Effect of platinum on the growth rate of the oxide scale formed on cast nickel aluminide intermetallic alloys

Thermo-Gravimetric Analysis ( TGA) and Scanning Electron M icroscopy ( SEM ) data of the initial stages of oxidation of Ni50Al50 and Ni40Pt10Al50 alloys of low and high sulfur content at 900◦ C and 1100◦ C are reported. The results show that the addition of Pt promotes the growth of the transient θ- Al2O3 oxide scale. This effect is particularly sensitive in the initial stages of oxidation at 1100◦ C where Pt considerably increases the total mass gain. It is attenuated in the presence of a high sulfur content in the alloy, indicating a competitive effect of Pt and S on the segregation of Al. The slower θ-to- α transition observed in the presence of Pt leads to an extended lifetime of the θ phase layer, which is proposed to be benecial to the relaxation of the stresses created by the growth of α-Al2O3

Ni–W diffusion barrier: Its influence on the oxidation behaviour of a β-(Ni,Pt)Al coated fourth generation nickel-base superalloy

A Ni–W base diffusion barrier (DB) has been developed to limit interdiffusion between a fourth generation Ni-base superalloy (MCNG) and a Pt-modified nickel aluminide bondcoat. After long term oxidation, the DB layer permits to reduce the Al depletion in the coating and to delay the phase transformations in the coating. But despite this result, the oxidation behaviour of the system with DB is slightly worse than without the DB. This difference may be caused by the addition of S and/orWin the coating of the system with the DB. The DB layer also delays the Secondary Reaction Zone (SRZ) formation. Nevertheless, the propagation of the SRZ is similar in systems with and without a DB, with growth kinetics which are driven by interdiffusion

Geochemical evidence of Milankovitch cycles in Atlantic Ocean ferromanganese crusts

Hydrogenetic ferromanganese crusts are considered a faithful record of the isotopic composition of seawater influenced by weathering processes of continental masses. Given their ubiquitous presence in all oceans of the planet at depths of 400–7000 meters, they form one of the most well-distributed and accessible records of water-mass mixing and climate. However, their slow accumulation rate and poor age constraints have to date limited their use to explore 100 ka paleoclimatic phenomena. Here it is shown how the Pb isotope signature and major element content of a Fe-Mn crust from the north-east Atlantic responded to changes in the intensity and geographic extent of monsoonal rainfall over West Africa, as controlled by climatic precession during the Paleocene. The studied high-spatial resolution (4 μm) laser-ablation multi-collector inductively coupled plasma mass spectrometer (LA-MC-ICP-MS) Pb isotope data is a nearly 2 order of magnitude improvement in spatial and temporal resolution compared to micro-drill subsamples. The record demonstrates cyclicity of the 206Pb/204Pb and 208, 207Pb/206Pb ratios at the scale of single Fe-Mn oxide laminae, in conjunction with variations in the Fe/Mn ratio, Al, Si and Ti content. Time-frequency analysis and astronomical tuning of the Pb isotope data demonstrates the imprint of climatic precession (∼20 ka) modulated by eccentricity (∼100 and 405 ka), yielding growth rates of 1.5–3.5 mm/Ma consistent with previous chemostratigraphic age models. In this context, boreal summer at the perihelion causes stronger insolation over West Africa, resulting in more intense and geographically extended monsoonal rainfalls compared to aphelion boreal summer conditions. This, in turn, influences the balance between the weathering endmembers feeding the north-east Atlantic basin. These results provide a new approach for calibrating Fe-Mn crust records to astronomical solutions, and allow their isotopic and chemical archive to be exploited with an improved temporal resolution of 1000–5000 years

Controls on metal enrichment in ferromanganese crusts: temporal changes in oceanic metal flux or phosphatisation?

Oceanic hydrogenetic ferromanganese (Fe-Mn) crusts are a major repository for many metals, such as Co, Ni, Cu, Pt, Te and REE, which are essential for decarbonisation of transport and energy systems. Secondary mineralisation processes, occurring during phosphatisation episodes, commonly impregnate the shallower deposits with carbonate fluorapatite (CFA). The suboxic oceanic conditions during such events are frequently invoked to explain the lower Co content and unusually high Ni, Cu, Zn and Pt content of older phosphatised crusts. Here, the hypothesis of suboxic diagenetic recrystallization induced by phosphatisation episodes as a driving mechanism for Ni, Cu, Zn and Pt enrichment and Co depletion is evaluated. Accurately dated geochemical profiles, spanning 75 Ma of depositional history, for a shallow (1100 mbsl) phosphatised sample and a deeper (3100 mbsl) unphosphatised sample from Tropic Seamount in the north-east Atlantic, are compared. An isocon analysis, which allows to quantitively evaluate chemical gains and losses in mass transfer and therefore permits compensation for the dilution effect induced by the addition of CFA in the Fe-Mn crusts, demonstrates that no loss of Co has occurred in the phosphatised crust, whilst Pt, Te, Cu, Ni and Zn are enriched relative to younger, unphosphatised Fe-Mn crust. Both geochemical profiles show sympathetic trends and similar amplitudes of variation in concentration. This excludes phosphatisation as the driving mechanism for the metal enrichment and depletion. Systematic differences in metal content between the two samples, such as higher Cu and lower Co content in the deeper sample, are consistent with the depth profile of dissolved metal concentrations in the water column. The variability observed in the geochemical profiles is consistent with temporal changes in metal fluxes to the ocean, as a result of the evolving climate and oceanographic configuration of the north-east Atlantic Ocean through the Cenozoic. It is concluded that changing metal fluxes, rather than secondary mineralisation process associated with phosphatisation, is the dominant control on the primary metal content in Fe-Mn crust deposits at Tropic Seamount

