It is well known that thin coatings can provide increased lifetime and reduced energy consumption for tools and components. During use, e.g. in sliding contact, mechanical and chemical reactions often lead to the formation of new surface layers, tribofilms, possessing different properties compared to the original surface, hence affecting the overall performance. In this work, analytical electron microscopy was applied to investigate the structure and composition of tribofilms. Concerning coatings, deposition parameter dependencies, stability and tribology were investigated. The carbon content of hydrogen-free TiCx coatings was shown to significantly influence the morphology. Low carbon content resulted in columnar grains with a strong texture while high carbon content led to the formation of randomly ordered TiCx crystals. The application of positive bias to the substrate as opposed to the normally used negative bias gave a fibrous structure of sputtered TiB2 and low residual stress with maintained hardness. Further, oxidation stability was examined on a (Ta,Al)C:C coating where oxidation led to partial oxidation and formation of AlTaO4 with an 8 nm interface. A focused ion beam instrument was used to extract samples from certain areas of worn specimens. Tribological contact was observed to result in phase changes and intermixing of materials present in the contact. Sliding contact involving a Co-alloy led to a phase change from fcc to hcp. A 30 nm Co-rich tribofilm was observed with basal planes parallel to the surface. Fully formulated oil was found to inflict considerable wear to a metal doped carbon film through chemical reaction with the metal dopant. WC/Co cemented carbide used for rock drilling exhibited intermixing of rock and Co binder phase after field tests. Chemical vapour deposited diamond worn in nitrogen and argon showed formation of wear debris with amorphous structure containing nitrogen and graphitic like structure, respectively.

Submitted by Renan Kenji Oshiro (renan.oshiro@gmail.com) on 2016-03-09T13:29:06Z No. of bitstreams: 1 OSHIRO - Estruturas de governança corporativa e financial distress.pdf: 1792395 bytes, checksum: 0816d14d773c954b257c5ad3f90312d1 (MD5) / Approved for entry into archive by Renata de Souza Nascimento (renata.souza@fgv.br) on 2016-03-11T13:13:34Z (GMT) No. of bitstreams: 1 OSHIRO - Estruturas de governança corporativa e financial distress.pdf: 1792395 bytes, checksum: 0816d14d773c954b257c5ad3f90312d1 (MD5) / Made available in DSpace on 2016-03-22T16:13:01Z (GMT). No. of bitstreams: 1 OSHIRO - Estruturas de governança corporativa e financial distress.pdf: 1792395 bytes, checksum: 0816d14d773c954b257c5ad3f90312d1 (MD5) Previous issue date: 2016-02-15 / In this master’s thesis it was analyzed if there is a significant relationship among governance structures (structure and board composition) and financial distress. This essay focused on this issue because academic studies in corporate governance and its relation to financial distress are still largely unexplored. In addition, the topic has relevance in the corporate world, since understanding which board structures and its compositions would be more efficient to avoid financial distress is attractive for many stakeholders, mainly for shareholders and creditors. To check the existence of this relationship, it was used data from Brazilian public companies and logit models of financial distress were developed. With financial distress as response variable and starting from a base model with financial control variables, new determinants and combinations of these variables were added step by step to set up intermediate models. At last, the final model included all relevant explanatory variables. The variables can be classified into governance structure variables (DUA, GOV and COF), board quality (QUA) and ownership structure (PRO1 and PRO2). The following base models were used: Daily and Dalton (1994a) and an own model, which was developed to model better financial distress and its relation to the governance structure variables. In several tested models, significant relationships were found in the percentage of dependent directors (GOV), percentage of education’s elite directors (QUA), percentage of discriminated stock (PRO1) and percentage of relevant state stock ownership (PRO2). Hence, the hypothesis that more dependent directors, less education’s elite directors and less concentrated ownership structures contribute to a future financial distress situation cannot be rejected. On the other hand, in dummy variables as duality (DUA) and supervisory board (COF) were not found statistical significance. / Nesta dissertação foi analisada se há uma relação significante entre estruturas de governança (estrutura e composição de conselho) e financial distress. Este trabalho focou neste tema porque os estudos acadêmicos em governança corporativa e sua relação com financial distress ainda são pouco explorados. Além disso, o tema tem relevância no mundo corporativo, pois entender quais estruturas e composições de conselho seriam mais eficientes para evitar financial distress é interessante para diversos stakeholders, principalmente para os acionistas e os credores. Para verificar a existência dessa relação, foram