Fatigue crack propagation mechanisms in a thermally aged duplex stainless steel

Zeron 100 duplex stainless steel is susceptible to embrittlement following ageing at temperatures between 350 °C and 450 °C. The embrittlement is associated with cleavage of the age-hardened ferrite phase, initiated by deformation twinning. This can result in order of magnitude increases in the fatigue crack propagation rate. The effects of ageing on the mechanisms of fatigue crack propagation in Zero 100 are investigated, and a quantitative model is developed, accounting for the effects of hardness, temperature, stress level and microstructure on the fatigue crack growth rate. © 1994.

Crack closure and residual stress effects in fatigue of a particle-reinforced metal matrix composite

A study of the influence of macroscopic quenching stresses on long fatigue crack growth in an aluminium alloy-SiC composite has been made. Direct comparison between quenched plate, where high residual stresses are present, and quenched and stretched plate, where they have been eliminated, has highlighted their rôle in crack closure. Despite similar strength levels and identical crack growth mechanisms, the stretched composite displays faster crack growth rates over the complete range of ΔK, measured at R = 0.1, with threshold being displaced to a lower nominal ΔK value. Closure levels are dependent upon crack length, but are greater in the unstretched composite, due to the effect of surface compressive stresses acting to close the crack tip. These result in lower values of ΔKeff in the unstretched material, explaining the slower crack growth rates. Effective ΔKth values are measured at 1.7 MPa√m, confirmed by constant Kmax testing. In the absence of residual stress, closure levels of approximately 2.5 MPa√m are measured and this is attributed to a roughness mechanism.

Modelling short crack growth behaviour in nickel-base superalloys

This paper provides a description of the features and mechanisms of facetted short crack growth in Ni-base superalloys, and briefly reviews existing short crack growth models in terms of their application to Ni-base alloys. The concept of “soft barriers” is introduced to produce a new two-phase model for local microstructural effects on short crack growth in Waspaloy. This is derived from detailed observations of crack growth through individual grains. The model differs from all previous approaches in highlighting the importance of crack path perturbations within grains. Potential applications of the model in alloy development are discussed.

A preliminary evaluation of a novel method to monitor a triple antioxidant combination (vitamins E, C and alpha-lipoic acid) in diabetic volunteers using in vitro methaemoglobin formation

Eight otherwise healthy diabetic volunteers took a daily antioxidant supplement consisting of vitamin E (200 IU), vitamin C (250 mg) and α-lipoic acid (90 mg) for a period of 6 weeks. Diabetic dapsone hydroxylamine-mediated methaemoglobin formation and resistance to erythrocytic thiol depletion was compared with age and sex-matched non-diabetic subjects. At time zero, methaemoglobin formation in the non-diabetic subjects was greater at all four time points compared with that of the diabetic subjects. Resistance to glutathione depletion was initially greater in non-diabetic compared with diabetic samples. Half-way through the study (3 weeks), there were no differences between the two groups in methaemoglobin formation and thiol depletion in the diabetic samples was now lower than the non-diabetic samples at 10 and 20 min. At 6 weeks, diabetic erythrocytic thiol levels remained greater than those of non-diabetics. HbA1c values were significantly reduced in the diabetic subjects at 6 weeks compared with time zero values. At 10 weeks, 4 weeks after the end of supplementation, the diabetic HbA1c values significantly increased to the point where they were not significantly different from the time zero values. Total antioxidant status measurement (TAS) indicated that diabetic plasma antioxidant capacity was significantly improved during antioxidant supplementation. Conversion of α-lipoic acid to dihydrolipoic acid (DHLA) in vivo led to potent interference in a standard fructosamine assay kit, negating its use in this study. This report suggests that triple antioxidant therapy in diabetic volunteers attenuates the in vitro experimental oxidative stress of methaemoglobin formation and reduces haemoglobin glycation in vivo. © 2003 Elsevier Science B.V. All rights reserved.

