Crystal structure and crystal chemistry of fluorannite and its relationships to annite

This contribution deals about the crystal chemical characterization of fluorannite from Katugin Ta-Nb deposit, Chitinskaya Oblast’, Kalar Range, Transbaikalia, Eastern-Siberian Region, Russia. The mineral chemical formula is (K0.960Na0.020Ba0.001) (Fe2+2.102Fe3+0.425Cr3+0.002Mg0.039Li0.085Ti0.210Mn0.057) (Al0.674 Si3.326) O10 (F1.060OH0.028O0.912). This mica belongs to 1M polytype (space group C2/m) with layer parameters a = 5.3454(2) Å, b = 9.2607(4) Å, c = 10.2040(5) Å, beta = 100.169(3)°. Structure refinement, using anisotropic displacement parameters, converged at R = 0.0384. When compared to annite, fluorannite shows a smaller cell volume (Vfluorannite = 497.19 Å3; Vannite = 505.71 Å3), because of its smaller lateral dimensions and its reduced c parameter. The flattening of the tetrahedral basal oxygen atoms plane decreases with F content, together with the A-O4 distance (i.e., the distance between interlayer A cation and the octahedral anionic position) because of the reduced repulsion between the interlayer cation and the anion sited in O4

Evolution of the Microstructure and Performance of Pd/Ag - Based Thick Conductors

Pd/Ag-based inks are probably the most commonly used conductors in thick-film hybrid technology. The evolution of the microstructure of these films was studied on samples fired with isochronal cycles at a peak temperature in the range from 300℃ up to 850℃. The samples were investigated by means of X-ray diffraction, SEM and EDAX analysis techniques; the results of these analyses as well as those of thermogravimetry (TG, DTG) and differential thermal analysis (DTA), enable one to obtain a clear picture of the complex evolution of the microstructure of these conductors, which correlates quite strictly with the performance of the films in terms of resistivity and adhesion

Layer charge and heavy metals structures in hydrated 2 : 1 silicates:state of the art and new advances on cadmium

This study will discuss how layer charge can affect chemical speciation and topology of heavy metals adsorbed to 2:1 layer silicates, by providing: i) an overview of literature data; ii) experimental data on Cd complexes adsorbed by 2:1 layer silicates with different layer charge (montmorillonite and vermiculite); iii) a comparison between our results and literature data. This study will also be supported by several different experimental techniques such as chemical and thermal analyses, X-ray powder diffraction and X-ray absorption spectroscopy.Based on our data Cd atoms were found to complex water molecules in both clay minerals and to show four-fold coordination in montmorillonite (CdO distances of 2.24 Å) and six-fold coordination in vermiculite (CdO distances of 2.16 and 2.28 Å). Furthermore our models clearly suggest that Cd mainly bonds to interlayer water, without neglecting the more limited, but still significant, Cd multinuclear surface complexes at the octahedral broken edges. Both clay minerals show H2O/Cd ratio, as evidenced by thermal analyses, drastically higher than expected from X-ray adsorption spectroscopy data, thus implying that most of the water molecules are only loosely coordinated to interlayer cations

Interlayer potassium and its neighboring atoms in micas : Crystal-chemical modeling and XANES spectroscopy

A detailed description of the interlayer site in trioctahedral true micas is presented based on a statistical appraisal of crystal-chemical, structural, and spectroscopic data determined on two sets of trioctahedral micas extensively studied by both X-ray diffraction refinement on single crystals (SC-XRD) and X-ray absorption fine spectroscopy (XAFS) at the potassium K -edge. Spectroscopy was carried out on both random powders and oriented cleavage flakes, the latter setting taking advantage of the polarized character of synchrotron radiation. Such an approach (AXANES) is shown to be complementary to crystal-chemical investigation based on SC-XRD refinement. However, the results are not definitive as they focus on few samples having extreme features only (e.g., end-members, unusual compositions, and samples with extreme and well-identified substitution mechanisms). The experimental absorption K -edge (XANES) for potassium was decomposed by calculation and extrapolated into a full in-plane absorption component (σ||) and a full out-of-plane absorption component (σ⊥). These two patterns reflect different structural features: σ|| represents the arrangement of the atoms located in the mica interlayer space and facing tetrahedral sheets; σ⊥ is associated with multiple-scattering interactions entering deep into the mica structure, thus also reflecting interactions with the heavy atoms (essentially Fe) located in the octahedral sheet. The out-of-plane patterns also provide insights into the electronic properties of the octahedral cations, such as their oxidation states (e.g., Fe2+ and Fe3+) and their ordering (e.g., trans - vs. cis -setting). It is also possible to distinguish between F- and OH-rich micas due to peculiar absorption features originating from the F vs. OH occupancy of the O4 octahedral site. Thus, combining crystal-chemical, structural, and spectroscopic information is shown to be a practical method that allows, on one hand, assignment of the observed spectroscopic features to precise structural pathways followed by the photoelectron within the mica structure and, on the other hand, clarification of the amount of electronic interactions and forces acting onto the individual atoms at the various structural sites