utilizados dados de empresas brasileiras de capital aberto e foram desenvolvidos modelos logit de financial distress. Sendo a variável resposta financial distress, partiu-se de um modelo base com variáveis financeiras de controle e, por etapas, foram adicionadas novos determinantes e combinações dessas variáveis para montar modelos intermediários. Por fim, o modelo final contou com todas as variáveis explicativas mais relevantes. As variáveis de estudo podem ser classificadas em variáveis de estrutura de governança (DUA, GOV e COF), qualidade do conselho (QUA) e estrutura de propriedade (PRO1 e PRO2). Os modelos base utilizados foram: Daily e Dalton (1994a) e um próprio, desenvolvido para modelar melhor financial distress e sua relação com as variáveis de estrutura de governança. Nos diversos modelos testados foram encontradas relações significativas no percentual de conselheiros dependentes (GOV), percentual de conselheiros da elite educacional (QUA), percentual de ações discriminadas (PRO1) e percentual de ações de acionista estatal relevante (PRO2). Portanto, não se descartam as hipóteses de que mais conselheiros dependentes, menos conselheiros da elite educacional e estrutura de propriedade menos concentrada contribuem para uma situação de financial distress futura. Entretanto, as variáveis dummy de dualidade (DUA) e de conselho fiscal (COF) não apresentaram significância estatística.

This thesis deals with the investigations on the dielectric properties of polycrystalline ceramics having uncommon substitutions in barium titanate and other related phases of BaTiO3-CaTiO3, MgTiO3-CaTiO3 and MgTiO3-BaTiO3 systems. After presenting a brief introduction on the ceramic materials studied in terms of their crystal structures, electrical properties, nonstoichiometry and microstructural characteristics. The thesis describes the synthesis of the ceramics and the methodology of different techniques utilized in characterizing the samples. Barium calcium titanate was synthesized through novel wet chemical techniques and the dielectric properties of calcium substituted barium titanate do not reveal multi-site occupancy whereas they are predominantly influenced by the A/B cationic ratio. The role of transition metals of the 3d series from vanadium (Z=23) to zinc (Z=30) in modifying the crystallographic phase content, microstructure and the dielectric properties of BaTiO3 ceramics containing 10 at% impurities were studied. All the transition metals brought about the phase conversion to hexagonal BaTiO3, although no systematics could be arrived at relating the hexagonal content to the 3d electronic configuration of the impurities. The relaxor dielectrics arising from the titanate solid solution with uncommon substitution and its interconversion to normal ferroelectrics is studied. The effects of cationic substitutions of iron and niobium for titanium in BaTiO3 pervoskite lattice in crystal symmetry and dielectric properties were investigated. The above dielectric characteristics are comparable in a converse way to those of the well known Pb(Mg1/3Nb2/3)O3-PbTiO3 system wherein the relaxor behaviour occurs within the lower lead titanate compositional limits. The modification in -T characteristics of positive temperature coefficient in resistance (PTCR) by the addition of segregative additives such as B2O3, Al2O3 etc in BaTiO3 and its conversion to grain boundary layer capacitance is studied. The presence of Al-related hole centers at the grain boundary regions resulted in charge redistribution across the modified phase transition temperatures due to symmetry-related vibronic interactions, which result in broad PTCR characteristics extending to higher temperatures. The processing of high permittivity ceramics by the manipulation of microstructural features in semiconducting BaTiO3 is studied wherein the grain boundary layer effect superimposed with the contributions from the barrier layers formed during electroding related to microstructure is proposed to be responsible for the unusual high permittivity in semiconducting BaTiO3. The influence of Mg2+ as a substituent in modifying the crystallographic phase contents, microstructure and the dielectric properties of (Ba1-xMgx)TiO3 ceramics, (x ranging from zero to 1.0 ) is studied. The results point to the dual occupancy of Mg2+ both in A and B sublattice and the role of oxygen vacancy as well as (Ti3+ –VO) defects in stabilization of hexagonal phase to lower temperatures. The microwave dielectrics of the BaMg6Ti6O19 phase formed in the compositional range of x=0.4 to 0.7 was investigated for suitable application in microwave dielectrics. Extensive miscibility between the ilmenite-type MgTiO3 and perovskite-type CaTiO3 over a wide compositional range is brought about by the simultaneous equivalent substitution of Al3+ and La3+. The resulting Mg1-(x+y)CaxLay)(Ti1-yAly)O3 ceramics exhibit improved microwave dielectric properties by way of high permittivity, low TCK and high quality factor. The elemental distribution reveals the complexity in the Mg/Ca distribution and its correlation with the solid state miscibility as well as dielectric properties. Microwave dielectric property of Mg4Al2Ti9O25 which is detected as secondary phase is studied in detail.

