X-ray Powder Diffraction Experiments Research Articles

High-pressure synthesized perovskite-type CeTaN<sub>2</sub>O and its magnetic and electrical properties

Recently, it has been discovered that the <i>AB</i>(N,O)<sub>3</sub>-type perovskite oxynitrides exhibit excellent dielectric, ferroelectric, and photocatalytic properties, promising for applications in the fields of optoelectronics, energy storage, and communication. Due to the differences in charge, ionic radius, and covalent bonding between N<sup>3–</sup> ion and O<sup>2–</sup> ion, the N substitution for O enhances the <i>B</i>(N,O)<sub>6</sub> octahedron tilting, giving rise to exotic properties and functionalities. However, the current fabrication process for this type of material is rather time-consuming, leading to products with an appreciable quantity of impurities. In this study, using oxide precursors and sodium amide as the nitrogen source, high-purity perovskite-type oxynitride CeTaN<sub>2</sub>O bulk materials are successfully synthesized under high-temperature and high-pressure conditions provided by a cubic-anvil press. The synthesis time decreases to 1 h, achieving rapid production. The lattice structure and physical properties of the obtained samples are comprehensively investigated. X-ray powder diffraction experiments and subsequent Rietveld refinement indicate that the title material shows an orthorhombic crystal structure with the space group of <i>Pnma</i>. The X-ray absorption spectra confirm the charge configuration and the anion composition as Ce<sup>3+</sup>Ta<sup>5+</sup>N<sub>2</sub>O. Magnetization and specific heat measurements reveal that the exchange interactions are mainly antiferromagnetic, with a potential magnetic transition below 2 K. The electrical transport data demonstrate typical semiconductor behaviors, which can be further explained by a three-dimensional variable-range hopping model. Our study paves the way for putting this exotic perovskite oxynitride into practical applications.

An anthracene-containing crown ether: synthesis, host-guest properties and modulation of solid state luminescence.

Organic solid state vapochromic materials are of great significance for the development of supramolecular chemistry and materials science. Herein, we synthesize a crown ether derivative (An34C10) containing two anthracene units and construct new crown ether-based vapochromic host-guest co-crystals. Due to the presence of anthracene, An34C10 not only shows good fluorescence properties but also displays mechanochromism. Single crystal structural analysis, powder X-ray diffraction and differential scanning calorimetry experiments demonstrate that the transformation between different stacking modes of An34C10 is responsible for mechanochromism. In addition, An34C10 can complex with 1,2,4,5-tetracyanobenzene (TCNB) to form host-guest complex (An34C10@TCNB) co-crystals. Because organic solvent fuming alters charge-transfer interactions in An34C10@TCNB, the fluorescence of the co-crystals can be turned on and off by 4-methylpyridine and chloroform vapors, respectively, realizing selective detection with opposite emission outputs. Meanwhile, the stimuli-responsive properties of An34C10 and An34C10@TCNB possess good cycling performance. This work provides a new strategy for the construction of organic solid state luminescent materials.

Guest-selective shape-memory effect in a switchable metal-organic framework DUT-8(Zn).

Crystal size engineering allows tailoring of flexible metal-organic frameworks (MOFs) to achieve new properties. The gating type flexibility of the DUT-8(Zn) ([Zn2(2,6-ndc)2(dabco)]n, 2,6-ndc = 2,6-naphthalene dicarboxylate, dabco = 1,4-diazabicyclo-[2.2.2]-octane) compound is known to be extremely particle size sensitive. Here, the physisorption of ethanol vapor gives rise to so-called shape-memory effect, leading to rigidification and flexibility suppression. According to powder X-ray diffraction and nitrogen physisorption experiments, the open pore phase is retained selectively after desorption of alcohols, which could be attributed to the nano-structuring and surface deformation of the crystals as a result of exposure to alcohols.

