Surface studies of some metallic thin films by optical methods

The thesis aims to present the results of experimental investigations on the changes of optical properties of metallic thin films due to heating. The parameters which are measured are reflectivity, refractive indices and the ellipsometric quantities V and A . The materials used in the studies are metals like Silver, Aluminium and Copper. By applying the optical method the interdiffusion taking place in multilayer ‘films of Aluminium and Silver has also been studied. Special interest has been taken to reveal the mechanisms of the hillock growth and surface roughness caused by heating and their relation with the stress in the film

Changes in guava (Psidium guajava L. var. Paluma) nectar volatile compounds concentration due to thermal processing and storage

Guava nectars were formulated for approximately 10, 12, or 14 ºBrix, with 40% guava pulp. Sodium benzoate, 500 mg.kg-1 was used as preservative. The Brix value was adjusted with saturated sucrose syrup. The guava nectar was pasteurized (85 ºC/42 seconds) in tubular heat exchanger and then hot filled in 500 mL white glass bottles. The products were stored either at room temperature (25 ± 5 ºC) or refrigerated (5 ± 2 ºC) under fluorescent light exposure and analyzed on the day after processing (time zero) and also 40, 80, and 120 days of storage. Eight compounds were identified and quantified by Gas Chromatography (GC) -Mass Spectrometry (MS): hexanal, (E)-hex-2-enal, 1-hexenol, (Z)-hex-3-enol, (Z)-hex-3-enyl acetate, phenyl-3-propyl acetate, cinnamyl acetate, and acetic acid. There was no significant effect of thermal treatment on the volatile compound concentrations, except for a significant decrease (p = 0.0001) in hexanal and (Z)-hex-3-enyl acetate (p = 0.0029). As for the storage time, there was a much greater decrease in the esters contents, such as (Z)-hex-3-enyl and phenyl-3-propyl acetates. Cinnamyl acetate had the greatest decrease over storage time. Refrigeration was better than room temperature for guava nectar volatile compounds stability over storage time, mainly for esters compounds, which are important for the product aroma and flavor

Correlation between pH and surface structural changes on human enamel submitted to different tooth whitening agents

The intense valuation of an esthetic pleasant smile guided the dentistry to bleached tooth due the popularity of whitening treatments. The consequence of it is an increasing interest in searching the effect of peroxides in hard dental tissues. The aim of this work was to analyze qualitatively in vitro the human enamel after three different bleaching treatments: Opalescence PF 10%, White Class 7.5% and Opalescence Xtra Boost 38%, correlating the structural changes in the surface of the enamel with its respective pH. A total of 40 sound human pre-molars were randomly divided into four groups of 10 elements, which had been immersed in artificial saliva during all the experiment. Bleaching protocols followed the recommendations of the respective manufacturers. Each bleached sample and control group were submitted to a scanning electronic microscopy analysis and compared with one another. Bleaching agents used in this experiment had modified the morphologic aspect of the surface of the dental enamel; however, it did not have correlation between the degrees of severity of the alterations and pH. There is a correlation between hydrogen peroxide concentration and changes in the enamel, where G4 showed more severe alterations, followed for G3 and G2.

Changes in wood-water relationship due to heat treatment assessed on micro-samples of three Eucalyptus species

Wood-water relationship of untreated and heat-treated wood was studied. Specimens of Eucalyptus grandis, E saligna, and E citriodora were submitted to five conditions of heat treatment: 180 degrees C and 220 degrees C with air; 220 degrees C, 250 degrees C, and 280 degrees C with N(2). The wood-water relationships were accurately studied in a special device, in which the moisture content (MC) of the sample was measured with a highly sensitive electronic microbalance placed in a climatic chamber. The dimensions of the sample were collected continuously without contact by means of two high-speed laser scan micrometers. Sorption curves and shrinkage-MC relationships were observed. To study the effects of heat treatment, the following parameters were also determined: fiber saturation point (FPS), wood anisotropy (T/R ratio), shrinkage slope, reduction in hygroscopicity, and anti-shrink efficiency (ASE). The physical properties were significantly affected only at 220 degrees C and above. At heat temperature levels higher than 220 degrees C, the reduction in hygroscopicity and ASE are higher than 40% and continue to be reduced with increasing temperature level. This work also demonstrates that heat treatment does not change the slope of the curves shrinkage vs. MC, proving that heat treatment affects the domain of alterations in wood properties, but not the behavior within this domain.

Changes in the influence of board characterisitcs on corporate results due to the recent global financial crisis

The main purpose of this study is to analyse the changes caused by the global financial crisis on the influence of board characteristics on corporate results, in terms of corporate performance, corporate risk-taking, and earnings management. Sample comprises S&P 500 listed firms during 2002-2008. This study reveals that the environmental conditions call for different behaviour from directors to fulfil their responsibilities and suggests changes in normative and voluntary guidelines for improving good practices in the boardroom.