Among dinitrogen (N2)-fixing some cyanobacteria can establish symbiosis with a broad range of host plants from all plant lineages including bryophytes, ferns, gymnosperms, and angiosperms. In the boreal forests, the symbiosis between epiphytic cyanobacteria and feathermosses Hylocomium splendens and Pleurozium schreberi is ecologically important. The main input of biological N to the boreal forests is through these cyanobacteria, and thus, they greatly contribute to the productivity of this ecosystem. Despite the ecological relevance of the feathermoss symbiosis, our knowledge about the establishment and maintenance of cyanobacterial-plant partnerships in general is limited, and particularly our understanding of the feathermoss symbiosis is rudimentary. The first aim of this thesis was to gain insight on the genomic rearrangements that enabled cyanobacteria to form a symbiosis with feathermosses, and their genomic diversity and similarities with other plant-symbiotic cyanobacteria partnerships. Genomic comparison of the feathermoss isolates with the genomes of free-living cyanobacteria highlighted that functions such as chemotaxis and motility, the transport and metabolism of organic sulfur, and the uptake of phosphate and amino acids were enriched in the genome of plant-symbiotic cyanobacteria. The second aim of this PhD study was to identify cyanobacterial molecular pathways involved in forming the feathermoss symbiosis and the regulatory rewiring needed to maintain it. Global transcriptional and post-transcriptional regulation in cyanobacteria during the early phase of establishment of the feathermoss symbiosis, and after colonization of the moss were investigated. The results revealed that the putative symbiotic gene repertoire includes pathways never before associated with cyanobacteria-plant symbioses, such as nitric-oxide sensing and regulation, and the transport and metabolism of aliphatic sulfonate. The third aim was to explore the role of the cyanobacterial community in contributing to the temporal variability of N2-fixation activity. Results from a field-study showed that temporal variation in N2-fixation rates could be explained to a high degree by changes in cyanobacterial community composition and activity. In particular, the cyanobacteria belonging to the genus Stigonema - although not dominating the community- appeared to be the main contributors to the N2-fixation activities. Based on this result, it is suggested that this genus is responsible for the main input of N in the boreal forest ecosystems. The last aim was to understand how the relationship between cyanobacterial community composition and N2-fixation activity will be affected by climatic changes such as, increased temperature (11oC compared to 19oC) and CO2 level (500 ppm compared to 1000 ppm). Laboratory experiments highlighted that 30 weeks of combined elevation of temperature and CO2 resulted in increased N2-fixation activity and moss growth rates. The observed increases were suggested to be allocated to reduced cyanobacterial diversity and changes in community composition, resulting in the dominance of cyanobacteria adapted to the future abiotic condition. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 1: Manuscript. Paper 4: Manuscript.</p>

Submitted by Renan Kenji Oshiro (renan.oshiro@gmail.com) on 2016-03-14T17:17:08Z No. of bitstreams: 1 OSHIRO - Estruturas de governança corporativa e financial distress.pdf: 1792395 bytes, checksum: 0816d14d773c954b257c5ad3f90312d1 (MD5) / Approved for entry into archive by Renata de Souza Nascimento (renata.souza@fgv.br) on 2016-03-14T17:20:18Z (GMT) No. of bitstreams: 1 OSHIRO - Estruturas de governança corporativa e financial distress.pdf: 1792395 bytes, checksum: 0816d14d773c954b257c5ad3f90312d1 (MD5) / Made available in DSpace on 2016-03-14T17:42:57Z (GMT). No. of bitstreams: 1 OSHIRO - Estruturas de governança corporativa e financial distress.pdf: 1792395 bytes, checksum: 0816d14d773c954b257c5ad3f90312d1 (MD5) Previous issue date: 2016-02-15 / In this master’s thesis it was analyzed if there is a significant relationship among governance structures (structure and board composition) and financial distress. This essay focused on this issue because academic studies in corporate governance and its relation to financial distress are still largely unexplored. In addition, the topic has relevance in the corporate world, since understanding which board structures and its compositions would be more efficient to avoid financial distress is attractive for many stakeholders, mainly for shareholders and creditors. To check the existence of this relationship, it was used data from Brazilian public companies and logit models of financial distress were developed. With financial distress as response variable and starting from a base model with financial control