In-situ X-ray diffraction study of Nb-doped Bi2Se3 crystal growth revealing unavoidable misfit layer compound

Temperature-resolved in-situ powder X-ray diffraction (PXRD) experiments were performed during synthesis of Nb-doped Bi2Se3 to gain important insights into the phase formation. The crystallization of phases upon heating the pure elements with the nominal composition of Nb0.25Bi2Se3, displays the formation of a misfit layer compound, (BiSe)1.1NbSe2, as a secondary phase. It was also discovered that a misfit-related intermediate phase appears right before Bi2Se3 melts and then misfit (BiSe)1.1NbSe2 crystallizes. This implies that to prevent the formation of the misfit phase, the synthesis temperature should remain well below the melting point of Bi2Se3. Powder samples of Nb-doped Bi2Se3, synthesized at 600 and 650∘C, aimed for this, however, they all displayed traces of the misfit phase. Additionally, multiple superconducting transitions were observed as non-quenched samples showed signs of NbSe2, which were removed by quenching the samples. This study has important implications for the synthesis and properties of Nb-doped Bi2Se3, towards the realization of topological superconductors.

Towards understanding the functional mechanism and synergistic effects of LiMn2O4 - LiNi0.5Mn0.3Co0.2O2 blended positive electrodes for Lithium-ion batteries

Blended positive electrodes consisting of mixtures of LiMn2O4 spinel (LMO) and layered LiNi0.5Mn0.3Co0.2O2 (NMC) have been studied by coupling electrochemical testing to operando synchrotron based X-ray absorption and powder diffraction experiments to shed light on their redox mechanism. Blending NMC with LMO results in enhanced energy density at high rates, with the composition with 25% LMO exhibiting the best electrochemical performance. Tests with a special electrochemical setup detecting the contribution of each blend component indicate that the effective current load on each blend component can be significantly different from the nominal rate and also varies as function of SoC. Operando studies enabled to monitor the evolution of oxidation state and changes in the crystal structure, which are in agreement with the expected behaviour of the individual components considering the material specific electrochemical current loads. These findings should contribute to a deeper mechanistic understanding of blended electrodes to foster a rational driven approach for their design.

A pH-Stable Tb-MOF as Luminescence Sensor for Highly Sensitive Detection of Amino Acids through Diverse Sensing Mechanism.

A luminescent Tb-MOF with excellent stability and dual-emitting properties was constructed with an amide-functionalized tetracarboxylate ligand. Tb-MOFs were initially assembled on one-dimensional Tb3+ chains, then formed a two-dimensional double-decker layer through the synergistic linking of organic ligands and bridging formic acid anions, and further fabricated the final three-dimensional structure through the connection of the organic ligands. Powder X-ray diffraction experiments revealed that Tb-MOFs not only exhibited excellent stability in water but also maintained structural integrity in the pH range of 2-12. Importantly, this Tb-MOF provided the first example of a metal-organic framework (MOF)-based luminescence sensor that can simultaneously detect two acid amino acids (aspartic and glutamic acids) through a turn-off sensing mechanism and two basic amino acids (lysine and arginine acids) through unusual turn-on and turn-off-on sensing mechanisms. Moreover, high sensitivity, low detection limit, and excellent recyclability of this sensor endow Tb-MOFs with great potential as a highly efficient amino acid fluorescence sensor in chemical detection and biological environments.

Crystal structure simulation of cationic cholesteric Liquid-Crystal polyesters. Non-Viral vectors

