Synchrotron Radiation Powder X-ray Diffraction Research Articles

Structural fluctuation of Pb(Mg1/3Nb2/3)O3 in the cubic phase

To investigate the structural fluctuations of relaxor Pb(Mg1/3Nb2/3)O3 (PMN) in the cubic phase, the probability density function of each atom was determined by high-energy synchrotron radiation X-ray powder diffraction measurements and a Rietveld analysis with anharmonic temperature factors. A rotator-like behavior of the Pb ion was observed in the cubic phase. The off-center behavior along the 〈1 1 1〉 directions became pronounced with decreasing temperature. The ferroelectricity of PMN was attributed to a combination of the freezing of the 〈1 1 1〉-preferred rotator-like disorder and the ferroelectric distortion of the B–O6 octahedron.

Ethanol- and Methanol-Coordinated and Solvent-Free Dodecahydro closo-Dodecaborates of 3d Transition Metals and of Magnesium

Magnesium and 3d transition metals closo-borates were prepared by mechanosynthesis (ball milling) of the mixtures Na2B12H12 + MCl2 (M = Mn, Fe, Co, Ni, Mg), followed by addition of ethanol or methanol and drying under dynamic vacuum. The dead mass of NaCl is partly removed by filtration. The crystal structures of solvent-coordinated and solvent-free closo-borates have been characterized by temperature dependent synchrotron radiation X-ray powder diffraction, ab initio calculations, thermal analysis and infrared spectroscopy. Various solvated complexes containing six, four, three, two or one solvent molecules were obtained by successive removal of the solvent until in most case the solvent-free metal closo-borates were obtained with the exception of Mg whose hypothetical crystal structure, however, could have its prototype in MnB12H12. The 3d transition metal closo-borates were studied in the view of their potential use as Na- or Li-ion battery electrodes in combination with Na or Li closo-borate solid electrolytes. The metal oxidation state (II) obtained in compounds presented here does not allow such application.

Hydrogen storage in high-entropy alloys with varying degree of local lattice strain

We have investigated the structure and hydrogen storage properties of a series of Ti, V, Zr, Nb and Ta based high-entropy alloys (HEAs) with varying degree of local lattice strain by means of synchrotron radiation powder X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry and manometric measurements in a Sieverts apparatus. The obtained alloys have body-centred cubic (bcc) crystal structures and form face-centred cubic (fcc) metal hydrides with hydrogen-to-metal ratios close to 2. No correlation between the hydrogen storage capacity and the local lattice strain δr is observed in this work. Both bcc and fcc unit cells expand linearly with the zirconium-to-metal ratio [Zr]/[M], and increased concentration of Zr stabilizes the hydrides. When heated, the hydrides decompose into the original bcc alloys if [Zr]/[M]<12.5 at.%. The hydrides phase-separate in a hydrogen-induced decomposition type process for [Zr]/[M]≥12.5 at.%. The result is then a combination of two bcc phases, one with a larger and the other with a smaller unit cell than the original bcc alloy.

Hydrated and anhydrous dodecahydro closo-dodecaborates of 3d transition metals and of magnesium

Magnesium and 3d transition metals closo-dodecaborates were prepared by mechanosynthesis (ball milling) of the mixtures Na2B12H12 + MCl2 (M = Ti, Cr, Mn, Fe, Co, Cu, Zn, Mg) and CuCl, followed by hydration and drying under dynamic vacuum. The crystal structures of hydrated and anhydrous closo-dodecaborates have been characterized by temperature dependent synchrotron radiation X-ray powder diffraction, ab initio calculations, thermal analysis and infrared spectroscopy. Three different complexes containing water were found: a homoleptic octahedral complex in M(H2O)6B12H12 crystallizing in three different deformation variants of the complex centred closo-dodecaborate cube, a heteroleptic octahedral complex in M(H2O)4B12H12 containing four water molecules and two hydrogens from a closo-dodecaborate centring also a deformed closo-dodecaborate cube, and a heteroleptic octahedral complex in Fe(H2O)2B12H12 containing two water molecules where four hydrogen atoms are bridging two closo-dodecaborates. Anhydrous cobalt(II) and copper(I) closo-dodecaborates were obtained by drying the hydrated sample under dynamic vacuum. Both compounds crystallize with bcc packing of closo-dodecaborates where the metal is in octahedral coordination by hydrogen H6 for cobalt, and a tetrahedral coordination H4 is found for copper, bridging two closo-dodecaborates in an infinite chain. The orbital overlap between transition metal and closo-anion leads to directional covalent bonding. While CoB12H12 has trigonal symmetry (R3) allowing for an ordered metal position, Cu2B12H12 follows the cubic symmetry of bcc packing, which leads to a disordered metal position. The structure of NiB12H12, originally published as monoclinic (I2), is revised based on the trigonal structural model of CoB12H12.

