Vibrations and chemical states of iron ions in soda‐lime glasses determined by element‐specific X‐ray analyses

We systematically study medium‐range structures including more than three neighboring atoms around iron ions (Fe²⁺ and Fe³⁺) in soda‐lime glass samples with low iron oxide concentrations (M_Fe2O3) and a wide number ratio of Fe²⁺ to all iron ions (Fe²⁺/Σ_nFe). The precise medium‐range structures around iron ions in glass have not yet been revealed because of a lack of the appropriate measurement methods. To avoid this problem, we used element‐specific nuclear resonant inelastic scattering (NRIS) with synchrotron X‐rays to observe the vibrations of iron ions (⁵⁷Fe). The vibrations are related to medium‐range structures with more than three neighboring atoms and to the potential asymmetry and the coordination environment, around iron ions. The NRIS method has high sensitivity and can measure over a wide concentration range. Linear combination fitting of the X‐ray absorption fine structure spectra, which measures only the first neighbors but is a faster than using the NRIS method, was also used additionally. A systematically produced set of glasses with 0.015–5 wt% M_Fe2O3 and 0–0.85 Fe²⁺/Σ_nFe was measured with these methods. It was found that the soda‐lime glass possessed two different medium‐range structures with different iron ion valences (~2+ or ~3+), which were determined by the Fe²⁺/Σ_nFe, and that these structures were generated during production of the glass. Moreover, these medium‐range structures were the same from 0.015 to 5 wt% M_Fe2O3.     

Simultaneous calorimetric and quick‐EXAFS measurements to study the crystallization process in phase‐change materials

A Calvet‐type differential scanning calorimeter has been implemented on a synchrotron beamline devoted to X‐ray absorption spectroscopy. As a case study, the complex crystallization process in amorphous Ge₁₅Sb₈₅ phase‐change material is followed by simultaneous calorimetric and quick‐EXAFS measurements. A first crystallization at 514(1) K is related to the crystallization of an Sb‐rich phase accompanied by segregation of Ge atoms. Upon further heating, the as‐formed amorphous Ge regions crystallize at 604(1) K. A quantitative analysis of the latent heat allows a Ge₁₁Sb₈₉ stoichiometry to be proposed for the first crystallized phase.     

Raman and ab initio study of the conformational isomerism in the 1‐ethyl‐3‐methyl‐imidazolium bis(trifluoromethanesulfonyl)imide ionic liquid

The calculated and experimental Raman spectra of the (EMI⁺)TFSI⁻ ionic liquid, where EMI⁺ is the 1‐ethyl‐3‐methylimidazolium cation and TFSI⁻ the bis(trifluoromethanesulfonyl)imide anion, have been investigated for a better understanding of the EMI⁺ and TFSI⁻ conformational isomerism as a function of temperature. Characteristic Raman lines of the planar (p) and non‐planar (np) EMI⁺ conformers are identified using the reference (EMI⁺)Br⁻ salt. The anion conformer of C₂ symmetry is confirmed to be more stable than the cis (C₁) one by 4.5 ± 0.2 kJ mol⁻¹. At room temperature, the population of trans (C₂) anions and np cations is 75 ± 2% and 87 ± 4%, respectively. Fast cooling quenches a metastable glassy phase composed of mainly C₂ anion conformers and p cation conformers, whereas slow cooling gives a crystalline phase composed of C₁ anion conformers and of np cation conformers. Copyright © 2006 John Wiley & Sons, Ltd.     

Interactions of ferrimagnetic glass/glass-ceramics with bovine serum albumin

Glasses/glass-ceramics with nominal composition 34 SiO₂-(45 − x)CaO-16P₂O₅-4.5MgO-0.5CaF₂ − xFe₂O₃ (where x = 10, 15, 20 wt%) have been prepared by melt quenching technique. These are characterized for structural and micro structural properties by using XRD and Raman spectroscopy. Interaction of glass-ceramics samples with bovine serum albumin (BSA) has been studied using SEM and TOF-SIMS. The formation of magnetite, apatite and wollastonite phases are observed. Typical sizes of crystallites as seen from SEM measurement are 30-50 nm. The progressive addition of iron oxide to glass leads to increase in number of non-bridging oxygen, which in turn affects the response of glass-ceramics when immersed in BSA. The samples with 15 and 20 wt% Fe₂O₃ have shown nearly full surface coverage with BSA, while the sample with 10 wt% Fe₂O₃ shows poor adhesion.     