The role of the interplay between polymer architecture and bacterial surface properties on the microbial adhesion to polyoxazoline-based ultrathin films

Surface platforms were engineered from poly(L-lysine)-graft-poly(2-methyl-2-oxazoline) (PLL-g-PMOXA) copolymers to study the mechanisms involved in the non-specific adhesion of Escherichia coli (E. coli) bacteria. Copolymers with three different grafting densities (PMOXA chains/Lysine residue of 0.09, 0.33 and 0.56) were synthesized and assembled on niobia (Nb O ) surfaces. PLL-modified and bare niobia surfaces served as controls. To evaluate the impact of fimbriae expression on the bacterial adhesion, the surfaces were exposed to genetically engineered E. coli strains either lacking, or constitutively expressing type 1 fimbriae. The bacterial adhesion was strongly influenced by the presence of bacterial fimbriae. Non-fimbriated bacteria behaved like hard, charged particles whose adhesion was dependent on surface charge and ionic strength of the media. In contrast, bacteria expressing type 1 fimbriae adhered to the substrates independent of surface charge and ionic strength, and adhesion was mediated by non-specific van der Waals and hydrophobic interactions of the proteins at the fimbrial tip. Adsorbed polymer mass, average surface density of the PMOXA chains, and thickness of the copolymer films were quantified by optical waveguide lightmode spectroscopy (OWLS) and variable-angle spectroscopic ellipsometry (VASE), whereas the lateral homogeneity was probed by time-of-flight secondary ion mass spectrometry (ToF-SIMS). Streaming current measurements provided information on the charge formation of the polymer-coated and the bare niobia surfaces. The adhesion of both bacterial strains could be efficiently inhibited by the copolymer film only with a grafting density of 0.33 characterized by the highest PMOXA chain surface density and a surface potential close to zero.

The impacts of volcanic aerosol on stratospheric ozone and the Northern Hemisphere polar vortex: separating radiative-dynamical changes from direct effects due to enhanced aerosol heterogeneous chemistry

After major volcanic eruptions the enhanced aerosol causes ozone changes due to greater heterogeneous chemistry on the particle surfaces (HET-AER) and from dynamical effects related to the radiative heating of the lower stratosphere (RAD-DYN). We carry out a series of experiments with an atmosphere–ocean–chemistry–climate model to assess how these two processes change stratospheric ozone and Northern Hemispheric (NH) polar vortex dynamics. Ensemble simulations are performed under present day and preindustrial conditions, and with aerosol forcings representative of different eruption strength, to investigate changes in the response behaviour. We show that the halogen component of the HET-AER effect dominates under present-day conditions with a global reduction of ozone (−21 DU for the strongest eruption) particularly at high latitudes, whereas the HET-AER effect increases stratospheric ozone due to N2O5 hydrolysis in a preindustrial atmosphere (maximum anomalies +4 DU). The halogen-induced ozone changes in the present-day atmosphere offset part of the strengthening of the NH polar vortex during mid-winter (reduction of up to −16 m s-1 in January) and slightly amplify the dynamical changes in the polar stratosphere in late winter (+11 m s-1 in March). The RAD-DYN mechanism leads to positive column ozone anomalies which are reduced in a present-day atmosphere by amplified polar ozone depletion (maximum anomalies +12 and +18 DU for present day and preindustrial, respectively). For preindustrial conditions, the ozone response is consequently dominated by RAD-DYN processes, while under present-day conditions, HET-AER effects dominate. The dynamical response of the stratosphere is dominated by the RAD-DYN mechanism showing an intensification of the NH polar vortex in winter (up to +10 m s-1 in January). Ozone changes due to the RAD-DYN mechanism slightly reduce the response of the polar vortex after the eruption under present-day conditions.

Variation in the global-scale impacts of climate change on crop productivity due to climate model uncertainty and adaptation