Bi2SiO5@g-SiO2 upconverting nanoparticles: a bismuth-driven core-shell self-assembly mechanism.

Core-shell systems have attracted increasing interest among the research community in recent years due to their unique properties and structural features, and the development of new synthetic strategies is still a challenge. In this work, we have investigated lanthanide-doped Bi2SiO5 nanocrystal formation inside mesoporous silica nanoparticles (MSNs). The role of both synthesis temperature and concentration of the bismuth precursor impregnated into the MSNs is discussed, showing an unprecedented strategy for the simultaneous stabilization of a crystalline core and a glassy shell. Temperature dependent synchrotron radiation X-ray powder diffraction (SR-XRPD) and high resolution transmission electron microscopy (HR-TEM) analyses allow one to follow the crystalline core growth. A mechanism for the formation of a Bi2SiO5@g-SiO2 core-shell nanosystem is proposed. In addition, the easy tunability of the color output of the upconverting system is demonstrated by means of suitable doping lanthanide ions with potential applications in several fields.

In-depth study of the mechanism of heavy metal trapping on the surface of hydroxyapatite

In the present study, the efficiency and selectivity and the role of surface groups of hydroxyapatite in the Cr(III) trapping, present in solution as single species or in co-presence of Ni(II) and Pb(II), have been investigated. Transmission electron microscopy (TEM) analysis and synchrotron radiation X-ray powder diffraction (XRPD) measurements provided comprehensive descriptions of the HAP surface and structure. The surface chemical properties, density and strength of the acid and base sites of HAP, have been determined by 2-phenylethylamine and benzoic acid probe adsorption, respectively. The amphoteric properties of HAP turned over to only acid property in water solution. The sorption capacity of HAP has been batch-tested in simulated polluted waters containing Cr(III) at different initial concentrations (from ca. 0.3 to ca.6 mM) and pH values (from 4 to 9). Competitive adsorption phenomena in multi-metal systems (Cr(III) with Ni(II) and Pb(II)) have also been studied. An appropriate set of analytical techniques, XRPD, TEM, STEM-EDX, N2 adsorption-desorption analyses, FT-IR spectroscopy, have been used to characterize the metal loaded hydroxyapatite samples. Different mechanisms of metal uptake were active depending on the nature of the metal species and pH value of solutions: surface complexation, precipitation, ion-exchange, or dissolution-precipitation.

Positive and negative monoclinic deformation of corundum-type trigonal crystal structures of M 2O3 metal oxides

The crystal structures of several transition metal oxides, Ti2O3, V2O3, Cr2O3, Al2O3 and α-Fe2O3, are studied using synchrotron radiation X-ray powder diffraction. The observed angular dependence of the integral breadths is described by two models: (i) the distorted corundum-type structure model described by the space group C2/c and (ii) the Stephens model of anisotropic Bragg peak broadening. These two models are shown to be equivalent. Ti2O3, V2O3 and Cr2O3 show a `positive' distortion which is related to the possible metal–metal bond suggested by Goodenough in the literature (the deformation leads to shorter metal–metal distances) whereas Al2O3 and α-Fe2O3 show a `negative' distortion which leads to relatively longer metal–metal distances.

