Eutectic modification of Al-Si alloys with rare earth metals

The effects of different concentrations of individual additions of rare earth metals (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) on eutectic modification in Al-10mass%Si has been studied by thermal analysis and optical microscopy. According to the twin-plane re-entrant edge (TPRE) and impurity induced twinning mechanism, rare earth metals with atomic radii of about 1.65 times larger than that of silicon, are possible candidates for eutectic modification. All of the rare earth elements caused a depression of the eutectic growth temperature, but only Eu modified the eutectic silicon to a fibrous morphology. At best, the remaining elements resulted in only a small degree of refinement of the plate-like silicon. The samples were also quenched during the eutectic arrest to examine the eutectic solidification modes. Many of the rare-earth additions significantly altered the eutectic solidification mode from that of the unmodified alloy. It is concluded that the impurity induced twinning model of modification, based on atomic radius alone, is inadequate and other mechanisms are essential for the modification process. Furthermore, modification and the eutectic nucleation and growth modes are controlled independently of each other.

Rare earth element geochemistry of Late Devonian reefal carbonates, canning basin, Western Australia: Confirmation of a seawater REE proxy in ancient limestones

Rare earth element and yttrium (REE+Y) concentrations were determined in 49 Late Devonian reefal carbonates from the Lennard Shelf, Canning Basin, Western Australia. Shale-normalized (SN) REE+Y patterns of the Late Devonian samples display features consistent with the geochemistry of well-oxygenated, shallow seawater. A variety of different ancient limestone components, including microbialites, some skeletal carbonates (stromatoporoids), and cements, record seawater-like REE+Y signatures. Contamination associated with phosphate, Fe-oxides and shale was tested quantitatively, and can be discounted as the source of the REE+Y patterns. Co-occurring carbonate components that presumably precipitated from the same seawater have different relative REE concentrations, but consistent REE+Y patterns. Clean Devonian early marine cements (n = 3) display REE+Y signatures most like that of modern open ocean seawater and the highest Y/Ho ratios (e.g., 59) and greatest light REE (LREE) depletion (average Nd-SN/Yb-SN = 0.413, SD = 0.076). However, synsedimentary cements have the lowest REE concentrations (e.g., 405 ppb). Non-contaminated Devonian microbialite samples containing a mixture of the calcimicrobe Renalcis and micritic thrombolite aggregates in early marine cement (n = 11) have the highest relative REE concentrations of tested carbonates (average total REE = 11.3 ppm). Stromatoporoid skeletons, unlike modern corals, algae and molluscs, also contain well-developed, seawater-like REE patterns. Samples from an estuarine fringing reef have very different REE+Y patterns with LREE enrichment (Nd-SN/Yb-SN > 1), possibly reflecting inclusion of estuarine colloidal material that contained preferentially scavenged LREE from a nearby riverine input source. Hence, Devonian limestones provide a proxy for marine REE geochemistry and allow the differentiation of co-occurring water masses on the ancient Lennard Shelf. Although appropriate partition coefficients for quantification of Devonian seawater REE concentrations from out data are unknown, hypothetical Devonian Canning Basin seawater REE patterns were obtained with coefficients derived from modern natural proxies and experimental values. Resulting Devonian seawater patterns are slightly enriched in LREE compared to most modem seawaters and suggest higher overall REE concentrations, but are very similar to seawaters from regions with high terrigenous inputs. Our results suggest that most limestones should record important aspects of the REE geochemistry of the waters in which they precipitated, provided they are relatively free of terrigenous contamination and major diagenetic alteration from fluids with high, non-seawater-like REE contents. Hence, we expect that many other ancient limestones will serve as seawater REE proxies, and thereby provide information on paleoceanography, paleogeography and geochemical evolution of the oceans. Copyright (C) 2004 Elsevier Ltd.

The behaviour of the rare earth elements during estuarine mixing-revisited

Complete rare earth element (except Eu) and Y concentrations from the estuarine mixing zone (salinity =0.2 to 33) of Elimbah Creek, Queensland, Australia, were measured by quadrupole ICP-MS without preconcentration. High sampling density in the low salinity regime along with high quality data allow accurate tracing of the development of the typical marine rare earth element anomalies as well as Y/Ho fractionation. Over the entire estuary, the rare earth elements are strongly removed relative to a freshwater endmember (60-80% removal). This large overall removal occurs despite a strong remineralisation peak (190% for La, 130% for Y relative to the freshwater endmember) in the mid-salinity zone. Removal and remineralisation are accompanied by fractionation of the original (freshwater) rare earth element pattern, resulting in light rare earth element depletion. Estuarine fractionation generates a large positive La anomaly and a superchondritic Y/Ho ratio. Conversely, we observe no evidence to support the generation of the negative Ce anomaly in the estuary. With the exception of Ce, the typical marine rare earth element features can thus be attributed to estuarine mixing processes. The persistence of these features in hydrogenous sediments for at least 3.71 Ga highlights the importance of estuarine processes for marine chemistry on geological timescales. (c) 2005 Elsevier B.V. All rights reserved.

