Modern major element concentrations and ratios measured in Atlantic surface sediments (36°N-49°S)

Numerous studies use major element concentrations measured on continental margin sediments to reconstruct terrestrial climate variations. The choice and interpretation of climate proxies however differ from site to site. Here we map the concentrations of major elements (Ca, Fe, Al, Si, Ti, K) in Atlantic surface sediments (36°N-49°S) to assess the factors influencing the geochemistry of Atlantic hemipelagic sediments and the potential of elemental ratios to reconstruct different terrestrial climate regimes. High concentrations of terrigenous elements and low Ca concentrations along the African and South American margins reflect the dominance of terrigenous input in these regions. Single element concentrations and elemental ratios including Ca (e.g., Fe/Ca) are too sensitive to dilution effects (enhanced biological productivity, carbonate dissolution) to allow reliable reconstructions of terrestrial climate. Other elemental ratios reflect the composition of terrigenous material and mirror the climatic conditions within the continental catchment areas. The Atlantic distribution of Ti/Al supports its use as a proxy for eolian versus fluvial input in regions of dust deposition that are not affected by the input of mafic rock material. The spatial distributions of Al/Si and Fe/K reflect the relative input of intensively weathered material from humid regions versus slightly weathered particles from drier areas. High biogenic opal input however influences the Al/Si ratio. Fe/K is sensitive to the input of mafic material and the topography of Andean river drainage basins. Both ratios are suitable to reconstruct African and South American climatic zones characterized by different intensities of chemical weathering in well-understood environmental settings.

Enviromagnetic, major element, and grain-size analyses of surface sediment samples along the continental margin between East Brazil and Patagonia

Continental margin sediments of SE South America originate from various terrestrial sources, each conveying specific magnetic and element signatures. Here, we aim to identify the sources and transport characteristics of shelf and slope sediments deposited between East Brazil and Patagonia (20°-48°S) using enviromagnetic, major element, and grain-size data. A set of five source-indicative parameters (i.e., chi-fd%, ARM/IRM, S0.3T, SIRM/Fe and Fe/K) of 25 surface samples (16-1805 m water depth) was analyzed by fuzzy c-means clustering and non-linear mapping to depict and unmix sediment-province characteristics. This multivariate approach yields three regionally coherent sediment provinces with petrologically and climatically distinct source regions. The southernmost province is entirely restricted to the slope off the Argentinean Pampas and has been identified as relict Andean-sourced sands with coarse unaltered magnetite. The direct transport to the slope was enabled by Rio Colorado and Rio Negro meltwaters during glacial and deglacial phases of low sea level. The adjacent shelf province consists of coastal loessoidal sands (highest hematite and goethite proportions) delivered from the Argentinean Pampas by wave erosion and westerly winds. The northernmost province includes the Plata mudbelt and Rio Grande Cone. It contains tropically weathered clayey silts from the La Plata Drainage Basin with pronounced proportions of fine magnetite, which were distributed up to ~24° S by the Brazilian Coastal Current and admixed to coarser relict sediments of Pampean loessoidal origin. Grain-size analyses of all samples showed that sediment fractionation during transport and deposition had little impact on magnetic and element source characteristics. This study corroborates the high potential of the chosen approach to access sediment origin in regions with contrasting sediment sources, complex transport dynamics, and large grain-size variability.

Compositional data analysis of Holocene sediments from the West Bengal Sundarbans, India: Geochemical proxies for grain-size variability in a delta environment

This paper is part of a special issue of Applied Geochemistry focusing on reliable applications of compositional multivariate statistical methods. This study outlines the application of compositional data analysis (CoDa) to calibration of geochemical data and multivariate statistical modelling of geochemistry and grain-size data from a set of Holocene sedimentary cores from the Ganges-Brahmaputra (G-B) delta. Over the last two decades, understanding near-continuous records of sedimentary sequences has required the use of core-scanning X-ray fluorescence (XRF) spectrometry, for both terrestrial and marine sedimentary sequences. Initial XRF data are generally unusable in ‘raw-format’, requiring data processing in order to remove instrument bias, as well as informed sequence interpretation. The applicability of these conventional calibration equations to core-scanning XRF data are further limited by the constraints posed by unknown measurement geometry and specimen homogeneity, as well as matrix effects. Log-ratio based calibration schemes have been developed and applied to clastic sedimentary sequences focusing mainly on energy dispersive-XRF (ED-XRF) core-scanning. This study has applied high resolution core-scanning XRF to Holocene sedimentary sequences from the tidal-dominated Indian Sundarbans, (Ganges-Brahmaputra delta plain). The Log-Ratio Calibration Equation (LRCE) was applied to a sub-set of core-scan and conventional ED-XRF data to quantify elemental composition. This provides a robust calibration scheme using reduced major axis regression of log-ratio transformed geochemical data. Through partial least squares (PLS) modelling of geochemical and grain-size data, it is possible to derive robust proxy information for the Sundarbans depositional environment. The application of these techniques to Holocene sedimentary data offers an improved methodological framework for unravelling Holocene sedimentation patterns.

