Synchrotron Radiation X-ray Diffraction Measurements Research Articles

Quantitative phase analysis and molecular structure of human gallstones using synchrotron radiation X-ray diffraction and FTIR spectroscopy

Human gallstones are the most common disorder in the biliary system, affecting up to 20 % of the adult population. The formation of gallstones is primarily due to the supersaturating of cholesterol in bile. In order to comprehend gallstone disease in detail, it is necessary to have accurate information about phase identification and molecular structure. Different types of gallstone samples were collected from the Middle East area after surgical operations including; cholesterol, pigment, and mixed gallstones. To estimate the basic information about the stone formation and the pathophysiology of cholelithiasis as well as to classify the collected human gallstones, attenuated total reflection Fourier transform Infrared spectrometry (ATR-FTIR) was used to analyze the different gallstone structures in the wavenumber range from 400 to 4000 cm−1. Calcium bilirubinate was specified by the bands at 1662 cm−1, 1626 cm−1, and 1572 cm−1, while cholesterol rings were designated by the bands at 1464, 1438, 1055, and 1022 cm−1. It can be assumed that all samples consist of mixed gallstones based on the doublets at 1375 cm−1 and 1365 cm−1. The levels of calcium bilirubin and various minerals varied among the analyzed samples, indicating the heterogeneity in their composition and suggesting potential implications for gallstone formation. Based on the quantitative phase analysis using synchrotron radiation X-ray diffraction (SR-XRD), two phases of anhydrous cholesterol as a major content and one phase of monohydrate cholesterols as trace content represent the main components of most of the gallstones. Additional phases of calcium carbonate in the form of calcite, vaterite, aragonite, and bilirubinate were also quantified. According to the outcomes of the FTIR and the SR-XRD measurements, there exists a statistical correlation between the different types of chemical constituents of the gallstones.

Effects and Mode of Action of Oleic Acid and Tween 80 on Skin Permeation of Disulfiram.

Oral disulfiram (DSF) has been used clinically for alcohol dependence and recently has been found to have antitumor activity. A transdermal delivery system would be useful for maintaining drug concentration and reducing the frequency of administration of DSF for cancer treatment. Penetrating the stratum corneum (SC) barrier is a challenge to the transdermal delivery of DSF. Therefore, we investigated the promoting effects and mechanism of action of the combination of oleic acid (OA) and Tween 80 on the skin permeation of DSF. Hairless mouse skin was exposed to OA and Tween 80, combined in various ratios (1 : 0, 2 : 1, 1 : 1, 1 : 2, and 0 : 1). A permeation experiment was performed, and total internal reflection IR spectroscopic measurements, differential scanning calorimetry, and synchrotron radiation X-ray diffraction measurements were taken of the SC with each applied formulation. The combination of OA and Tween 80 further enhanced the absorption-promoting effect of DSF, compared with individual application. The peak of the CH2 inverse symmetric stretching vibration near the skin surface temperature was shifted by a high frequency due to the application of OA, and DSF solubility increased in response to Tween 80. We believe that the increased fluidity of the intercellular lipids due to OA and the increased solubility of DSF due to Tween 80 promoted the absorption of DSF. Our study clarifies the detailed mechanism of action of the skin permeation and promoting effect of DSF through the combined use of OA and Tween 80, contributing to the development of a transdermal preparation of DSF.

Synchrotron Radiation X-ray Diffraction Measurements of the Thermal Response of a Processing-Induced NiTi Strain Glass Alloy

Synchrotron Radiation X-ray Diffraction Measurements of the Thermal Response of a Processing-Induced NiTi Strain Glass Alloy

Lattice-dynamics-based characterization of La1-xAxCoO3-δ (A = Sr, Ba) nanoparticles for an inert anode in molten salts