Trapping at the Solid−Gas Interface: Selective Adsorption of Naphthalene by Montmorillonite Intercalated with a Fe(III)− Phenanthroline Complex

In this study, stable hybrid materials (Mt−Fe(III)Phen), made by the μ-oxo Fe(III)−phenanthroline complex [(OH2)3(Phen)- FeOFe(Phen)(OH2)3]4+ (Fe(III)Phen) intercalated in different amounts into montmorillonite (Mt), were used as a trap for immobilizing gaseous benzene and naphthalene and their mono chloro-derivatives at 25 and 50 °C. The entrapping process was studied through elemental analysis, magic angle spinning NMR spectroscopy, thermal analysis, and evolved gas mass spectrometry. Naphthalene and 1-chloronaphthalene were found to be immobilized in large amount at both temperatures. Molecular modeling allowed designing of the structure of the interlayer in the presence of the immobilized aromatic molecules. Adsorption is affected by the amount of the Fe complex hosted in the interlayer of the entrapping hybrid materials. On the contrary, under the same conditions, benzene and chlorobenzene were not adsorbed. Thermal desorption of naphthalenes was obtained under mild conditions, and immobilization was found to be reversible at least for 20 adsorption/desorption cyclesThe authors are thankful to the University of Modena and Reggio Emilia for FAR 2016 funding program (PAsTIME Project, grant number: FAR2016DIPBORSARI), for the Visiting Professor program, and for the facilities provided by the Centro Interdipartimentale Grandi Strumenti, to MIUR for funding program FFABR 2017, to the Computational Centre of University of Granada and CINECA of Bologna for the high-performance computing service, and to the Andalusian project RMN1897 and the Spanish projects FIS2013-48444- C2-2-P and FIS2016-77692-C2-2-P for financial support

The interlayer structure of trioctahedral lithian micas: An AXANES spectroscopy study at the potassium K-edge

abstra C t We recorded angle-dependent XANES (AXANES) spectra at the potassium K-edge for three compositionally intermediate polylithionite-siderophyllite trioctahedral 1 M-micas using polarized synchrotron radiation. We evaluated the experimental spectra for both their in-plane and out-of-plane component fractions of the electric dipole contribution using the analytical formulae of Brouder (1990), referring to theory to extract the origin of their multiple-scattering pathways of Natoli et al. (2003). This analysis was extended to a fourth lithian mica studied previously and allowed characterization of the local environment and ordering around the potassium atoms in the interlayer of the entire set of micas. The AXANES in-plane components are notably similar to the XANES spectra recorded on randomly oriented powders, provided these are oriented at the "magic angle" (Pettifer et al. 1992). Most observed contributions arise from multiple-scattering interactions of the photoelectron ejected from the potassium absorber colliding with atoms located in the interlayer itself. Note that this includes not only interactions with other coplanar potassium and/or alkali atoms distributed along the interlayer plane, but also with their near- and next-nearest neighboring oxygen atoms which lie on the basal planes of the tetrahedral sheets facing the interlayer. By contrast, the AXANES out-of-plane component suggests that several multiple-scattering pathways cross the energetic and structural barrier represented by the tetrahedral sheets. They reach not only the X anions that are located on the upper level of the octahedral sheets, at the center of the open cavity in the tetrahedral sheet, but also the metal cations centering the octahedral sheet itself. Therefore, the out-of-plane components provide indirect information on the number of independent octahedral sites, the cation oxidation state, and the trans- vs. cis-orientation of the anionic sites

Interlayer-Confined Cu(II) Complex as an Efficient and Long-Lasting Catalyst for Oxidation of H2S on Montmorillonite