Effect of adding mineral additives to alkali-activated natural pozzolan paste

Natural pozzolans are raw materials from geological deposits with a range of chemical compositions that when combined with suitable alkali activators can be converted to geopolymer cement for concrete production. In this paper the concept of adding mineral additives to enhance the properties of geopolymer cement is introduced. Taftan andesite, a natural Iranian pozzolan, was used to study the effect of adding mineral additives such as kaolinite, lime and other calcined pozzolans on the compressive strength of geopolymer cement under both normal and autoclave curing. Scanning electron microscopy (SEM)/energy dispersive X-ray (EDX) was used to determine the composition of the gel phase in both alkali-activated Taftan pozzolan with and without mineral additions. The work has shown that deficiencies in SiO2, Al2O3 and CaO content in the raw natural pozzolan can be compensated for by adding mineral additives for enhanced properties.

Optimization of wastepaper sludge ash (WSA) in robust cementitious systems

Abstract : Wastepaper sludge ash (WSA) is generated by a cogeneration station by burning wastepaper sludge. It mainly consists of amorphous aluminosilicate phase, anhydrite, gehlenite, calcite, lime, C2S, C3A, quartz, anorthite, traces of mayenite. Because of its free lime content (~10%), WSA suspension has a high pH (13). Previous researchers have found that the WSA composition has poor robustness and the variations lead to some unsoundness for Portland cement (PC) blended WSA concrete. This thesis focused on the use of WSA in different types of concrete mixes to avoid the deleterious effect of the expansion due to the WSA hydration. As a result, WSA were used in making alkali-activated materials (AAMs) as a precursor source and as a potential activator in consideration of its amorphous content and the high alkaline nature. Moreover, the autogenous shrinkage behavior of PC concrete at low w/b ratio was used in order to compensate the expansion effect due to WSA. The concrete properties as well as the volume change were investigated for the modified WSA blended concrete. The reaction mechanism and microstructure of newly formed binder were evaluated by X-ray diffraction (XRD), calorimetry, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). When WSA was used as precursor, the results showed incompatible reaction between WSA and alkaline solution. The mixtures were not workable and provided very low compressive strength no matter what kinds of chemical activators were used. This was due to the metallic aluminum in WSA, which releases abundant hydrogen gas when WSA reacts with strong alkaline solution. Besides, the results of this thesis showed that WSA can activate the glassy phase contained in slag, glass powder (GP) and class F fly ash (FFA) with an optimum blended ratio of 50:50. The WSA/slag (mass ratio of 50:50) mortar (w/b of 0.47) attained 46 MPa at 28 days without heat curing assistance. A significant fast setting was noticed for the WSA-activated binder due to the C3A phase, free lime and metallic aluminum contained in the WSA. Adding 5% of gypsum can delay the fast setting, but this greatly increased the potential risk of intern sulfate attack. The XRD, TGA and calorimetry analyses demonstrated the formation of ettringite, C-S-H, portlandite, hydrogarnet and calcium carboaluminate in the hydrated binder. The mechanical performance of different binder was closely related to the microstructure of corresponding binder which was proved by the SEM observation. The hydrated WSA/slag and WSA/FFA binder formed a C-A-S-H type of gel with lower Ca/Si ratio (0.47~1.6). A hybrid gel (i.e. C-N-A-S-H) was observed for the WSA/GP binder with a very low Ca/Si ratio (0.26) and Na/Si ratio (0.03). The SEM/EDX analyses displayed the formation of expansive gel (ettringite and thaumasite) in the gypsum added WSA/slag concrete. The gradual emission of hydrogen gas due to the reaction of WSA with alkaline environment significantly increased the porosity and degraded the microstructure of hydrated matrix after the setting. In the last phase of this research WSA-PC blended binder was tailored to form a high autogenous shrinkage concrete in order to compensate the initial expansion. Different binders were proportioned with PC, WSA, silica fume or slag. The microstructure and mechanical properties of concrete can be improved by decreasing w/b ratios and by incorporating silica fume or slag. The 28-day compressive strength of WSA-blended concrete was above 22 MPa and reached 45 MPa when silica fume was added. The PC concrete incorporating silica fume or slag tended to develop higher autogenous shrinkage at low w/b ratios, and thus the ternary binder with the addition of WSA inhibited the long term shrinkage due to the initial expansion property to WSA. In the restrained shrinkage test, the concrete ring incorporating the ternary binder (PC/WSA/slag) revealed negligible potential to cracking up to 96 days as a result of the offset effect by WSA expansion. The WSA blended regular concrete could be produced for potential applications with reduced expansion, good mechanical property and lower permeability.

