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Acta Crystallographica. Section A,... Sep 2021In a powder diffraction experiment the resolution function defines the instrumental contribution to the peak widths as a function of the Bragg angle. The Caglioti...
In a powder diffraction experiment the resolution function defines the instrumental contribution to the peak widths as a function of the Bragg angle. The Caglioti formula is frequently applied to model the instrumental broadening and used in structural refinement. The parameters in the Caglioti formula are linked to physically meaningful parameters for most diffraction geometries. However, this link is lost for the now very popular powder diffraction geometry using large 2D area detectors. Here we suggest a new physical model for the instrumental broadening specifically developed for powder diffraction data measured with large 2D area detectors. The model is verified using data from two synchrotron diffraction beamlines with the Pilatus2M and MAR345 detectors. Finally, a functional form is proposed to replace the Caglioti formula for this geometry in the Rietveld method and profile refinements.
PubMed: 34473102
DOI: 10.1107/S2053273321007506 -
Geoderma Oct 2020Soil mineral compositions are often complex and spatially diverse, with each mineral exhibiting characteristic chemical properties that determine the intrinsic total...
Soil mineral compositions are often complex and spatially diverse, with each mineral exhibiting characteristic chemical properties that determine the intrinsic total concentration of soil nutrients and their phyto-availability. Defining soil mineral-nutrient relationships is therefore important for understanding the inherent fertility of soils for sustainable nutrient management, and data-driven approaches such as cluster analysis allow for these relations to be assessed in new detail. Here the fuzzy-c-means clustering algorithm was applied to an X-ray powder diffraction (XRPD) dataset of 935 soils from sub-Saharan Africa, with each diffractogram representing a digital signature of a soil's mineralogy. Nine mineralogically distinct clusters were objectively selected from the soil mineralogy continuum by retaining samples exceeding the quantile of the membership coefficients in each cluster, yielding a dataset of 239 soils. As such, samples within each cluster represented mineralogically similar soils from different agro-ecological environments of sub-Saharan Africa. Mineral quantification based on the mean diffractogram of each cluster illustrated substantial mineralogical diversity between the nine groups with respect to quartz, K-feldspar, plagioclase, Fe/Al/Ti-(hydr)oxides, phyllosilicates (1:1 and 2:1), ferromagnesians, and calcite. Mineral-nutrient relationships were defined using the clustered XRPD patterns and corresponding measurements of total and/or extractable (Mehlich-3) nutrient concentrations (B, Mg, K, Ca, Mn, Fe, Ni, Cu and Zn) in combination with log-ratio compositional data analysis. Fe/Al/Ti/Mn-(hydr)oxides and feldspars were found to be the primary control of total nutrient concentrations, whereas 2:1 phyllosilicates were the main source of all extractable nutrients except for Fe and Zn. Kaolin minerals were the most abundant phyllosilicate group within the dataset but did not represent a nutrient source, which reflects the lack of nutrients within their chemical composition and their low cation exchange capacity. Results highlight how the mineral composition controls the total nutrient reserves and their phyto-availability in soils of sub-Saharan Africa. The typical characterisation of soils and their parent material based on the clay particle size fraction (i.e. texture) and/or the overall silica component (i.e. acid and basic rock types) alone may therefore mask the intricacies of mineral contributions to soil nutrient concentrations.
PubMed: 33012837
DOI: 10.1016/j.geoderma.2020.114474 -
Journal of Applied Crystallography Oct 2022Powder X-ray diffraction (PXRD) and neutron powder diffraction (NPD) have been used to investigate the crystal structure of CoFeO nanoparticles prepared different...
