Degree Of Structural Control Research Articles

CaLi2PN3 - A Quaternary Chain-Type Nitridophosphate by Medium-Pressure Synthesis.

Nitridophosphates are in the focus of current research interest due to their structural versatility and properties, such as ion conductivity, ultra-incompressibility and luminescent properties when doped with suitable activator ions. Multinary representatives often require thorough investigation due to the competition with the thermodynamically more stable binary and ternary compounds. Another point of concern is the synthetic control of structural details, which is usually limited by conventional bottom-up syntheses. In this study, we report on the synthesis and characterization of the quaternary nitridophosphate CaLi2PN3. Various synthesis protocols were used for the preparation of CaLi2PN3, including the novel nitridophosphate double salt approach. The crystal structure was solved and refined from single-crystal X-ray diffraction data and confirmed by Rietveld refinement, solid-state NMR spectroscopy, EDX measurements and low-cost crystallographic calculations. The experimental results were corroborated by DFT calculations, which revealed the electronic band structure. Formation energy calculations allowed conclusions to be drawn about the stability in comparison to the initial ternary nitridophosphates. The synthesis of CaLi2PN3 exemplifies the enormous potential of medium-pressure syntheses in the field of nitridophosphate research. Furthermore, the presented new synthesis route allows a certain degree of structural control, which is a promising addition to previous synthesis strategies in nitridophosphate chemistry.

Achieving Functionality and Multifunctionality through Bulk and Interfacial Structuring of Colloidal-Crystal-Templated Materials.

Over the past 25 years, the field of colloidal crystal templating of inverse opal or three-dimensionally ordered macroporous (3DOM) structures has made tremendous progress. The degree of structural control over multiple length scales, understanding of mechanical properties, and complexity of systems in which 3DOM materials are a component have increased substantially. In addition, we are now seeing applications of 3DOM materials that make use of multiple features of their architecture at the same time. This Feature Article focuses on the different properties of 3DOM materials that provide functionality, including a relatively large surface area, the interconnectedness of the pores and the resulting good accessibility of the internal surface, the nanostructured features of the walls, the structural hierarchy and periodicity, well-defined surface roughness, and relative mechanical robustness at low density. It provides representative examples that illustrate the properties of interest related to applications including energy storage and conversion systems, sensors, catalysts, sorbents, photonics, actuators, and biomedical materials or devices.

Impact of in situ stress and fault reactivation on seal integrity in the East Irish Sea Basin, UK

Abstract Despite having been affected by several stages of exhumation during the Cretaceous and Cenozoic, the contemporary stress state of the East Irish Sea Basin (EISB) is poorly characterised. As the basin is mature in terms of exploitation of hydrocarbons, future exploration beyond the conventional Sherwood Sandstone Group reservoir (Triassic) necessitates a greater understanding of the in situ stress field, while proposed natural gas storage and carbon sequestration schemes also require detailed stress field information. Using petroleum well data, the in situ stress field of the EISB has been characterised to assess the mechanical seal integrity. A strike-slip stress regime most-likely prevails in the basin, meaning the Maximum Horizontal Stress (SHmax) is the greatest of the principal stresses. Interpretation of stress orientation data suggests that SHmax is oriented 152° ± 12°, consistent with mean stress orientations across the wider region associated with plate boundary forces. Some degree of structural control appears to influence the orientation of SHmax, with orientations locally aligned sub-parallel to major Permo-Triassic basin-bounding faults. Fault reactivation risk is evaluated through modelling the pore pressure increase required to induce failure on pre-existing faults. Vertical faults striking 30° from SHmax are optimally-oriented to become reactivated under elevated pore pressure conditions. For any project relying on an element of fault seal for the containment of buoyant fluids at the average reservoir depth of 800 m, pore pressure increase should be less than 3.3 MPa to avoid reactivating pre-existing optimally-oriented faults. Higher pressure increases would be required to initiate reactivation of faults with other orientations. Vertical faults striking perpendicular to SHmax are least likely to become reactivated, and in the absence of halite, seal integrity would instead be limited by caprock strength and capillary-entry pressure. Major faults affecting the basin have been analysed for their slip tendency (ratio of shear to normal stress), which provides an indication of their susceptibility to become reactivated. Although the analysis is limited due to lack of an accurate 3D representation of the fault network, the results suggest that many of the fault orientations observed in the EISB exhibit high slip tendencies, including N–S striking faults to the north and west of the East Deemster Fault, where the SHmax orientation is NW–SE. Faults striking perpendicular to SHmax, such as the Lagman Fault, are least likely to become reactivated due to higher normal stresses that inhibit frictional sliding, while faults striking parallel or very close to SHmax also exhibit low slip tendency as they are not subjected to significant shear stresses.

