Mineral and chemical compositions of a ferromanganese nodule from Station DM41-3911-76

Processes of authigenic manganese ore formation in sediments of the North Equatorial Pacific are considered on the basis of a study of the surface layer (<2 mm) of a ferromanganese nodule and four micronodule size fractions from associated surface sediment (0-7 cm). Inhomogeneity of nodule composition is shown. Mn/Fe ratio is maximal in samples from lateral sectors of the nodule at the water-sediment interface. Compositional differences of nodules are related to preferential accumulation of trace elements in iron oxyhydroxides (P, Sr, Pb, U, Bi, Th, Y, and REE), manganese hydroxides (Co, Ni, Cu, Zn, Cd, Mo, Tl, W), and lithogenic component trapped during nodule growth (Ga, Rb, Ba, and Cs). Ce accumulation in the REE composition is maximal in the upper and lower parts of the nodule characterized by minimal Mn/Fe values. A compositional comparison of manganese micronodules and surface layers of the nodule demonstrates that micronodule material was subjected to more intense reworking during diagenesis of sediments. The micronodules are characterized by higher Mn/Fe and P/Fe, but lower Ni/Cu and Co/Ni ratios. The micronodules and nodules do not differ in terms of contents of Ce and Th that are the least mobile elements during diagenesis. Differences in chemical composition of the micronodules and nodules are related not only to additional input of Mn in the process of diagenesis, but also to transformation of iron oxyhydroxides after removal of Mn from the close association with Fe formed in suspended matter during sedimentation.

Annotated record and chemical analyses of a polygenetic manganese nodule (slab) from the Scott Plateau, Indian Ocean (core VA-16-13KD)

A large manganese nodule (manganese slab) was dredged from 2100 m on the Scott Plateau by R.V. Valdivia in 1977. It is an irregular ellipsoid, with a maximum dimension of 28 cm, parallel to the sea floor. Chemical analyses show that Mn and Fe proportions are comparable, and total Ni + Cu + Co content averages 0.7%. The nodule has a complex growth history which started with radial upward growth leading to coalescing into a continuous crust. The crust was coated with horizontal layers. After fracturing and infilling of cracks with calcareous sediment, further layers encased the nodule.

(Table 3, page 280) Chemical composition of micronodules from a series of stations and sediment depths from Areas C, F, G and K in the Pacific Ocean from R/V Sonne Cruise SO06

Compositional data for coexisting manganese nodules, micronodules, sediments and pore waters from five areas in the equatorial and S.W. Pacific have been obtained. This represents the largest study of its type ever undertaken to establish the distribution of elements between the various phases within the sediment column. The composition of manganese nodules, micronodules and sediments (on a carbonate-free basis) shows marked differences between the equatorial high productivity zone and the low productivity region of the S.W. Pacific. In the case of the nodules, th is reflects an increased supply of transition elements (notably Ni, Cu and Zn) to the nodules as a result of the in situ dissolution of siliceous tests within the sediment column in the equatorial Pacific high productivity zone. Micronodules display similar, but somewhat different, compositions to those of the associated nodules in each area. Micronodule composition is therefore influenced by the same basic factors that control nodule composition, but is modified by dissolution of the micronodules in situ within the sediment column. Locally, as in the area immediately south of the Marquesas Fracture Zone, the micronodule population is contaminated by small, angular volcanic rock fragments; this leads to apparently anomalous micronodule compositions. Micronodules appear to be a transient feature in the sediment column, especially in the equatorial Pacific. Dissolution of micronodules in the sediment column therefore represents an important source of elements for the growth of manganese nodules in the equatorial Pacific. Sediment composition is markedly influenced by the carbonate content. On a carbonate-free basis, the sediments from the equatorial high productivity zone are quite distinct in composition from those in the S.W. Pacific. This reflects differences in the lithology of the sediments. In the Aitutaki Passage, the local influence of volcanoclastic material in sediment composition has been established. The major cations and anions in pore waters measured here show no major differences between equatorial and S.W. Pacific sediments. Silica is, however, higher in equatorial Pacific pore waters reflecting the dissolution of siliceous tests in these sediments.

Annotated record of the detailed examination of Mn deposits from R/V Xiang Yang Hong 16 stations (1983) in the Pacific Ocean

Electron microprobe and X-ray diffraction data for north Pacific manganese nodules reveal that the transition metal distributions are controlled by the mineralogy. Microlayers rich in 10Å-manganates generally have high Mn/Fe ratios and positive correlations between Ni, Cu and Mn, and between Co and Fe. Microlayers rich in vernadite, on the other hand, show low Mn/Fe ratios, and Co, Ni and Cu all show positive correlations with Mn. The 10Å-manganates form mainly in porewaters with high Mn/Fe ratios. The Ni2+ and Cu2+ ions are post-depositionally incorporated into the interlayers of the manganates, whereas Co3+ is substituted for Fe3+ in ferric oxyhydroxides. In seawater with a low Mn/Fe ratio, on the other hand, the adsorption of positively charged ferric oxyhydroxides on negatively charged [MnO6] octahedral layers suppresses the growth of 10Å-manganates, enhancing the formation of vernadite. Positively charged hydroxides of Co3+, Ni2+ and Cu2+ are also adsorbed on the [MnO6] layers. These mechanisms of mineral formation and metal uptake are corroborated by data for other oceanic non-hydrothermal manganese nodules and crusts.