The crystal structure of six cationic cholesteric liquid crystal polyesters with choline, ammonium, and amide end groups are reported: PTOBEE-Choline [(C26H20O8)n-C5H13N]; PTOBDME-Choline [(C34H36O8)n-C5H13N]; PTOBEE-Ammonium [(C26H20O8)n-C5H13N]; PTOBDME-Ammonium [(C34H36O8)n-C5H13N]; PTOBEE-Amide (C26H19O9N)n and PTOBUME-Amide (C33H33O9N)n, have demonstrated non-viral vector properties in gene therapy by delivering DNA to the cell nucleus. They were synthesized by functionalization of precursor racemic polyesters via a condensation reaction between 4,4′-(terephthaloyl-di-oxydibenzoic chloride) (TOBC) and the racemic mixture of glycol (R-S-1,2-butanediol) or (R-S-1,2-dodecanediol), respectively. The resulting helical macromolecular structures exhibit unexpected optical activity and chiral morphology, previously attributed to the kinetic resolution of one preferable helical conformer of the possible four observed by NMR. Conformational analysis and energy minimization are performed on the four helical conformer monomeric models which are then polymerized to obtain helical chains. Three levels of chirality were observed in these polymer structures. Crystal models are built in triclinic primitive P1cells, with their molecular chains oriented parallel to the Z-axis (c lattice parameter equal to the helical pitch length), the cell parameters are obtained by performing geometry optimization tasks. A raw estimation of the relative weight of the four possible helical conformers on each synthetic cationic polymer has been performed on ideal mixtures considering their approximate known crystal structure with their experimental X-ray powder diffraction by Powder Quantitative Phase Analysis. The results would confirm the theory of the preferable recrystallization of a diastereoisomer, among the four possible, during the synthetic procedures. These findings shed light on the observed optical activity and provide insights into the crystal structure of these cationic polymers. The morphology of the cationic polymers is studied by ESEM in wet samples and crystals after drying the solvent.

Na6Li4MO4(CO3)4 (M = W and Mo): An Alternative Electrolyte for High-Temperature Electrochemical Cells.

Two new acentric oxycarbonates Na6Li4MO4(CO3)4 (M = W and Mo) were synthesized via a conventional solid-state route. Their structure was determined from X-ray diffraction data on single crystals. Na6Li4MO4(CO3)4 (M = W and Mo) crystallizes in the acentric cubic P-43m space group (a ≈ 7.15 Å). It is composed of MLi4O16 units built from MO4 and LiO4 tetrahedra and linked by CO32- groups to form a three-dimensional framework in which Na+ ions are inserted. We showed from differential scanning calorimetry and powder X-ray diffraction experiments that the melting is congruent (T ∼525 °C). In the solid and molten forms, conductivity was measured for both oxycarbonates by electrochemical impedance spectroscopy with three various gas compositions (CO2 100 vol %, CO2-air 70-30 vol %, and CO2-air 20-80 vol %). Each time, the stability of the electrical behavior was checked via heating and cooling cycles. The conductivity of both solid and molten phases is purely ionic and in the same order of magnitude as for the classical molten alkali electrolyte made of Li-Na or Li-K carbonates. As activation energies are also comparable, those new oxycarbonates appear to be promising electrolytes for electrochemical devices.

Graphite resistive heated diamond anvil cell for simultaneous high-pressure and high-temperature diffraction experiments.

High-pressure and high-temperature experiments using a resistively heated diamond anvil cell have the advantage of heating samples homogeneously with precise temperature control. Here, we present the design and performance of a graphite resistive heated diamond anvil cell (GRHDAC) setup for powder and single-crystal x-ray diffraction experiments developed at the Extreme Conditions Beamline (P02.2) at PETRA III, Hamburg, Germany. In the GRHDAC, temperatures up to 2000K can be generated at high pressures by placing it in a water-cooled vacuum chamber. Temperature estimates from thermocouple measurements are within +/-35K at the sample position up to 800K and within +90K between 800 and 1400K when using a standard seat combination of cBN and WC. Isothermal compression at high temperatures can be achieved by employing a remote membrane control system. The advantage of the GRHDAC is demonstrated through the study of geophysical processes in the Earth's crust and upper mantle region.

