High-resolution Powder Diffraction Research Articles

High Resolution X-ray Diffraction Studies of the Natural Minerals of Gas Hydrates and Occurrence of Mixed Phases

The types and concentrations of gas hydrates collected from four different geological sites were analyzed using high-resolution angular dispersive X-ray powder diffraction, with synchrotron radiation as the source. Measurements were taken across a temperature range of 80 to 300 K and a pressure range of 0.1 to 80 MPa. All four gas hydrate samples showed the presence of three mixed crystal structures: structures I, II, and H. Additionally, the ice Ih structure was inherently present in all the natural gas hydrate minerals. The variation in the types and concentrations of gas hydrates can be attributed to the diversity of natural gases at different geographic locations.

Quantifying the Hydration-Dependent Dynamics of Cu Migration and Activity in Zeolite Omega for the Partial Oxidation of Methane.

Copper-exchanged zeolite omega (Cu-omega) is a potent material for the selective conversion of methane-to-methanol (MtM) via the oxygen looping approach. However, its performance exhibits substantial variation depending on the operational conditions. Under an isothermal temperature regime, Cu-omega demonstrates subdued activity below 230 °C, but experiences a remarkable increase in activity at 290 °C. Applying a high-temperature activation protocol at 450 °C causes a rapid deactivation of the material. This behavioral divergence is investigated by combining reactivity studies, neutron diffraction and in situ high-resolution anomalous X-ray powder diffraction (HR-AXRPD), as well as electron paramagnetic resonance spectroscopy, to reveal that the migration of Cu throughout the framework is the primary cause of these behaviors, which in turn is predominantly governed by the degree of hydration of the system. This work suggests that control over the Cu migration throughout the zeolite framework may be harnessed to significantly increase the activity of Cu-omega by generating more active sites for the MtM conversion. These results underscore the power of in situ HR-AXRPD for unraveling the behavior of materials under reaction conditions and suggest that a re-evaluation of Cu-zeolites priorly deemed inactive for the MtM conversion across a broader range of conditions and looping protocols may be warranted.

High-throughput and high-resolution powder X-ray diffractometer consisting of six sets of 2D CdTe detectors with variable sample-to-detector distance and innovative automation system.

The demand for powder X-ray diffraction analysis continues to increase in a variety of scientific fields, as the excellent beam quality of high-brightness synchrotron light sources enables the acquisition of high-quality measurement data with high intensity and angular resolution. Synchrotron powder diffraction has enabled the rapid measurement of many samples and various in situ/operando experiments in nonambient sample environments. To meet the demands for even higher throughput measurements using high-energy X-rays at SPring-8, a high-throughput and high-resolution powder diffraction system has been developed. This system is combined with six sets of two-dimensional (2D) CdTe detectors for high-energy X-rays, and various automation systems, including a system for automatic switching among large sample environmental equipment, have been developed in the third experimental hutch of the insertion device beamline BL13XU at SPring-8. In this diffractometer system, high-brilliance and high-energy X-rays ranging from 16 to 72 keV are available. The powder diffraction data measured under ambient and various nonambient conditions can be analysed using Rietveld refinement and the pair distribution function. Using the 2D CdTe detectors with variable sample-to-detector distance, three types of scan modes have been established: standard, single-step and high-resolution. A major feature is the ability to measure a whole powder pattern with millisecond resolution. Equally important, this system can measure powder diffraction data with high Q exceeding 30 Å-1 within several tens of seconds. This capability is expected to contribute significantly to new research avenues using machine learning and artificial intelligence by utilizing the large amount of data obtained from high-throughput measurements.

On the resolution of the three-axis neutron diffractometer setting optimized for some powder diffractometry studies

Presented three-axis neutron diffractometer performance documents the feasibility of using it in special cases high-resolution powder diffraction studies, namely, for elastic and plastic deformation studies of bulk polycrystalline samples when the whole powder diffraction spectrum is not required. Contrary to the conventional double-axis setting the suggested alternative consists of an unconventional three axis set-up employing a bent perfect crystal (BPC) monochromator and analyzer with a polycrystalline sample in between. The analysis of the profile of the beam diffracted by a sample is carried out by rocking the BPC-analyzer and the neutron signal is registered by a point detector. Though the diffractometer alternative is, for measurements, much more time consuming, its resolution is, however, substantially higher and permits also plastic deformation studies on the basis of analysis of the sample diffraction profiles. The so-called analyzer rocking curve then provides a sample diffraction profile and could reflect the lattice or structural changes. Moreover, much larger widths (up to 10 mm) of the irradiated gauge volumes can be investigated when just slightly affecting the resolution of the experimental setting.