Avaliação do potencial genotóxico e citotóxico associado a queima artesanal da castanha de caju no Município de João Câmara

The Brazil is the third largest producer of cashew nuts in the world. Despite the social and economic importance of the cashew nut, its production is still carried out artisanally. One of the main problems encountered in the cashew production chain are the conditions under which the roasting of the nut occurs to obtain the kernel from the shell. In the present study was conducted a biomonitoring of the genotoxic and cytotoxicity effects associated with the elements from the cashew nut roasting in João Câmara - RN, semi-arid region of Brazil. To assess the genotoxic was used the bioassay of micronucleus (MN) in Tradescantia pallida. In addition, it was performed a comparative between the Tradescantia pallida and KU-20 and other biomarkers of DNA damage, such as the nucleoplasmic bridges (NBP) and nuclear fragments (NF) were quantified. The levels of particulate matter (PM1.0, PM2.5, PM10) and black carbon (BC) were also measured and the inorganic chemical composition of the PM2.5 collected was determined using X-ray fluorescence spectrometry analysis and the assessment of the cytotoxicity by MTT assay and exclusion method by trypan blue. . For this purpose, were chosen: the Amarelão community where the roasting occurs and the Santa Luzia farm an area without influence of this process. The mean value of PM2.5 (Jan 2124.2 μg/m3; May 1022.2 μg/m3; Sep 1291.9 μg/m3) and BC (Jan 363.6 μg/m3; May 70.0 μg/m3; Sep 69.4 μg/m3) as well as the concentration of the elements Al, Si, P, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Se, Br and Pb obtained at Amarelão was significantly higher than at Santa Luzia farm. The genotoxicity tests with T. pallida indicated a significant increase in the number of MN, NBP and NF and it was found a negative correlation between the frequency of these biomarkers and the rainfall. The concentrations of 200 μg/mL and 400 μg/mL of PM2.5 were cytotoxic to MRC-5 cells. All together, the results indicated genotoxicity and citotoxicity for the community of Amarelão, and the high rates of PM2.5 considered a potential contributor to this effect, mainly by the high presence of transition metals, especially Fe, Ni, Cu, Cr and Zn, these elements have the potential to cause DNA damage. Other nuclear alterations, such as the NPBs and NFs may be used as effective biomarkers of DNA damage in tetrads of Tradescantia pallida. The results of this study enabled the identification of a serious occupational problem. Accordingly, preventative measures and better practices should be adopted to improve both the activity and the quality of life of the population. These measures are of fundamental importance for the sustainable development of this activity.

Nuevas cromitas de composición La1-xMxCr0.9Ni0.1O3(M=Sr, ND, Ca; x<0.3) con tamaño de A y desorden fijados, para su uso como ánodos de pilas SOFCs

Póster presentado en el XIV Congreso Nacional de Materiales (CNMAT) en Gijón (España), del 8 al 10 de Junio de 2016

Efeito das variáveis laboratoriais protéticas na adesão da porcelana com ligas de níquel-cromo

The metalceramic crowns are usually used in dentistry because they provide a resistant structure due to its metallic base and its aesthetics from the porcelain that recovers this structure. To manufacture these crowns, a series of stages should be accomplished in the prosthetic laboratories, and many variables can influence its success. Changes in these variables cause alterations in the metallic alloy and in the porcelain, so, as consequence, in the adhesion between them. The composition of the metal alloy can be modified by recasting alloys, a common practice in some prosthetic laboratories. The aim of this paper is to make a systematic study investigating metalceramic crowns as well as analyzing the effect of recasting Ni-Cr alloys. Another variable which can influence the mechanism of metalceramic union is the temperature used in firing porcelain procedure. Each porcelain has to be fired in a fixed temperature which is determined by the manufacturer and its change can cause serious damages. This research simulate situations that may occur on laboratory procedures and observe their consequences in the quality of the metalceramic union. A scanning eletron microscopy and an optic microscopy were accomplish to analyse the metal-ceramic interface. No differences have been found when remelting alloys were used. The microhardness were similar in Ni-Cr alloys casted once, twice and three times. A wettability test was accomplished using a software developed at the Laboratório de Processamento de Materiais por Plasma, on the Universidade Federal do Rio Grande do Norte. No differences were found in the contact angle between the solid surface (metallic substratum) and the tangencial plane to the liquid surface (opaque). To analyse if the temperature of porcelain firing procedure could influence the contact area between metal and porcelain, a variation in its final temperature was achieve from 980° to 955°C. Once more, no differences have been found