Structural Variations in Hybrid All-Nanoparticle Gibbsite Nanoplatelet/Cellulose Nanocrystal Multilayered Films.

Cellulose nanocrystals (CNCs) are promising biosourced building blocks for the production of high performance materials. In the last ten years, CNCs have been used in conjunction with polymers for the design of multilayered thin films via the layer-by-layer assembly technique. Herein, polymer chains have been replaced with positively charged inorganic gibbsite nanoplatelets (GN) to form hybrid "nanoparticle-only" composite films. A combination of atomic force microscopy and neutron reflectivity experiments was exploited to investigate the growth and structure of the films. Data show that the growth and density of GN/CNC films can be tuned over a wide range during preparation by varying the ionic strength in the CNC suspension and the film drying protocol. Specifically, thin and dense multilayered films or very thick, more porous mixed slabs, as well as intermediate internal structures, could be obtained in a predictable manner. The influence of key physicochemical parameters on the multilayer film buildup was elucidated and the film architecture was linked to the dominating interaction forces between the components. The degree of structural control over these hybrid nanoparticle-only films is much higher than that reported for CNC/polymer films, which offers new properties and potential applications as separation membranes or flame retardant coatings.

Geology and geochemistry of fault-hosted hydrothermal and sedimentary manganese deposits in the Oakover Basin, east Pilbara, Western Australia

ABSTRACTManganese mineralisation in the Oakover Basin is associated with Mesoproterozoic extension, basin formation and deposition of the Manganese Group. The underlying basement architecture of the Oakover Basin (a local half-graben geometry), inherited from the Neoarchean rifting event, plays an important role on the distribution, style and timing of manganese deposits. Fault-hosted manganese deposits are dominant along the ‘active’ faulted eastern margin, whereas flat-lying sedimentary deposits are dominant along the western ‘passive’ margin reflecting differences in ore-forming processes. The large number of significant manganese deposits in the Oakover Basin, previously thought to reflect a spatial association with Carawine Dolomite, more likely reflects the restricted nature of the Mesoproterozoic basin and development of a large reservoir of Mn2+ and Fe2+ in an anoxic zone of a stratified basin. Low O2 conditions in the basin were caused by a paleotopographic high forming a barrier to open ocean circulation. The western margin sedimentary deposits formed later than the fault-hosted hydrothermal deposits along the eastern margin, once a significant reservoir of Mn2+ and Fe2+ had developed, and when there was sufficient subsidence to allow migration of the redox front onto the shallow shelf, with Mn precipitation on and within the seafloor sediments. The sedimentary manganese deposits are not uniformly distributed along the western edge of the basin; instead they are concentrated into discrete areas (e.g. Mt Cooke–Utah–Mt Rove, Bee Hill, Skull Springs and the Ripon Hills districts), suggesting a degree of structural control on their distribution. Fault-hosted manganese is observed beneath and adjacent to many of the sedimentary deposits. Marked geochemical differences are observed between the Woodie Woodie hydrothermal deposits and the sedimentary deposits. Woodie Woodie deposits display higher Ba, U, Mo, As, Sn, Bi, Pb, S and Cu than the sedimentary deposits, reflecting the composition of the hydrothermal fluids. The Al2O3 values of the Ripon Hills and Mt Cooke deposits are much higher than the Woodie Woodie deposits, reflecting the composition of the dominant host rock, as Al2O3 is typically <5 wt% in the Carawine Dolomite, but is >10 wt% in basal shale units of the Manganese Group. Highly variable Mn:Fe ratios (≫5:1) in the hydrothermal manganese at Woodie Woodie reflects rapid deposition of Mn in and around fault zones. In contrast, slower accumulation of Mn oxides on and within the seafloor to form the large sedimentary deposits results in Mn:Fe ratios closer to 1:1 and elevated Co + Ni and REE values.