Aquatic geochemistry of the rare earth elements and yttrium in the Pioneer River catchment, Australia

The rare earth elements are strong provenance indicators in geological materials, yet the potential for tracing provinciality in surface freshwater samples has not been adequately tested. Rare earth element and yttrium concentrations were measured at 33 locations in the Pioneer River catchment, Mackay, central Queensland, Australia. The rare earth element patterns were compared on the basis of geological, topographical and land-use features in order to investigate the provenancing potential of these elements in a small freshwater system. The rare earth element patterns of streams draining single lithological units with minor land modification show strongly coherent normalised behaviour, with a loss of coherence in agricultural locations. Evidence is reported for an anthropogenic Gd anomaly that may provide a useful hydrological tracer in this region since the introduction of magnetic resonance imaging in 2003. Several samples display a superchondritic Y/Ho mass ratio (up to 44), which is not explainable within the constraints imposed by local geology. Instead, it is suggested that the additional Y is derived from a marine source, specifically marine phosphorites, which are a typical source of fertiliser phosphorus. The data indicate that, under some circumstances, scaled and normalised freshwater rare earth patterns behave conservatively.

Effects of rare-earth co-doping on the local structure of rare-earth phosphate glasses using high and low energy X-ray diffraction

Rare-earth co-doping in inorganic materials has a long-held tradition of facilitating highly desirable optoelectronic properties for their application to the laser industry. This study concentrates specifically on rare-earth phosphate glasses, (R2O3)x(R'2O3)y(P2O5)1-(x+y), where (R, R') denotes (Ce, Er) or (La, Nd) co-doping and the total rare-earth composition corresponds to a range between metaphosphate, RP3O9, and ultraphosphate, RP5O14. Thereupon, the effects of rare-earth co-doping on the local structure are assessed at the atomic level. Pair-distribution function analysis of high-energy X-ray diffraction data (Qmax = 28 Å-1) is employed to make this assessment. Results reveal a stark structural invariance to rare-earth co-doping which bears testament to the open-framework and rigid nature of these glasses. A range of desirable attributes of these glasses unfold from this finding; in particular, a structural simplicity that will enable facile molecular engineering of rare-earth phosphate glasses with 'dial-up' lasing properties. When considered together with other factors, this finding also demonstrates additional prospects for these co-doped rare-earth phosphate glasses in nuclear waste storage applications. This study also reveals, for the first time, the ability to distinguish between P-O and PO bonding in these rare-earth phosphate glasses from X-ray diffraction data in a fully quantitative manner. Complementary analysis of high-energy X-ray diffraction data on single rare-earth phosphate glasses of similar rare-earth composition to the co-doped materials is also presented in this context. In a technical sense, all high-energy X-ray diffraction data on these glasses are compared with analogous low-energy diffraction data; their salient differences reveal distinct advantages of high-energy X-ray diffraction data for the study of amorphous materials. © 2013 The Owner Societies.

Observations and rare earth element composition of manganese nodules during Atlantis cruise AT266, Blake Plateau

An area of about 22,000 km² on the northern Blake Plateau, off the coast of South Carolina, contains an estimated 2 billion metric tons of phosphorite concretions, and about 1.2 billion metric tons of mixed ferromanganese-phosphorite pavement. Other offshore phosphorites occur between the Blake Plateau and known continental deposits, buried under variable thicknesses of sediments. The phosphorite resembles other marine phosphorites in composition, consisting primarily of carbonate-fluorapatite, some calcite, minor quartz and other minerals. The apatite is optically pseudo-isotropic and contains about 6% [CO3]**2- replacing [PO4]**3- in its structure. JOIDES drillings and other evidence show that the phosphorite is a lag deposit derived from Miocene strata correlatable with phosphatic Middle Tertiary sediments on the continent. It has undergone variable cycles of erosion, reworking, partial dissolution and reprecipitation. Its present form varies from phosphatized carbonate debris, loose pellets, and pebbles, to continuous pavements, plates, and conglomeratic boulders weighing hundreds of kilograms. No primary phosphatization is currently taking place on the Blake Plateau. The primary phosphate-depositing environment involved reducing conditions and required at least temporary absence of the powerful Gulf Stream current that now sweeps the bottom of the Blake Plateau and has eroded away the bulk of the Hawthorne-equivalent sediments with which the phosphorites were once associated.