Structure factors and charge-density study of diamond at 800 K

The structure factors of diamond were determined by synchrotron radiation X-ray powder diffraction at 800 K at sin θ/λ ≤ 2.2 Å−1 reciprocal resolution. The structure factors were estimated using six powder profiles measured on beamline BL02B2 at SPring-8 (Hyogo, Japan). A high reciprocal resolution at sin θ/λ ≤ 2.2 Å−1 was required to reveal the temperature dependence of the charge density, due to the high Debye temperature of θD = 1860 K of diamond. Wide 2θ angle data with the highest counting statistics are crucial for accurate data analysis. The periodic noise of every six-pixel step was observed in the highest counting statistics imaging plate (IP) data scanned by a BAS2500 IP scanner. It was found that the noise originated from the six-sided polygonal mirror in the scanner. The intensity fluctuation at every six-pixel step was also found in the Fourier series expansion of the powder profiles. The ratio of the maximum fluctuation was estimated as 0.4% by summing all six-pixel step data. The powder profiles were corrected by multiplying the ratios. The intensity fluctuation in the background region was reduced to less than 50% of the uncorrected data. The weak 888 Bragg reflection, with an intensity of 0.005% of that of the 111 Bragg reflection at 800 K, was readily observed in the corrected data. Finally, the structure factors determined at 800 K were successfully applied to a charge-density study by multipole modelling. The reliability factors and multipole parameters at 800 K are in agreement with those at 300 K. The differences in the charge density at the bond midpoint and ∇2ρ at the bond-critical point were less than 1% and 2%, respectively.

X-ray powder diffraction study of the stability of clathrate hydrates in the presence of salts with relevance to the Martian cryosphere

Water on the present day Martian surface is thought to exist in two thermally distinct sub-surface reservoirs: as ice in the cryosphere and as groundwater located deeper in the crust. These sub-surface environments are thought to contain saline, rather than pure, water and laboratory studies on whether or not clathrate hydrates can form in such environments are lacking. We fill this gap by performing synchrotron radiation X-ray powder diffraction to investigate the formation and evolution of clathrate hydrates in weak chloride solutions at CO2 pressures, and over temperature ranges, that are similar to those found in the Martian regolith. We have found that clathrate hydrates can form under conditions relevant to the Martian cryosphere, despite the presence of chloride salts. We find that the dissociation temperatures for CO2 clathrate hydrates formed in saline solutions are depressed by 10–20 K relative to those formed in pure water, depending on the nature of the salt and the CO2 pressure. We suggest that the inhibiting effect that salts such as MgCl2, CaCl2 and NaCl have on clathrate hydrate formation could also be related to the salts’ effect on the formation of the low temperature phase of ice. However, despite the inhibiting effect of the salts, we conclude that the presence of clathrate hydrates should still be possible under conditions likely to exist within the Martian cryosphere.

Study of materials structure physics of isomorphic LiNbO3 and LiTaO3 ferroelectrics by synchrotron radiation X-ray diffraction

Electron charge density studies of stoichiometric LiNbO3 and LiTaO3 ferroelectrics have been carried out by analyzing the synchrotron radiation X-ray powder diffraction data using a combination of the Rietveld and maximum entropy methods. The clear relationships between the Nb(Ta)–O bond length, the electron charge density on the Nb(Ta)–O bond, and the phase transition temperature TC are revealed for isomorphic structures. Nb(Ta)–O bonding plays an important role in the elevation of TC. The TC in LiNbO3 being higher than that in LiTaO3 is attributed to the larger lattice distortion of the Nb–O oxygen octahedron in LiNbO3. The validity of estimating TC for LiNbO3 family crystals from the degree of lattice distortion in the ferroelectric structure is discussed.