Hydration and carbonation of monoclinic C2S and C3S studied by Raman spectroscopy

We present a micro‐Raman study on the hydration and carbonation of the main silicate phases of Portland cement, i.e. monoclinic dicalcium silicate (C₂S) and monoclinic tricalcium silicate (C₃S). We investigate the reaction products and the loss of crystallinity induced by hydration on these two compounds. In the CO₂‐contaminated pastes we find that calcite, aragonite, and vaterite are inhomogeneously formed. We study sample cross sections to evaluate the maximum depth at which CaCO₃ is formed. We find that carbonation is limited to the first 500–1000 µm from the surface in the C₃S pastes, while in C₂S pastes CaCO₃ is formed well beyond this depth. Our results show the great potential of Raman spectroscopy in the study of the chemistry of cements. Copyright © 2006 John Wiley & Sons, Ltd.     

The hydrogen‐bond effect on the high pressure behavior of hydrazinium monochloride

The first high pressure study of solid hydrazinium monochloride has been performed by in situ Raman spectroscopy and synchrotron X‐ray diffraction (XRD) experiments in diamond anvil cell (DAC) up to 39.5 and 24.6 GPa, respectively. The structure of phase I at room temperature is confirmed to be space group C2/c by the Raman spectral analysis and Rietveld refinement of the XRD pattern. A structural transition from phase I to II is observed at 7.3 GPa. Pressure‐induced position variation of hydrogen atoms in NH₃⁺ unit during the phase transition is attributed to the formation of N―H…Cl hydrogen‐bonds, which play a vital role in the stability and subsequent structural changes of this high energetic material under pressure. This inference is proved from the abnormal pressure shifts and obvious Fermi resonance in NH stretching mode of N₂H₅⁺ ion in the Raman experiment. Finally, a further transition from phase II to III accompanied with a slight internal distortion in the N₂H₅⁺ ions occurs above 19.8 GPa, and phase III persists up to 39.5 GPa. Copyright © 2015 John Wiley & Sons, Ltd.     

Phase‐specific Raman analysis of n‐alkane melting by moving‐window two‐dimensional correlation spectroscopy

We use moving‐window two‐dimensional correlation spectroscopy (MW‐2DCOS) for phase‐specific Raman analysis of the n‐alkane (C₂₁H₄₄) during melting from the crystalline solid phase to the intermediate rotator phase and to the amorphous molten phase. In MW‐2DCOS, individual peak‐to‐peak correlation analysis within a small subset of spectra provides both temperature‐resolved and spectrally disentangled Raman assignments conducive to understanding phase‐specific molecular interactions and chain configurations. We demonstrate that autocorrelation MW‐2DCOS can determine the phase transition temperatures with a higher resolving power than commonly used analysis methods including individual peak intensity analysis or principal component analysis. Besides the enhanced temperature resolving power, we demonstrate that asynchronous 2DCOS near the orthorhombic‐to‐rotator transition temperature can spectrally resolve the two overlapping peaks embedded in the Raman CH₂ twisting band in the orthorhombic phase, which had been only predicted but not observed because of thermal broadening near the melting temperature. Published 2016. This article is a U.S. Government work and is in the public domain in the USA.     

Observation of insulating–insulating monoclinic structural transition in macro‐sized VO2 single crystals

VO₂ single crystals with unprecedented quality, exhibiting a first‐order metal–insulator transition (MIT) at 67.8 °C and an insulator –insulator transition (IIT) at ～49 °C, are grown using a self‐flux evaporation method. Using synchrotron‐based X‐ray microdiffraction analysis, it is shown that the IIT is related to a structural phase transition (SPT) from the monoclinic M2 phase to the M1 phase upon heating while the MIT occurs together with a SPT of M1 to the rutile R phase. All previous reports have shown that VO₂ exists in the M1 phase at room temperature in contrast to the M2 phase observed in this work. We suggest that internal strain inside single crystal VO₂ may generate the previously unobserved IIT and the unusual room temperature structure. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