Air sensitivity of MoS2, MoSe2, MoTe2, HfS2 and HfSe2

A surface sensitivity study was performed on different transition-metal dichalcogenides (TMDs) under ambient conditions in order to understand which material is the most suitable for future device applications. Initially, Atomic Force Microscopy and Scanning Electron Microscopy studies were carried out over a period of 27 days on mechanically exfoliated flakes of 5 different TMDs, namely, MoS2, MoSe2, MoTe2, HfS2, and HfSe2. The most reactive were MoTe2 and HfSe2. HfSe2, in particular, showed surface protrusions after ambient exposure, reaching a height and width of approximately 60 nm after a single day. This study was later supplemented by Transmission Electron Microscopy (TEM) cross-sectional analysis, which showed hemispherical-shaped surface blisters that are amorphous in nature, approximately 180–240 nm tall and 420–540 nm wide, after 5 months of air exposure, as well as surface deformation in regions between these structures, related to surface oxidation. An X-ray photoelectron spectroscopy study of atmosphere exposed HfSe2 was conducted over various time scales, which indicated that the Hf undergoes a preferential reaction with oxygen as compared to the Se. Energy-Dispersive X-Ray Spectroscopy showed that the blisters are Se-rich; thus, it is theorised that HfO2 forms when the HfSe2 reacts in ambient, which in turn causes the Se atoms to be aggregated at the surface in the form of blisters. Overall, it is evident that air contact drastically affects the structural properties of TMD materials. This issue poses one of the biggest challenges for future TMD-based devices and technologies.

Use of Spirulina platensis micro and nanoparticles for the removal synthetic dyes from aqueous solutions by biosorption

In this research, micro and nanoparticles of Spirulina platensis dead biomass were obtained, characterized and employed to removal FD&C red no. 40 and acid blue 9 synthetic dyes from aqueous solutions. The effects of particle size (micro and nano) and biosorbent dosage (from 50 to 750 mg) were studied. Pseudofirst order, pseudo-second order and Elovich models were used to evaluate the biosorption kinetics. The biosorption nature was verified using energy dispersive X-ray spectroscopy (EDS). The best results for both dyes were found using 250 mg of nanoparticles, in these conditions, the biosorption capacities were 295 mg g−1 and 1450 mg g−1, and the percentages of dye removal were 15.0 and 72.5% for the FD&C red no. 40 and acid blue 9, respectively. Pseudo-first order model was the more adequate to represent the biosorption of both dyes onto microparticles, and Elovich model was more appropriate to the biosorption onto nanoparticles. The EDS results suggested that the dyes biosorption onto microparticles occurred mainly by physical interactions, and for the nanoparticles, chemisorption was dominant.