Powder X-ray diffraction (PXRD) and neutron powder diffraction (NPD) have been used to investigate the crystal structure of CoFeO nanoparticles prepared different hydro-thermal synthesis routes, with particular attention given to accurately determining the spinel inversion degrees. The study is divided into four parts. In the first part, the investigations focus on the influence of using different diffraction pattern combinations (NPD, Cu-source PXRD and Co-source PXRD) for the structural modelling. It is found that combining PXRD data from a Co source with NPD data offers a robust structural model. The second part of the study evaluates the reproducibility of the employed multipattern Rietveld refinement procedure using different data sets collected on the same sample, as well as on equivalently prepared samples. The refinement procedure gives reproducible results and reveals that the synthesis method is likewise reproducible since only minor differences are noted between the samples. The third part focuses on the structural consequences of (i) the employed heating rate (achieved using three different hydro-thermal reactor types) and (ii) changing the cobalt salt in the precursors [aqueous salt solutions of Co(CHCOOH), Co(NO) and CoCl] in the synthesis. It is found that increasing the heating rate causes a change in the crystal structure (unit cell and crystallite sizes) while the Co/Fe occupancy and magnetic parameters remain similar in all cases. Also, changing the type of cobalt salt does not alter the final crystal/magnetic structure of the CoFeO nanoparticles. The last part of this study is a consideration of the chemicals and parameters used in the synthesis of the different samples. All the presented samples exhibit a similar crystal and magnetic structure, with only minor deviations. It is also evident that the refinement method used played a key role in the description of the sample.
PubMed: 36249502
DOI: 10.1107/S1600576722008123 -
Physical Review Letters May 2022A potential for propagation of a wave in two dimensions is constructed from a random superposition of plane waves around all propagation angles. Surprisingly, despite...
A potential for propagation of a wave in two dimensions is constructed from a random superposition of plane waves around all propagation angles. Surprisingly, despite the lack of periodic structure, sharp Bragg diffraction of the wave is observed, analogous to a powder diffraction pattern. The scattering is partially resonant, so Fermi's golden rule does not apply. This phenomenon would be experimentally observable by sending an atomic beam into a chaotic cavity populated by a single mode laser.
PubMed: 35657885
DOI: 10.1103/PhysRevLett.128.200402 -
Journal of Synchrotron Radiation Jan 2023In situ synchrotron high-energy X-ray powder diffraction (XRD) is highly utilized by researchers to analyze the crystallographic structures of materials in functional...
In situ synchrotron high-energy X-ray powder diffraction (XRD) is highly utilized by researchers to analyze the crystallographic structures of materials in functional devices (e.g. battery materials) or in complex sample environments (e.g. diamond anvil cells or syntheses reactors). An atomic structure of a material can be identified by its diffraction pattern along with a detailed analysis of the Rietveld refinement which yields rich information on the structure and the material, such as crystallite size, microstrain and defects. For in situ experiments, a series of XRD images is usually collected on the same sample under different conditions (e.g. adiabatic conditions) yielding different states of matter, or is simply collected continuously as a function of time to track the change of a sample during a chemical or physical process. In situ experiments are usually performed with area detectors and collect images composed of diffraction patterns. For an ideal powder, the diffraction pattern should be a series of concentric Debye-Scherrer rings with evenly distributed intensities in each ring. For a realistic sample, one may observe different characteristics other than the typical ring pattern, such as textures or preferred orientations and single-crystal diffraction spots. Textures or preferred orientations usually have several parts of a ring that are more intense than the rest, whereas single-crystal diffraction spots are localized intense spots owing to diffraction of large crystals, typically >10 µm. In this work, an investigation of machine learning methods is presented for fast and reliable identification and separation of the single-crystal diffraction spots in XRD images. The exclusion of artifacts during an XRD image integration process allows a precise analysis of the powder diffraction rings of interest. When it is trained with small subsets of highly diverse datasets, the gradient boosting method can consistently produce high-accuracy results. The method dramatically decreases the amount of time spent identifying and separating single-crystal diffraction spots in comparison with the conventional method.
PubMed: 36601933
DOI: 10.1107/S1600577522011274 -
Journal of Synchrotron Radiation Jan 2021For high-resolution powder diffraction in material science, high photon energies are necessary, especially for in situ and in operando experiments. For this purpose, a...