Ferromagnetism of concrete

Studying the intrinsic properties of concrete is essential for addressing various aspects of concrete structure design, material selection, and sustainability. In this study, a suspended strong magnetic torsion balance device was designed and constructed to investigate the ferromagnetic properties of concrete specimens and their constituent materials. It was found that sand and cement generally exhibit ferromagnetic properties, while aggregates do not possess ferromagnetic properties. Analysis using powder X-ray diffraction (XRD) and chemical experiments confirmed that the ferromagnetic material in sand and cement is elemental iron. A simplified calculation formula for the magnetic force between concrete specimens and an external magnetic field was derived. Three sets of specimens were designed and fabricated for experimental exploration of ferromagnetic properties and magnetic force measurements. The experimental results demonstrate that plain concrete possesses measurable ferromagnetic properties. The magnetic force of concrete initially experiences a rapid decay followed by a gradual leveling off as the distance (from the magnetic field source to the concrete surface) increases. The decay rate approximately follows a fourth-power relationship with distance. Under a loading condition with an applied magnetic field intensity of 0.2 T, the optimal measurement range for ferromagnetic force in concrete is between 0.02 m and 0.05 m.

Synthesis of Silver Nanowires with Different Morphologies for Lung Cancer Treatment

In this publication, three silver nanowires (Ag NWs) with different morphologies were prepared via the polyol process synthesis method by changing the amount and kinds of inorganic agents in the synthesis procedure. The as-synthesized Ag NWs showed high yield and purity. The samples were fully characterized by scanning electron microscopy (SEM) and powder X-ray diffraction (PXRD). The SEM results revealed that Ag NWs 1–3 have diameters of 95, 70, and 55–65 nm, respectively, and lengths of 20–30, 30–40, and 40–50 μm, respectively. The PXRD experiments showed that the as-synthesized samples display four typical diffraction peaks at 38.2°, 44.5°, 64.5°, and 77.4°, which are consistent with the face-centered cubic lattice for Ag. The inhibitory activities of the Ag NWs on the viability of lung cancer cells was measured with cell counting kit-8 assay. The activation activity of the vascular endothelial growth factor signaling pathway in the cancer cells was measured with real-time polymerase chain reaction.

High Proton Conductivity of the UiO-66-NH2-SPES Composite Membrane Prepared by Covalent Cross-Linking.

A sulfonated poly(ethersulfone) (SPES)-metal-organic framework (MOF) film with excellent proton conductivity was synthesized by anchoring UiO-66-NH2 to the main chain of the aromatic polymer through the Hinsberg reaction. The chemical bond was formed between the amino group in MOFs and the -SO2Cl group in chlorosulfonated poly(ethersulfones) to conduct protons in the proton channel of the membrane, making the membrane have excellent proton conductivity. UiO-66-NH2 is successfully prepared as a result of the consistency of the experimental and simulated powder X-ray diffraction (PXRD) patterns of MOFs. The existence of absorption peaks of characteristic functional groups in Fourier transform infrared (FTIR) spectra proved the successful preparation of SPES, PES-SO2Cl, and a composite film. The results of the AC impedance test indicate that the composite film with a 3% mass fraction has the best proton conductivity of 0.215 S·cm-1, which is 6.2 times higher than that of the blended film without a chemical bond at 98% RH and 353 K. To our knowledge, there are rarely any reports on the preparation of a composite membrane by directly linking MOFs and the membrane matrix with chemical bonds. This work provides a good way to synthesize the highly conductive proton exchange film.

Pseudotetrahedral C2-symmetrical Co/Zn(II)-achiral Schiff base complexes with Δ/Λ-chirality induction at-metal as a racemic mixture

