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Silver sulfide, Ag2S, is most commonly known as the tarnish that forms on silver surfaces due to the exposure of silver to hydrogen sulfide. The mineral acanthite is a monoclinic crystalline form of Ag2S that is stable to 176°C. Upon heating above 176°C, there is a phase conversion to a body-centered cubic (bcc) form referred to as argentite. Further heating above 586°C results in conversion of the bcc phase to a face-centered cubic (fcc) phase polymorph. Both high-temperature cubic phases are solid-state silver ion conductors. In situ high-temperature X-ray diffraction was used to better understand the polymorphs of Ag2S on heating. The existing powder diffraction file (PDF) entries for the high-temperature fcc polymorph are of questionable reliability, prompting a full Rietveld structure refinement of the bcc and fcc polymorphs. Rietveld analysis was useful to show that the silver atoms are largely disordered and can only be described by unreasonably large isotropic displacement parameters or split site models.
The crystal structures of marialite (Me6) from Badakhshan, Afghanistan and meionite (Me93) from Mt. Vesuvius, Italy were obtained using synchrotron high-resolution powder X-ray diffraction (HRPXRD) data and Rietveld structure refinements. Their structures were refined in space groups I4/m and P42/n, and similar results were obtained. The Me6 sample has a formula Ca0.24Na3.37K0.24[Al3.16Si8.84O24]Cl0.84(CO3)0.15, and its unit-cell parameters are a=12.047555(7), c=7.563210(6) Å, and V=1097.751(1) Å3. The average ⟨T1-O⟩ distances are 1.599(1) Å in I4/m and 1.600(2) Å in P42/n, indicating that the T1 site contains only Si atoms. In P42/n, the average distances of ⟨T2-O⟩=1.655(2) and ⟨T3-O⟩=1.664(2) Å are distinct and are not equal to each other. However, the mean ⟨T2,3-O⟩=1.659(2) Å in P42/n and is identical to the ⟨T2′-O⟩=1.659(1) Å in I4/m. The ⟨M-O⟩ =2.754(1) Å (M site is coordinated to seven framework O atoms) and M-A=2.914(1) Å; these distances are identical in both space groups. The Me93 sample has a formula of Na0.29Ca3.76[Al5.54Si6.46O24]Cl0.05(SO4)0.02(CO3)0.93, and its unit-cell parameters are a=12.19882(1), c=7.576954(8) Å, and V=1127.535(2) Å3. A similar examination of the Me93 sample also shows that both space groups give similar results; however, the C–O distance is more reasonable in P42/n than in I4/m. Refining the scapolite structure near Me0 or Me100 in I4/m forces the T2 and T3 sites (both with multiplicity 8 in P42/n) to be equivalent and form the T2′ site (with multiplicity 16 in I4/m), but ⟨T2-O⟩ is not equal to ⟨T3-O⟩ in P42/n. Using different space groups for different regions across the series implies phase transitions, which do not occur in the scapolite series.
An in situ time-resolved XRD system for hydrothermal reaction has been developed in order to investigate the phase evolution during autoclave process in autoclaved aerated concrete (AAC) formation. The system includes a novel autoclave cell for transmission XRD with thin beryllium windows, a two-dimensional photon-counting pixel array detector, and uses high energy X-rays from a synchrotron radiation source. The temperature and pressure inside the cell are extremely stable during hydrothermal reaction over the course of several hours. The system was utilized for the formation reaction of AAC. Phase evolution was clearly observed, including several intermediate phases, and detailed information on the structural changes during the hydrothermal reaction were obtained.
The microstructural evolution of Fe–Mn–C austenitic steels, which exhibit outstanding high-ductile deformation in their plastic regions, was characterized by line-profile and texture analyses. The convolutional multiple whole profile fitting procedure was used for a line-profile analysis of 2θ−θ diffraction data to evaluate variations of crystallite size, dislocation density, and dislocation arrangement. A substantial refinement of the crystallite size proceeded at an early deformation stage. In addition, the dislocation density increased with an increase in the tensile strain. Texture evolution was characterized by the analysis of orientation distribution functions. Three texture components grew with an increase in the tensile strain. According to the pole figure describing the full width at half maximum (FWHM) distribution of the 220 reflection, the nontextured grains had more microstructural defects than the textured grains. To evaluate the microstructural defects in detail, the 220 reflection observed at each texture orientation was analyzed by the single-line-profile method. The crystallite size and dislocation density were almost comparable, irrespective of the kind of texture component. The crystallite size of the nontextured grains was also comparable to that of the textured grains, whereas the nontextured grains had a dislocation density several times that of the textured grains.