La1-xAxCoO3-δ (A = Sr, Ba) nanoparticles used as an inert anode in molten salts were characterized using phonon vibrations, and their compositions and morphologies were investigated. These nanoparticles were used for nanostructure fabrication of an inert anode to reduce oxide ion transportation. The singularity structure changes with increasing Sr ion content in La1-xSrxCoO3-δ nanoparticles showed a transient of spin state change from a low-spin state to intermediate- and/or high-spin states. The valencies of Co ion in La1-xSrxCoO3-δ were 3.2 and 3.3 for La0.8Sr0.2CoO3-δ and La0.6Sr0.4CoO3-δ, respectively, suggesting that oxygen defects were introduced by Sr ion doping in La1-xSrxCoO3-δ nanoparticles. In contrast, the valencies of Co ion in La1-xBaxCoO3-δ were 3.1 and 3.0 for La0.5Ba0.5CoO3-δ and La0.4Ba0.6CoO3-δ, respectively, suggesting that oxygen defects were introduced slightly by Ba ion doping in La1-xBaxCoO3-δ nanoparticles. The isotropic phonon vibrations of La1-xAxCoO3-δ nanoparticles were estimated using high-temperature synchrotron radiation X-ray diffraction measurements. Crystal anisotropy measurements of phonon vibrations indicated that the oxide ions diffused preferentially along the (a, b) plane in the La1-xSrxCoO3-δ crystal lattice and toward the c-axis direction in the La1-xBaxCoO3-δ crystal lattice. These results suggest that the oxide ion transportation was curtailed using layered nanoparticles to fabricate an inert anode.

Effects of micro-alloying with lead for battery grid material

Pb-alloys are used as grid material for lead-acid batteries and have been implemented for years, and studying these Pb-alloys is critical to understanding the effects minor alloying additions on material characteristics. The current objective of this research is to evaluate the effects of minor alloying additions of Sb, As, Ca, Sn, Al, In, and Bi in Pb-alloy grid material during thermal cycling. In this study, Pb-grid material alloyed with a combination of elements mentioned above are examined using high-energy Synchrotron radiation X-ray diffraction measurements during in situ thermal cycling from RT to 75 °C to analyze grain inhibition and potential phase evolution. In addition, sulfation studies are performed in a solution of approximately 0.5 M H2SO4 and the Pb-alloys are added to an electrochemical cell to undergo cyclic voltammetry. Results show In mitigates grain growth, and, during electrochemical testing, increases passivation of Pb-alloys. Bi causes increased grain growth during thermal cycling and promotes sulfate formation. Ca refines and stabilizes grains during thermal cycling and increases corrosion resistance during cyclic voltammetry testing. Sn and Al attribute to texturing in the material and increase corrosion rates.

Origin of Selective Nitrate Removal by Ni2+–Al3+ Layered Double Hydroxides in Aqueous Media and Its Application Potential in Seawater Purification

Abstract To understand the origin of the nitrate anion selectivity in layered double hydroxide (LDH; [Ni1−xAlx(OH)2]Clx) materials (i.e., Cl−-NiAl(x)LDH; x = 1/3 and 1/5) comprising Ni2+, Al3+, and exchangeable chloride anions, the equilibrium and kinetic properties of the chloride-to-nitrate anion exchange reaction were investigated in aqueous media. The anion exchange isotherms of the studied systems showed that the nitrate anion selectivity was significantly higher at x = 1/5 than at x = 1/3. The fine crystal structures of the LDH materials and the hydration states of the nitrate anions in their interlayer spaces were identified by synchrotron-radiation X-ray diffraction (SXRD) and Raman spectroscopy, respectively. The nitrate anion selectivities of Cl−-NiAl(x)LDH (x = 1/3 and 1/5) were determined by the relationship between the magnitudes of the thermal vibration parameters of the chloride and nitrate anions; the anion exchange reaction primarily gave NiAl(x)LDH containing anions with smaller thermal vibration parameters. Time-resolved SXRD measurements of the anion exchange reaction revealed that the exchange pathway differed depending on the nitrate anion selectivity. The nitrate anion removal ability and selectivity of Cl−-NiAl(x)LDH (x = 1/3 and 1/5) in artificial seawater were maintained, suggesting that Cl−-NiAl(1/5)LDH could be used for nitrate removal from contaminated seawater.

