Multipeak fitting analysis of Raman spectra on DLCH film

The hydrogenated diamond‐like carbon (DLCH) film with 1‐µm thickness is deposited by direct hydrocarbon gas ion beam method on silicon wafer and annealed at 400 °C. Detailed Raman spectra feature are fitted from nine sets of different peak fitting functions, including Gaussian, Lorentzian and Breit‐Wigner‐Fano (BWF) functions. These fitting results obtained from a two‐peak combination show some specific variances on the G peak position, FWHM_G and I_D/I_G ratio for as‐deposited and as‐annealed DLCH films. The most popular two‐peak fitting method with full Gaussian function tends to exhibit a higher ratio of the G peak position shift and higher I_D/I_G ratio than others fitting methods, the drastic difference among the most popular G (G) & G (D) and B (G) & L (D) schemes also have brought out in I_D/I_G ratio. However, for a more complex four‐peak Gaussian function fitting Raman spectra, the I_D/I_G ratio is close to that of a two‐peak fitting function with a mixture functions of BWF (G) and L (D). Furthermore, a series of systematic peak fitting procedures and comparisons of Raman spectra have been discussed in this study. Copyright © 2009 John Wiley & Sons, Ltd.     

Fast X‐ray powder diffraction on I11 at Diamond

The commissioning and performance characterization of a position‐sensitive detector designed for fast X‐ray powder diffraction experiments on beamline I11 at Diamond Light Source are described. The detecting elements comprise 18 detector‐readout modules of MYTHEN‐II silicon strip technology tiled to provide 90° coverage in 2θ. The modules are located in a rigid housing custom designed at Diamond with control of the device fully integrated into the beamline data acquisition environment. The detector is mounted on the I11 three‐circle powder diffractometer to provide an intrinsic resolution of Δ2θ? 0.004°. The results of commissioning and performance measurements using reference samples (Si and AgI) are presented, along with new results from scientific experiments selected to demonstrate the suitability of this facility for powder diffraction experiments where conventional angle scanning is too slow to capture rapid structural changes. The real‐time dehydrogenation of MgH₂, a potential hydrogen storage compound, is investigated along with ultrafast high‐throughput measurements to determine the crystallite quality of different samples of the metastable carbonate phase vaterite (CaCO₃) precipitated and stabilized in the presence of amino acid molecules in a biomimetic synthesis process.     

Model‐independent structure factors from powder X‐ray diffraction: a novel approach

Under the experimental condition that all Bragg peaks in a powder X‐ray diffraction (PXRD) pattern have the same shape, one can readily obtain the Bragg intensities without fitting any parameters. This condition is fulfilled at the P02.1 beamline at PETRA III using the seventh harmonic from a 23 mm‐period undulator (60 keV) at a distance of 65 m. For grain sizes of the order of 1 µm, the Bragg peak shape in the PXRD is entirely determined by the diameter of the capillary containing the powder sample and the pixel size of the image plate detector, and consequently it is independent of the scattering angle. As an example, a diamond powder has been chosen and structure factors derived which are in accordance with those calculated from density functional theory methods of the WIEN2k package to within an accuracy that allows a detailed electron density analysis.     

Characterization of ashes from greenhouse crops plant biomass residues using X‐ray fluorescence analysis and X‐ray diffraction

A characterization of ashes obtained by thermal treatments on greenhouse crops plant biomass residues is presented. The chemical analysis, by X‐ray fluorescence (wavelength‐dispersive X‐ray fluorescence), and phase analysis, by X‐ray diffraction, of the resultant ashes are reported. Thermal treatments of selected samples of these residues increase the relative amounts of inorganic Mg, Si, P, and S in the ashes, being these amounts as high as increasing temperature. As an opposite effect, Na, Cl, and K contents decrease as increasing temperature by a volatilization process of the chlorides, as confirmed by X‐ray diffraction. The crystalline phase analysis of the ashes demonstrates the formation of inorganic constituents of the biomass, including alkaline chlorides and calcium salts (calcite, anhydrite, and apatite). Progressive thermal treatments induce the formation of new silicate phases (akermanite and grossularite) and silica (α‐quartz and cristobalite). Furthermore, the particle size of the starting biomass samples does not influence the evolution of the crystalline phases by thermal treatments. In contrast, a previous leaching using water and subsequent heating at 1,000 °C produces the formation of periclase (MgO), lime (CaO), and the silicate gehlenite, without the presence of anhydrite. This study is interesting for future investigations on the residues as a profitable biomass source for energy production and sustainable large‐scale management. Some potential applications of the resultant ashes can be proposed.     