Temperature-dependent synchrotron XRD study and electrical properties of the (1-x)BZT-(x)BCT lead-free piezoceramics

In recent years, researchers have shown the feasibility of the BZT-xBCT lead-free piezoelectric ceramics for using in various applications such as actuator, energy harvester, high-frequency ultrasonic transducer, etc. However, little evidence of temperature-dependent electrical properties of the BZT-xBCT ceramic was found. Moreover, some researchers have utilized Raman spectroscopy to observe the phase transition of the BZT-xBCT ceramic, but the Raman spectra of ferroelectric polymorphic phases are almost identical and hard to distinguish. In contrast, synchrotron radiation exhibits a high degree of monochromatization and collimation with smaller wavelength than x-ray tubes, resulting in the improvement of resolution for identifying the overlapping peaks. Therefore, this work aims to determine phase coexistence of the BZT-xBCT ceramic near phase boundary region by using high-resolution synchrotron x-ray powder diffraction in comparison with the temperature-dependent electrical properties. This work found that the occurrence of thermally-induced polymorphic phase transformations for the BZT-xBCT ceramics plays a significant role in the observed temperature-dependent electrical properties. Moreover, this work observed a trace of surface damaged layer (the presence of low-angle shoulder in the synchrotron XRD profiles) from mechanical grinding during sample preparation for XRD measurement, which has not previously been found in the BZT-xBCT ceramics. These finding will help to better understand the temperature-dependent functional properties of the BZT-xBCT ceramic for transferring into practical applications.

ISODISTROTLaMTeO6 (M = Ga3+ and Mn3+): the critical role of electronic configuration and cation ordering in crystal structures.

In this work, PbSb2O6-type oxides LaMTeO6 (M = Ga3+ and Mn3+) were synthesized and structurally characterized by Rietveld refinements against high-resolution X-ray powder diffraction data. The Ga3+/Te6+ partial ordering within the honeycomb-like two-dimensional [GaTeO6]3- anionic layer leads to the loss of the inversion center between Ga3+ and Te6+; however the inversion center on the 3̄-roto-inversion axis is preserved, thereby resulting in a 2-fold PbSb2O6-type superstructure by doubling the c-axis associated with a structural symmetry descending from the original P3̄1m to P3̄1c symmetry. In contrast, LaMnTeO6 (P21/c) adopts a monoclinically distorted 4-fold superstructure with lattice dimensions of a ≈ aH, b ≈ √3aH, c ≈ 2cH, where aH and cH represent the lattice parameters of trigonal PbSb2O6. The formation of this P21/c-superstructure is attributed to the combination of complete Mn3+/Te6+ ordering and the first-order Jahn-Teller distortion of Mn3+ with the electronic configuration of d4. Such a monoclinic distortion can effectively lift the Mn3+ spin moments arranged on the triangular sublattice, resulting in a sharp peak for antiferromagnetic transition, which is in stark contrast to subtle magnetic transitions for PbSb2O6-type tellurates AMn(VI)TeO6 (A = alkaline earth and Pb2+) and LnCrTeO6 (Ln = rare earth) with higher structural symmetry. Our findings highlight that the electronic configuration effects of M-cations play a critical role in controlling the structure symmetry of LaMTeO6, providing a strategy to fine-tune the crystal structures and physical properties.

Geometric and Hydrophilic Effects of Oxirane Compounds with a Four-Carbon Backbone on Clathrate Hydrate Formation.

