquises par OES. Deux séries d’analyse PLSR ont été réalisées. La première examine la corrélation entre les paramètres du procédé et les caractéristiques du plasma pour obtenir une meilleure compréhension du processus de dépôt. La deuxième série montre le potentiel de la technique d’OES comme outil de surveillance du procédé et de prédiction des propriétés de la couche déposée. Les résultats montrent que la prédiction des propriétés des revêtements DLC qui était possible jusqu’à maintenant en se basant sur les paramètres du procédé (la pression, la puissance, et le mode du plasma), serait envisageable désormais grâce aux informations obtenues par OES du plasma (particulièrement les indices qui sont reliées aux concentrations des espèces dans le plasma). En effet, les données obtenues par OES peuvent être utilisées pour surveiller directement le processus de dépôt plutôt que faire une étude complète de l’effet des paramètres du processus, ceux-ci étant strictement reliés au réacteur plasma et étant variables d’un laboratoire à l’autre. La perspective de l’application d’un modèle PLSR intégrant les données de l’OES est aussi démontrée dans cette recherche afin d’élaborer et surveiller un dépôt avec une structure graduelle.

Microstructure, vibrational and visible emission properties of low frequency ultrasound (42 kHz) assisted ZnO nanostructures

Size and shape tuneable ZnO nanostructures were prepared by a low frequency ultrasound (42 kHz) route using various organic solvents as the reaction media. The crystalline nature, lattice parameters and microstructural parameters such as microstrain, stress and energy density of the prepared ZnO nanostructures were revealed through X-ray diffraction (XRD) analysis. The organic solvents influenced the size and morphology of the ZnO nanostructures, and interesting morphological changes involving a spherical to triangular shaped transition were observed. The visible emission properties and lattice vibrational characteristics of the nanostructures were drastically modified by the changes in size and shape. Raman spectral measurements revealed the presence of multiphonon processes in the ZnO nanostructures. The intensity of the visible emission band was found to vary with the size and morphology of the structures. The strongest visible emission band corresponded to the structure with the largest surface/volume ratio and could be attributed to surface oxygen vacancies. The control over the size and morphology of ZnO nanostructures has been presented as a means of determining the intensity of the visible emission band

Ruminal methane emission by dairy cattle in southeast Brazil.

ABSTRACT: Ruminal gases, particularly methane, generated during the fermentative process in rumen, represent a partial loss of feed energy and are also pointed to as an important factors in greenhouse effect. This study aimed at quantifying methane (CH 4) emission rates from lactating and dry cows and heifers, 24 month-old in average, on pasture under Southeast Brazil tropical conditions, using the tracer gas technique, sulphur hexafluoride (SF 6), four animals per category, distributed in four blocks. Measurements were performed in February and June, 2002, with Holstein and Brazilian Dairy Crossbred (Holstein ¾ x Gir (Zebu) ¼), maintained on fertilized Tanzania-grass (Panicum maximum Jacq. cv. Tanzania) and fertilized Brachiaria-grass (Brachiaria decumbens cv. Basilisk) pastures. Heifers of both breeds were maintained on unfertilized Brachiaria-grass to simulate conditions of extensive cattle farming systems. CH 4 and SF 6 levels were measured with gas chromatography. Differences in CH4 emissions were measured (p < 0.05) for genetical groups. Holstein produced more methane (299.3g day?1) than the Crossbred (264.2 g day?1). Lactating cows produced more methane (353.8 g day?1) than dry cows (268.8 g day?1) and heifers (222.6 g day?1). Holstein, with greater milk production potential, produced less CH4 (p < 0.05) per unit of dry matter intake (19.1 g kg?1) than the Crossbred (22.0 g kg?1). Methane emission by heifers grazing fertilized pasture (intensive system) was 222.6 g day?1, greater (p < 0.05) than that of heifers on unfertilized pasture (179.2 g day?1). Methane emission varied as function of animal category and management intensity of production system.