Rare earth element concentrations and geochemistry of carbonate minerals from the Logatchev Hydrothermal Field and the Gakkel Ridge

The ultramafic-hosted Logatchev Hydrothermal Field (LHF) at 15°N on the Mid-Atlantic Ridge and the Arctic Gakkel Ridge (GR) feature carbonate precipitates (aragonite, calcite, and dolomite) in voids and fractures within different types of host rocks. We present chemical and Sr isotopic compositions of these different carbonates to examine the conditions that led to their formation. Our data reveal that different processes have led to the precipitation of carbonates in the various settings. Seawater-like 87Sr/86Sr ratios for aragonite in serpentinites (0.70909 to 0.70917) from the LHF are similar to those of aragonite from the GR (0.70912 to 0.70917) and indicate aragonite precipitation from seawater at ambient conditions at both sites. Aragonite veins in sulfide breccias from LHF also have seawater-like Sr isotope compositions (0.70909 to 0.70915), however, their rare earth element (REE) patterns show a clear positive europium (Eu) anomaly indicative of a small (< 1%) hydrothermal contribution. In contrast to aragonite, dolomite from the LHF has precipitated at much higher temperatures (~100 °C), and yet its 87Sr/86Sr ratios (0.70896 to 0.70907) are only slightly lower than those of aragonite. Even higher temperatures are calculated for the precipitation of deformed calcite veins in serpentine-talc fault schists form north of the LHF. These calcites show unradiogenic 87Sr/86Sr ratios (0.70460 to 0.70499) indicative of precipitation from evolved hydrothermal fluids. A simple mixing model based on Sr mass balance and enthalpy conservation indicates strongly variable conditions of fluid mixing and heat transfers involved in carbonate formation. Dolomite precipitated from a mixture of 97% seawater and 3% hydrothermal fluid that should have had a temperature of approximately 14 °C assuming that no heat was transferred. The much higher apparent precipitation temperatures based on oxygen isotopes (~ 100 °C) may be indicative of conductive heating, probably of seawater prior to mixing. The hydrothermal calcite in the fault schist has precipitated from a mixture of 67% hydrothermal fluid and 33% seawater, which should have had an isenthalpic mixing temperature of ~ 250 °C. The significantly lower temperatures calculated from oxygen isotopes are likely due to conductive cooling of hydrothermal fluid discharging along faults. Rare earth element patterns corroborate the results of the mixing model, since the hydrothermal calcite, which formed from waters with the greatest hydrothermal contribution, has REE patterns that closely resemble those of vent fluids from the LHF. Our results demonstrate, for the first time, that (1) precipitation from pure seawater, (2) conductive heating of seawater, and (3) conductive cooling of hydrothermal fluids in the sub-seafloor all can lead to carbonate precipitation within a single ultramafic-hosted hydrothermal system.

Effect of rare earth dopants on structural and mechanical properties of nanoceria synthesized by combustion method

Structural characteristics of combustion synthesized, calcined and densified pure and doped nanoceria with tri-valent cations of Er, Y, Gd, Sm and Nd were analyzed by X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). The results showed that the as-synthesized and calcined nanopowders were mesoporous and calculated lattice parameters were close to theoretical ion-packing model. The effect of dopants on elastic modulus, microhardness and fracture toughness of sintered pure and doped ceria were investigated. It was observed that tri-valent cation dopants increased the hardness of the ceria, whereas the fracture toughness and elastic modulus were decreased.

Sandwich complexes of naphthalocyanine with the rare earth metals

Over the past two decades and in particular the past five years, numerous sandwich-type rare earth complexes containing naphthalocyanine ligands have been synthesized. The more extended delocalized π-electron system of naphthalocyanine in comparison with phthalocyanine generates unique physical, spectroscopic, electrochemical and photoelectrochemical properties which have aroused significant research interest in these compounds. This review summarizes recent progress in research on this important class of molecular materials and overviews the current status of the field.