Late Cretaceous and Cenozoic paleoceanography from north-east Atlantic ferromanganese crust microstratigraphy

Oceanic hydrogenetic ferromanganese (Fe-Mn) crusts precipitate directly from ambient seawater over millions of years. Their very slow growth rates and physio-chemical properties mean that they adsorb numerous elements from seawater. As such, they provide condensed records of seawater evolution through time that can be used for paleoceanographic reconstruction. Here, we present the results of a high-resolution, stratigraphic, textural and geochemical investigation of a core sample, obtained from a Fe-Mn crust pavement, located on the summit of Tropic Seamount in the tropical north-east Atlantic Ocean. A number of observations and interpretations are proposed, within the context of a well-constrained age model, spanning the last 75 ± 2 Myr. This core has textural stratigraphic coherence with Pacific Fe-Mn crusts formed since the Late Cretaceous, highlighting that global oceanic and climatic phenomena exert first-order controls on Fe-Mn crust development. All major hiatuses observed in the Fe-Mn crusts are contemporaneous with erosion events occurring throughout the Atlantic Ocean. High-resolution geochemical data indicate that there is variability in the composition of Fe-Mn crusts at the cm to μm scale. The dominant factors controlling this include major oceanographic events, mineral textures and micro-topography

Development of a NiW in-situ diffusion barrier on a fourth generation nickel-base superalloy

A diffusion barrier based on a NiW electrolytic coating has been developed to limit interdiffusion between a Ni-base superalloy (MCNG) and a β-NiAl bondcoating. Isothermal oxidation tests of 50h at 1100°C confirmed that W-rich layer formed with NiW coating modifies the oxidation behaviour of the bondcoat and limits interdiffusion. The diffusion barrier reduced β-NiAl γ’-Ni3Al transformation in the bondcoating and prevented SRZ formation

Improving confidence in ferromanganese crust age models: a composite geochemical approach

Accurate age models for marine ferromanganese (Fe-Mn) crusts are essential to understand paleoceanographic changes and variations in local environmental factors affecting crust growth rate and their lateral continuity. However, no absolute method exists for dating these deposits beyond the age of 10 Myr, which requires the combination of a number of approaches. Here, we present a composite age model for a 15 cm thick Fe-Mn crust sample obtained by unique core drilling using a remotely operated vehicle at a water depth of 1130 m, on the summit of Tropic Seamount, in the north-east Atlantic. The age model is based on cross-validation of laser-ablation U-Pb dating, Co-chronometry and Os isotopes. These enable robust calibration of the age-depth model using the Bayesian statistical modelling of Markov Chain Monte Carlo (MCMC) simulations. The results show that this Fe-Mn crust commenced growth in the Late Cretaceous between 73 and 77 Ma, and grew at a rate between 1 and 24 mm/Myr, averaging 4 mm/Myr. The phosphatised carbonate substrate, capping Tropic Seamount and underlying most of the Fe-Mn crusts, yields a U-Pb age of 84 ± 4 Myr, and provides the upper age limit for the model. Less radiogenic excursions of 188Os/187Os in the vertical profile through the crust permit the identification of key inflection points in the Os isotope seawater curve at the Eocene-Oligocene and Cretaceous-Paleogene transitions. Growth rates estimated from the empirical Co-chronometer are combined with the age envelope defined by the Os data and used to validate the MCMC simulations. The model identifies five hiatuses that occurred during the Pliocene (2.5 ± 1.9–5.3 ± 1.7 Ma), Early Miocene (16 ± 1–27 ± 2 Ma), Oligocene (29 ± 2–32 ± 1 Ma), Eocene (41 ± 2–52 ± 0.6 Ma), and the Late Paleocene (55 ± 1–59 ± 1.4 Ma). A major phosphatisation event affecting the Fe-Mn core can be dated to the Late Eocene (38 ± 1.2 Ma), which coincides with a recorded change in the global oceanic system, from warm and sluggish circulation to cold and vigorous thermohaline-driven meridional overturn at the onset of Antarctic glaciation