Crop production is inherently sensitive to fluctuations in weather and climate and is expected to be impacted by climate change. To understand how this impact may vary across the globe many studies have been conducted to determine the change in yield of several crops to expected changes in climate. Changes in climate are typically derived from a single to no more than a few General Circulation Models (GCMs). This study examines the uncertainty introduced to a crop impact assessment when 14 GCMs are used to determine future climate. The General Large Area Model for annual crops (GLAM) was applied over a global domain to simulate the productivity of soybean and spring wheat under baseline climate conditions and under climate conditions consistent with the 2050s under the A1B SRES emissions scenario as simulated by 14 GCMs. Baseline yield simulations were evaluated against global country-level yield statistics to determine the model's ability to capture observed variability in production. The impact of climate change varied between crops, regions, and by GCM. The spread in yield projections due to GCM varied between no change and a reduction of 50%. Without adaptation yield response was linearly related to the magnitude of local temperature change. Therefore, impacts were greatest for countries at northernmost latitudes where warming is predicted to be greatest. However, these countries also exhibited the greatest potential for adaptation to offset yield losses by shifting the crop growing season to a cooler part of the year and/or switching crop variety to take advantage of an extended growing season. The relative magnitude of impacts as simulated by each GCM was not consistent across countries and between crops. It is important, therefore, for crop impact assessments to fully account for GCM uncertainty in estimating future climates and to be explicit about assumptions regarding adaptation.

Investigating responses of calcium carbonate nucleation rates in artificial seawater to changes in saturation states due to ocean acidification

Senior thesis written for Oceanography 445

False phylogenies on wood mice due to cryptic cytochrome-b pseudogene.

The phylogeny and phylogeography of the Old World wood mice (subgenus Sylvaemus, genus Apodemus, Muridae) are well-documented. Nevertheless, the distributions of species, such as A. fulvipectus and A. ponticus remain dubious, as well as their phylogenetic relationships with A. sylvaticus. We analysed samples of Apodemus spp. across Europe using the mitochondrial cytochrome-b gene (cyt-b) and compared the DNA and amino-acid compositions of previously published sequences. The main result stemming from this study is the presence of a well-differentiated lineage of Sylvaemus including samples of various species (A. sylvaticus, A. fulvipectus, A. ponticus) from distant locations, which were revealed to be nuclear copies of the mitochondrial cyt-b. The presence of this cryptic pseudogene in published sequences is supported by different pathways. This has led to important errors in previous molecular trees and hence to partial misinterpretations in the phylogeny of Apodemus.

Degradation of the surface of a metasilicate glass due to atmosphere moisture

Glasses with low silica content are very susceptible to suffer pronounced degradation when exposed to room atmosphere during short times. In this work the results of the degradation of the surface of a metasilicate glass with composition 2Na2O.1CaO.3SiO2 are presented. Optical and scanning electron microscopy observations, X-ray diffraction, infrared and Raman microprobe spectroscopic measurements of the modified surface of this glass show strong evidences that it is formed essentially by a crystalline carbonate layer.

Gochnatia polymorpha (Less.) Cabrera (Asteraceae) changes in leaf structure due to differences in light and edaphic conditions

Gochnatia polymorpha (Less.) Cabrera é uma espécie de Asteraceae com ampla distribuição no bioma cerrado, sendo encontrada em diversas fisionomias florestais da região sudeste do Brasil. O presente estudo descreve alguns caracteres anatômicos foliares dessa espécie e os analisa quantitativamente em função de sua ocorrência nas formações florestais e também das diferenças de luminosidade. Foram encontradas diferenças quantitativas em todos os parâmetros anatômicos analisados. Os resultados demonstram que a alta plasticidade anatômica foliar nesta espécie pode ser considerada como uma vantagem adaptativa que a permite ocorrer em diversos ambientes do cerrado.

Degradation of the surface of a metasilicate glass due to atmosphere moisture

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of surface treatments on the resin bond to zirconium-based ceramic

Purpose: This study tested the hypothesis that the tribochemical silica coating on ceramic surfaces increases the bond strength of resin cement to a glass-infiltrated zirconium-based ceramic. Materials and Methods: Fifteen blocks of In-Ceram Zirconia from CEREC InLab (5 per group) and 15 composite blocks (Z-250) 5 mm x 5 mm x 4 mm were made. The ceramic surfaces were polished, and the blocks were divided into three groups: (1) airborne abrasion with 110-μm aluminum oxide particles; (2) Rocatec system, tribochemical silica coating; and (3) CoJet system, tribochemical silica coating. The ceramic blocks were cemented to the composite blocks using Panavia F according to the manufacturer's specifications. All samples were stored in 37°C distilled water for 7 days and later sectioned in two axes using a diamond disk under cooling to obtain specimens with a cross-sectional area of approximately 1 mm2 (n = 45). Each specimen was then attached with cyanoacrylate glue to an adapted device for the microtensile test, which was carried out on a universal testing machine. Results: The results were subjected to ANOVA and Tukey's test. Group 2 (23.0 ± 6.7 MPa) and group 3 (26.8 ± 7.4 MPa) showed greater bond strength than group 1 (15.1 ± 5.3 MPa). There was no significant difference between groups 2 and 3. All failures were in the adhesive zone. Conclusion: The hypothesis was confirmed - the tribochemical systems increased the bond strength between Panavia F and In-Ceram Zirconia.