The physicochemical properties of clathrate hydrates are influenced by the chemical nature and three-dimensional (3D) geometry of the added molecules. This study investigates the effects of five oxirane compounds: cis-2,3-epoxybutane (c23EB), trans-2,3-epoxybutane (t23EB), 1,2-epoxybutane (12EB), 1,2,3,4-diepoxybutane (DEB), and 3,3-dimethylepoxybutane (33DMEB) on CH4 hydrate formation. Despite having a four-carbon backbone, these compounds differ in their 3D geometries. The structures and stabilities of CH4 hydrates containing each compound were analyzed using high-resolution powder diffraction, solid-state 13C NMR, and phase equilibrium measurements. The experimental results revealed that c23EB, 12EB, and 33DMEB act as sII/sH hydrate formers and thermodynamic promoters, whereas t23EB and DEB have opposite roles. These results were analyzed in relation to the 3D geometries and relative stabilities of various rotational isomers using DFT calculations. Hydrate structure was influenced by both the length and thickness of the added compounds. Moreover, an appropriate level of (not excessive) hydrophilicity induced by an oxirane group appeared to enhance the thermodynamic stability of the hydrates. This study provides insights into how the chemical nature of additives influences the structure and stability of clathrate hydrates.

A-Site Cation Disorder in SrxBa1-xNb2O6 (x = 0.25, 0.33, 0.50, 0.61) Studied by High-Resolution Resonant X-ray Powder Diffraction.

The dielectric and ferroelectric properties of SrxBa1-xNb2O6 (SBN, 0.2 < x < 0.8) are known to be affected by the Sr fraction and can be further controlled by various quenching schemes. Changes in A-site cation configuration are believed to be linked to these changes in properties. In this work, we study the A-site cation disorder in SBN by the use of high-resolution resonant X-ray powder diffraction. The experimental results show that the larger Ba2+ is found exclusively on the larger A2 site, while Sr2+ is found on both the A1 and A2 sites, with an increasing amount on A2 with an increasing Sr fraction. At elevated temperatures, a small migration of Sr2+ from A1 to A2 is observed for SBN50 and SBN61. Linking this change in occupancies to changes in the average cation size on the A1 and A2 sites allows for rationalization of the property changes observed for quenched samples. Furthermore, SBN25 is shown to deviate from the tetragonal P4bm structure and is found to be orthorhombic with a Cmm2 structure.

Revisiting the structures and phase transitions of Ba2NaNb5O15.

The room-temperature and low-temperature structure(s) of Ba2NaNb5O15 (BNN) have been debated since the structure was proposed in the 1960s. This work revisits the structures and phase transitions of BNN, combining high-resolution X-ray and neutron powder diffraction with density functional theory calculations. Temperature-dependent high-resolution X-ray powder diffraction patterns are collected from 4 to 918 K, and sequential batch Rietveld refinement using a symmetry mode approach to describe the structure is used to extract the main structural changes as a function of temperature. The data show that the average structure of BNN is best described by the Ama2 space group, and no other structural phase transitions were observed below the ferroelastic transition. The symmetry mode analysis, combining results from diffraction and density functional theory, shows significant octahedral tilting and corrugations of both the A1 and A2 sites along the c direction. A strong correlation between the spontaneous strain and the octahedral tilting was observed, and a potential connection with emerging microstructure at low temperatures is proposed, all enabled by the symmetry mode approach used in this work.

Mixed A-site occupancy in Sr x Ba1−x Nb2O6 studied by high-resolution resonant X-ray powder diffraction

Mixed <i>A</i>-site occupancy in Sr_<i>x</i>Ba_1−<i>x</i>Nb₂O₆ studied by high-resolution resonant X-ray powder diffraction

High-throughput and high-resolution powder diffraction measurement system for accelerating green materials science and engineering

High-throughput and high-resolution powder diffraction measurement system for accelerating green materials science and engineering

Exploring water harvesting potential in CAU-10-H: an in situ high-resolution powder diffraction study

Exploring water harvesting potential in CAU-10-H: an <i>in situ</i> high-resolution powder diffraction study

High-resolution powder diffraction data collection on beamline ID22 at ESRF

High-resolution powder diffraction data collection on beamline ID22 at ESRF

Structural effects of Mn-substitution in β-FeSe

In the present work the structural and microstructural properties of Mn substituted β-FeSe are inspected by using high-resolution synchrotron X-ray powder diffraction data collected between 10 K and 150 K. It is demonstrated that the thermal increase of the structural strain in the tetragonal phase progressively breaks the 4-fold symmetry at the local scale, qualitatively tracing the development of anisotropy measured in some physical properties, generally ascribed to nematicity. This result points to a close relationship and interplay between structural strain and physical properties; with this notion, the structural strain can be considered as the origin of the unexpected anisotropy observed in some physical properties. Remarkably, incommensurate satellite peaks are observed in the diffraction pattern collected in the low-temperature orthorhombic phase field, likely related to the occurrence of a charge-density-wave instability.