Application of random-forest machine learning algorithm for mineral predictive mapping of Fe-Mn crusts in the World Ocean

Mineral prospectivity mapping constitutes an efficient tool for delineating areas of highest interest to guide future exploration. Multiple knowledge-driven approaches have been applied for the creation of prospectivity maps for deep-sea ferromanganese (Fe-Mn) crusts over the last decades. The results of a data-driven approach making use of an extensive data collection exercise on occurrences of Fe-Mn crusts in the World Ocean and recent increase in global marine datasets are presented. A Random Forest machine learning algorithm is applied, and results compared with previously established expert-driven maps. Optimal predictive conditions for the algorithm are observed for (i) a forest size superior to a hundred trees, (ii) a training dataset larger than 10%, and (iii) a number of predictors to be used as nodes superior to two. The confusion matrix and out-of-bag errors on the remaining unused data highlight excellent predictive capabilities of the trained model with a prediction accuracy for Fe-Mn crusts of 87.2% and 98.2% for non-crusts locations, with a Kohen’s K index of 0.84, validating its application for prediction at the World scale. The slope of the seafloor, sediment thickness, sediment type, biological productivity, and abyssal mountain constitute the five strongest explanatory variables in predicting the occurrence of Fe-Mn crusts. Most ‘hand-drawn’ knowledge-driven prospective areas are also considered prospective by the random forest algorithm with notable exceptions along the coast of the American continent. However, poor correlation is observed with knowledge-driven GIS-based criterion mapping as the Random Forest considers un-prospective most target areas from the GIS approach. Overall, the Random Forest prediction performs better in predicting a high chance of Fe-Mn crust occurrence in ISA licensed area than the GIS approach, which constitutes an external validation of the predictive quality of the random forest model

Origin and Composition of Ferromanganese Deposits of New Caledonia Exclusive Economic Zone

Located in the South-West Pacific, at the northern extremity of the mostly submerged Zealandia continent, the New Caledonian Exclusive Economic Zone (EEZ) covers 1,470,000 km² and includes basins, ridges and seamounts where abundant ferromanganese crusts have been observed. Several investigations have been conducted since the 1970s on the nature and composition of ferromanganese crusts from New Caledonia’s seamounts and ridges, but none have covered the entire EEZ. We present data from 104 ferromanganese crusts collected in New Caledonia’s EEZ during twelve oceanographic cruises between 1974 and 2019. Samples were analysed for mineralogy, geochemical compositions, growth rates, and through a statistical approach using correlation coefficients and factor analysis. Crust thicknesses range from 1 mm to 115 mm, with growth rates between 0.45 mm/Ma and 102 mm/Ma. Based on textures, structures, discrimination plots, and growth rates, we distinguish a group of hydrogenetic crusts containing the highest mean contents of Co (0.42 wt%), Ni (0.31 wt%), and high contents of Mo, V, W, Pb, Zn, Nb, from a group of hydrothermal and/or diagenetic deposits showing high mean contents of Mn (38.17 wt%), Ba (0.56 wt%) and low contents of other trace metals. Several samples from this later group have exceptionally high content of Ni (0.7 wt%). The data shows that crusts from the southern part of the EEZ, notably seamounts of the Loyalty Ridge and the Lord Howe Rise, present high mineral potential for prospectivity owing to high contents of valuable metals, and constitute a great target for further investigatio

Single-cell scattering and auto-fluorescence-based fast antibiotic susceptibility testing for gram-negative and gram-positive bacteria

In this study, we assess the scattering of light and auto-fluorescence from single bacterial cells to address the challenge of fast (<2 h), label-free phenotypic antimicrobial susceptibility testing (AST). Label-free flow cytometry is used for monitoring both the respiration-related auto-fluorescence in two different fluorescence channels corresponding to FAD and NADH, and the morphological and structural information contained in the light scattered by individual bacteria during incubation with or without antibiotic. Large multi-parameter data are analyzed using dimensionality reduction methods, based either on a combination of 2D binning and Principal Component Analysis, or with a one-class Support Vector Machine approach, with the objective to predict the Susceptible or Resistant phenotype of the strain. For the first time, both Escherichia coli (Gram-negative) and Staphylococcus epidermidis (Gram-positive) isolates were tested with a label-free approach, and, in the presence of two groups of bactericidal antibiotic molecules, aminoglycosides and beta-lactams. Our results support the feasibility of label-free AST in less than 2 h and suggest that single cell auto-fluorescence adds value to the Susceptible/Resistant phenotyping over single-cell scattering alone, in particular for the mecA+ Staphylococcus (i.e., resistant) strains treated with oxacillin