Hydrothermal formation reaction of tobermorite in the autoclaved aerated concrete (AAC) process has been investigated by in situ X-ray diffraction. High-energy X-rays from a synchrotron radiation source in combination with a newly developed autoclave cell and a photon-counting pixel array detector were used. XRD measurements were conducted in a temperature range 100–190°C throughout 12 h of reaction time with a time interval of 4.25 min under a saturated steam pressure. To clarify the tobermorite formation mechanism in the AAC process, the effect of Al addition on the tobermorite formation reaction was studied. As intermediate phases, non-crystalline calcium silicate hydrate (C-S-H), hydroxylellestadite (HE), and katoite (KA) were clearly observed. Consequently, it was confirmed that there were two reaction pathways via C-S-H and KA in the tobermorite formation reaction of Al containing system. In addition, detailed information on the structural changes during the hydrothermal reaction was obtained.
Coatings of plasma sprayed hydroxyapatite (HAp), incubated in simulated body fluid for periods varying from 1 to 56 days, were characterized using conventional laboratory X rays. Quantitative phase analysis, employing TOPAS software, showed an opposite trend in the two main phases of the coating, viz., HAp and tetracalcium phosphate (TTCP). The former increased within the first 7 days of incubation whilst the latter decreased during the same period; both phases stabilized with further incubation. The crystallinity of the coatings exhibited a trend similar to that of HAp i.e., an increase in the early stages of incubation stabilization with further incubation. Results of residual stress determined with Bruker’s D8 Discover and analyzed with LEPTOS software, showed both the normal stress tensor components, σ11 and σ22, to be tensile, relaxing significantly in the early stages of incubation before stabilizing with further incubation.
In an effort to better understand the structural changes occurring during hydrogen loading of erbium target materials, we have performed in situ D2 loading of erbium metal (powder) at temperature (450°C) with simultaneous neutron diffraction analysis. This experiment tracked the conversion of Er metal to the α erbium deuteride (solid-solution) phase and then into the β (fluorite) phase. Complete conversion to ErD2.0 was accomplished at 10 Torr D2 pressure with deuterium fully occupying the tetrahedral sites in the fluorite lattice.
Three polyureas with decreasing soft segment molecular weights of 1000, 650, and a 250/1000 blend were molded onto circular steel plates and then impacted with a high speed (275 m/s) conical-shaped steel cylinder. The polyurea layer of the post mortem bilayers was characterized on a molecular level by small angle synchrotron X-ray scattering (SAXS) at the Advanced Photon Source at the Argonne National Laboratory. Analysis revealed that the hard domains of the polyureas with lower molecular weight soft segments reformed and oriented over a greater area of the coating, thus increasing the polymer strain hardening and resulting in visibly less out of plane bilayer deformation. This agrees with the hypothesis that polymer strain hardening is a mechanism that retards necking failure of the metal plate.
This report describes SRM 660b, the third generation of this powder diffraction SRM used primarily for determination of the instrument profile function (IPF). It is certified with respect to unit-cell parameter. It consists of approximately 6 g LaB6 powder prepared using a 11B isotopically enriched precursor material so as to render the SRM applicable to the neutron diffraction community. The microstructure of the LaB6 powder was engineered to produce a crystallite size above that where size broadening is typically observed and to minimize the crystallographic defects that lead to strain broadening. A NIST -built diffractometer, incorporating many advanced design features, was used to certify the unit-cell parameter of the LaB6 powder. Both type A, statistical, and type B, systematic, errors have been assigned to yield a certified value for the unit-cell parameter of a=0.415691(8) nm at 22.5°C.
Divalent metal ions are crucial as cofactors for a variety of intracellular enzymatic activities. Mg2+, as an example, mediates binding of deoxyribonucleoside 5′-triphosphates followed by their hydrolysis in the active site of DNA polymerase. It is difficult to study the binding of Mg2+ to an active site because Mg2+ is spectroscopically silent and Mg2+ binds with low affinity to the active site of an enzyme. Therefore, we substituted Mg2+ with Mn2+:Mn2+ that is not only visible spectroscopically but also provides full activity of the DNA polymerase of bacteriophage T7. In order to demonstrate that the majority of Mn2+ is bound to the enzyme, we have applied site-directed titration analysis of T7 DNA polymerase using X-ray near edge spectroscopy. Here we show how X-ray near edge spectroscopy can be used to distinguish between signal originating from Mn2+ that is free in solution and Mn2+ bound to the active site of T7 DNA polymerase. This method can be applied to other enzymes that use divalent metal ions as a cofactor.
