Time-resolved Synchrotron X-ray Research Articles

Poly (3-hydroxybutyrate-co-3-hydroxyvalerate)/cellulose nanocrystal films: artificial weathering, humidity absorption, water vapor transmission rate, antimicrobial activity and biocompatibility

Bionanocomposite films of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) with different cellulose nanocrystal (CNC) loadings were prepared. Effects of artificial weathering, humidity absorption, water vapor transmission rate (WVTR), antimicrobial activity and biocompatibility were studied. Differential scanning calorimetry (DSC) and time resolved synchrotron X-ray diffraction were used to provide information about the effect of CNC on the crystalline structure of PHBV in the bionanocomposites. The incorporation of CNC accelerated the crystallization rate of PHBV due to a nucleating effect. DSC results showed first a decrease of crystallization and then the occurrence of secondary crystallization after artificial weathering. Scanning electron microscopy images implied well CNC distribution before artificial weathering and formation of blister—like points due to artificial weathering. Hydrophobicity of bionanocomposites was found to be slightly lower than for the PHBV in the humidity absorption tests. Bionanocomposites exhibited smaller WVTR due to restricted PHBV chain mobility. Samples with zinc oxide and silver showed antimicrobial inhibition activities against S. enterica, L. monocytogenes, S. aureus and E. coli. Results of cell viability and nitrite accumulation tests showed that PHBV and its bionanocomposites were biocompatible.

Time-resolved synchrotron X-ray micro-tomography datasets of drainage and imbibition in carbonate rocks

Multiphase flow in permeable media is a complex pore-scale phenomenon, which is important in many natural and industrial processes. To understand the pore-scale dynamics of multiphase flow, we acquired time-series synchrotron X-ray micro-tomographic data at a voxel-resolution of 3.28 μm and time-resolution of 38 s during drainage and imbibition in a carbonate rock, under a capillary-dominated flow regime at elevated pressure. The time-series data library contains 496 tomographic images (gray-scale and segmented) for the complete drainage process, and 416 tomographic images (gray-scale and segmented) for the complete imbibition process. These datasets have been uploaded on the publicly accessible British Geological Survey repository, with the objective that the time-series information can be used by other groups to validate pore-scale displacement models such as direct simulations, pore-network and neural network models, as well as to investigate flow mechanisms related to the displacement and trapping of the non-wetting phase in the pore space. These datasets can also be used for improving segmentation algorithms for tomographic data with limited projections.

Thermal stability of the layered modification of Cu0.5ZrTe2 in the temperature range 25–900 °C

The thermal stability of the layered modification of the Cu0.5ZrTe2 polycrystalline intercalation compound, synthesized at room temperature, has been studied in the temperature range 25-900 °C. A change in the occupation of the octahedral and tetrahedral coordinated sites in the interlayer space of the zirconium ditelluride was observed using in-situ time-resolved synchrotron X-ray powder diffraction experiments. The formation of the rhombohedral CuZr2Te4 phase, which is stable in the temperature range 300-700 °C, has been observed. The copper intercalation at room temperature leads to the formation of a phase in which the Cu atoms occupy only octahedral sites in the interlayer space. At temperatures above the decay temperature of the rhombohedral CuZr2Te4, a layered phase with Cu atoms uniformly distributed between octahedral and tetrahedral sites in the interlayer space is stable. The changes in the crystal structure independent of temperature are in agreement with the previously proposed model, according to which the stability of the layered or the rhombohedral phase is determined by the entropy factor associated with the distribution of the intercalated atoms between the octahedral and tetrahedral sites in the interlayer space.

Synchrotron-based measurement of aluminum agglomerates at motor conditions

Solid rocket propellant combustion is hindered by agglomeration of aluminum particles on its burning surface and determining the particle size has been a problem for half a century. The actual size of the agglomerates at motor pressures is unknown due to the opacity of the combustion plume, particularly at the elevated pressures seen in operational rocket motors. Sampling techniques can provide data at elevated pressure but may be biased due to the sampling method and do not provide information on the dynamics of agglomerate formation. This study uses time-resolved synchrotron x-ray imaging (with both absorption and phase contrast) to view aluminum agglomerate formation in situ at relevant rocket pressures. We have for the first time observed agglomerate formation at motor-relevant pressures in real time with unprecedented fidelity, providing critical data for understanding the combustion of aluminized solid rocket propellants.

Isothermal Crystallization Kinetics of Palm Oil as Influenced by Addition of a Commercial Phytosterol Ester Mixture.

In literature there is good agreement on the health-promoting effects of phytosterols. However, addition of phytosterol esters (PEs) to lipid (containing food products) may influence its crystallization behavior. This study investigated the crystallization kinetics of palm oil (PO) after addition of PEs in high concentrations (≥10%). The isothermal crystallization of the PE-PO blends was analyzed at a temperature of 20 °C and at a supercooling of 18.7 °C using differential scanning calorimetry and time-resolved synchrotron X-ray diffraction. At increasing PE concentrations, PO crystallization at an isothermal temperature of 20 °C started later and was slower and a smaller amount of crystals were formed. Furthermore, a delay in polymorphic transition from α to β' was observed. When the blends were isothermally crystallized at a supercooling of 18.7 °C, only two of these effects remained: the delay in polymorphic transition and the decrease in crystalline content.

