This study focuses on the mineralogical characterization of four raw clay samples from Dobrodo deposit, Serbia. Several analytical methods were applied to determine the chemical and mineralogical composition, morphology and physical properties (colour, plasticity, specific surface area, particle size and cation-exchange capacity) of the clay samples. Kaolinite, smectite and illite are the predominant phases in all of the samples studied that contain between 60.2 and 87.1 wt.% of clay. Quartz, feldspars, paragonite and Ti- and Fe-bearing phases were also identified. The relatively high SiO2/Al2O3 mass ratio indicates abundant quartz. The cation-exchange capacity of the samples varied between low and moderately charged clay minerals (12–52 mmol 100 g–1) with specific surface area values ranging from 94 to 410 m2 g–1. The plasticity index values (11–23%) suggest low to moderate plasticity. Preliminary results show that most of the raw clay from Dobrodo deposit might be suitable for use in ceramic applications.
Microbiologically induced CaCO3 precipitation (MICP) is a well-known bio-based solution with application in environmental, geotechnical, and civil engineering. The significance of the MICP has increased explorations of process efficiency and specificity via natural bacterial isolates. In this study, comprehensive profiling of five soil ureolytic Bacillus strains was performed through a newly formed procedure that involved six steps from selection and identification, through kinetic study, to the characterization of the obtained precipitates, for the first time. To shorten the whole selection procedure of 43 bioagents with the MICP potential, Standard Score Analysis was performed and five selected bacteria were identified as Bacillus muralis, B. lentus, B. simplex, B. firmus, and B. licheniformis by the MALDI-TOF mass spectrometry. Despite following the targeted activity, kinetic studies were included important aspects of ureolysis and the MICP such as cell concentration, pH profiling, and reduction in calcium ion concentration. At the final step, characterization of the obtained precipitates was performed using FTIR, XRD, Raman, DTA/TGA, and SEM analysis. Although all tested strains showed significant potential in terms of precipitation of calcite or calcite and vaterite phase, the main differences in the MICP behavior can be observed at the bacterial strain level. B. licheniformis showed favorable behavior compared to the reference Sporosarcina pasteurii DSM 33.
Two polymorphs of tripotassium erbium disilicate, K3ErSi2O7, were synthesized by high‐temperature flux crystal growth during the exploration of the flux technique for growing new alkali rare‐earth elements (REE) containing silicates. Their crystal structures were determined by single‐crystal X‐ray diffraction analysis. One of them (denoted 1) crystallizes in the space group P63/mmc and is isostructural with disilicates K3LuSi2O7, K3ScSi2O7 and K3YSi2O7, while the other (denoted 2) crystallizes in the space group P63/mcm and is isostructural with disilicates K3NdSi2O7, K3REESi2O7 (REE = Gd–Yb), K3YSi2O7, K3(Y0.9Dy0.1)Si2O7 and K3SmSi2O7. In the crystal structure of polymorph 1, the Er cations are in an almost perfect octahedral coordination, while in the crystal structure of polymorph 2, part of the Er cations are in a slightly distorted octahedral coordination and the other part are in an ideal trigonal prismatic coordination environment. Sharing six corners, disilicate Si2O7 groups in the crystal structure of polymorph 1 link six ErO6 octahedra, forming a three‐dimensional network and nine‐coordinated potassium cations are located in its holes. In the crystal structure of polymorph 2, the disilicate Si2O7 groups connect four ErO6 octahedra, as well as one ErO6 trigonal prism. Three differently coordinated potassium cations are situated between them. Different site symmetries of the erbium cations in the crystal structures of polymorphs 1 and 2 affect their photoluminescence properties. Only polymorph 2 exhibits luminescence. Intense narrow lines in the emission spectrum are a result of the 4f–4f transition. The green emission line at 560 nm is the result of the Er3+ transition 4S3/2→4I15/2, and the luminescence line at 690 nm is the result of a 4F9/2→4I15/2 transition. The crystal morphologies of the two polymorphs are similar. Crystals of polymorph 1 are in the form of a hexagonal prism in combination with a hexagonal base, while crystals of polymorph 2 contain a dihexagonal prism in combination with a hexagonal base, although poorly developed faces of the dihexagonal pyramid can also be noticed.
Four novel microporous compounds H2(C2H8N2)(ZnAsO4)2 (1), H2(C2H8N2)(Co0.1Zn0.9AsO4)2 (2), H1.8(C2H8N2)(Fe0.1Zn0.9AsO4)2 (3) and H2(C2H8N2)(ZnPO4)2 (4) containing ethylenediammonium cation, H2(C2H8N2)2+ (H2en2+), and ethylenediamine molecule, C2H8N2 (en), have been hydrothermally synthesized. While 1-3 exhibit twinned DFT-zeotype structure and crystallize in P42/n, the 4 is characterized by the appearance of new orthorhombic space group Pcca, previously not observed among the known DFT-zeotype compounds. The symmetry relationships analyses revealed the extended Bärnighausen tree. The main feature of the cobalt blue and reddish brown compounds 2 and 3 is their novel chemical composition which was confirmed by SEM/EDX analysis. In the structure of 1, H-atoms positions, previously not reported, were calculated and refined to reasonable positions using riding model. The DFT anionic frameworks of 1-4 are characterized by 4M, 6M and 8M tetrahedral rings, which produce three mutually perpendicular 8M ring channels. At the intersections of these channels H2en2+ cations are accommodated and hydrogen-bonded to the adjacent oxygen atoms of the framework. Only in 3, H2en2+ is partly substituted by electroneutral en to maintain charge compensation. The singlecrystal Raman spectra and Fourier transform infrared (FTIR) absorption spectra were interpreted on the basis of characteristic vibrations of AsO4 and PO4 groups, as well as of NH3, NH2 and CH2 groups from the H2en2+ cation or en molecule. The results of lattice distortion and similarity analyses showed that the DFT-zeotype structures, which incorporate larger tetrahedral cations, have a higher degree of lattice distortion and are less similar to the ideal structural models derived from the aristotype.
The new ambient-temperature hexagonal (space group P63 /mmc) polymorph of tripotassium ytterbium(III) disilicate (β-K3YbSi2O7) has been synthesized by the high-temperature flux method and subsequently structurally characterized. In the course of the temperature-dependent single-crystal diffraction experiments, a phase transformation of β-K3YbSi2O7 to a novel low-temperature orthorhombic phase (β′-K3YbSi2O7, space group Cmcm) has been observed at about 210 K. β-K3YbSi2O7 is isostructural with K3ErSi2O7, whereas β′-K3YbSi2O7 adopts a new type of structure. Both compounds can be built up from a regular alternation of layers of two types, which are parallel to the (001) plane. In the octahedral layer, YbO6 octahedra are isolated and linked by K1O6+3 polyhedra. The second, slightly thicker sorosilicate layer is formed by a combination of Si2O7 dimers and K2O6+3 polyhedra. The boundary between the layers is a pseudo-kagome oxide sheet based on 3.6.3.6 meshes. The phase transition is due to a tilt of the two SiO4 tetrahedra forming a single dimer which induces a decrease of the Si—O—Si angle between bridging Si—O bonds from 180° (dictated by symmetry in space group P63/mmc) to ≃164°. Magnetic characterization indicates that K3YbSi2O7 remains paramagnetic down to 2 K, showing no apparent influence of the phase transformation on its magnetic properties. Analysis of the magnetization data revealed the positions of the three lowest crystal field levels of the Yb3+ cations, as well as the corresponding projections of their angular momentum on the direction of the magnetic field.
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