Heavy metal release due to aging effect during zero valent iron nanoparticles remediation

Zero valent iron nanoparticles (nZVI) represent a promising agent for environmental remediation. Nevertheless, their application presents some limitations regarding their rapid oxidation and aggregation in the media. The aim of this study was to determine the effect that nZVI aging has in heavy metal remediation in water. Contaminants studied were Zn, Cd, Ni, Cu and Cr, which are typical elements found in ground and wastewater. Results show a high contaminant removal capacity by the nZVI in the first 2 h of reaction. Nevertheless, for longer reaction times, some of the metal ions that had already been adsorbed in the nZVI were delivered to the water. Cd and Ni show the maximum delivery percentages (65 and 27% respectively after 21 days of contact time). The starting delivery time was shortened when applying lower nZVI amounts. No re-dissolution of Cr was observed in any circumstance because it was the only element incorporated into the nanoparticles core, as TEM images showed. Contaminant release from nZVI is probably due to nanoparticles oxidation caused by aging, which produced a pH decrease and nZVI surface crystallization.

Avaliação da composição mineral de vinhos de talha do Alentejo usando ICP-MS

Os Vinhos de Talha do Alentejo representam uma herança da presença romana na península ibérica e a sua compreensão e análise são muito importantes para a sua preservação. O trabalho que aqui se apresenta, representa uma parte de um estudo alargado sobre vinhos de talha que procura compreender a influência do método de vinificação em talha na composição química destes vinhos, de modo a poder caracterizá-los num contexto mais abrangente de preservação de um património cultural. Com este trabalho procurou-se saber se as características únicas destes vinhos, conferem alguma alteração na sua composição mineral e se os valores encontrados estão dentro dos valores de referência, nomeadamente no que diz respeito a questões de segurança alimentar, com particular atenção para alguns metais pesados como o Manganês, Níquel, Cobre, Zinco, Cádmio e Chumbo. Para tal, usámos 16 vinhos tintos, 16 vinhos brancos e 15 vinhos palhetes que foram gentilmente cedidos pela organização do concurso VITIFRADES do ano de 2014, e estudou-se a sua composição química elementar em 32 elementos (Na, Mg, Al, P, K, Ca, Sc, Mn, Fe, Co, Ni, Cu, Zn, Se, Sr, Cd, In, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Er, Tm, Yb, Pb e Bi) através de ICP-MS. Os resultados da análise multielementar permitiram concluir que os valores encontrados para estes vinhos estão dentro dos limites esperados, não se verificando nenhuma contaminação metálica, especialmente no que diz respeito a alguns elementos que podem levantar questões importantes de segurança alimentar devido à sua toxicidade

Effect of Nb Content on the Microstructure and Mechanical Properties of Zr-Cu-Ni-Al-Nb Glass Forming Alloys

(Zr65Al10Ni10Cu15)(100-x) Nb-x glass forming alloys with Nb contents ranging from 0 to 15 at.% were prepared by water-cooled copper mould cast. The alloys with different Nb contents exhibited different microstructures and mechanical properties. Unlike the monolithic Zr65Al10Ni10Cu15 bulk metallic glass, only a few primary bee beta-Ti phase dendrites were found to distribute in the glassy matrix of the alloys with x = 5. For alloys with x = 10, more beta-phase dendrites forms, together with quasicrystalline particles densely distributed in the matrix of the alloys. For alloys with x = 15, the microstructure of the alloy is dominated by a high density of fully developed P-phase dendrites and the volume fraction of quasicrystalline particles significantly decreases. Room temperature compression tests showed that the alloys with x = 5 failed at 1793 MPa and exhibited an obvious plastic strain of 3.05%, while the other samples all failed in a brittle manner. The ultimate fracture strengths are 1793, 1975 and 1572 MPa for the alloys with x = 0, 10 and 15 at.% Nb, respectively.

Glass forming ability and stability: Ternary Cu bearing Ti, Zr, Hf alloys

Four Cu bearing alloys of nominal composition Zr25Ti25Cu50, Zr34Ti16Cu50, Zr25Hf25Cu50 and Ti25Hf25Cu50 have been rapidly solidified in order to produce ribbons. All the alloys become amorphous after meltspinning. In the Zr34Ti16Cu50 alloy localized precipitation of cF24 Cu5Zr phase can be observed in the amorphous matrix. The alloys show a tendency of phase separation at the initial stages of crystallization. The difference in crystallization behavior of these alloys with Ni bearing ternary alloys can be explained by atomic size, binary heat of mixing and Mendeleev number. It has been observed that both Laves and Anti-Laves phase forming compositions are suitable for glass formation. The structures of the phases, precipitated during rapid solidification and crystallization can be viewed in terms of Bernal deltahedra and Frank-Kasper polyhedra.