Removal of highly toxic H2S for pollution control and operational safety is a pressing need. For this purpose, a montmorillonite intercalated with Cu(II)-phenanthroline complex [Cu[(Phen)(H2O)2]2+ (Mt-CuPhen) was prepared to capture gaseous H2S under mild conditions. This hybrid material was simple to obtain and demonstrated an outstanding ability to entrap H2S at room temperature, retaining high efficiency for a very long time (up to 36.8 g of S/100 g Mt-CuPhen after 3 months of exposure). Sorbent and H2S uptake were investigated by elemental analysis, X-ray powder diffraction measurements, diffuse reflectance (DR) UV–Vis and infrared spectroscopy, thermal analysis and evolved gas mass spectrometry, scanning electron microscopy equipped with energy-dispersive X-ray spectrometer, and X-ray absorption spectroscopy. The H2S capture was studied over time and a mechanism of action was proposed. The entrapping involves a catalytic mechanism in which [Cu[(Phen)(H2O)2]2+ acts as catalyst for H2S oxidation to S0 by atmospheric oxygen. The low cost and the long-lasting performance for H2S removal render Mt-CuPhen an extremely appealing trap for H2S removal and a promising material for many technological applications

Pre-amyloid oligomers budding:a metastatic mechanism of proteotoxicity

The pathological hallmark of misfolded protein diseases and aging is the accumulation of proteotoxic aggregates. However, the mechanisms of proteotoxicity and the dynamic changes in fiber formation and dissemination remain unclear, preventing a cure. Here we adopted a reductionist approach and used atomic force microscopy to define the temporal and spatial changes of amyloid aggregates, their modes of dissemination and the biochemical changes that may influence their growth. We show that pre-amyloid oligomers (PAO) mature to form linear and circular protofibrils, and amyloid fibers, and those can break reforming PAO that can migrate invading neighbor structures. Simulating the effect of immunotherapy modifies the dynamics of PAO formation. Anti-fibers as well as anti-PAO antibodies fragment the amyloid fibers, however the fragmentation using anti-fibers antibodies favored the migration of PAO. In conclusion, we provide evidence for the mechanisms of misfolded protein maturation and propagation and the effects of interventions on the resolution and dissemination of amyloid pathology

The Copper Chemical Garden as a Low Cost and Efficient Material for Breaking Down Air Pollution by Gaseous Ammonia

Chemical garden (CG) from copper(II) sulfate, nitrate and chloride (CG CuSO, CG Cu(NO), CG CuCl) were grown, and characterized from the structural and compositional point of view by using scanning electron microscopy, X-ray powder diffraction, elemental analysis, thermogravimetric analysis coupled with mass spectrometry, and DR (diffuse reflectance) UV-Vis-NIR spectroscopy. The main crystalline phases, controlled by the anion of the starting salt, were brochantite and kobyashevite for CG CuSO, gerhardtite, rouaite and anthonyite for CG Cu(NO), and atacamite for CG CuCl. The materials were then exposed to ammonia vapors to test the effectiveness of their entrapping property. All materials proved to be very efficient and rapid in the uptake of ammonia, which invariably results in the formation of a Cu(II)/NH complex. However, after a few tens of minutes, CG Cu(NO) and CG CuCl release water and get wet, thereby resulting unsuitable for applications. Only CG CuSO remains dry for at least 25 hours. This makes it a valid candidate for building devices for trapping ammonia, and possibly other gases capable of interacting with Cu(II). The entrapment of ammonia by this material was also characterized by H and Si MAS-NMR XAS spectroscopies.The authors would like to acknowledge the contribution of the European Cooperation in Science and Technology (COST Action, grant number CA17120) supported by the EU Framework Programme Horizon 2020. This research is also under the contribution of progetti di rilevante interesse nazionale (PRIN2017)(it) “Mineral Reactivity, a Key to Understand Large-Scale Processes: from Rock Forming Environments to Solid Waste Recovering/Lithification”, grant number 2017 L83S77

Quantitative local structure determination in mica crystals: ab initio simulations of polarization XANES at the potassium K-edge.

An attempt to refine the local structure of a layered structure such as mica is made by combining angle-resolved XANES (AXANES) and single-crystal X-ray diffraction (SC-XRD) experiments. Ab initio calculations of AXANES spectra of several tri-octahedral micas have been used to further interpolate experimental data and to deduce physico/chemical effects. Structural distortions have been found highly correlated with the compositional disordering that arises from electronic interactions between anions and cations, and extend the interlayer entering deep into nearby tetrahedral and octahedral sheets. Multiple occupations at the same atomic site have been investigated in detail both in the parallel and perpendicular components of AXANES spectra. Finally, the best fit obtained, computed in the framework of the multiple-scattering theory, is presented and the limitations of the muffin-tin potential in layered systems are briefly discussed