The Metallogeny of Late Triassic Rifting of the Alexander Terrane in Southeastern Alaska and Northwestern British Columbia

A belt of unusual volcanogenic massive sulfide (VMS) occurrences is located along the eastern margin of the Alexander terrane throughout southeastern Alaska and northwestern British Columbia and exhibits a range of characteristics consistent with a variety of syngenetic to epigenetic deposit types. Deposits within this belt include Greens Creek and Windy Craggy, the economically most significant VMS deposit in Alaska and the largest in North America, respectively. The occurrences are hosted by a discontinuously exposed, 800-km-long belt of rocks that consist of a 200- to 800-m-thick sequence of conglomerate, limestone, marine clastic sedimentary rocks, and tuff intercalated with and overlain by a distinctive unit of mafic pyroclastic rocks and pillowed flows. Faunal data bracket the age of the host rocks between Anisian (Middle Triassic) and late Norian (late Late Triassic). This metallogenic belt is herein referred to as the Alexander Triassic metallogenic belt. The VMS occurrences show systematic differences in degree of structural control, chemistry, and stratigraphic setting along the Alexander Triassic metallogenic belt that suggest important spatial or temporal changes in the tectonic environment of formation. At the southern end of the belt, felsic volcanic rocks overlain by shallow-water limestones characterize the lower part of the sequence. In the southern and middle portion of the belt, a distinctive pebble conglomerate marks the base of the section and is indicative of high-energy deposition in a near slope or basin margin setting. At the northern end of the belt the conglomerates, limestones, and felsic volcanic rocks are absent and the belt is composed of deep-water sedimentary and mafic volcanic rocks. This northward change in depositional environment and lithofacies is accompanied by a northward transition from epithermal-like structurally controlled, discontinuous, vein- and pod-shaped, Pb-Zn-AgBa-(Cu) occurrences with relatively simple mineralogy, to sulfosalt-enriched VMS occurrences exhibiting characteristics of vein, diagenetic replacement, and exhalative styles of mineralization, and finally to Cu-Zn-(Co-Au) occurrences with larger and more clearly stratiform orebody morphologies. Occurrences in the middle of the belt are transitional in nature between structurally controlled types of mineralization that formed in a shallow-water, near-arc setting, to those having a more stratiform appearance, formed in a deeper water, rift-basin setting. The geologic setting in the south is consistent with shallow subaqueous emplacement on the flanks of the Alexander terrane. Northward, the setting changes to an increasingly deeper back- or intra-arc rift basin. Igneous activity in the Alexander Triassic metallogenic belt is characterized by a bimodal suite of volcanic rocks and a previously unrecognized association with mafic-ultramafic hypabyssal intrusions. Immobile trace and rare earth element (REE) geochemical data indicate that felsic rocks in the southern portion of the belt are typical calc-alkaline rhyolites, which give way in the middle of the belt to peralkaline rhyolites. Rhyolites are largely absent in the northern part of the belt. Throughout the belt, the capping basaltic rocks have transitional geochemical signatures. Radiogenic isotope data for these rocks are also transitional (basalts and gabbros: eNd = 4–9 and 87Sr/86Sr initial at 215 Ma = 0.7037–0.7074). Together these data are interpreted to reflect variable assimilation of mature island-arc crust by more primitive melts having the characteristics of either mid-ocean ridge (MORB) or intraplate (within-plate) basalts (WPB). The ore and host-rock geochemistry and the sulfosalt-rich mineralogy of the deposits are strikingly similar to recent descriptions of active sea-floor hydrothermal (white smoker) systems in back arcs of the southwest Pacific Ocean. These data, in concert with existing faunal ages, record the formation of a belt of VMS deposits and occurrences in a propagating intra- to back-arc rift tectonic setting during the Late Triassic. A modern analogue having similar tectonic and metallogenic features is the southward projection of the Lau basin, from the active sea-floor hydrothermal vents of the Valu Fa Ridge to the Taupo volcanic zone of the North Island, New Zealand.

The morphology and hydrology of some Jamaican karst depressions

AbstractAn area of shallow karst depressions in St. Ann parish, Jamaica is examined. Shallow, ‘temperate’ forms such as these are common in tropical karst areas.Depressions are analyzed morphometrically and a considerable degree of structural control appears to be exhibited. Some morphometric parameters, in particular the depth/diameter ratio, which have been used to postulate depression origin, are examined.Depression hydrology is investigated. Depressions appear to exhibit characteristics of small drainage basins. The occurrence of sporadic flood events is suggested as an important element in the development of surface channel networks. The integration of the depressions into the regional drainage system is investigated by water tracing of ‘underground flow sections’.Chemical analysis of waters in various parts of the drainage system reveals variations which point to the importance of solutional activity at the soil‐bedrock interface. The influence of a soil cover in promoting solutional activity is indicated.