Anharmonicity effects and thermal expansion of thermoelectric (M,M’,M”)NiSn (M,M’,M”=Ti, Zr, Hf) half-Heusler alloys

High-resolution synchrotron radiation X-ray powder diffraction was used for the structural characterization of half-Heusler alloys with compositions MNiSn, M0.5M′0.5NiSn, and M0.5M′0.25M”0.25NiSn ((M, M′, M”) = Ti, Zr, Hf). These alloys were synthesized by arc melting and subsequent thermal annealing. Rietveld refinements of the room temperature patterns revealed that the unit cell parameter is larger for ZrNiSn and smaller for TiNiSn, in accordance with the respective atomic radii. The site occupation of each atomic species exhibited similar trends to those reported in the literature. The values of the linear coefficient of thermal expansion (α) for all the investigated phases within the alloys are < 10−5 K−1. In addition, the value of the Debye temperature (θD) is estimated by analyzing the temperature dependence of the isotropic atomic displacement parameters. In the case of these half-Heusler alloys, it is observed that a lower θD corresponds to a lower α. The good agreement between the temperature dependence of the Debye temperature and the calculated values using the Thirring-Stern expansion enables us to demonstrate the significant role of anharmonicity: the lighter the compound, the lower the anharmonicity. Furthermore, we also discuss the implications of anharmonicity on the thermal conductivity of this family of half-Heusler compounds at room temperature.

Cd-Doped Li4–xCdxTi5O12 (x = 0.20) as a High Rate Capable and Stable Anode Material for Lithium-Ion Batteries

Li4Ti5O12 (LTO), an excellent anode for lithium-ion batteries (LIBs), suffers from low electronic conductivity, limiting its high-power rate application. An aliovalent metal ion doping strategy that tunes the electronic/ionic conductivity can mitigate this issue. In this work, we investigated a series of Cd2+ dopings on the Li4–xCdxTi5O12 (x = 0, 0.05, 0.10, and 0.20) anode material by considering its effect on structural and electrochemical performance in Li- and Na-ion batteries. Combined Rietveld refinement and X-ray absorption spectroscopy (XAS) analysis explicitly identified Cd2+ doping into the Li(8a) tetrahedral site of the cubic spinel LTO structure. According to high-resolution powder diffraction (HRPD), scanning electron microscopy (SEM), 4-point probe, and X-ray photoelectron spectroscopy (XPS), an increase in Cd2+ doping from 5 to 20% at the Li (8a) site in the LTO results in a reduction in particle size, an expansion of lattice, an increase in conductivity, and an increase in Ti3+ content to Ti4+ ratio. High-resolution scanning transmission electron microscopy (HR-STEM) confirms that cadmium ions are interstitially doped in the LTO structure. Compared to the pristine LTO electrode in the Li half cell, the Li3.80Cd0.20Ti5O12 (Cd0.20-LTO) electrode showed a significant improvement in capacity at high rates and excellent cycling performance. The improvement in performance for Cd0.20-doped LTO is a consequence of the reduction in the diffusion path and the faster Li-ion kinetics. Therefore, this Cd-doped LTO series of electrodes demonstrates advantageous features for Li-ion battery systems.

Nature of magnetic transitions and evidence for magnetoelastic coupling in the biskyrmion-host hexagonal compound MnNiGa