Micro‐Raman spectroscopy on analcime and pollucite in comparison to X‐ray diffraction

Natural and synthetic samples of analcime and pollucite (both zeolites belonging to the analcime group) were studied by means of micro‐Raman spectrometry, X‐ray fluorescence analysis (XFA) and X‐ray diffraction (XRD). On knowing the chemical and structural characteristics of each solid‐solution member, the observed shift in the spectral position of the Raman active modes can be explained and used for phase determination. As shown, the distinction between members of the analcime–pollucite solid‐solution series using Raman spectroscopy is significantly more conclusive than the corresponding XRD findings. Also, information about the structurally bound water inside the zeolite structure can be gained using Raman spectroscopy as long as a suitable exciting wavelength is selected. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman scattering and X‐ray diffraction on YBiTi2O7 prepared at low temperature

The conditions of preparation of a pure YBiTi₂O₇ phase by sol–gel were optimised. A single phase was obtained at temperature as low as 800 °C when triethanolamine/diethanolamine was used as additional ligands. The expected composition was confirmed by energy dispersive spectroscopy (EDS) and X‐ray diffraction (XRD). YBiTi₂O₇ exhibits the pyrochlore structure with a unit‐cell parameter of 10.2117(5) Å. This structure was confirmed by Raman spectroscopy, which revealed a shift of the main E_g mode towards lower wavenumbers when bismuth is introduced in the structure. Broad bands were observed for all the recorded spectra, which characterise rather a disorder due to bismuth III cations in the structure than an effect of particle size. This study confirmed the possibility to lower the temperature of preparation of pyrochlores containing bismuth, which could be of interest as photocatalyst for the decomposition of organic and toxic materials. Copyright © 2008 John Wiley & Sons, Ltd.     

Identification and spectra–structure determination of soil minerals: Raman study supported by IR spectroscopy and X‐ray powder diffraction

Raman and IR spectroscopy were used for the characterization of several minerals in morphologically similar vertisol sequences from Kiževak (Serbia). It helped us to establish the surface layer transition going from calcic vertisols (containing gypsum and calcite) to calcimagnesic vertisols (containing aragonite, magnesium‐calcite and dolomite) derived from peridotite and serpentinite. The observed band positions are found to be solely characteristic for each carbonate mineral and are used to discuss the main structural features of carbonates and sulfates present in the studied soil. It was found that the dolomite, calcite and aragonite concretions are present in the deepest layer of the soil, whereas the gypsum is found in the topsoil. The identification was confirmed of the carbonates having calcite and aragonite structure, and the representative from the sulfate group (gypsum) was confirmed by X‐ray powder diffraction. Copyright © 2009 John Wiley & Sons, Ltd.     

In situ synchrotron X‐ray diffraction analysis of deformation behaviour in Ti–Ni‐based thin films

Deformation mechanisms of as‐deposited and post‐annealed Ti_50.2Ni_49.6, Ti_50.3Ni_46.2Cu_3.5 and Ti_48.5Ni_40.8Cu_7.5 thin films were investigated using the in situ synchrotron X‐ray diffraction technique. Results showed that initial crystalline phases determined the deformation mechanisms of all the films during tensile loading. For the films dominated by monoclinic martensites (B19′), tensile stress induced the detwinning of 〈011〉 type‐II twins and resulted in the preferred orientations of (002)_B19′ parallel to the loading direction (∥ LD) and (020)_B19′ perpendicular to the LD (⊥ LD). For the films dominated by austenite (B2), the austenite directly transformed into martensitic variants (B19′) with preferred orientations of (002)_B19′ ∥ LD and (020)_B19′ ⊥ LD. For the Ti_50.3Ni_46.2Cu_3.5 and Ti_48.1Ni_40.8Cu_7.5 films, martensitic transformation temperatures decreased apparently after post‐annealing because of the large thermal stress generated in the films due to the large differences in thermal expansion coefficients between the film and substrate.     