In situ synchrotron diffraction studies on the formation kinetics of jarosites

This paper reports the results of time‐resolved synchrotron powder diffraction experiments where jarosites with different K/H₃O, K/Na and Na/H₃O ratios were synthesized in situ at temperatures of 353, 368 and 393 K in order to observe the effect on kinetics and species produced. The Na/H₃O sample formed monoclinic jarosite at all three temperatures, whereas the K/H₃O and K/Na samples formed as rhombohedral jarosites at 353 K, and as mixtures of rhombohedral and monoclinic jarosites at the higher temperatures. The relative amount of the monoclinic phase increased with increase in temperature. Unit‐cell parameter changes with reaction time could be explained by changes in iron stoichiometry (samples become more stoichiometric with time) together with changes in K/H₃O and Na/H₃O ratios. The reaction kinetics have been fitted using a two‐stage Avrami model, with two different Avrami exponents corresponding to initial two‐dimensional growth followed by one‐dimensional diffusion‐controlled growth. Activation energies for the initial growth stage were calculated to be in the range 90–126 kJ mol^?1.     

In situ synchrotron high‐energy X‐ray diffraction analysis on phase transformations in Ti–Al alloys processed by equal‐channel angular pressing

Mixtures of 47‐Al and 53‐Ti powders (atomic %) have been consolidated using back pressure equal‐channel angular pressing starting with both raw and ball‐milled powders. In situ synchrotron high‐energy X‐ray diffraction studies are presented with continuous Rietveld analysis obtained upon a heating ramp from 300 K to 1075 K performed after the consolidation process. Initial phase distributions contain all intermetallic compounds of this system except Al, with distribution maxima in the outer regions of the concentrations (α‐Ti, TiAl₃). Upon annealing, the phase evolution and lattice parameter changes owing to chemical segregation, which is in favour for the more equilibrated phases such as γ‐TiAl, α₂‐Ti₃Al and TiAl₂, were followed unprecedentedly in detail. An initial δ‐TiH₂ content with a phase transition at about 625 K upon heating created an intermediate β‐Ti phase which played an important role in the reaction chain and gradually transformed into the final products.     

Nanoscale C‐Rich SixC1−x Bus/Ring Waveguide Based Cross‐Wavelength Data Converter

The carbon‐rich silicon carbide (C‐rich Si_xC_1?x) micro‐ring channel waveguide with asymmetric core aspect is demonstrated for all‐optical cross‐wavelength pulsed return‐to‐zero on‐off keying (PRZ‐OOK) data conversion. Enhanced nonlinear optical Kerr switching enables 12‐Gbit per second data processing with optimized modulation depth. The inverse tapered waveguide at end‐face further enlarges the edge‐coupling efficiency, and the asymmetric channel waveguide distinguishes the polarization modes. To prevent data shape distortion, the bus/ring gap spacing is adjusted to control the quality factor (Q‐factor) of the micro‐ring. Designing the waveguide cross section at 500 × 350 nm² provides the C‐rich Si_xC_1?x channel waveguide to induce strong transverse electric mode (TE‐mode) confinement with a large Kerr nonlinearity of 2.44 × 10^?12 cm² W^?1. Owing to the trade‐off between the Q‐factor and the on/off extinction ratio, the optimized bus/ring gap spacing of 1400 nm is selected to provide a coupling ratio at 5–6% for compromising the modulation depth and the switching throughput. Such a C‐rich Si_xC_1?x micro‐ring with asymmetric channel waveguide greatly enhances the cross‐wavelength data conversion efficiency to favor its on‐chip all‐optical data processing applications for future optoelectronic interconnect circuits.     

High pressure synthesis of LiMeO2–ZnO (Me=Fe 3+, Ti3+) solid solutions with a rock salt structure

Metastable LiMeO₂–ZnO (Me=Fe ³⁺, Ti³⁺) solid solutions with a rock salt crystal structure have been synthesized by the solid-state reaction of ZnO with LiMeO₂ complex oxides at 7.7 GPa and 1350–1450 K. The structure, phase composition, thermal stability and thermal expansion of the recovered samples have been studied by X-ray diffraction with synchrotron radiation. At ambient pressure, rock salt LiMeO₂–ZnO solid solutions are kinetically stable up to 670–800 K, depending on the composition.     

A furnace and environmental cell for the in situ investigation of molten salt electrolysis using high‐energy X‐ray diffraction

This paper describes the design, construction and implementation of a relatively large controlled‐atmosphere cell and furnace arrangement. The purpose of this equipment is to facilitate the in situ characterization of materials used in molten salt electrowinning cells, using high‐energy X‐ray scattering techniques such as synchrotron‐based energy‐dispersive X‐ray diffraction. The applicability of this equipment is demonstrated by quantitative measurements of the phase composition of a model inert anode material, which were taken during an in situ study of an operational Fray–Farthing–Chen Cambridge electrowinning cell, featuring molten CaCl₂ as the electrolyte. The feasibility of adapting the cell design to investigate materials in other high‐temperature environments is also discussed.     