Effect of Pavement-Vehicle Interaction on Highway Fuel Consumption and Emission

Vehicle fuel consumption and emission are two important effectiveness measurements of sustainable transportation development. Pavement plays an essential role in goals of fuel economy improvement and greenhouse gas (GHG) emission reduction. The main objective of this dissertation study is to experimentally investigate the effect of pavement-vehicle interaction (PVI) on vehicle fuel consumption under highway driving conditions. The goal is to provide a better understanding on the role of pavement in the green transportation initiates. Four study phases are carried out. The first phase involves a preliminary field investigation to detect the fuel consumption differences between paired flexible-rigid pavement sections with repeat measurements. The second phase continues the field investigation by a more detailed and comprehensive experimental design and independently investigates the effect of pavement type on vehicle fuel consumption. The third study phase calibrates the HDM-IV fuel consumption model with data collected in the second field phase. The purpose is to understand how pavement deflection affects vehicle fuel consumption from a mechanistic approach. The last phase applies the calibrated HDM-IV model to Florida’s interstate network and estimates the total annual fuel consumption and CO2 emissions on different scenarios. The potential annual fuel savings and emission reductions are derived based on the estimation results. Statistical results from the two field studies both show fuel savings on rigid pavement compared to flexible pavement with the test conditions specified. The savings derived from the first phase are 2.50% for the passenger car at 112km/h, and 4.04% for 18-wheel tractor-trailer at 93km/h. The savings resulted from the second phase are 2.25% and 2.22% for passenger car at 93km/h and 112km/h, and 3.57% and 3.15% for the 6-wheel medium-duty truck at 89km/h and 105km/h. All savings are statistically significant at 95% Confidence Level (C.L.). From the calibrated HDM-IV model, one unit of pavement deflection (1mm) on flexible pavement can cause an excess fuel consumption by 0.234-0.311 L/100km for the passenger car and by 1.123-1.277 L/100km for the truck. The effect is more evident at lower highway speed than at higher highway speed. From the network level estimation, approximately 40 million gallons of fuel (combined gasoline and diesel) and 0.39 million tons of CO2 emission can be saved/reduced annually if all Florida’s interstate flexible pavement are converted to rigid pavement with the same roughness levels. Moreover, each 1-mile of flexible-rigid conversion can result in a reduction of 29 thousand gallons of fuel and 258 tons of CO2 emission yearly.

Effects Of Misalignments In The Retinal Nerve Fiber Layer Thickness Measurements With Spectral Domain Optical Coherence Tomography.

Purpose. To investigate misalignments (MAs) on retinal nerve fiber layer thickness (RNFLT) measurements obtained with Cirrus(©) SD-OCT. Methods. This was a retrospective, observational, cross-sectional study. Twenty-seven healthy and 29 glaucomatous eyes of 56 individuals with one normal exam and another showing MA were included. MAs were defined as an improper alignment of vertical vessels in the en face image. MAs were classified in complete MA (CMA) and partial MA (PMA), according to their site: 1 (superior, outside the measurement ring (MR)), 2 (superior, within MR), 3 (inferior, within MR), and 4 (inferior, outside MR). We compared RNFLT measurements of aligned versus misaligned exams in all 4 sectors, in the superior area (sectors 1 + 2), inferior area (sectors 3 + 4), and within the measurement ring (sectors 2 + 3). Results. RNFLT measurements at 12 clock-hour of eyes with MAs in the superior area (sectors 1 + 2) were significantly lower than those obtained in the same eyes without MAs (P = 0.043). No significant difference was found in other areas (sectors 1 + 2 + 3 + 4, sectors 3 + 4, and sectors 2 + 3). Conclusion. SD-OCT scans with superior MAs may present lower superior RNFLT measurements compared to aligned exams.

Vertical Bone Measurements From Cone Beam Computed Tomography Images Using Different Software Packages.

This article aimed at comparing the accuracy of linear measurement tools of different commercial software packages. Eight fully edentulous dry mandibles were selected for this study. Incisor, canine, premolar, first molar and second molar regions were selected. Cone beam computed tomography (CBCT) images were obtained with i-CAT Next Generation. Linear bone measurements were performed by one observer on the cross-sectional images using three different software packages: XoranCat®, OnDemand3D® and KDIS3D®, all able to assess DICOM images. In addition, 25% of the sample was reevaluated for the purpose of reproducibility. The mandibles were sectioned to obtain the gold standard for each region. Intraclass coefficients (ICC) were calculated to examine the agreement between the two periods of evaluation; the one-way analysis of variance performed with the post-hoc Dunnett test was used to compare each of the software-derived measurements with the gold standard. The ICC values were excellent for all software packages. The least difference between the software-derived measurements and the gold standard was obtained with the OnDemand3D and KDIS3D (-0.11 and -0.14 mm, respectively), and the greatest, with the XoranCAT (+0.25 mm). However, there was no statistical significant difference between the measurements obtained with the different software packages and the gold standard (p> 0.05). In conclusion, linear bone measurements were not influenced by the software package used to reconstruct the image from CBCT DICOM data.