Inter-subjective and transnational racial effects: The role of the United States in the formation and evolution of the collective perception and racial relations in Cuba, 1898–1902

Since the arrival of the first African slaves to Cuba in 1524, the issue of race has had a long-lived presence in the Cuban national discourse. However, despite Cuba’s colonial history, it has often been maintained by some historians that race relations in Cuba were congenial with racism and racial discrimination never existing as deep or widespread in Cuba as in the United States (Cannon, 1983, p. 113). In fact, it has been argued that institutionalized racism was introduced into Cuban society with the first U.S. occupation, during 1898–1902 (Cannon, 1983, p. 113). This study of Cuba investigates the influence of the United States on the development of race relations and racial perceptions in post-independent Cuba, specifically from 1898-1902. These years comprise the time period immediately following the final fight for Cuban Independence, culminating with the Cuban-Spanish-American War and the first U.S. occupation of Cuba. By this time, the Cuban population comprised Africans as well as descendants of Africans, White Spanish people, indigenous Cubans, and offspring of the intermixing of the groups. This research studies whether the United States’ own race relations and racial perceptions influenced the initial conflicting race relations and racial perceptions in early and post-U.S. occupation Cuba. This study uses a collective interpretative framework that incorporates a national level of analysis with a race relations and racial perceptions focus. This framework reaches beyond the traditionally utilized perspectives when interpreting the impact of the United States during and following its intervention in Cuba. Attention is given to the role of the existing social, political climate within the United States as a driving influence of the United States’ involvement with Cuba. This study reveals that emphasis on the role of the United States as critical to the development of Cuba’s race relations and racial perceptions is credible given the extensive involvement of the U.S. in the building of the early Cuban Republic and U.S. structures serving as models for reconstruction. U.S. government formation in Cuba aligned with a governing system reflecting the existing governing codes of the U.S. during that time period.

Organic Biogeochemistry of Detrital Flocculent Material (Floc) in a Subtropical, Coastal Wetland

Flocculent materials (floc), in aquatic systems usually consist of a non-consolidated layer of biogenic, detrital material relatively rich in organic matter which represents an important food-web component for invertebrates and fish. Thus, variations in its composition could impact food webs and change faunal structure. Transport, remineralization rates and deposition of floc may also be important factors in soil/sediment formation. In spite of its relevance and sensitivity to external factors, few chemical studies have been carried out on the biogeochemistry of floc material. In this study, we focused on the molecular characterization of the flocculent organic matter (OM), the assessment of its origin and its environmental fate at five stations along a freshwater to marine ecotone, namely the Taylor Slough, Everglades National Park (ENP), Florida. To tackle this issue, suspended, unconsolidated, detrital floc samples, soils/sediments and plants were analyzed for bulk properties, biomarkers and pigments. Both geochemical proxies and biomass-specific biomarkers were used to assess OM sources and transformations. Our results show that the detrital organic matter of the flocculent material is largely regulated by local vegetation inputs, ranging from periphyton, emergent and submerged plants and terrestrial plants such as mangroves, with molecular evidence of different degrees of diagenetic reworking, including fungal activity. Evidence is presented for both hydrodynamic transport of floc materials, and incorporation of floc OM into soils/sediments. However, some molecular parameters showed a decoupling between floc and underlying soil/sediment OM, suggesting that physical transport, incorporation and degradation/remineralization of OM in floc may be controlled by a combination of a variety of complex biogeochemical variables including hydrodynamic transport, hydroperiod characteristics, primary productivity, nutrient availability, and OM quality among others. Further investigations are needed to better understand the ecological role of floc in freshwater and coastal wetlands.

Dissolved Black Nitrogen (DBN) in Freshwater Environments

Biomass burning results in the formation and accumulation of pyrogenic products such as black carbon (BC) and black nitrogen (BN) in soils. The ubiquitous presence of pyrogenic products in natural dissolved organic matter (DOM) and potential implications in global carbon cycling have recently been reported. However, little is known about the environmental dynamics or the importance in the global N cycle of dissolved BN (DBN; or heteroaromatic N). Here we report the coupling between DBN and dissolved BC (DBC) in ultrafiltered DOM from six headwater streams across a climatic region of North America, suggesting similar combustion sources, and that DOC may play an important role in the translocation of soil BN to the dissolved phase. The export of potentially recalcitrant riverine DBN to the ocean may affect the biogeochemical cycling of N and possibly the microbial community structure in aquatic environments.