Novel characterization of lead-based micro-alloys for battery applications

Although Pb-alloy acid batteries have been incorporated in vehicles for decades, a significant gap exists in the scientific understanding of minor alloying elements in the complex Pb-alloy grid materials. The aim of this research is to close this gap by using modern analytical techniques to examine the effects associated with adding minor alloying elements, less than 100 ppm, in Pb-alloy grid materials during isothermal holds and thermal cycling at relatively high temperatures. In this study, pure Pb, Pb-Bi, and Pb-Ba foils are examined using high-energy synchrotron radiation X-ray diffraction measurements during in situ isothermal holding at 85 °C and thermal cycling from RT to 85°C to analyze the grain inhibition and phase evolution. It is observed that Ba inhibits grain growth while Bi does not, when compared to pure Pb. Furthermore, no obvious phase evolution in any of the three cases is observed. After the synchrotron radiation X-ray diffraction measurements, the three materials are examined ex situ using scanning electron microscopy to verify the results. Additionally, baseline sulfation studies were performed in a solution of approximately 5 M H2SO4 and Pb-Bi and Pb-Ba were added to the electrochemical cell to undergo cyclic voltammetry.

In situ synchrotron radiation X-ray diffraction measurements of Fe–Mo alloy hydrides formed under high pressure and high temperature

Conventional hydrides obtained thus far contain at least one type of metal with high hydrogen affinity, which can form metal hydrides near ambient pressure. In contrast, we synthesized metal hydrides comprising only metals with low hydrogenation affinity which are metals that do not form metal hydrides MHx (M stands for metal element, x > 0.5) below 1 GPa. This is because such hydrides are rare and would demonstrate novel properties and functionalities. To provide a guideline for synthesizing such hydrides, we clarified the hydrogenation reaction processes of FexMo1−x alloys at 6 GPa and 750 °C over a wide composition range of 0.41 ≤ x ≤ 0.88, where both Fe and Mo demonstrate low hydrogen affinities. Depending on the alloy composition, the hydrogenation reaction process can be classified into three types. Two kinds of novel hydrides were synthesized herein. First, FexMo1−xH (0.50 ≤ x ≤ 0.74) with metal elements at the vertices of hexagonal close-packed (hcp) lattices, and second, Fe0.88Mo0.12H with a complex crystal structure, which is likely to be a long-period close-packed structure.

Controlling the phase transformation window during stages of hot/cold forging of Ni-rich Ni–Ti alloy

A detailed microstructural analysis during the intermediate stages of fabrication of NiTi orthodontic archwire is carried out in this study. These microstructural findings were related to the phase transformation characteristics such as start and finish transformation temperature, thermal hysteresis, etc. The objective was to monitor the transformation window during the different stages of thermomechanical processing. The casted alloy was further subjected to combinations of hot and cold forging steps with intermediate annealing. Four different sample conditions were prepared. The microstructure development in these samples was studied through electron back-scattered diffraction and synchrotron radiation X-ray diffraction (SR-XRD) techniques. The phase transformation temperatures were determined by differential scanning calorimetric measurements. The microstructures showed grain boundary serrations, very large grains of austenite, twin-like features within austenite grains and mixed-phase distribution of austenite and martensite. The differences in microstructures were also clear in terms of local in-grain misorientation and grain boundary fractions. SR-XRD measurements further revealed possible precipitation of Ni4Ti3 and Ni3Ti. The martensite start temperature (Ms) was seen to be a clear function of high angle grain boundary fraction, while the finish temperature (Mf) showed an inverse trend. The transformation interval, Ms–Mf is related to the stored energy of austenite grains that determines the driving force to overcome the frictional work opposing the movement of the habit plane, while and Af –As largely depends on the elastic energy stored of the martensite plates during its growth. The hysteresis during reverse transformation (M → A) was related to the local in-grain misorientation.