Reaction of achiral Schiff base ligands 1-((X-phenylimino)methyl)naphthalen-2-ol {X = 2-ethyl (HL1) or 4-methyl (HL2)} with cobalt(II) or zinc(II) acetate provided the corresponding bis[1-((X-phenylimino)methyl)naphthalen-2-olato-k2N,O]cobalt(II) or zinc(II) {X = 2-ethyl: M = Co (1) and Zn (2) or X = 4-methyl: M = Co (3) and Zn (4)} complexes. The molecules crystallize in the centrosymmetric space groups R–3 (1) and P–1 (3 or 4). Molecular structures determinations showed coordination of two molecules of the N,O-chelate ligands to the metal ion and formation of pseudotetrahedral complexes with C2-symmetry. Furthermore, coordination of two unsymmetrical achiral N,O-chelates induces Λ/Δ-chirality at the metal atom as a racemic mixture in the centrosymmetric space groups. Structural analyses further reveal that incorporation of 2-ethyl (1) or 4-methyl (3 or 4) group on the N-bound phenyl ring leads to an increase of both the O1-M-O2 and N1-M-N2 bond angles on going from 1 to 3 or 4, with the N1-M-N2 angle increasing to a much greater extent. The fair matching of the experimental and simulated powder X-ray diffraction patterns confirms the phase purity of bulk microcrystalline sample. Differential scanning calorimetry (DSC) results suggest an irreversible phase transformation from solid crystals to isotropic-liquids and subsequent thermal stability of the complexes. Cyclic voltammograms indicate a quasi-reversible two one electron charge transfer processes for 1 or 3 in N,N-dimethylformamide (DMF). Optimized geometry and excited state properties by density functional theory (DFT) and time dependent-density functional theory (TD-DFT) calculations correspond well to the experimental results.

From Ce(OH)3 to Nanoscaled CeO2: Identification and Crystal Structure of a Cerium Oxyhydroxide Intermediate Phase

Cerium oxide is a pivotal compound in catalysis, both as a support and as an active phase. However, its fine features, such as the Ce(III) to Ce(IV) ratio, strongly depend on the protocol used to prepare it. While the literature contains tens of protocols to prepare cerium oxide nanoparticles from Ce(III) precursors, there is still an open question regarding the time at which the cerium oxidation occurs and the role of hydroxide phases in this process. This article identifies an oxyhydroxide phase of Ce(IV) as a key intermediate and proposes a crystal structure for it. For this purpose, phase-pure cerium trihydroxide (Ce(OH)3) nanorods (<20 nm) were first prepared by hydrothermal treatment of a cerium nitrate salt (Ce(NO3)3·6H2O) in the presence of KOH. Aging of this phase in air was monitored by X-ray absorption spectroscopy, which confirmed the formation of an intermediate Ce(IV) crystalline compound, unreferenced so far. Based on X-ray and neutron powder diffraction experiments combined with DFT calculations, we propose that this new phase is a cerium oxyhydroxide of the chemical formula CeO(OH)2, for which a structural model is proposed. Thermodiffraction experiments finally established that this compound is an observable intermediate in the synthesis of cerium dioxide CeO2 by calcination of Ce(OH)3 in air.

Structural Reconstruction of Hydrothermally Grown BaTiO3 Nanoparticles Based on High-Resolution Synchrotron Powder X-ray Diffraction

Barium titanate (BaTiO3) is a versatile material for industrial and research purposes owing to its various and excellent properties, including its ferroelectricity. The demand for ultrafine BaTiO3 nanoparticles via a robust synthesis route capable of mass production, such as hydrothermal reactions, has increased owing to the rapid advancement of highly integrated electronic components. In this study, BaTiO3 nanopowders smaller than 150 nm are synthesized using a facile hydrothermal method to obtain ultrafine and highly uniform nanoparticles. The synthesized nanopowders are analyzed via high-resolution synchrotron powder X-ray diffraction experiments. Based on Rietveld refinement studies, a three-phase composite model is shown to be reasonable for investigating the nanopowders. The analytical results are summarized in detail for a set of BaTiO3 nanopowders. Nanoparticles are reconstructed based on the thicknesses obtained from the calculated phase weight fractions for each case.