Application of biomarkers and compound specific stable isotopes for the assessment of hydrology as a driver of organic matter dynamics in the Everglades ecosystem

The Everglades is a sub-tropical coastal wetland characterized among others by its hydrological features and deposits of peat. Formation and preservation of organic matter in soils and sediments in this wetland ecosystem is critical for its sustainability and hydrological processes are important divers in the origin, transport and fate of organic matter. With this in mind, organic matter dynamics in the greater Florida Everglades was studied though various organic geochemistry techniques, especially biomarkers, bulk and compound specific δ13C and δD isotope analysis. The main objectives were focused on how different hydrological regimes in this ecosystem control organic matter dynamics, such as the mobilization of particulate organic matter (POM) in freshwater marshes and estuaries, and how organic geochemistry techniques can be applied to reconstruct Everglades paleo-hydrology. For this purpose organic matter in typical vegetation, floc, surface soils, soil cores, and estuarine suspended particulates were characterized in samples selected along hydrological gradients in the Water Conservation Area 3, Shark River Slough and Taylor Slough. ^ This research focused on three general themes: (1) Assessment of the environmental dynamics and source-specific particulate organic carbon export in a mangrove-dominated estuary. (2) Assessment of the origin, transport and fate of organic matter in freshwater marsh. (3) Assessment of historical changes in hydrological conditions in the Everglades (paleo-hydrology) though biomarkes and compound specific isotope analyses. This study reports the first estimate of particulate organic carbon loss from mangrove ecosystems in the Everglades, provides evidence for particulate organic matter transport with regards to the formation of ridge and slough landscapes in the Everglades, and demonstrates the applicability of the combined biomarker and compound-specific stable isotope approach as a means to generate paleohydrological data in wetlands. The data suggests that: (1) Carbon loss from mangrove estuaries is roughly split 50/50 between dissolved and particulate carbon; (2) hydrological remobilization of particulate organic matter from slough to ridge environments may play an important role in the maintenance of the Everglades freshwater landscape; and (3) Historical changes in hydrology have resulted in significant vegetation shifts from historical slough type vegetation to present ridge type vegetation. ^

An investigation by AFM and TEM of the mechanism of anodic formation of nanoporosity in n-InP in KOH

The early stages of nanoporous layer formation, under anodic conditions in the absence of light, were investigated for n-type InP with a carrier concentration of ∼3× 1018 cm-3 in 5 mol dm-3 KOH and a mechanism for the process is proposed. At potentials less than ∼0.35 V, spectroscopic ellipsometry and transmission electron microscopy (TEM) showed a thin oxide film on the surface. Atomic force microscopy (AFM) of electrode surfaces showed no pitting below ∼0.35 V but clearly showed etch pit formation in the range 0.4-0.53 V. The density of surface pits increased with time in both linear potential sweep and constant potential reaching a constant value at a time corresponding approximately to the current peak in linear sweep voltammograms and current-time curves at constant potential. TEM clearly showed individual nanoporous domains separated from the surface by a dense ∼40 nm InP layer. It is concluded that each domain develops as a result of directionally preferential pore propagation from an individual surface pit which forms a channel through this near-surface layer. As they grow larger, domains meet, and the merging of multiple domains eventually leads to a continuous nanoporous sub-surface region.

Citizenship formation for a new millennium in Sweden : a prognosis of our time

The aim of this article is to forecast the present situation of citizenship formation in the field of Swedish education. In highlighting trends and tendencies in the educational assignment to provide for democratic citizenship in the first decade of the 21st century, which can be characterised as lacking collective visions for change, three depictions of citizenship are prevailing: citizenship formation for deliberation, for entrepreneurship and for therapeutic intervention. These depictions are analysed in terms of the direction for action taking and attention that they stress and produce as concerns citizenship in the making. The first one, citizenship formation for deliberation, stresses an inward-looking and inward-feeling citizenship. The second one, citizenship formation for entrepreneurship, stresses an inward-looking and outward-making citizenship, and the third one, citizenship formation for therapeutic intervention, stresses an inward-looking and outward-making citizenship. Taking on this forecast, which actualises democracy as something that is already achieved as a consequence of an assumedly post political situation, we argue that citizenship as well as society itself risks being pictured as apolitical and democratically “saturated.” This situation is hazardous, we argue, as it does not open up for change to come into question as desirable or even possible. Put differently, it leaves us with the notion that things have to be as they are, as we are living in the best of worlds. 

Inter-industry differences in local banks' effect on new firm formation : A regional study of entrepreneurship in Sweden

Formation of new firms is important, since new firms create jobs and economic growth. When entrepreneurs lack the financial resources which are needed to start a firm, they often turn to banks to borrow money. Previous research has shown that relationships between banks and new business borrowers most often are local and that the dependence on banks differs across industries. In light of this, the purpose of this paper is to investigate if local access to banks has a stronger relationship with the rate of new firm formation in some industries than in others. Based on cross-sectional data on all Swedish municipalities in 2009, a series of OLS regressions are estimated to test if variables used to describe the bank market in a municipality are related with the new firm formation rate, both in total and in different industry categories. The results show that the number of bank branches per capita is positively related with the total new firm formation rate. In regards to the inter-industry differences, the findings indicate that local access to banks is more important for new firm formation in some industries than in others. 