Shape memory effect in metallic glasses

Shape memory effect in metallic glasses

Understanding the electrical transports of p-type polycrystalline SnSe with effective medium theory

SnSe crystal is one of the most potential thermoelectric materials due to its excellent transport properties. The electrical conductivity of p-type SnSe crystal gradually decreases with increasing temperature, while that of the polycrystalline sample shows a completely different trend. We revealed that below 400 K, the existence of plentiful grain boundaries dominates the carrier scattering and determines the electrical transport of p-type polycrystalline SnSe, while at high temperatures, from 400 to 800 K, the electrical transport and conductivity curve still requires a clear understanding. In this study, by conducting the high-temperature synchrotron radiation x-ray diffraction (SR-XRD) measurements and refining the patterns, we obtained the phase fractions of Pnma and Cmcm phases in this temperature range. Using the derived single-phase theoretical electrical conductivity, combined with the self-consistent effective medium theory, the electrical conductivity of p-type polycrystalline SnSe between 400 and 800 K was simulated. This study provides a perspective and simulation method to understand the electrical transport of p-type polycrystalline SnSe.

Non-Destructive Analysis of Crystal Structure Changes of Component Materials in Cylindrical Lithium-Ion Batteries at Elevated Temperature By Synchrotron Radiation x-Ray Diffraction Measurement

Temperature is one of the important factors for lithium-ion battery (LIB) which accelerates degradation of the performance. In many cases, degradation mechanism is studied by post-mortem analysis with destruction of degraded LIBs to obtain their component materials. However, these studies has a risk that any chemical and structural changes may have occurred in the samples during preparation process after destruction. Hence, development of in-situ and non-destructive analytical methods are strongly required. In this study, we report x-ray diffraction (XRD) measurement system using synchrotron radiation facility by which cylindrical LIB itself can be used as the sample without destruction and XRD patterns of cathode and anode layers are obtained separately. In addition, temperature of the sample can be controlled between RT and 250 °C.18650 type cylindrical LIBs were used as the sample of which capacity were ca. 1.2 Ah. The cathode active material was Li(Ni1/3Mn1/3Co1/3)O2 and the anode active material was graphite.XRD measurement was performed at BL46XU in SPring-8 with Huber multi-axis diffractometer. The incident beam was high-energy (72 keV) x-ray. A LaBr3 scintillation counter was used as the detector. The temperature of the sample batteries was controlled by specially designed system. Figure 1 shows XRD patterns of the anode layer of a sample LIB located at 1.65 mm inner from surface of the case. While only stage-1 structure (LiC6) was observed at RT, a new peak of stage-2 (LiC12) appeared and increased after the temperature beyond 90 °C which suggested that self-discharge would be accelerated at 90 °C and above. Figure 1

Growth and stress analyses of vanadium dioxide nanomembranes for controllable rolling

Vanadium dioxide (VO2)-based microactuators with fast and highly efficient dynamic responses have become one of the best candidates for microrobots and micromuscles. VO2 microstructures fabricated by rolling nanomembranes with component gradient along the vertical direction are considered to be promising for future applications, and thus need further investigation. Here, we quantify the effects of substrate temperature on the initial internal stress of the nanomembranes and achieve rolled-up single-component VO2 nanomembranes via stress engineering. Through synchrotron radiation x-ray diffraction (XRD) measurements, we find that the stress of nanomembranes is negatively correlated with substrate temperature, and its exact value can be calculated from the shift of the XRD peaks. Moreover, experimental results demonstrate that VO2 nanomembranes deposited on a Si/SiO2 substrate possess lower phase transition temperature and narrower hysteresis loops than those grown on quartz and Al2O3 substrates with similar surface morphology. The upward bending of the VO2 nanomembrane due to the tensile stress gradient from temperature changing during deposition is demonstrated, and the rolled-up VO2 microstructures with tunable stress and narrow hysteresis loops are considered to have advantageous applications in microactuators.