For high-resolution powder diffraction in material science, high photon energies are necessary, especially for in situ and in operando experiments. For this purpose, a multi-analyser detector (MAD) was developed for the high-energy beamline P02.1 at PETRA III of the Deutsches Elektronen-Synchrotron (DESY). In order to be able to adjust the detector for the high photon energies of 60 keV, an individually adjustable analyser-crystal setup was designed. The adjustment is performed via piezo stepper motors for each of the ten channels. The detector shows a low and flat background as well as a high signal-to-noise ratio. A range of standard materials were measured for characterizing the performance. Two exemplary experiments were performed to demonstrate the potential for sophisticated structural analysis with the MAD: (i) the structure of a complex material based on strontium niobate titanate and strontium niobate zirconate was determined and (ii) an in situ stroboscopy experiment with an applied electric field on a highly absorbing piezoceramic was performed. These experiments demonstrate the capabilities of the new MAD, which advances the frontiers of the structural characterization of materials.
PubMed: 33399563
DOI: 10.1107/S1600577520013223 -
Acta Crystallographica. Section A,... Mar 2021Powder X-ray diffraction has some inherent advantages over traditional single-crystal X-ray diffraction in accurately determining electron densities and structural...
Powder X-ray diffraction has some inherent advantages over traditional single-crystal X-ray diffraction in accurately determining electron densities and structural parameters due to the lower requirements for sample crystallinity, simpler corrections and measurement simultaneity. For some simple inorganic materials, it has been shown that these advantages can compensate for disadvantages such as peak overlap and error-prone background subtraction. Although it is challenging to extend powder X-ray diffraction-based electron-density studies to organic materials with significant peak overlap, previous results using a dedicated vacuum diffractometer with a large image-plate camera (AVID) demonstrated that it can be done. However, the vacuum setup with the off-line detector system was found to prohibit a widespread use. Fast microstrip detectors, which have been employed at a number of powder diffraction beamlines, have the potential to facilitate electron-density studies. Nevertheless, no electron-density studies even for materials with slight peak overlap have been performed with microstrip detectors. One of the most critical problems has been a difference in sensitivity between microstrip channels, which substantially defines the dynamic range of a detector. Recently, a robust approach to this problem has been developed and applied to a total scattering measurement system (OHGI) with 15 MYTHEN microstrip modules. In the present study, synchrotron powder X-ray diffraction data obtained with OHGI are evaulated in terms of multipole electron densities and structural parameters (atomic positions and displacement parameters). These results show that, even without a dedicated setup and perfect samples, electron-density modelling can be carried out on high-quality powder X-ray diffraction data. However, it was also found that the required prior information about the sample prohibits widespread use of the method. With the presently obtainable data quality, electron densities of molecular crystals in general are not reliably obtained from powder data, but it is an excellent, possibly superior, alternative to single-crystal measurements for small-unit-cell inorganic solids. If aspherical atomic scattering factors can be obtained from other means (multipole databases, theoretical calculations), then atomic positions (including for hydrogen) and anisotropic atomic displacement parameters (non-hydrogen atoms) of excellent accuracy can be refined from synchrotron powder X-ray diffraction data on organic crystals.
PubMed: 33646194
DOI: 10.1107/S2053273320016605 -
Journal of Applied Crystallography Jun 2022A description is given of the program . This program is used for visualizing powder diffraction data and models published in powder CIF format (pdCIF). In particular,...
A description is given of the program . This program is used for visualizing powder diffraction data and models published in powder CIF format (pdCIF). In particular, support for the visualization of multi-pattern data sets, such as diffraction experiments, is provided by means of stack and surface plots. is written in Python 3 and can run wherever a compatible runtime is available. macros for the production of pdCIF files are also presented.
PubMed: 35719308
DOI: 10.1107/S1600576722003478 -
Acta Crystallographica. Section E,... Dec 2023Reaction of FeCl·4HO with KSCN and 3-cyano-pyridine (pyridine-3-carbo-nitrile) in ethanol accidentally leads to the formation of single crystals of...