Nickel isotope fractionation during laterite Ni ore smelting and refining: implications for tracing the sources of Ni in smelter-affected soils

Nickel isotope ratios were measured in ores, fly ash, slags and FeNi samples from two metallurgical plants located in the Goiás State, Brazil (Barro Alto, Niquelândia). This allowed investigating the mass-dependent fractionation of Ni isotopes during the Ni-laterite ore smelting and refining. Feeding material exhibits a large range of δ60Ni values (from 0.02 ± 0.10 ‰ to 0.20 ± 0.05 ‰, n=7), explained by the diversity of Ni-bearing phases, and the average of δ60Nifeeding materials was found equal to 0.08 ± 0.08‰ (2SD, n=7). Both δ60Ni values of fly ash (δ60Ni = 0.07 ± 0.07‰, n=10) and final FeNi produced (0.05 ± 0.02 ‰, n=2) were not significantly different from the feeding materials ones. These values are consistent with the very high production yield of the factories. However, smelting slags present the heaviest δ60Ni values of all the smelter samples, with δ60Ni ranging from 0.11 ± 0.05 ‰ to 0.27 ± 0.05 ‰ (n=8). Soils were also collected near and far from the Niquelândia metallurgical plant, to evaluate the potential of Ni isotopes for tracing the natural vs anthropogenic Ni in soils. The Ni isotopic composition of the non-impacted topsoils developed on ultramafic rocks ranges from -0.26 ± 0.09 ‰ to -0.04 ± 0.05 ‰ (n=20). On the contrary, the Ni isotopic composition of the non-ultramafic topsoils, collected close to the plant, exhibit a large variation of δ60Ni, ranging from -0.19 ± 0.13 ‰ up to 0.10 ± 0.05 ‰ (n=4). This slight but significant enrichment in heavy isotopes highlight the potential impact of smelting activity in the surrounding area, as well as the potential of Ni isotopes for discerning anthropogenic samples (heavier δ60Ni values) from natural ones (lighter δ60Ni values). However, given the global range of published δ60Ni values (from -1.03 to 2.5 ‰) and more particularly those associated to natural weathering of ultramafic rocks (from -0.61 to 0.32‰), the use of Ni isotopes for tracing environmental contamination from smelters will remain challenging.

Modeling the Effect of Vapor Wall Deposition on the Formation of Secondary Organic Aerosol in Chamber Studies

Laboratory chamber experiments are used to investigate formation of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors under a variety of environmental conditions. Simulations of these experiments test our understanding of the prevailing chemistry of SOA formation as well as the dynamic processes occurring in the chamber itself. One dynamic process occurring in the chamber that was only recently recognized is the deposition of vapor species to the Teflon walls of the chamber. Low-volatility products formed from the oxidation of volatile organic compounds (VOCs) deposit on the walls rather than forming SOA, decreasing the amount of SOA formed (quantified as the SOA yield: mass of SOA formed per mass of VOC reacted). In this work, several modeling studies are presented that address the effect of vapor wall deposition on SOA formation in chambers.

A coupled vapor-particle dynamics model is used to examine the competition among the rates of gas-phase oxidation to low volatility products, wall deposition of these products, and mass transfer to the particle phase. The relative time scales of these rates control the amount of SOA formed by affecting the influence of vapor wall deposition. Simulations show that an effect on SOA yield of changing the vapor-particle mass transfer rate is only observed when SOA formation is kinetically limited. For systems with kinetically limited SOA formation, increasing the rate of vapor-particle mass transfer by increasing the concentration of seed particles is an effective way to minimize the effect of vapor wall deposition.

This coupled vapor-particle dynamics model is then applied to α-pinene ozonolysis SOA experiments. Experiments show that the SOA yield is affected when changing the oxidation rate but not when changing the rate of gas-particle mass transfer by changing the concentration of seed particles. Model simulations show that the absence of an effect of changing the seed particle concentration is consistent with SOA formation being governed by quasi-equilibrium growth, in which gas-particle equilibrium is established much faster than the rate of change of the gas-phase concentration. The observed effect of oxidation rate on SOA yield arises due to the presence of vapor wall deposition: gas-phase oxidation products are produced more quickly and condense preferentially onto seed particles before being lost to the walls. Therefore, for α-pinene ozonolysis, increasing the oxidation rate is the most effective way to mitigate the influence of vapor wall deposition.