Reaction‐Induced Phase Separation in Polyoxyethylene/Polystyrene Blends. I. Ternary Phase Diagram

Abstract

Reaction‐induced, phase separation has been studied in polymer blends. A model crystalline‐amorphous system consisted of semicrystalline polyoxyethylene (POE) dissolved in the monomer styrene, which was used as a reactive solvent to ease processing. When the styrene was polymerized to polystyrene (PS) in the mold, phase separation and phase inversion are induced, and a polymer blend was formed. Polyoxyethylene was selected with a molar mass, M _n  = 8578 g mol^?1 and a polydispersity of 1.19, as determined by using gel permeation chromatography. The polymerization of styrene was initiated by using 1 wt% benzoin methyl ether and 0.2 wt% 2,2′‐azobisisobutyronitrile under ultraviolet light. The polymerization kinetics were determined by monitoring the reduction in the intensity of the C?C stretching vibration band at 1631 cm^?1 in the Raman spectrum of styrene. The onset times for the liquid–solid (L–S) phase separation and crystallization of POE from styrene/PS were observed by using simultaneous small‐angle x‐ray scattering (SAXS) and wide‐angle x‐ray scattering. Onset times for L–S phase separation determined from the SAXS data were combined with the styrene polymerization kinetics to plot the L–S phase separation data onto a ternary phase diagram for the reactive system POE/styrene/PS at 45°C and 50°C.     

A valence-band and core-level photoemission study of a-SixC1-x thin films grown by low-temperature low-pressure chemical vapour deposition

Amorphous Si_xC_1-x thin films have been grown by low-pressure chemical vapour deposition at 800 K from Si₂H₆ and C₂H₂ in the x concentration range 0.5≤x<0.7. Measurements of the valence-band and core-level photoemission spectra using X-ray photoemission spectroscopy and synchrotron radiation have shown a clear change in the electronic structure for 0.55xC_1-x films obtained by excimer laser annealing during growth have shown the formation of a dominant 3C-SiC phase up to x=0.6, while for higher x the growth of a poly-Si phase has been observed . PACS 81.15.Gh; 79.60.Dp     

Extended X‐ray absorption fine structure and multiple‐scattering simulation of nickel dithiolene complexes Ni[S2C2(CF3)2]2n (n = −2, −1, 0) and an olefin adduct Ni[S2C2(CF3)2]2(1‐hexene)

A series of Ni dithiolene complexes Ni[S₂C₂(CF₃)]₂ⁿ (n = ?2, ?1, 0) ( 1 , 2 , 3 ) and a 1‐hexene adduct Ni[S₂C₂(CF₃)₂]₂(C₆H₁₂) ( 4 ) have been examined by Ni K‐edge X‐ray absorption near‐edge structure (XANES) and extended X‐ray absorption fine‐structure (EXAFS) spectroscopies. Ni XANES for 1 – 3 reveals clear pre‐edge features and approximately +0.7 eV shift in the Ni K‐edge position for `one‐electron' oxidation. EXAFS simulation shows that the Ni—S bond distances for 1 , 2 and 3 (2.11–2.16 Å) are within the typical values for square planar complexes and decrease by ～0.022 Å for each `one‐electron' oxidation. The changes in Ni K‐edge energy positions and Ni—S distances are consistent with the `non‐innocent' character of the dithiolene ligand. The Ni—C interactions at ～3.0 Å are analyzed and the multiple‐scattering parameters are also determined, leading to a better simulation for the overall EXAFS spectra. The 1‐hexene adduct 4 presents no pre‐edge feature, and its Ni K‐edge position shifts by ?0.8 eV in comparison with its starting dithiolene complex 3 . Consistently, EXAFS also showed that the Ni—S distances in 4 elongate by ～0.046 Å in comparison with 3 . The evidence confirms that the neutral complex is `reduced' upon addition of olefin, presumably by olefin donating the π‐electron density to the LUMO of 3 as suggested by UV/visible spectroscopy in the literature.     