Sensibilidade à mudança de trajetória de deformação no aço TWIP980

Resultante dos avanços tecnológicos, conseguiu-se obter um aço que elimina o paradigma de se aliar alta ductilidade e resistência mecânica. Assim foi desenvolvido durante a última década o aço TWIP, deformação induzida por maclação, tendo como principal mecanismo de deformação a maclação. Este presente trabalho teve como principal objetivo caraterizar o aço TWIP980 em três temáticas diferentes: química, mecânica e microestrutura. Na primeira temática, a química, esta teve como objetivo encontrar a designação do aço TWIP em estudo. Sendo apenas conhecida a direção de laminação, RD, e a empresa que forneceu as chapas, a POSCO, o objetivo era obter a sua designação. Através da comparação das curvas de tração encontradas para o material em estudo, e conjuntamente, com as diversas curvas de tração de vários aços TWIP da empresa POSCO, realizou-se a comparação. Visto ter-se ficado reduzido a dois possíveis aços TWIP, foi através de uma análise à composição química, EDS - Espectroscopia da energia dispersa por raios-X, que se concluiu que o aço em estudo era o TWIP980. Na caraterização mecânica, e através de ensaios de tração, foram estudadas propriedades como: o módulo de elasticidade, tensão limite elástico, ductilidade, anisotropia, coeficiente de encruamento e Poisson. Estas propriedades foram estudas para três mudanças na trajetória de deformação e quatro pré-deformações em estudo. Assim estudou-se a alteração de trajetória para os ângulos a 0º, 45º e 90º em relação a RD, para as deformações de engenharia de 0%, 10%, 20% e 30%. Por último, na análise à microestrutura, esta teve como objetivo obter valores para o tamanho de grão e de macla bem como as suas orientações cristalográficas. Também a densidade de deslocações e maclação para cada uma das 4 pré-deformações esteve em estudo. Estes parâmetros foram obtidos através de microscopia ótica, eletrónica de varrimento, MEV e eletrónica de transmissão, MET.

Metallurgia del piombo e siderurgia nel sito protostorico di Brunku ’e s’Omu (Sardegna centro-occidentale): inquadramento funzionale dei manufatti e ricostruzione dei processi produttivi

The archaeological excavations carried out in 2013 in the hut n. 16 of the protohistoric settlement of Brunku ’e s’Omu (central-western Sardinia) returned some metal products. The morpho-metric and functional study of these artifacts al-lowed the identification of two mending strips and other remains related to Bronze Age (late II millennium BC) ceramic vessels reparing. Some uncertainly dated slags and metal fragments were also identified. Visual examination and archaeometric investigation carried out by means of portable energy dispersive X-ray fluores-cence spectrometry (pXRF) were performed on these metals. The analyses were able to relate some remains to iron manufacturing and highlighted the lead composition of the other ones. The chosen approach further clarified some as-pects of nuragic metallurgists’ behaviour in selecting and processing metalliferous geo-materials.

Engineering thin films of magnetic alloys and semiconductor oxides at the nanoscale

The thesis aims to exploit properties of thin films for applications such as spintronics, UV detection and gas sensing. Nanoscale thin films devices have myriad advantages and compatibility with Si-based integrated circuits processes. Two distinct classes of material systems are investigated, namely ferromagnetic thin films and semiconductor oxides. To aid the designing of devices, the surface properties of the thin films were investigated by using electron and photon characterization techniques including Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), grazing incidence X-ray diffraction (GIXRD), and energy-dispersive X-ray spectroscopy (EDS). These are complemented by nanometer resolved local proximal probes such as atomic force microscopy (AFM), magnetic force microscopy (MFM), electric force microscopy (EFM), and scanning tunneling microscopy to elucidate the interplay between stoichiometry, morphology, chemical states, crystallization, magnetism, optical transparency, and electronic properties. Specifically, I studied the effect of annealing on the surface stoichiometry of the CoFeB/Cu system by in-situ AES and discovered that magnetic nanoparticles with controllable areal density can be produced. This is a good alternative for producing nanoparticles using a maskless process. Additionally, I studied the behavior of magnetic domain walls of the low coercivity alloy CoFeB patterned nanowires. MFM measurement with the in-plane magnetic field showed that, compared to their permalloy counterparts, CoFeB nanowires require a much smaller magnetization switching field , making them promising for low-power-consumption domain wall motion based devices. With oxides, I studied CuO nanoparticles on SnO2 based UV photodetectors (PDs), and discovered that they promote the responsivity by facilitating charge transfer with the formed nanoheterojunctions. I also demonstrated UV PDs with spectrally tunable photoresponse with the bandgap engineered ZnMgO. The bandgap of the alloyed ZnMgO thin films was tailored by varying the Mg contents and AES was demonstrated as a surface scientific approach to assess the alloying of ZnMgO. With gas sensors, I discovered the rf-sputtered anatase-TiO2 thin films for a selective and sensitive NO2 detection at room temperature, under UV illumination. The implementation of UV enhances the responsivity, response and recovery rate of the TiO2 sensor towards NO2 significantly. Evident from the high resolution XPS and AFM studies, the surface contamination and morphology of the thin films degrade the gas sensing response. I also demonstrated that surface additive metal nanoparticles on thin films can improve the response and the selectivity of oxide based sensors. I employed nanometer-scale scanning probe microscopy to study a novel gas senor scheme consisting of gallium nitride (GaN) nanowires with functionalizing oxides layer. The results suggested that AFM together with EFM is capable of discriminating low-conductive materials at the nanoscale, providing a nondestructive method to quantitatively relate sensing response to the surface morphology.