Comparing CALPHAD predictions with high energy synchrotron radiation X-ray diffraction measurements during in situ annealing of Al0.3CoCrFeNi high entropy alloy

High-entropy alloys (HEAs) offer the unique ability to tailor microstructures through thermal processing techniques. One family of alloys of interest is AlxCoCrFeNi, where x varies from 0.0 to 2.0 molar fraction which allows for a transition from face-centered cubic (FCC) to body-centered cubic (BCC) crystal structure, as well as the formation of various secondary phases, such as B2, sigma, and L12. In this study, we focus on the Al0.3CoCrFeNi HEA. Based on CALPHAD simulations, the Al0.3CoCrFeNi HEA consists of the following phases from highest to lowest temperature: a) FCC at high temperature, followed by b) B2 precipitation in an FCC matrix, c) then B2 and σ phase co-precipitation in an FCC matrix, d) then B2, σ phase, and L12 phase in an FCC matrix, and finally e) B2, σ phase, and L12 phase in a BCC matrix at low temperature. The purpose of our study is to compare phases observed using high-energy synchrotron radiation X-ray diffraction measurements during in situ annealing with the equilibrium phases predicted using CALPHAD. Phase evolution and dissolution are discussed and compared with the CALPHAD simulation predictions. Our experimental results matched well with the CALPHAD predictions of the phase evolution for the B2 phase, however, the phase dissolution of L12 and σ phases was incomplete, which is likely only observable using high resolution synchrotron radiation X-ray diffraction. Better CALPHAD models are needed as well as longer annealing times due to the complexity of achieving phase equilibrium in multi-phase HEAs.

InOOH Bulk Crystals and Ultrathin Nanowires under Compression.

InOOH bulk crystals and ultrathin nanowires have been investigated under high pressures by in situ synchrotron radiation X-ray diffraction measurements at ambient temperature. The anisotropic compression indicates that the b-axis is more compressible than the other two axes in InOOH under hydrostatic conditions. Two inflection points, which are associated with the hydrogen-bond strengthening, can be reflected in the plots of b/c ratio versus pressure (b/c–P plots). The size-induced enhancement of the bulk modulus can be visualized from the P–V plots. By comparing the differences in the compression of bulk InOOH and ultrathin nanowires, it is validated that the nanosize effects play an important role in the high-pressure behaviors of InOOH.

Utilization of unsaponifiable matter from rice bran oil fatty acid distillate for preparing an antioxidant-rich oleogel and evaluation of its properties

Rice bran oil fatty acid distillate (RBOFAD) is an important by-product obtained from the physical refining process. This fatty acid distillate contains high a amount of Unsaponifiable Matter (γ-oryzanol 3.27 gm/100gm UM; total tocopherol 10.93 mg/100 g UM; total phytosterol 21.81 g/100g UM; squalene 1.15 g/100 g UM and total fatty alcohol 73.34 g/100 g UM) and free fatty acids. Antioxidant-rich Oleogels were obtained from rice bran wax (RBW), rice bran oil fatty acid distillate (RBOFAD) and refined rice bran oil. The main objective of this study was to utilize the antioxidant-rich unsaponifiable matter of RBOFAD (UMRBOFAD) as an organogelator along with rice bran wax, which also acts as a good organogelator. Antioxidant-rich oleogel was prepared using UMRBFAD, ethylcellulose (EC) and RBW at 2%, 2%, 3% on weight basis, respectively, in refined rice bran oil and this antioxidant-rich oleogel was compared with rice bran oil oleogel using RBW at 7% on weight basis of rice bran oil. These oleogels were evaluated using a combination of techniques such as differential scanning calorimetry (DSC), polarized light microscopy (PLM), Viscosity, synchrotron radiation X-ray diffraction (SR-XRD) and FTIR Spectroscopy. The differential scanning calorimetry (DSC) measured the thermal properties of rice bran oil oleogel and high antioxidant-rich oleogel. Polarized light microscopy images revealed needle-like crystals for RBW. SR-XRD measurements were used for clarification of the crystal structures of the building blocks of these oleogels. The antioxidant activities of oleogels were evaluated involving DPPH and ABTS assays.