Interference phenomena of synchrotron radiation in TEY spectra for silicon‐on‐insulator structure

The general matrix theory of the photoelectron/fluorescence excitation in anisotropic multilayer films at the total reflection condition of X‐rays has been developed. In a particular case the theory has been applied to explain the oscillation structure of L_2,3 XANES spectra for a SiO₂/Si/SiO₂/c‐Si sample in the pre‐edge region which has been observed by a sample current technique at glancing angles of synchrotron radiation. Remarkably the phase of the oscillations is reversed by a ～2° angle variation. The observed spectral features are found to be a consequence of waveguide mode creation in the middle layer of strained Si, which changes the radiation field amplitude in the top SiO₂ layer. The fit of the data required the correction of the optical constants for Si and SiO₂ near the Si L_2,3‐edges.     

Delayed phase separation in growth of organic semiconductor blends with limited intermixing

Binary mixed thin films of picene (C₂₂H₁₄, PIC) and pentacene (C₂₂H₁₄, PEN) consist of crystallites with a statistical occupation of the lattice sites by either PEN or PIC and unit cell parameters continuously changing with the mixing ratio. For high PIC ratios a PIC phase forms which corresponds to a limited intermixing of the two compounds. The growth behavior of these mixtures is investigated in situ and in real‐time using grazing incidence X‐ray diffraction. We observe a delayed phase separation in PIC‐rich blends, i.e. complete intermixing in the monolayer range and the nucleation of a pure PIC‐phase in addition to the intermixed phase starting from the second monolayer.

Growth scenario of picene‐rich pentacene‐picene blends.     

Dimensional characterization of selected elements in airborne PM10 samples using μ‐SRXRF

Micro synchrotron radiation X‐ray fluorescence (μ‐SRXRF) is a powerful spectroscopy technique that uses synchrotron radiation to induce X‐ray fluorescence in samples and provides exhaustive information on the micron and submicron scale. Among the major advantages of μ‐SRXRF spectroscopy are its nondestructive nature and that samples can usually be analyzed without pretreatment. At the ESRF (Grenoble, France) ID‐21 beamline, we examined PM₁₀ samples collected at two sites in the Province of Trieste, Italy, in order to determine possible correlations among some low‐ to mid‐Z elements (S, Cl, K, Ca, Ti, V, Cr, Mn, and Fe), as well as investigated the possibility of using synchrotron radiation imaging techniques as a way to examine the granulometry of PM₁₀ particles containing the various chemical elements. A consistent significant correlation between Ca and S has been found, which, coupled with the data obtained in a related study, indicates that a major part of the sulfate is present as CaSO₄. Granulometry measurement via imaging techniques has shown that some elements such as Fe, Ca, and S are more amenable to this type of analysis than others. Additionally, the spatial homogeneity of a PM_2.5 certified reference material (NIST SRM‐2783) has been investigated by analyzing four adjacent areas on the certified sample (total area 1 mm²). The certified reference material has shown a percentage relative standard deviation less than 7% for Al, Si, P, S, Cl, K, Ca, V, Cr, and Fe, and close to 17% for Ti and Mn. Copyright © 2011 John Wiley & Sons, Ltd.     

Two salts and the salt cocrystal of ciprofloxacin with thiobarbituric and barbituric acids: The structure and properties

Ciprofloxacin (CfH, C₁₇H₁₈FN₃O₃) crystallizes with 2‐thiobarbituric (H₂tba) and barbituric acid (H₂ba) in the aqueous solution to yield salt CfH₂(Htba)·3H₂O ( 1 ), salt cocrystal CfH₂(Hba)(H₂ba)·3H₂O ( 2 ), and salt CfH₂(Hba)·H₂O ( 3 ). The compounds are structurally characterized by the X‐ray single‐crystal diffraction. The numerous intermolecular hydrogen bonds N–H?O and O–H?O formed by water molecules, Htba^?/Hba^? and CfH₂⁺ ions, and H₂ba molecules stabilize the crystal structures of 1 to 3 . Hydrogen bonds form a 2D plane network in the salts of 1 and 3 and a 3D network in the salt cocrystal of 2 . There are different π‐π interactions in 1 to 3 . The compounds have been characterized by powder X‐ray diffraction, thermogravimetry/differential scanning calorimetry, and Fourier transform infrared spectroscopy. The compounds dehydration ends at 130°C to 150°C, and their oxidative decomposition is observed in the range of 250°C to 275°C.