Effect of Ni content on the diffusion-controlled growth of the product phases in the Cu(Ni)-Sn system

A strong influence of Ni content on the diffusion-controlled growth of the (Cu,Ni)(3)Sn and (Cu,Ni)(6)Sn-5 phases by coupling different Cu(Ni) alloys with Sn in the solid state is reported. The continuous increase in the thickness ratio of (Cu,Ni)(6)Sn-5 to (Cu,Ni)(3)Sn with the Ni content is explained by combined kinetic and thermodynamic arguments as follows: (i) The integrated interdiffusion coefficient does not change for the (Cu,Ni)(3)Sn phase up to 2.5 at.% Ni and decreases drastically for 5 at.% Ni. On the other hand, there is a continuous increase in the integrated interdiffusion coefficient for (Cu,Ni)(6)Sn-5 as a function of increasing Ni content. (ii) With the increase in Ni content, driving forces for the diffusion of components increase for both components in both phases but at different rates. However, the magnitude of these changes alone is not large enough to explain the high difference in the observed growth rate of the product phases because of Ni addition. (iv) Kirkendall marker experiments indicate that the Cu6Sn5 phase grows by diffusion of both Cu and Sn in the binary case. However, when Ni is added, the growth is by diffusion of Sn only. (v) Also, the observed grain refinement in the Cu6Sn5 phase with the addition of Ni suggests that the grain boundary diffusion of Sn may have an important role in the observed changes in the growth rate.

Effect of adding 0.3 wt% Ni into the Sn–0.7 wt%Cu solder: part I: wetting behavior on Cu and Ni substrates

Comparative wetting behavior of Sn-0.7Cu and Sn-0.7Cu-0.3Ni solders on Cu and Ni substrates were assessed through the wetting balance test. No-clean (NC), non-activated (R) and water soluble organic acid (WS) fluxes were used to assess the wetting behavior for three different solder bath temperatures of 255, 275 and 295 °C. Experimental results unveiled that adding of 0.3 wt% Ni into Sn-0.7Cu solder can improve the wetting on Cu substrate when NC and WS fluxes are used. However, such addition of Ni did not improve the wetting of Sn-0.7Cu solder for R-type flux. In the case of Ni substrate, addition of Ni helped to improve the wetting for all three types of fluxes as higher wetting forces were documented for Sn-0.7Cu-0.3Ni solder compared to the Sn-0.7Cu solder. Among the fluxes, worst performance was observed for R-type flux. Very large contact angles were recorded for both solders with this kind of flux. Experimental results also revealed that higher solder bath temperature played an important role to lower the contact angle, to increase the wetting force and to enhance the wetting. Computer modeling of wetting balance test also revealed that both the wetting force and meniscus height are inversely proportional to the contact angles. Besides, solder bath depth and radius do not affect significantly on the wetting behavior.

Effect of adding 0.3wt% Ni into the Sn-0.7wt% Cu solder - Part II: Growth of intermetallic layer with Cu during wetting and aging

The growth behavior of intermetallic layer with or without adding 0.3 wt% Ni into the Sn-0.7Cu solder was studied during the wetting reaction on Cu-substrate and thereafter in solid-state aging condition. The Cu-solder reaction couple was prepared at 255, 275 and 295 °C for 10 s. The samples reacted at 255 °C were then isothermally aged for 2-14 days at 150 °C. The reaction species formed for the Sn-0.7Cu/Cu and Sn-0.7Cu-0.3Ni/Cu soldering systems were Cu6Sn5 and (CuNi)6Sn5, respectively. The thickness of the intermetallic compounds formed at the solder/Cu interfaces and also in the bulk of both solders increased with the increase of reaction temperature. It was found that Ni-containing Sn-0.7Cu solder exhibited lower growth of intermetallic layer during wetting and in the early stage of aging and eventually exceeded the intermetallic layer thickness of Sn-0.7Cu/Cu soldering system after 6 days of aging. As the aging time proceeds, a non-uniform intermetallic layer growth tendency was observed for the case of Sn-0.7Cu-0.3Ni solder. The growth behavior of intermetallic layer during aging for both solders followed the diffusion-controlled mechanism. The intermetallic layer growth rate constants for Sn-0.7Cu and Sn-0.7Cu-0.3Ni solders were calculated as 1.41 × 10-17 and 1.89 × 10-17 m2/s, respectively which indicated that adding 0.3 wt% Ni with Sn-0.7Cu solder contributed to the higher growth of intermetallic layer during aging. © 2006 Elsevier B.V. All rights reserved.