Caracterização elementar de ligas metálicas em implantes dentários

An ideal biomaterial for dental implants must have very high biocompatibility, which means that such materials should not provoke any serious adverse tissue response. Also, used metal alloys must have high fatigue resistance due the masticatory force and good corrosion resistance. These properties are rendered by using alpha and beta stabilizers, such as Al, V, Ni, Fe, Cr, Cu, Zn. Commercially pure titanium (TiCP) is used often for dental and orthopedic implants manufacturing. However, sometimes other alloys are employed and consequently it is essential to research the chemical elements present in those alloys that could bring prejudice for the health. Present work investigated TiCP metal alloys used for dental implant manufacturing and evaluated the presence of stabilizing elements within existing limits and standards for such materials. For alloy characterization and identification of stabilizing elements it was used EDXRF technique. This method allows to perform qualitative and quantitative analysis of the materials using the spectra of the characteristic X-rays emitted by the elements present in the metal samples. The experimental setup was based on two X- rays tubes (AMPTEK Mini X model with Ag and Au targets), a X-123SDD detector (AMPTEK) and a 0.5mm Cu collimator, developed due to the sample characteristics. The other experimental setup used as a complementary technique is composed of an X-ray tube with a Mo target, collimator 0.65mm and XFlash (SDD) detector - ARTAX 200 (BRUKER). Other method for elemental characterization by energy dispersive spectroscopy (EDS) applied in present work was based on Scanning Electron Microscopy (SEM) EVO® (Zeeis). This method also was used to evaluate the surface microstructure of the sample. The percentual of Ti obtained in the elementary characterization was among 93.35 ± 0.17% and 95.34 ± 0.19 %. These values are considered below the reference limit of 98.635% to 99.5% for TiCP, established by Association of metals centric materials engineers and scientists Society (ASM). The presence of elements Al and V in all samples also contributed to underpin the fact that are not TiCP implants. The values for Al vary between 6.3 ± 1.3% and 3.7 ± 2.0% and for V, between 0.26 ± 0.09% and 0.112 ± 0.048%. According to the American Society for Testing and Materials (ASTM), these elements should not be present in TiCP and in accordance with the National Institute of Standards and Technology (NIST), the presence of Al should be <0.01% and V should be of 0.009 ± 0.001%. Obtained results showed that implant materials are not exactly TiCP but, were manufactured using Ti-Al-V alloy, which contained Fe, Ni, Cu and Zn. The quantitative analysis and elementary characterization of experimental results shows that the best accuracy and precision were reached with X-Ray tube with Au target and collimator of 0.5 mm. Use of technique of EDS confirmed the results of EDXRF for Ti-Al-V alloy. Evaluating the surface microstructure by SEM of the implants, it was possible to infer that ten of the thirteen studied samples are contemporaneous, rough surface and three with machined surface.

Estudo da intercalação de fontes de potássio em caulinita pura, com tratamento térmico e ativação ácida

The chemical changes in clay minerals has been widely studied in order to improve its properties for use in various applications. However kaolinite has strong hydrogen bonds between their adjacent layers hindering the process changes in its structure. With the objective to facilitate the process of intercalation monobasic potassium phosphate, bibasic potassium phosphate and potassium acetate we was performed on kaolinite heat treatment at 600 °C and activated acidic with phosphoric acid and 5 to 10 mol L-1. The samples they were characterized by energy dispersive spectroscopy (EDS), X-Ray Diffraction (XRD), Infrared Spectroscopy Fourier Transform (FTIR) and Thermogravimetric Analysis (TG) and Differential Thermal Analysis (DTG) and the superficial and textural changes the samples with heat treatment and acid activation they were characterized by scanning electron microscopy (SEM) and Textural Analysis of Adsorption/desorption N2. With the help of the techniques found that, the heat treatment becomes more susceptible to acid activation kaolinite making the samples with two treatments show larger amounts of phosphorus. It was also found that bibasic potassium phosphate binds more strongly the structure of kaolinite by having a structure with two-coordinating oxygens and intercalation with potassium acetate in acid-activated kaolin increases the interlayer distance of the kaolinite and the intercalation occurs with higher response index (RI) for samples with acid activation to 5 mol /L.