Unraveling the origin of stress-dependent glass transition temperature in metallic glasses

The effect of externally applied stress on glass transition temperature Tg, whose underlying mechanism remains a fascinating and open question in materials science and condense-matter physics, has been explored in a range of metallic glasses (MGs) in the last decades. Recent studies have found that hydrostatic pressure leads to a slight increase in Tg, while uniaxial compression causes notable decrement. However, the origin of stress-dependent Tg variation is largely unknown. Here we report new results of tensile stress effect on Tg in a Ni60Nb40 (at.%) MG through in situ tensile loading and high temperature synchrotron radiation X-ray diffraction measurements. Combining our experimental data with available reports on hydrostatic pressure and uniaxial compression, a universal picture of stress-induced variation in Tg of MGs under various stress states was obtained. We elucidate the physics underlying the stress-induced Tg variation by decomposing the uniaxial tensile stress into a hydrostatic stress combined with two pure shear stresses, and investigating the individual contributions of the decomposed stress states on Tg by atomistic simulations. Our results reveal an enhanced stress effect on Tg through a combination of different stress components. The variation in Tg was linked with stress-aided changes in local atomic configurations. Our theoretical predictions are shown to be in remarkable agreement with experiments, and fill the gap in the current understanding of stress-dependent Tg in MGs.

Direct Evaluation of Local Dynamic Viscoelastic Properties of Isotactic Polypropylene Films Based on a Dynamic μ-Beam X-ray Diffraction Method.

The local mechanical properties of crystalline polymer were evaluated using synchrotron radiation X-ray diffraction with 10 μm lateral resolution. A nonoriented isotactic polypropylene (iPP) film with isolated spherulites in a crystallized matrix was used as a model sample. In situ wide-angle X-ray diffraction (WAXD) measurement was performed on the iPP film using a microbeam synchrotron radiation X-ray under sinusoidal strain. The lattice spacing of the crystal planes increased and decreased in response to the applied sinusoidal strain. Local dynamic viscoelastic functions (dynamic storage and loss moduli (E' and E″)) were calculated at room temperature from the relationship between the calculated applied stress and the response strain obtained by dynamic μ-beam WAXD measurement inside and outside of the spherulites. The E' values inside and outside of spherulite obtained from the change in spacing of the (110) plane were 1.8 and 1.1 GPa, respectively. Furthermore, the E' value inside of spherulite obtained from the change in spacing of the (1̅13) plane was 6.0 GPa. These values can be explained by the deformation of crystallite, which depends on the direction of crystal planes. The results obtained here revealed that synchrotron radiation X-ray diffraction measurement gives not only structural information but also the local mechanical properties of the materials E'.

High-energy synchrotron radiation X-ray diffraction measurements during in situ aging of a NiTi-15 at. % Hf high temperature shape memory alloy

NiTiHf high temperature shape memory alloys (HTSMAs) have begun to show considerable progress in their ability to be manufactured and are now on the cusp of becoming viable alloys for use in the aerospace industry, mainly as actuation devices. By aging the alloys at intermediate temperatures between 450 and up to 700 °C, Ni-rich NiTiHf HTSMAs form the H-phase, a Ni-rich nanoscale precipitate which can be used to strengthen the alloy and improve the shape memory response; however, precipitate phase evolution and growth has not yet been studied in-situ nor have the effects of previous thermo-mechanical processing on their formation. In this study, H-phase precipitate formation is observed experimentally in situ during aging of a Ni-rich NiTiHf alloy using high energy synchrotron radiation X-ray diffraction (SR-XRD) measurements. The effects of prior thermo-mechanical treatments, i.e. hot and cold rolling, on its formation rate and coarsening rate are compared. It is shown that growth of the H-phase can be observed in situ using SR-XRD and the H-phase formation rate seems to exhibit linear growth when aging at 550 °C, while increasing the temperature to 650 °C shows a logarithmic trend that plateaus after approximately 1 h of aging. Other properties such as incubation time, austenite lattice strains, texture evolution, and overall comparison between hot and cold rolling are discussed. New potential peak age conditions are suggested based on the diffraction data and evaluated using three-point bending and TEM imaging.

Crystal Structure Analysis of Al / Ni Multilayer Powder during Exothermic Reaction by Synchrotron Radiation X-ray Diffraction Measurement

Crystal Structure Analysis of Al / Ni Multilayer Powder during Exothermic Reaction by Synchrotron Radiation X-ray Diffraction Measurement