Thermodynamic and Kinetic Mechanism of the Phase Transition from Aztreonam Dihydrate to Anhydrates

In this work, two anhydrates (form A and form B) and one dihydrate (form C) of aztreonam were found and were characterized by powder X-ray diffraction (PXRD), thermogravimetric analysis, differential thermal analysis, and Fourier transform infrared spectroscopy. Dynamic vapor adsorption and variable-temperature PXRD experiments were carried out to study their thermal stability and moisture absorption stability. Furthermore, the critical water activity of aztreonam at 10–45 °C was determined, and it was found that the water activity determines the dehydration process of form C. The solubility of form A and form B in methanol solvent was measured at 10–45 °C to decide the thermodynamic stability of the polymorphs, and it was found that form B is thermodynamically stable below 28 °C, while form A is thermodynamically stable above 28 °C. The competitive suspension experiments further proved that form A and form B are enantiotropic polymorphs. In addition, the solution-mediated phase transition (SMPT) process of aztreonam form C was in situ monitored using Raman spectroscopy. The results show that the SMPT process is jointly controlled by the dissolution of the dihydrate and the nucleation of anhydrates, in which temperature plays a very important role. Finally, the SMPT mechanism of the dihydrate form is proposed.

Comparative Study of Experiments and Calculations on the Guest Molecules’ Escaping Mechanism of CL-20-Based Host–Guest Energetic Materials

CL-20-based host–guest energetic materials have high application value in the field of energetic materials. The phase-transition inhibition and stabilization mechanisms of CL-20-based host–guest energetic materials were revealed by combining experiments with molecular dynamics (MD) simulation. Based on the crystal structures, the super-cell models of host–guest energetic materials including CL-20/H2O, CL-20/H2O2, CL-20/N2O, and CL-20/CO2 were constructed. The phase transformation behavior and stability sequence of CL-20-based host–guest energetic materials were investigated using MD integrated with in situ powder X-ray diffraction (PXRD) and differential scanning calorimetry-thermogravimetry (DSC-TG) experiments. The escaping abilities of guest molecules from (002), (020), (021), (102), and (111) crystal faces of CL-20/H2O, CL-20/H2O2, CL-20/N2O, and CL-20/CO2 were evaluated using the target-MD method. It is proposed that the guest molecules could escape from the (002) crystal face more easily than the other faces. The escaping behaviors were studied using MD simulations. Based on the analysis of mean-square displacement (MSD), diffusion coefficients, and binding energies at different temperatures, the thermal stability order of the four CL-20-based host–guest materials was CL-20/CO2 > CL-20/N2O > CL-20/H2O2 > CL-20/H2O. This is consistent with experimental observations by in situ XRD and DSC analyses on these host–guest energetic materials. Meanwhile, by studying the escape paths of guest molecules, it was concluded that the escape method of guest molecules from a CL-20 crystal cell is “jumping” diffusion. By studying the MSD of host molecule CL-20 and the radial distribution function between the host molecule and the guest molecule, the structural stabilization mechanism of host–guest energetic materials was revealed. Our findings will help to reveal the solid-phase-transition inhibition mechanism of host–guest energetic materials and promote the development of host–guest explosives as smart materials.

Metalo Hydrogen-Bonded Organic Frameworks Self-Assembled by Charge-Assisted Synthons for Ultrahigh Proton Conduction

Hydrogen-bonded organic frameworks (HOFs) have been well recognized for constructing solid-state proton-conducting materials due to their inherent well-defined H-bonded networks; however, the design and synthesis of stable HOFs showing ultrahigh superprotonic conductivity is still challenging. Herein, we reported a facile and effective synthetic strategy to build high proton-conducting metalo hydrogen-bonded organic–inorganic frameworks (MHOFs) through charge-assisted inorganic and organic synthons. The supramolecular self-assembly of simple metal salts and tetra-carboxylic acids gives rise to two hydrogen-bonded frameworks, [M(H2O)6][H2tcba] (M = Zn2+, Ni2+; H4tcba = 1,2,4,5-benzenetetracarboxylic acid). X-ray crystallography and gas adsorption confirmed the nonporous nature of the HOIFs. Variable-temperature single-crystal and powder X-ray diffraction experiments reveal the thermal and water stability of the supramolecular structures sustained by exclusively charge-assisted hydrogen bonds. The high density of carboxylic acid groups and coordinated water molecules provide ample protons and hydrophilic environments for efficient proton transport; therefore, variable-temperature and -humidity electrochemical impedance spectroscopy revealed that MHOFs are good supramolecular proton conductors with conductivities up to 1.1 × 10–2 and 2.1 × 10–2 S·cm–1 for 1 and 2, respectively, at 80 °C under 97% RH. Our study demonstrates great potential of charge-assisted inorganic and organic synthons in the design and construction of proton-conducting HOIFs.