Polarization analysis in soft X‐ray diffraction to study magnetic and orbital ordering

An experimental approach to the analysis of charge, magnetic and orbital ordering in 3d transition‐metal oxides is presented. The technique combines two important components: azimuthal rotations around the Bragg wavevector and polarization analysis of the Bragg intensities in the range 500–900 eV. The polarization analysis is performed using graded multilayers, which are translated and rotated in the vacuum chamber. It is shown why these two components are important to determine the origin of the Bragg scattered signals and how they allow us to separate the different contributions. Examples are given for the oxygen K and the Mn, Co, Ni and Cu L_2,3‐edges, and the advantages and drawbacks of this experimental technique are discussed.     

An assessment study of tiles from Topkapı Palace Museum with energy‐dispersive X‐ray and Raman spectrometers

A limited number of studies concerning Ottoman ceramic technology have been performed using the scanning electron microscopy‐energy dispersive X‐ray spectrometry and micro‐Raman spectroscopy techniques. The discovery of the ceramics, which were described as ‘Iznik’, at excavation sites outside of the city of Iznik, caused disagreements over the exact origin of Iznik products. In this study, bodies, glazes, and pigments of 46 tile/ceramic shards of unknown origin, which were supplied from the vaults of Topkapı Palace Museum, and two reference tile fragments, known as Kütahya products, supplied from the demolished Surp Krikor Lusavoriç church and, additionally, two Iznik reference tiles were examined using the scanning electron microscopy‐energy dispersive X‐ray spectrometry and micro‐Raman spectroscopy techniques. Results of both techniques were evaluated together for the first time to determine the power of nondestructive Raman spectroscopy technique in differentiation of Ottoman tiles. In this work, bodies of the Kütahya tiles were found to be different than Iznik and Tekfur stone‐paste bodies, which are rich in clay rather than quartz. Two different lead‐alkali glaze compositions were found for Kütahya tiles; one was rich in PbO (over 35%) and the other one was rich in alkali (PbO less than 25%). Barite inclusions were detected in the bodies and in the glazes of some Ottoman tiles, which could be the fingerprint for the Kütahya products. It was found that the under glaze red decoration is essentially a mixture of hematite and quartz in different proportions. Shades of red decoration mainly depend on the amount of hematite in the mixture. Sixteenth century tomato red decoration contains more quartz compared with 17th century dark red decoration. This study showed that a similar technology was also applied at Kütahya in the 16th century. A linear correlation was found between the position of the Raman intense stretching peak Q₃ and lead oxide content of lead‐alkali glazes, which could allow for the differentiation of Ottoman tiles based on the nondestructive Raman analysis. This study provides an important additional reference data and discussion for the Ottoman tiles. Copyright © 2011 John Wiley & Sons, Ltd.     

Naturally irradiated fluorite as a historic violet pigment: Raman spectroscopic and X‐ray diffraction study

Naturally irradiated violet fluorite, a cubic CaF₂ mineral, is a rare historic pigment. Its documented usage in Europe stretches from ca. 1450 to ca. 1550. The intensely coloured violetish black naturally irradiated fluorite is commonly called antozonite, which is only vaguely defined based on its dark colour and specific odour emanated during grinding. In the published literature, there have been some discrepancies about its Raman spectrum. Therefore, sixteen samples of antozonite were analysed by Raman (micro‐)spectroscopy using five different excitation laser wavelengths (445, 532, 633, 780 and 1064 nm), which revealed specific bands located below 500 cm⁻¹ probably related to radiation‐caused defects. Their intensity increased with increasing violet colour saturation, thus providing a specification for antozonite's definition. Spectra excited at 445 and 780 nm contained also numerous broad bands above 500 cm⁻¹, which seem to be caused by the presence of rare earth elements. The structural damage of antozonite samples has been assessed by X‐ray diffraction and related to their lightness using analysis of image histograms. The obtained results have been applied in the analysis of micro‐samples of a Late Gothic altarpiece located in an Italian Court in UNESCO city Kutná Hora, Czech Republic, which contained exceptionally large grains of deep violet fluorite identified as antozonite. Copyright © 2015 John Wiley & Sons, Ltd.     

