EPR and magnetism of the nanostructured natural carbonaceous material shungite

The X-band EPR and magnetic susceptibility in the temperature range 4.2–300 K study of the shungite-I, natural nanostructured material from the deposit of Shunga are reported. Obtained results allow us to assign the EPR signal to conduction electrons, estimate their number, N _P, and evaluate the Pauli paramagnetism contribution to shungite susceptibility. A small occupation (~5%) of the localized nonbonding π states in the zigzag edges of the open-ended graphene-like layers and/or on σ (sp ^2+x ) orbitals in the curved parts of the shungite globules has been also revealed. The observed temperature dependence of the EPR linewidth can be explained by the earlier considered interaction of conduction π electrons with local phonon modes associated with the vibration of peripheral carbon atoms of the open zigzag-type edges and with peripheral carbon atoms cross-linking different nanostructures. The relaxation time T ₂ and diffusion time T _D are found to have comparable values (2.84 × 10⁻⁸ and 1.73 × 10⁻⁸ s at 5.2 K, respectively), and similar dependence on temperature. The magnetic measurements have revealed the suppression of orbital diamagnetism due to small amount of large enough fragments of the graphene layers.     

Petrogenesis of continental mafic dykes from the Izera Complex, Karkonosze-Izera Block (West Sudetes, SW Poland)

The Izera Complex (West Sudetes) contains widespread bodies of metagabbro, metadolerite and amphibolite (the Izera metabasites), and less abundant dykes of weakly altered dolerites, emplaced in a continental setting. The primary magmas of the Izera metabasites were probably formed through adiabatic decompression melting of upwelling asthenosphere (mantle plume) that was associated with the early Palaeozoic fragmentation of Gondwana (initial rift). The rocks are mildly alkaline, transitional-to-tholeiitic basalts and have OIB-like trace element patterns. Trace element modelling reveals that the mafic magmas were generated by variable degrees of partial melting (1–7%) of fertile, garnet-bearing asthenospheric source similar in composition to primitive mantle. Together with an increase in degree of partial melting, the compositional affinity of the magmas and the depth of segregation changed progressively from ca. 70–90 km (mildly alkaline magmas of the metadolerites and amphibolites) to ca. 60–75 km (transitional-to-tholeiitic magmas of the metagabbros). The systematics of incompatible versus compatible element distribution, and major and trace element modelling, indicate that some rocks experienced low-pressure (<5 kbar) differentiation resulting in up to 50% fractionation of clinopyroxene, olivine and minor plagioclase and ilmenite. The genetically distinct weakly altered dolerites are basaltic andesite in composition and possibly related to late- or post-orogenic events in the Karkonosze-Izera Block. These rocks are calc-alkaline, with relatively flat MREE–HREE patterns, enrichment in LREE and other highly incompatible elements relative to primitive mantle, and negative Nb–Ta, Ti, P anomalies. The geochemical features and geochemical modelling, indicate that their primary magmas segregated at depths ≤70 km and were produced by ~2% melting of a metasomatized sublithospheric mantle source presumably containing small amounts of hydrated phases. Although the present study is inconclusive as to the origin of the metasomatic component in the source (? slab-derived fluid/melts, OIB-like alkaline melt percolation of subcontinental lithosphere), the genesis of the Izera basaltic andesites is seemingly related to upwelling of asthenosphere and heat flow triggered by a postulated decoupling of the mantle lithosphere and post-collisional extensional collapse and uplift in the Karkonosze-Izera Block.     

Modelling hydraulic and capillary-driven two-phase fluid flow in unsaturated concretes at the meso-scale with a unique coupled DEM-CFD technique

The goal of the research was to demonstrate the impact of thin porous interfacial transition zones (ITZs) between aggregates and cement matrix on fluid flow in unsaturated concrete caused by hydraulic/capillary pressure. To demonstrate this impact, a novel coupled approach to simulate the two-phase (water and moist air) flow of hydraulically and capillary-driven fluid in unsaturated concrete was developed. By merging the discrete element method (DEM) with computational fluid dynamics (CFD) under isothermal settings, the process was numerically studied at the meso-scale in two-dimensional conditions. A flow network was used to describe fluid behaviour in a continuous domain between particles. Small concrete specimens of a simplified particle mesostructure were subjected to fully coupled hydro-mechanical simulation tests. A simple uniaxial compression test was used to calibrate the pure DEM represented by bonded spheres, while a permeability and sorptivity test for an assembly of spheres was used to calibrate the pure CFD. For simplified specimens of the pure cement matrix, cement matrix with aggregate, and cement matrix with aggregate and ITZ of a given thickness, DEM/CFD simulations were performed sequentially. The numerical results of permeability and sorptivity were directly compared to the data found in the literature. A satisfactory agreement was achieved. Porous ITZs in concrete were found to reduce sorption by slowing the capillary-driven fluid flow, and to speed the full saturation of pores when sufficiently high hydraulic water pressures were dominant.