Reactivity of magnesium borohydride – Metal hydride composites, γ-Mg(BH4)2-MHx, M = Li, Na, Mg, Ca

The reactivity and thermal decomposition of γ-Mg(BH4)2-MHx, M = Li, Na, Mg, and Ca composites has been examined with the objective of studying the hydrogen storage capability of the composites. The samples were prepared by manual grinding γ-Mg(BH4)2 with a metal hydride to obtain homogenous mixtures. In-situ synchrotron radiation powder X-ray diffraction (SR-PXD) and simultaneous thermogravimetric analysis, differential scanning calorimetry, and mass spectrometry was performed to analyse the decomposition mechanism, whereas solid-state 11B nuclear magnetic resonance spectroscopy and SR-PXD was used to investigate the decomposition products. Interestingly, substitution reactions take place between magnesium borohydride and lithium, sodium and calcium hydride forming the more stable metal borohydrides, M(BH4)x, M = Li, Na or Ca. The composite γ-Mg(BH4)2-LiH has a hydrogen release at T ∼380–420 °C, which indicates the formation of amorphous LiBH4 during decomposition. For the composites γ-Mg(BH4)2-NaH, formation of crystalline NaBH4 is observed by SR-PXD from T = 150–450 °C, and hydrogen release ascribed to NaBH4 is observed in MS data at T = 460–480 °C. γ-Mg(BH4)2-MgH2 composite decomposes as the individual constituents. β-Ca(BH4)2 is formed at T = 175–375 °C in the composites of γ-Mg(BH4)2-CaH2. Bragg diffraction from CaB6 at T > 370 °C is detected by SR-PXD for γ-Mg(BH4)2-CaH2 (1:0.5) but not for samples richer in CaH2. Release of diborane was not observed for any of the magnesium borohydride metal hydride composites.

The role of high-valent (Mo and V) cations in defect spinel iron oxide nanomaterials: Toward improving Li-ion storage

Defect spinel Fe3-δO4 samples doped with high-valent Mo and V cations have been prepared by sol-gel auto-combustion rout with increasing concentrations of Mo and V, respectively. Energy Dispersive X-ray fluorescence (EDXRF) and Attenuated Total Reflection Fourier transform Infrared (ATR-FTIR) spectroscopies have verified the compositions of the samples and the oxidation states of the metal cations. Synchrotron Radiation X-ray Powder Diffraction (SR-XRPD) patterns were measured at MCX beamline of ELETTRA synchrotron. Structure and microstructure of the samples were studied by the Rietveld method. Increasing densities of vacancies were found to be generated by the high-valent Mo and V cations which were correlated to the lattice parameter, crystallite size and microstrain of each sample. The hysteresis loops were measured at room temperature using the Vibrating Sample Magnetometer (VSM) and good agreement was found between the Fe-cation distributions revealed from Rietveld adjustments and those predicted by the saturation magnetization (Ms) measurements. The High-Resolution Transmission Electron Microscopy (HRTEM) confirmed the proposed isotropic crystallite size model implemented in the Rietveld adjustments. Finally, the results presented herein show agreement with previous works on iron oxide materials used as intercalation cathode for Li-ion batteries and predict better performance for the current Mo- and V-doped defect spinel.

Kinetics and thermodynamics of hydrogenation-dehydrogenation for Mg-25%TM (TM = Ti, Nb or V) composites synthesized by reactive ball milling in hydrogen

0.75Mg−0.25TM−H (TM = Ti, Nb or V) samples were mechano-chemically synthesized by reactive ball milling. The detailed reaction mechanism during hydrogen release and uptake was investigated by in-situ synchrotron radiation powder X-ray diffraction (SR-PXD) experiments. The thermodynamic and kinetic properties have been studied by Sievert's method. On the base of calculated values of the Gibbs free energy for reaction of hydrogen absorption (ΔG < 0) it reveals that hydrogenation reaction could thermodynamically proceed at room temperature, which is experimentally confirmed for all of the studied composites. It is clearly shown that β-MgH2 forms at RT under conditions of experiment. Comparative analysis of the MgTi, MgV and MgNb systems makes it possible to establish that the most effective additive facilitating hydrogen uptake, particularly at RT, is vanadium. It provides the degree of conversion into hydride phase α = 0.86 for the first minute of hydrogenation. In contrast, additives of Nb and Ti provide only α = 0.62 and 0.36, respectively, following the 30 min of exposure. However, this study reveals that for the dehydrogenation process, titanium is the best among the examined additives, which is evidenced by lowest value of activation energy Ea = 53.6 kJ/mol of the hydrogen desorption.