variables, new determinants and combinations of these variables were added step by step to set up intermediate models. At last, the final model included all relevant explanatory variables. The variables can be classified into governance structure variables (DUA, GOV and COF), board quality (QUA) and ownership structure (PRO1 and PRO2). The following base models were used: Daily and Dalton (1994a) and an own model, which was developed to model better financial distress and its relation to the governance structure variables. In several tested models, significant relationships were found in the percentage of dependent directors (GOV), percentage of education’s elite directors (QUA), percentage of discriminated stock (PRO1) and percentage of relevant state stock ownership (PRO2). Hence, the hypothesis that more dependent directors, less education’s elite directors and less concentrated ownership structures contribute to a future financial distress situation cannot be rejected. On the other hand, in dummy variables as duality (DUA) and supervisory board (COF) were not found statistical significance / Nesta dissertação foi analisada se há uma relação significante entre estruturas de governança (estrutura e composição de conselho) e financial distress. Este trabalho focou neste tema porque os estudos acadêmicos em governança corporativa e sua relação com financial distress ainda são pouco explorados. Além disso, o tema tem relevância no mundo corporativo, pois entender quais estruturas e composições de conselho seriam mais eficientes para evitar financial distress é interessante para diversos stakeholders, principalmente para os acionistas e os credores. Para verificar a existência dessa relação, foram utilizados dados de empresas brasileiras de capital aberto e foram desenvolvidos modelos logit de financial distress. Sendo a variável resposta financial distress, partiu-se de um modelo base com variáveis financeiras de controle e, por etapas, foram adicionadas novos determinantes e combinações dessas variáveis para montar modelos intermediários. Por fim, o modelo final contou com todas as variáveis explicativas mais relevantes. As variáveis de estudo podem ser classificadas em variáveis de estrutura de governança (DUA, GOV e COF), qualidade do conselho (QUA) e estrutura de propriedade (PRO1 e PRO2). Os modelos base utilizados foram: Daily e Dalton (1994a) e um próprio, desenvolvido para modelar melhor financial distress e sua relação com as variáveis de estrutura de governança. Nos diversos modelos testados foram encontradas relações significativas no percentual de conselheiros dependentes (GOV), percentual de conselheiros da elite educacional (QUA), percentual de ações discriminadas (PRO1) e percentual de ações de acionista estatal relevante (PRO2). Portanto, não se descartam as hipóteses de que mais conselheiros dependentes, menos conselheiros da elite educacional e estrutura de propriedade menos concentrada contribuem para uma situação de financial distress futura. Entretanto, as variáveis dummy de dualidade (DUA) e de conselho fiscal (COF) não apresentaram significância estatística

Throughout its current range, the Cross Timbers forest ecosystem is vulnerable to land-use change. In this study, we examined the surrounding land use matrix on the vegetation structure, composition and regeneration of six Cross Timbers forest fragments in Denton County, Texas (north of the Dallas-Fort Worth metroplex). Two fragments adjacent to agricultural land, two to residential neighborhoods, and two formally protected forest sites were selected. In summer 2015, five 100 m2 plots were randomly established in each fragment at least 200 meters from the edge. In each plot, all live and dead trees ≥ 3 cm diameter were identified and their height and diameter at breast height (DBH at 1.3 m aboveground) measured. Evidence of dumping (presence of trash) was recorded as an index of human frequentation. Differences in vegetation structure among the forest fragments were found. Most notably, fragments adjacent to agriculture contained 25% to 50% fewer trees per hectare than all other sites (Kruskal-Wallis, p < 0.02), especially trees <10 cm DBH. However, residential fragments had fewer trees that were ≥15 cm DBH compared to the other fragments, indicating that these are the youngest of the forest patches surveyed. Trash was observed in 60% of plots surveyed at residential forest sites, showing high levels of human frequentation compared to the protected and agricultural forest sites. Agricultural sites contained the lowest number of recorded tree species and were most similar to each other, sharing 91% of species. These findings indicate that surrounding land use affects forest structure and composition, consequently affecting valuable ecosystem services including wildlife habitat, aesthetics and recreation.