Measurements of jaw movements and TMJ pain intensity in patients treated with GaAlAs laser

The aim of this study was to evaluate the effectiveness of low-level laser therapy (LLLT) on the improvement of the mandibular movements and painful symptoms in individuals with temporomandibular disorders (TMD). Forty patients were randomly divided into two groups (n=20): Group 1 received the effective dose (GaAlAs laser ? 830 nm, 40 mW, 5J/cm2) and Group 2 received the placebo application (0 J/cm2), in continuous mode on the affected condyle lateral pole: superior, anterior, posterior, and posterior-inferior, twice a week during 4 weeks. Four evaluations were performed: E1 (before laser application), E2 (right after the last application), E3 (one week after the last application) and E4 (30 days after the last application). The Kruskal-Wallis test showed significant more improvements (p<0.01) in painful symptoms in the treated group than in the placebo group. A significant improvement in the range of mandibular movements was observed when the results were compared between the groups at E4. Laser application can be a supportive therapy in the treatment of TMD, since it resulted in the immediate decrease of painful symptoms and increased range of mandibular movements in the treated group. The same results were not observed in the placebo group.

Adhesion of an endodontic sealer to dentin and gutta-percha: shear and push-out bond strength measurements and SEM analysis

The use of an adequate method for evaluation of the adhesion of root canal filling materials provides more reliable results to allow comparison of the materials and substantiate their clinical choice. The aims of this study were to compare the shear bond strength (SBS) test and push-out test for evaluation of the adhesion of an epoxy-based endodontic sealer (AH Plus) to dentin and gutta-percha, and to assess the failure modes on the debonded surfaces by means of scanning electron microscopy (SEM). Three groups were established (n=7): in group 1, root cylinders obtained from human canines were embedded in acrylic resin and had their canals prepared and filled with sealer; in group 2, longitudinal sections of dentin cylinders were embedded in resin with the canal surface smoothed and turned upwards; in group 3, gutta-percha cylinders were embedded in resin. Polyethylene tubes filled with sealer were positioned on the polished surface of the specimens (groups 2 and 3). The push-out test (group 1) and the SBS test (groups 2 and 3) were performed in an Instron universal testing machine running at crosshead speed of 1 mm/min. Means (±SD) in MPa were: G1 (8.8±1.13), G2 (5.9±1.05) and G3 (3.8±0.55). Statistical analysis by ANOVA and Student's t-test (a=0.05) revealed statistically significant differences (p<0.01) among the groups. SEM analysis showed a predominance of adhesive and mixed failures of AH Plus sealer. The tested surface affected significantly the results with the sealer reaching higher bond strength to dentin than to gutta-percha with the SBS test. The comparison of the employed methodologies showed that the SBS test produced significantly lower bond strength values than the push-out test, was skilful in determining the adhesion of AH Plus sealer to dentin and gutta-percha, and required specimens that could be easily prepared for SEM, presenting as a viable alternative for further experiments.

Psychophysical measurements of luminance and chromatic spatial and temporal contrast sensitivity in Duchenne muscular dystrophy

In children with Duchenne muscular dystrophy, color vision losses have been related to dystrophin deletions downstream of exon 30, which affect a dystrophin isoform, Dp260, present in the retina. To further evaluate visual function in DMD children, we measured spatial, temporal, and chromatic red-green and blue-yellow contrast sensitivity in two groups of DMD children with gene deletion downstream and upstream of exon 30. Psychophysical spatial contrast sensitivity was measured for low, middle, and high spatial frequencies with achromatic gratings and for low and middle frequencies with red-green and blue-yellow chromatic gratings. Temporal contrast sensitivity was also measured with achromatic stimuli. A reduction in sensitivity at all spatial luminance contrasts was found for the DMD patients with deletion downstream of exon 30. Similar results were found for temporal luminance contrast sensitivity. Red-green chromatic contrast sensitivity was reduced in DMD children with deletion downstream of exon 30, whereas blue-yellow chromatic contrast sensitivity showed no significant differences. We conclude that visual function is impaired in DMD children. Furthermore, we report a genotype-phenotype relationship because the visual impairment occurred in children with deletion downstream but not upstream of exon 30, affecting the retinal isoform of dystrophin Dp260.

Time resolved emission spectroscopy of poly(2,5-dicyano-p-phenylene-vinylene) films

Films of poly (2,5-dicyano-p-phenylene vinylene), DCNPPV, were obtained by electrochemical synthesis over gold thin layer (20 nm) transparent electrode deposited on a glass plate. The DCNPPV films of 4 µm thickness were produced by electropolymerization process of α,α,α',α'-tetrabromo-2-5-dicyano-p-xilene at different applied potentials (-0.15, -0.25, -0.40, -0.60, -0.80, and -1.0 V) using 0.1 mol L-1 of tetraethylammonium bromide in acetonitrile as the supporting electrolyte. The emission decays have three exponential components: a fast component in the picosecond range (200-400 ps), and two other of about one and five nanoseconds at 293 K. The fluorescence quenching process seems to occur by exciton trapping in a low-energy site and quenching by residual bromine monomer attached at the end of the polymer chain. However, the electrochemical synthesis generates entrapped bromide or ion pairs during the growth step of the film which also contributes to the deactivation. The change of the electrolyte from bromide to perchlorate reduces significantly this additional quenching effect by allowing ion exchange of formed bromide with the nonquenching perchloride anion.