Results on using X-ray optics with a monocapillary attached to a microfocus Mo X-ray tube for a high-intensity XRF analysis are reported. Au-coated glass monocapillaries with 400 and 700 μm inner diameters were used to obtain focused and intensive incident Mo X-rays for the measurements of XRF intensities from pure metal samples. Intensity enhancements obtained by using the Au-coated monocapillaries were found to be up to 1.5 times higher than those obtained by using similar inner diameter uncoated glass capillaries. The XRF intensity profiles were measured by the wire scanning method to investigate the reasons. The traces of the incident X-rays were calculated by taking into account of X-ray total reflection of the incident X-rays from the inner wall of the capillaries. The calculated XRF intensity profiles agree with those of the measured XRF intensity profiles. The observed enhancements in XRF intensity were the results of the incident X-rays emitted from the Mo X-ray tube being totally reflected on the inner wall of the Au-coated monocapillaries.
To minimize waste, improve process safety, and reduce costs, modifications were implemented to a method for quantifying gallium in plutonium metal using wavelength dispersive X-ray fluorescence. These changes included reducing sample sizes, reducing ion exchange process volumes, using cheaper reagent grade acids, eliminating the use of HF acid, and using more robust containment films for sample analysis. Relative precision and accuracy achieved from analyzing multiple aliquots from a single parent sample were approximately 0.2 and 0.1%, respectively. The same precision was obtained from analyzing a total of four parent materials, and the average relative accuracy from all the samples was 0.4%, which is within programmatic uncertainty requirements.
The structures of anhydrous nickel, niobium, and tantalum chlorides have been investigated in situ in acidic and basic ionic liquids (ILs) of 1-methyl-3-ethylimidazolium chloride (EMIC)/AlCl3 with X-ray absorption spectroscopy (XAS). The coordination of NiCl2 changes from tetrahedral in basic solution to octahedral in acidic solution. The NiCl2 is a strong Lewis acid in that it can induce the AlCl3 to share its chlorides in the highly acidic IL, forming a structure with six near Cl− ions and eight further distant Al ions which share the chloride ions surrounding the Ni2+. When Nb2Cl10, a dimer, is added to the acidic or basic solution, the dimer breaks apart and forms two species. In the acid solution, two trigonal bipyramids are formed with five equal chloride distances, while in the basic solution, a square pyramid with four chlorides forming a square base and one shorter axial chloride bond. Ta2Cl10 is also a dimer and divides into half in the acidic solution and forms two trigonal bipyramids. In the basic solution, the dimer breaks apart but the species formed is sufficiently acidic that it attracts two additional chloride ions and forms a seven coordinated tantalum species.
A previous paper portrayed sample preparation by fusion methodology and the XRF analysis conditions for the calibration of cement materials [Bouchard et al., 2009. “Global cement and raw materials fusion/XRF analytical solution,” Adv. X-Ray Anal. 53, 263–279]. The results of two well known cement chemical analysis Standard Methods were also presented. These results proved that this robust analytical method is able to qualify by the ASTM C114 [ASTM C114-08 (2008). “Standard test methods for chemical analysis of hydraulic cement,” Annual Book of ASTM Standards Vol. 04.01 (ASTM International, West Conshohocken, PA), pp. 150–157)] and ISO/DIS 29581-2 [Draft Standard, 2007-07 (2007). “Methods of testing cement—Chemical analysis of cement—Part 2: Analysis by X-ray fluorescence” ISO/DIS 29581-2, 2007, pp. 1–30]. This robust analytical method was developed using an automated fusion instrument for the sample preparation and a WDXRF spectrometer for the determination of all elements of interest relating to the cement industry. This method was used to prepare finished products, process materials, as well as a very large range of raw materials. The first part of this second paper examines all the XRF analysis conditions for the calibration of the raw materials using the robust fusion sample preparation methodology as well as the numerous reference materials (RMs) used for this analytical application. All interesting results will be presented. The second part of this paper reveals the rapid analytical method results using sample preparation by fusion on nonignited samples. It will also be proven that this faster method, combined with the WDXRF spectrometer, complies with both cement analysis Standard Methods: ASTM C114 and ISO/DIS 29581-2.