Reaction of FeCl·4HO with KSCN and 3-cyano-pyridine (pyridine-3-carbo-nitrile) in ethanol accidentally leads to the formation of single crystals of Fe(NCS)(Cl)(3-cyano-pyridine) or [FeCl(NCS)(CHN)]. The asymmetric unit of this compound consists of one Fe cation, one chloride and one thio-cyanate anion that are located on a fourfold rotation axis as well as of one 3-cyano-pyridine coligand in a general position. The Fe cations are sixfold coordinated by one chloride anion and one terminally N-bonding thio-cyanate anion in -positions and four 3-cyano-pyridine coligands that coordinate the pyridine N atom to the Fe cations. The complexes are arranged in columns with the chloride anions, with the thio-cyanate anions always oriented in the same direction, which shows the non-centrosymmetry of this structure. No pronounced inter-molecular inter-actions are observed between the complexes. Initially, FeCl and KSCN were reacted in a 1:2 ratio, which lead to a sample that contains the title compound as the major phase together with a small amount of an unknown crystalline phase, as proven by powder X-ray diffraction (PXRD). If FeCl and KSCN is reacted in a 1:1 ratio, the title compound is obtained as a nearly pure phase. IR investigations reveal that the CN stretching vibration for the thio-cyanate anion is observed at 2074 cm, and that of the cyano group at 2238 cm, which also proves that the anionic ligands are only terminally bonded and that the cyano group is not involved in the metal coordination. Measurements with thermogravimetry and differential thermoanalysis reveal that the title compound decomposes at 169°C when heated at a rate of 4°C min and that the 3-cyano-pyridine ligands are emitted in two separate poorly resolved steps. After the first step, an inter-mediate compound with the composition Fe(NCS)(Cl)(3-cyano-pyridine) of unknown structure is formed, for which the CN stretching vibration of the thio-cyanate anion is observed at 2025 cm, whereas the CN stretching vibration of the cyano group remain constant. This strongly indicates that the Fe cations are linked by μ-1,3-bridg-ing thio-cyanate anions into chains or layers.
PubMed: 38313120
DOI: 10.1107/S205698902300988X -
Journal of Pharmaceutical Sciences Jan 2022The purpose of this study is to investigate the effects of dry and wet mechanochemical synthesis on piroxicam (PX) and saccharin (SA) mixtures. For this purpose, PX and...
Dry and Wet Mechanochemical Synthesis of Piroxicam and Saccharin Co-Crystals and Evaluation by Powder X-Ray Diffraction, Thermal Analysis and Mid- and Near- Infrared Spectroscopy.
The purpose of this study is to investigate the effects of dry and wet mechanochemical synthesis on piroxicam (PX) and saccharin (SA) mixtures. For this purpose, PX and SA mixtures prepared by wet mechanochemical processes using three solvents and by dry mechanochemical synthesis were evaluated by mid-and near-infrared spectroscopy, powder X-ray diffraction (PXRD), and differential scanning calorimetry (DSC). The mixtures of wet-type products were transformed into PX/SA 1:1 co-crystals. The effect of the solvent was key to the co-crystallization of PX and SA. The products from the dry process were transformed into the amorphous phase. For the sample of the amorphous mixture, two exothermic peaks due to crystallization were observed in the thermal analysis. Bulk PX was ground for the same number of times for transformation, but was not successfully transformed to the amorphous bulk; the same was observed for SA. It is suggested that the mutual existence of PX and SA promotes mutual amorphization.
Topics: Calorimetry, Differential Scanning; Piroxicam; Powder Diffraction; Powders; Saccharin; Solubility; Spectroscopy, Fourier Transform Infrared; Spectroscopy, Near-Infrared; X-Ray Diffraction
PubMed: 34139260
DOI: 10.1016/j.xphs.2021.06.024