The microbial aggregates (flocs) formed during secondary biological treatment of wastewater shield microbes from exposure to ultraviolet (UV) light, and decrease the efficiency of disinfection, causing the tailing phenomena. This thesis investigates whether the formation of compact cores within flocs induces higher levels of UV resistance. Moreover, it investigates the effect of secondary treatment conditions on the physicochemical properties of flocs’, effluent quality, and UV disinfection performance. Compact cores were isolated from the flocs using hydrodynamic shearing. The UV dose response curves (DRC) were constructed for flocs and cores, and the 53-63 μm cores showed 0.5 log less disinfectability, compared to flocs of similar size. Based on a structural model developed for the UV disinfection of flocs, floc disinfection kinetics was sensitive to the core’s relative volume, their density, and viability. The UV disinfection and floc properties of a conventional activated sludge (CAS) system, and a biological nutrient removal (BNR-UCT) system, including both biological nitrogen and phosphorus removal, was compared. The 32-53 μm flocs and the final effluent from the BNR-UCT reactor showed 0.5 log and 1 log improvement in UV disinfectability, respectively, compared to those from the CAS reactor. The BNR-UCT flocs were more irregular in structure, and accumulated polyphosphates through enhanced biological phosphorus removal. Polyphosphates were found to be capable of producing hydroxyl radicals under UV irradiation, causing the photoreactive disinfection of microorganisms embedded within the BNR-UCT flocs, accelerating their UV disinfection. Comparing the UV disinfection performance and floc properties at various operating conditions showed that increasing the operating temperature from 12 ºC to 22 ºC, improved the UV disinfection of effluent by 0.5 log. P-Starved condition, i.e. COD:N:P of 100:10:0.03, decreased the average floc size and sphericity, both by 50%. Despite the higher effluent turbidity of the P-Starved reactor, the final effluent’s UV disinfection improved by at least 1 log compared to the P-Normal and P-Limited conditions. The improvement in the floc and effluent disinfectability were accompanied by a decrease in floc sphericity and a decrease in the number of larger flocs in the effluent, respectively.

The microbial aggregates (flocs) formed during secondary biological treatment of wastewater shield microbes from exposure to ultraviolet (UV) light, and decrease the efficiency of disinfection, causing the tailing phenomena. This thesis investigates whether the formation of compact cores within flocs induces higher levels of UV resistance. Moreover, it investigates the effect of secondary treatment conditions on the physicochemical properties of flocs’, effluent quality, and UV disinfection performance. Compact cores were isolated from the flocs using hydrodynamic shearing. The UV dose response curves (DRC) were constructed for flocs and cores, and the 53-63 μm cores showed 0.5 log less disinfectability, compared to flocs of similar size. Based on a structural model developed for the UV disinfection of flocs, floc disinfection kinetics was sensitive to the core’s relative volume, their density, and viability. The UV disinfection and floc properties of a conventional activated sludge (CAS) system, and a biological nutrient removal (BNR-UCT) system, including both biological nitrogen and phosphorus removal, was compared. The 32-53 μm flocs and the final effluent from the BNR-UCT reactor showed 0.5 log and 1 log improvement in UV disinfectability, respectively, compared to those from the CAS reactor. The BNR-UCT flocs were more irregular in structure, and accumulated polyphosphates through enhanced biological phosphorus removal. Polyphosphates were found to be capable of producing hydroxyl radicals under UV irradiation, causing the photoreactive disinfection of microorganisms embedded within the BNR-UCT flocs, accelerating their UV disinfection. Comparing the UV disinfection performance and floc properties at various operating conditions showed that increasing the operating temperature from 12 ºC to 22 ºC, improved the UV disinfection of effluent by 0.5 log. P-Starved condition, i.e. COD:N:P of 100:10:0.03, decreased the average floc size and sphericity, both by 50%. Despite the higher effluent turbidity of the P-Starved reactor, the final effluent’s UV disinfection improved by at least 1 log compared to the P-Normal and P-Limited conditions. The improvement in the floc and effluent disinfectability were accompanied by a decrease in floc sphericity and a decrease in the number of larger flocs in the effluent, respectively.