IDATEN and G‐SITENNO: GUI‐assisted software for coherent X‐ray diffraction imaging experiments and data analyses at SACLA

Using our custom‐made diffraction apparatus KOTOBUKI‐1 and two multiport CCD detectors, cryogenic coherent X‐ray diffraction imaging experiments have been undertaken at the SPring‐8 Angstrom Compact free electron LAser (SACLA) facility. To efficiently perform experiments and data processing, two software suites with user‐friendly graphical user interfaces have been developed. The first is a program suite named IDATEN, which was developed to easily conduct four procedures during experiments: aligning KOTOBUKI‐1, loading a flash‐cooled sample into the cryogenic goniometer stage inside the vacuum chamber of KOTOBUKI‐1, adjusting the sample position with respect to the X‐ray beam using a pair of telescopes, and collecting diffraction data by raster scanning the sample with X‐ray pulses. Named G‐SITENNO, the other suite is an automated version of the original SITENNO suite, which was designed for processing diffraction data. These user‐friendly software suites are now indispensable for collecting a large number of diffraction patterns and for processing the diffraction patterns immediately after collecting data within a limited beam time.     

Rietveld and pair distribution function study of Hägg carbide using synchrotron X‐ray diffraction

Fischer–Tropsch (FT) synthesis is an important process in the manufacturing of hydrocarbons and oxygenated hydrocarbons from mixtures of carbon monoxide and hydrogen (syngas). The reduced iron catalyst reacts with carbon monoxide and hydrogen to form bulk Fe₅C₂ Hägg carbide (χ‐HC) during FT synthesis. Arguably, χ‐HC is the predominant catalyst phase present in the working iron catalyst. Deactivation of the working catalyst can be due to oxidation of χ‐HC to iron oxide, a step‐wise decarburization to cementite (θ‐Fe₃C), carbon formation or sintering with accompanying loss of catalytic performance. It is therefore critical to determine the precise crystal structure of χ‐HC for the understanding of the synthesis process and for comparison with the first‐principles ab initio modelling. Here the results of high‐resolution synchrotron X‐ray powder diffraction data are reported. The atomic arrangement of χ‐HC was confirmed by Rietveld refinement and subsequent real‐space modelling of the pair distribution function (PDF) obtained from direct Fourier transformation. The Rietveld and PDF results of χ‐HC correspond well with that of a pseudo‐monoclinic phase of space group Pī [a = 11.5661 (6) Å, b = 4.5709 (1) Å, c = 5.0611 (2) Å, α = 89.990 (5)°, β = 97.753 (4)°, γ = 90.195 (4)°], where the Fe atoms are located in three distorted prismatic trigonal and one octahedral arrangement around the central C atoms. The Fe atoms are distorted from the prismatic trigonal arrangement in the monoclinic structure by the change in C atom location in the structure.     

Combined PIXE and X‐ray diffraction analysis of accretionary lapilli from the Cretaceous/Paleogene boundary El Guayal Section,Tabasco, Mexico