Finally, the detailed model GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to simulate α-pinene photooxidation SOA experiments. Unexpectedly, α-pinene OH oxidation experiments show no effect when changing either the oxidation rate or the vapor-particle mass transfer rate, whereas GECKO-A predicts that changing the oxidation rate should drastically affect the SOA yield. Sensitivity studies show that the assumed magnitude of the vapor wall deposition rate can greatly affect conclusions drawn from comparisons between simulations and experiments. If vapor wall loss in the Caltech chamber is of order 10^-5 s^-1, GECKO-A greatly overpredicts SOA during high UV experiments, likely due to an overprediction of second-generation products. However, if instead vapor wall loss in the Caltech chamber is of order 10^-3 s^-1, GECKO-A greatly underpredicts SOA during low UV experiments, possibly due to missing autoxidation pathways in the α-pinene mechanism.

Genesis and classification of soils from subtropical mountain regions of Southern Brazil.

Soils formed in high mountainous regions in southern Brazil are characterized by great accumulation of organic matter (OM) in the surface horizons and variation in the degree of development. We hypothesized that soil properties and genesis are influenced by the interaction of parent materials and climate factors, which differ depending on the location along the altitudinal gradient. The goal of this study was to characterize and classify the soil, evaluate soil distribution, and determine the interactive effects of soil-forming factors in the subtropical mountain regions in Santa Catarina state. Soil samples were collected in areas known for wine production, for a total of 38 modal profiles. Based on morphological, physical, and chemical properties, soils were evaluated for pedogenesis and classified according to the Brazilian System of Soil Classification, with equivalent classes in the World Reference Basis (WRB). The results indicated that pedogenesis was strongly influenced by the parent material, weather, and relief. In the areas where basic effusive rocks (basalt) were observed, there was formation of extensive areas of clayey soils with reddish color and higher iron oxide contents. There was a predominance of Nitossolos Vermelhos and Háplicos (Nitisols), Latossolos Vermelhos (Ferralsols), and Cambissolos Háplicos (Cambisols), highlighting the pedogenetic processes of eluviation, illuviation of clay, and latosolization in conditions of year-long, large-volume, well-distributed rainfall and stability of land forms. In areas with acid effusive rocks (rhyodacites), medial or clayey soils were observed with lower iron oxide content, invariably acidic, and with low base content. For these soils, relief promoted substantial removal of material, resulting in intense rejuvenation, with a predominance of Cambissolos Háplicos (Cambisols) and lesser occurrence of Nitossolos Brunos (Nitisols) and Neossolos Litólicos (Leptosols). Soils formed from sedimentary rocks also tended to be more acidic, but with higher sand content, and the soils identified were Cambissolos Háplicos and Húmicos (Cambisols). Cluster analysis separated the soil profiles into three groups: the first and largest was formed by profiles originating from sedimentary rocks and rhyodacites; the second, smaller group was formed by four profiles in the Água Doce region (acidic rocks); and the third was formed by profiles derived from basalt. Discriminant analysis was effective in grouping soil classes. Thus, the study highlighted the importance of geology in the formation of soils in this landscape associated with climate and relief.

Changes In The Bacterial Community Of Soil From A Neutral Mine Drainage Channel.

Mine drainage is an important environmental disturbance that affects the chemical and biological components in natural resources. However, little is known about the effects of neutral mine drainage on the soil bacteria community. Here, a high-throughput 16S rDNA pyrosequencing approach was used to evaluate differences in composition, structure, and diversity of bacteria communities in samples from a neutral drainage channel, and soil next to the channel, at the Sossego copper mine in Brazil. Advanced statistical analyses were used to explore the relationships between the biological and chemical data. The results showed that the neutral mine drainage caused changes in the composition and structure of the microbial community, but not in its diversity. The Deinococcus/Thermus phylum, especially the Meiothermus genus, was in large part responsible for the differences between the communities, and was positively associated with the presence of copper and other heavy metals in the environmental samples. Other important parameters that influenced the bacterial diversity and composition were the elements potassium, sodium, nickel, and zinc, as well as pH. The findings contribute to the understanding of bacterial diversity in soils impacted by neutral mine drainage, and demonstrate that heavy metals play an important role in shaping the microbial population in mine environments.