Thermodynamic analysis and in situ powder X-ray diffraction investigation of the formation and transformation of mineral phases during pressure oxidation of pyrite

Acid oxidative pressure leaching is a cost-effective way for recovering gold from refractory gold ores such as gold-bearing pyrite, yet our knowledge of the dissolution, crystallization, and phase transformation during pressure leaching is still controversial. This is partially due to the lack of thermodynamic data and in situ studies of the leaching process. Here, we combine thermodynamic modelling and in situ powder X-ray diffraction (PXRD) to investigate mineralogical phase changes during oxidation of pyrite. The polyhedron method has been utilised to estimate the standard Gibbs free energy of formation (∆Gfo) and enthalpy of formation (∆Hfo) of 31 sulphate minerals from 25 °C to 300 °C. The calculated thermodynamic data for the sulphate minerals agree well with the literature, with an average relative error of 0.23% for both ∆Gfo and ∆Hfo demonstrating the reliability of the polyhedron method. Some new thermodynamic data for the mineral phases at elevated temperature was calculated and used to construct the Eh-pH diagrams for the Fe-S-H2O system at 225 °C, which were used to predict phase transformations and chemical reactions during oxidation of pyrite. Based on the analysis of thermodynamic diagrams, the formation of basic ferric sulphate (BFS: Fe(OH)SO4) is favoured at stronger acidic and higher solution redox potential conditions, while hematite and FeSO4∙H2O occur at low solution redox potential conditions. These predictions agreed with the results from laboratory-based in situ PXRD experiments, in which the mineralogical phase transformations were studied during acid pressure treatment of pyrite in a capillary. The influence of initial concentration of ferric ions on the change of mineral phase was revealed. The results confirmed the formation of FeSO4∙H2O and Fe(OH)SO4 phases during the heating (24–225 °C) and annealing stages. These phases may passivate pyrite surface and hence slow down further pyrite oxidation but were re-dissolved during the annealing and/or cooling stages, depending on the initial concentration of ferric ions.

Theoretical and 27Al NMR Spectroscopic Investigations of Binary Intermetallic Alkaline-Earth Aluminides.

The binary alkaline-earth aluminides AEAl2 (AE = Ca and Sr) and AEAl4 (AE = Ca-Ba) have been synthesized from the elements and investigated via powder X-ray diffraction experiments. CaAl2 adopts the cubic MgCu2-type structure (Fd3̅m), while SrAl2 crystallizes in the orthorhombic KHg2-type (Imma). LT-CaAl4 crystallizes with the monoclinic CaGa4-type (C2/m), while HT-CaAl4, SrAl4, and BaAl4 adopt the tetragonal BaAl4-type structure (I4/mmm). The close structural relation of the two CaAl4 polymorphs was established using a group-subgroup relation in the Bärnighausen formalism. In addition to the room-temperature and normal pressure phase of SrAl2, a high-pressure/high-temperature phase has been prepared using multianvil techniques, and its structural and spectroscopic parameters were determined. Elemental analysis by inductively coupled plasma mass spectrometry showed that no significant impurities with other elements besides the weighed ones are present and the chemical compositions match the synthesized ones. The title compounds have been furthermore investigated by 27Al solid-state magic angle spinning NMR experiments to validate the crystal structure and to gain information about the influence of the composition on the electron transfer and the NMR characteristics. This has also been investigated from a quantum chemical point of view using Bader charges, while the stabilities of the binary compounds in the three phase diagrams (Ca-Al, Sr-Al and Ba-Al) have been studied by calculations of formation energies per atom.