Crystal Structural Determination of SrAlD5 with Corner-Sharing AlD6 Octahedron Chains by X-ray and Neutron Diffraction

Aluminium-based complex hydrides (alanates) composed of metal cation(s) and complex anion(s), [AlH4]− or [AlH6]3− with covalent Al–H bonds, have attracted tremendous attention as hydrogen storage materials since the discovery of the reversible hydrogen desorption and absorption reactions on Ti-enhanced NaAlH4. In cases wherein alkaline-earth metals (M) are used as a metal cation, MAlH5 with corner-sharing AlH6 octahedron chains are known to form. The crystal structure of SrAlH5 has remained unsolved although two different results have been theoretically and experimentally proposed. Focusing on the corner-sharing AlH6 octahedron chains as a unique feature of the alkaline-earth metal, we here report the crystal structure of SrAlD5 investigated by synchrotron radiation powder X-ray and neutron diffraction. SrAlD5 was elucidated to adopt an orthorhombic unit cell with a = 4.6226(10) Å, b = 12.6213(30) Å and c = 5.0321(10) Å in the space group Pbcm (No. 57) and Z = 4. The Al–D distances (1.77–1.81 Å) in the corner-sharing AlD6 octahedra matched with those in the isolated [AlD6]3− although the D–Al–D angles in the penta-alanates are significantly more distorted than the isolated [AlD6]3−.

Half-Heusler phase formation and Ni atom distribution in M-Ni-Sn (M = Hf, Ti, Zr) systems

High resolution synchrotron radiation powder X-ray diffraction (SR-PXD) and scanning transmission electron microscopy (STEM) have been employed for structural characterization of MNiSn, M0.5M′0.5NiSn and M0.5M′0.25M″0.25NiSn (M, M′, M″ = Hf, Ti, Zr) half-Heusler compounds, synthesized by arc melting and thermal annealing. Rietveld refinement results demonstrate that ternary Ti- and Hf-based compositions crystallize with only one half-Heulser phase, while two cubic phases are found in samples with nominal composition ZrNiSn. The performed analysis does not suggest obvious presence of excess Ni in any of the ternary compounds. Instead, it shows disordered distribution of the stoichiometric Ni atoms over 4c and the nominally vacant 4d sites in ZrNiSn as well as formation of Ni vacancies at the 4c site in ZrNi0.98Sn.

Li+ ion doping into KI-KBH4 solid solvent systems: The role of the BH4− anion

In order to clarify the effect of BH4− anions on the Li+ ion doping into the KI-KBH4 solid solvent systems, the concentrations of the Li+ and BH4− ions in a solid solvent were separately controlled. The dissolving of LiI into the KI-KBH4 solid solvent was confirmed, while the formation of a solid solution between KI and LiI was not realized without the BH4− anions in the solid solvent. For the solid solvent doped with 10 mol% BH4− ions (9KI·KBH4), LiI could dissolve up to 6 mol%. The lattice parameters of the KI-KBH4 systems increased when the Li+ ions were doped. The 7Li MAS-NMR spectrum for the KI-KBH4 system dissolved with LiI showed one resonance peak at −0.72 ppm whose position is quite different from that for LiI (−4.57 ppm). These results indicated that the doped Li+ ions would not simply substitute the host K+ ions, but occupy the interstitial sites of the KI-KBH4 solid solvent. The results of the Rietveld analysis of the synchrotron radiation X-ray powder diffraction measurements showed that K+ vacancies are introduced by the doing of the interstitial Li+ ions as a charge balance.

Growth of NaO2 in Highly Efficient Na–O2 Batteries Revealed by Synchrotron In Operando X-ray Diffraction

The development of Na–O2 batteries requires understanding the formation of reaction products, as different groups reported compounds such as sodium peroxide, sodium superoxide, and hydrated sodium peroxide as the main discharge products. In this study, we used in operando synchrotron radiation powder X-ray diffraction (SR-PXD) to (i) quantitatively track the formation of NaO2 in Na–O2 cells and (ii) measure how the growth of crystalline NaO2 is influenced by the choice of electrolyte salt. The results reveal that the discharge could be divided into two time regions and that the formation of NaO2 during the major part of the discharge reaction is highly efficient. The findings indicate that the cell with NaOTf salt exhibited higher capacity than the cell with NaPF6 salt, whereas the average domain size of NaO2 particles decreases during the discharge. This fundamental insight brings new information on the working mechanism of Na–O2 batteries.