The hexagonal compound MnNiGa with Ni2In-type structure has emerged as an important biskyrmion-host system in which these textures are super-stable over a wide temperature range extending from 16 K to the Curie temperature TC ∼350 K under moderate fields. Both the intensity of the external magnetic field and the presence of magnetoelastic coupling are known to play key role in the stability of the skyrmionic textures. Here we present the results of the first comprehensive investigation of the order of the phase transitions and its field dependence along with magnetoelastic (i.e., spin-lattice) coupling using a combined magnetization and high-resolution synchrotron x-ray powder diffraction (SXRPD) study of MnNiGa. The temperature dependence of the magnetization M(T) exhibits a paramagnetic to collinear ferromagnetic (FM) transition at TC (∼347 ± 0.5 K) with thermal hysteresis and negative slope in the Arrott plots across the TC suggesting its first order character. The M(T) plot in the collinear FM phase exhibits an anomalously decreasing behaviour after reaching its peak value at 300 K followed by a step-like change below 210 K due to an additional spin reorientation transition (SRT) to a non-collinear FM phase with TSRT∼200 ± 1 K. The SRT also shows thermal hysteresis characteristic of a first order phase transition. Our field dependent studies reveal stabilization of the collinear FM phase to higher temperatures and destabilization of the SRT transition setting an upper limit on the magnetic field for the observation of biskyrmions in this system. The Rietveld analysis of the SXRPD data reveals anomalies in the unit cell parameters at TC and TSRT without any change in the crystal symmetry. The modelling of the temperature dependence of the unit cell volume in terms of the Debye-Grüneisen equation reveals significant deviation from phonon contributions and the presence of the quadratic spin-lattice coupling below the FM TC, in the precursor SRT regime as well as below TSRT. The present results on the magnetoelastic coupling in the hexagonal MnNiGa may provide the necessary insight towards understanding the extreme sensitivity of the magnetic skyrmionic textures to external stresses.

Electron doping of a double-perovskite flat-band system

Electronic structure calculations indicate that the Sr2FeSbO6 double perovskite has a flat-band set just above the Fermi level that includes contributions from ordinary subbands with weak kinetic electron hopping plus a flat subband that can be attributed to the lattice geometry and orbital interference. To place the Fermi energy in that flat band, electron-doped samples with formulas Sr2-xLaxFeSbO6 (0 ≤ x ≤ 0.3) were synthesized, and their magnetism and ambient temperature crystal structures were determined by high-resolution synchrotron X-ray powder diffraction. All materials appear to display an antiferromagnetic-like maximum in the magnetic susceptibility, but the dominant spin coupling evolves from antiferromagnetic to ferromagnetic on electron doping. Which of the three subbands or combinations is responsible for the behavior has not been determined.

High pO2 Flux Growth and Characterization of NdNiO3 Crystals

Single crystals of the perovskite nickelate NdNiO3 with dimensions of up to 50 μm on edge have been successfully grown using the flux method at a temperature of 400 °C and oxygen pressure of 200 bar. The crystals were investigated by a combination of techniques, including high-resolution synchrotron X-ray single-crystal and powder diffraction and physical property measurements such as magnetic susceptibility and resistivity. Resistivity measurements revealed a metal-insulator transition (MIT) at TMIT~180 K with apparent thermal hysteresis; however, no superlattice peaks or peak splitting below TMIT, which corresponds to a structural transition from Pbnm to P21/n, was observed. The successful growth of NdNiO3 crystals at relatively low temperatures and oxygen pressure provides an alternative approach for preparing single crystals of interesting perovskites such as RNiO3 (R = Sm-Lu) and parent phases of superconducting square planar nickelates.

Enhancement of oxygen adsorption using biomass-based oxidized porous carbon

The porous carbon adsorbent walnut-shell precursors-based biomass using the Hummer synthesis method was developed for oxidized porous carbon adsorbent. Adsorption-desorption of N2, high-resolution transmission electron microscopy (HRTEM), FESEM, FTIR spectra, and X-ray powder diffraction analyses were used to evaluate the morphology and structure of the specimens. The oxidized porous carbon adsorbent possessed a specific surface area (217.34 m2/g) and pore volume (0.1524 cm3/g). The oxidization process reduced the average volume of mesopores and micropores. Although the specific surface area of the oxidized sample was reduced, the oxygen adsorption capacity was improved by more than 1.4 times. Under 298 K and 9.55 bar pressure, the greatest adsorption capacities for oxygen and nitrogen were specified to be 4.11 (mmol/g) and 3.03 (mmol/g), respectively. The oxygen and nitrogen adsorption on the porous carbon closely was matched by the Fractional-order kinetic and Sips isotherm models, and thermodynamic analysis demonstrated that the physisorption process was confirmed. The improved adsorbent's oxygen adsorption selectivity was remarkable. Oxygen and nitrogen adsorption were increased by oxidized adsorbent by 40% and 14%, respectively. Ultimately, oxygen can be adsorbed by the oxidized sample with more efficiency than nitrogen gas.