By employing the techniques, X‐ray powder diffraction (XRPD) and particle‐induced X‐ray emission (PIXE), it could be obtained in a simply way an overall vision of the structure and chemical composition of a spheroid (lapillus) collected in the K/Pg deposit located at the place called El Guayal in Tabasco, Mexico. The XRPD analysis indicates the presence of an amorphous and four crystalline phases (quartz, calcite, ankerite, and montmorillonite) in the spheroid. None sulfur crystalline phases were detected. PIXE results show the presence of different atoms in a weight percentage that follows the sequence: Si > Al > Ca > Fe > Sr > Cu > Ti > Mn > Y > Rb > Zn > Pb. None of platinum group elements were detected. PIXE analysis by of the lapillus shows the presence of the most abundant atoms in the Earth's crust, but in this case, the relative abundance Fe‐Ca is inverted, and the Sr/Rb proportion is considerably higher than that observed in the crust. Additionally, nor sulfur or any of the platinum group elements was detected in the lapillus. Except for the case of trace elements detected, in general, no characteristic pattern is observed in the distribution of the most abundant elements. Copyright © 2015 John Wiley & Sons, Ltd.     

Characterization of pottery from Republic of Macedonia. III. A study of comparative mineralogical detection efficiency using micro‐Raman mapping and X‐ray diffraction

Point‐to‐point micro‐Raman and X‐ray diffraction (XRD) techniques were employed for characterization of minerals present in the pottery body of 27 glazed Byzantine and Ottoman pottery shreds, excavated at two different archaeological sites in the Republic of Macedonia: in Skopje (Skopsko Kale) and in Prilep (Markovi Kuli and Sv. Atanas Church). The Raman spectra of 18 Byzantine samples (dating from 12th−14th century) and nine Ottoman samples (dating from 17th−19th century) revealed 26 different minerals. XRD measurements were further performed on the same powder samples to validate the mineralogical assessment obtained by point‐to‐point micro‐Raman spectroscopy. Although only 13 different mineral phases were obtained by the XRD, the results obtained from the Raman and XRD spectra for the most abundant minerals in the investigated pottery bodies match quite well. However, the identification of the less abundant minerals in the clay matrixes from the XRD data was very difficult, if at all possible. The results emphasize the specifics of the applied techniques and their limits. Additionally, wavelength dispersive X‐ray fluorescence spectroscopy was used for the elemental analysis. Copyright © 2011 John Wiley & Sons, Ltd.     

Design and development of a controlled pressure/temperature set‐up for in situ studies of solid–gas processes and reactions in a synchrotron X‐ray powder diffraction station

A novel set‐up has been designed and used for synchrotron radiation X‐ray high‐resolution powder diffraction (SR‐HRPD) in transmission geometry (spinning capillary) for in situ solid–gas reactions and processes in an isobaric and isothermal environment. The pressure and temperature of the sample are controlled from 10^?3 to 1000 mbar and from 80 to 1000 K, respectively. To test the capacities of this novel experimental set‐up, structure deformation in the porous material zeolitic imidazole framework (ZIF‐8) by gas adsorption at cryogenic temperature has been studied under isothermal and isobaric conditions. Direct structure deformations by the adsorption of Ar and N₂ gases have been observed in situ, demonstrating that this set‐up is perfectly suitable for direct structural analysis under in operando conditions. The presented results prove the feasibility of this novel experimental station for the characterization in real time of solid–gas reactions and other solid–gas processes by SR‐HRPD.     

In situ synchrotron X‐ray powder diffraction for studying the role of induced structural defects on the thermoluminescence mechanism of nanocrystalline LiF

The correlation between the thermoluminescence (TL) response of nanocrystalline LiF and its microstructure was studied. To investigate the detailed TL mechanism, the glow curves of nanocrystalline LiF samples produced by high‐energy ball‐milling were analyzed. The microstructure of the prepared samples was analyzed by synchrotron X‐ray powder diffraction (XRPD) at room temperature. Then, the microstructure of a representative pulverized sample was investigated in detail by performing in situ XRPD in both isothermal and non‐isothermal modes. In the present study, the dislocations produced by ball‐milling alter the microstructure of the lattice where the relative concentration of the vacancies, responsible for the TL response, changes with milling time. An enhancement in the TL response was recorded for nanocrystalline LiF at high‐temperature traps (after dislocations recovery starts >425 K). It is also found that vacancies are playing a major role in the dislocations recovery mechanism. Moreover, the interactions among vacancies–dislocations and/or dislocations–dislocations weaken the TL response.