Elaborating the Crystal Structures of MgAgSb Thermoelectric Compound: Polymorphs and Atomic Disorders

Gaining insight into crystal structure is essential for understanding thermoelectric transport mechanisms and predicting thermoelectric properties. The main challenge in studying thermoelectric mechanisms is often imprecise or wrong models of the crystal structure. This work examines the structure modifications observed in MgAgSb thermoelectric materials by multitemperature high-resolution synchrotron radiation powder X-ray diffraction (SR-PXRD). Rietveld refinement reveals large atomic displacement parameters (ADPs) of the Ag1 atoms at the 4a position indicating possible atomic disorder, which may contribute to the low thermal conductivity observed in α-MgAgSb. The temperature dependence of anisotropic structural parameters indicates a tendency of increasing structural symmetry in α-MgAgSb with increasing temperature, largely contributing to the temperature evolution of the thermoelectric properties. Two MgAgSb polymorphs (β-MgAgSb and γ-MgAgSb) coexist at 700 K, and only the γ-MgAgSb crystalline phase i...

Stability of biological and inorganic hemimorphite: Implications for hemimorphite precipitation in non-sulfide Zn deposits

Hemimorphite, Zn4Si2O7(OH)2·H2O, one of the most common minerals in non-sulfide Zn deposits, together with smithsonite and hydrozincite, is one of the most abundant minerals in the “calamine” deposits in SW Sardinia. In spite of their importance for the development of ore genesis models, the stability properties of hemimorphite are poorly known. This paper presents solubility experiments on two different types of hemimorphite: a “geological” hemimorphite from a supergene non-sulfide Zn deposit, of supposed abiotic origin, and a hemimorphite precipitated by bacterial activity. Both specimens were characterized, before and after the experiment, by Synchrotron Radiation X-ray powder diffraction, Scanning Electron Microscopy, and X-ray Absorption Spectroscopy. The calculated solubility product constants (logKs) are similar for both “geological” and biogenic hemimorphite (30.3±0.4 and 30.5±0.1, respectively). During the solubility experiment, biological hemimorphite undergoes an amorphous to crystalline phase transition, and the distinctive features (mineralized bacterial sheaths and organic filaments), that allowed us to demonstrate its biological origin, are no longer recognizable by Scanning Electron Microscopy.The results of this study may be useful for developing ore genesis models, including evolution in a supergene environment, and in general for performing geochemical speciation and equilibrium calculations. Moreover, our findings open the way for a new interpretation of hemimorphite-forming processes, and suggest the possibility that bacteria may have played a role in the formation of this mineral in ore deposits.

Insight into Nucleation and Growth of Bi2–xSbxTe3 (x = 0–2) Nanoplatelets in Hydrothermal Synthesis

Controlled wet chemical synthesis of nanomaterials with tailored structures and properties, especially by hydrothermal/solvothermal methods, is difficult due to the complicated nucleation and growth processes. Therefore, it is important to gain a deeper understanding of the formation mechanisms involved in hydrothermal/solvothermal processes. In the present study, the formation mechanisms of Bi2–xSbxTe3 (x = 0–2) nanoplatelets under hydrothermal conditions are studied by in situ synchrotron radiation powder X-ray diffraction (SR-PXRD). Synthesis using glucose as the reducing agent results in direct nucleation of Bi2Te3 from Bi and Te precursors without the presence of any intermediate products, and the nucleation stage is completed in only about 1 min at 250 °C. When Sb is added, the nucleation process for Bi2–xSbxTe3 becomes slower with increasing Sb content. Depending on the Sb content and reaction temperature, an intermediate product of elemental Te nanostructures forms, and it is found to direct the m...