Determination and fractionation of barium in Brazil nuts

Several sample preparation strategies were employed for determination and fractionation of barium in Brazil nuts using measurements by graphite furnace atomic absorption spectrometry (GF AAS) and inductively coupled plasma optical emission spectrometry with axial view (ICP OES). This food is widely consumed because of its nutritional value and good taste. The chemical analysis of Brazil nuts is not trivial due to their complex matrix. The fractionation of barium in Brazil nuts was studied owing to the toxicity of this element and the strong correlation between chemical form and absorption. Total concentrations of barium varied from 860 to 2084 mg kg-1. Sequential extractions were performed based on solubility in different media and also according to lipids, proteins and low molecular weight fractions (LMW). The greatest contents of barium were determined in the LMW and in the water insoluble fractions with concentrations in the range 778 to 1606 and 551 to 1520 mg kg-1, respectively. Based on these results it can be inferred that Ba is not absorbed when Brazil nuts are ingested. Considering both the contents of barium and sulfur in different fractions and stoichiometric calculations it was also possible to assume that barium occurs mainly in the BaSO4 form. The presence of this chemical form was also confirmed by thermogravimetric measurements.

Metallochlorophylls of magnesium, copper and zinc: evaluation of the influence of the first coordination sphere on their solvatochromism and aggregation properties

In this study the role of different metal centers (magnesium, zinc and copper) on the enhancement of the hydrophilic character of metallochlorophylls, was evaluated. The solvatochromism as well as the aggregation process for these compounds in water/ethanol mixtures at different volume ratios were evaluated using Fluorescence, and Resonant Light Scattering (RLS) measurements, aiming to characterize the behavior of these compounds. Independently on the studied metallochlorophyll, the presence of at least 60% of water results in a considerable increase in the fluorescence emission, probably a direct consequence of a lower aggregation of these compounds, which is confirmed by the results from RLS measurements. Additionally, the results suggest that magnesium and zinc chlorophyll should be promising phototherapeutic agents for Photodynamic Therapy.

Reproducibility, reliability and validity of measurements obtained from Cecile3 digital models

The aim of this study was to determine the reproducibility, reliability and validity of measurements in digital models compared to plaster models. Fifteen pairs of plaster models were obtained from orthodontic patients with permanent dentition before treatment. These were digitized to be evaluated with the program Cécile3 v2.554.2 beta. Two examiners measured three times the mesiodistal width of all the teeth present, intercanine, interpremolar and intermolar distances, overjet and overbite. The plaster models were measured using a digital vernier. The t-Student test for paired samples and interclass correlation coefficient (ICC) were used for statistical analysis. The ICC of the digital models were 0.84 ± 0.15 (intra-examiner) and 0.80 ± 0.19 (inter-examiner). The average mean difference of the digital models was 0.23 ± 0.14 and 0.24 ± 0.11 for each examiner, respectively. When the two types of measurements were compared, the values obtained from the digital models were lower than those obtained from the plaster models (p < 0.05), although the differences were considered clinically insignificant (differences < 0.1 mm). The Cécile digital models are a clinically acceptable alternative for use in Orthodontics.

Load Ratio Estimation Through Striation Height and Spacing Analysis of an Aerospace Al Alloy 7475-T7351

It is well known that striation spacing may be related to the crack growth rate, da/dN, through Paris equation, as well as the maximum and minimum loads under service loading conditions. These loads define the load ratio, R, and are considered impossible to be evaluated from the inter-spacing striations analysis. In this way, this study discusses the methodology proposed by Furukawa to evaluate the maximum and minimum loads based on the experimental fact that the relative height of a striation, H, and the striation spacing, s, are strongly influenced by the load ratio, R. Fatigue tests in C(T) specimens were conducted on SAE 7475-T7351 Al alloy plates at room temperature and the results showed a straightforward correlation between the parameters H, s, and R. Measurements of striation height, H, were performed using scanning electron microscopy and field emission gun (FEG) after sectioning the specimen at a large inclined angle to amplify the height of the striations. The results showed that for increasing R the values of H/s tend to increase. Striation height, striation spacing, and load ratio correlations were obtained, which allows one to estimate service loadings from fatigue fracture surface survey.