Macromol. Mater. Eng. 2/2018

Front Cover: Screw-assisted melt extrusion 3D printing has been developed for tissue engineering applications. The cover page image illustrates the in situ characterization of the polycaprolactone crystal structure evolution during the scaffold printing process via time-resolved synchrotron X-ray diffraction. This is reported by Fengyuan Liu, Cian Vyas, Gowsihan Poologasundarampillai, Ian Pape, Sri Hinduja, Wajira Mirihanage, and Paulo Bartolo in article number 1700494.

Rationalization of Hydrothermal Synthesis of NaNbO3 by Rapid in Situ Time-Resolved Synchrotron X-ray Diffraction

In situ monitoring of the formation of crystalline phases during conventional hydrothermal synthesis is experimentally challenging. Here, we report an in situ time-resolved synchrotron X-ray diffraction study during hydrothermal synthesis of NaNbO3 using a high-pressure custom-made capillary cell penetrable to X-rays. The high time resolution (0.1 s) revealed a sequence of transient intermediate phases, including several unknown phases, before the final perovskite NaNbO3 was formed. These new findings highlight the complexity of the hydrothermal synthesis of NaNbO3 and demonstrate the potential for obtaining in-depth knowledge of the reactions taking place by time-resolved in situ X-ray diffraction.

Transformation of Coiled α-Helices into Cross-β-Sheets Superstructure.

The fibrous silk produced by bees, wasps, ants, or hornets is known to form a four-strand α-helical coiled coil superstructure. We have succeeded in showing the formation of this coiled coil structure not only in natural fibers, but also in artificial films made of regenerated silk of the hornet Vespa simillima xanthoptera using wide- and small-angle X-ray scatterings and polarized Fourier transform infrared spectroscopy. On the basis of time-resolved simultaneous synchrotron X-ray scattering observations for in situ monitoring of the structural changes in regenerated silk material during tensile deformation, we have shown that the application of tensile force under appropriate conditions induces a transition from the coiled α-helices to a cross-β-sheet superstructure. The four-stranded tertiary superstructure remains unchanged during this process. It has also been shown that the amorphous protein chains in the regenerated silk material are transformed into conventional β-sheet arrangements with varying orientation.

Changes in the structure of birnessite during siderophore-promoted dissolution: A time-resolved synchrotron X-ray diffraction study

We used time-resolved synchrotron X-ray diffraction to follow the complete dissolution of synthetic triclinic Na-birnessite as promoted by the trihydroxamate siderophore desferrioxamine B (DFOB). Many microorganisms employ siderophores to increase the availability of Fe, Mn, and other trace metals for metabolic processes. Our primary goal was to quantify the DFOB-assisted dissolution rate by direct, continuous observation of the solid phase. Our kinetic model indicates that the rate of dissolution is dependent on [DFOB] but not pH, and has a reaction order of 0.505 with a rate constant of 0.112wt%birnmin−1. The unit-cell dimensions of birnessite remained virtually constant within error throughout the dissolution process, showing only a 0.3% contraction along the c-axis.Despite the small changes in unit-cell volume, Rietveld analysis revealed that the occupancy of Mn within the octahedral sheets decreased from 100% to ~80%, presumably as the result of complexation of structural Mn3+ with DFOB followed by extraction of Mn3+ from the crystal structure. These observations suggest a critical lacunarity of ~20mol% Mn for triclinic Na-birnessite, below which the structure is destabilized. Moreover, this study reveals that DFOB-promoted dissolution must operate by a different mechanism from that engaged when bacterial membrane fractions directly transfer electrons to birnessite crystals. We propose that crystal structure analysis of minerals undergoing dissimilatory metal reduction can elucidate metabolic pathways employed by microorganisms.

Stability of retained austenite in martensitic high carbon steels. Part I: Thermal stability

Thermal stability of retained austenite in 1C-1.5Cr steels with two Si and Mn contents is studied. Time-resolved high resolution synchrotron X-ray radiation and dilatometry are employed. The threshold transformation temperatures, decomposition kinetics, associated transformation strain, as well as the influence of Si and Mn were investigated. The coefficients of linear thermal expansion for both the bulk materials and individual phases are also obtained. The results indicate that an increase in the Mn and Si contents show little influence on the onset of retained austenite decomposition, but result in more thermally stable austenite. The decomposition is accompanied by a simultaneous increase in ferrite content which causes an expansive strain in the order of 10−4, and subsequent cementite development from 300 to 350°C which causes a contraction that helps to neutralise the expansive strain. During decomposition, a continuous increase in the carbon content of austenite, and a reduction in that of the tempered-martensite/ferrite phase was observed. This process continued at elevated temperatures until full decomposition was reached, which could take less than an hour at a heating rate of 0.05°C/s. Additionally, the observation of austenite peak splitting on samples with high Mn and Si contents suggests the existence of austenite of different stabilities in such matrix.

The effect of adding a commercial phytosterol ester mixture on the phase behavior of palm oil

The objective of this study was to investigate in depth the non-isothermal crystallization and melting behavior of binary blends of palm oil (PO) with a commercial, multi-component phytosterol ester (PE) mixture. DSC and time-resolved synchrotron X-ray diffraction (XRD) experiments were conducted on blends with a PE concentration from 0 to 100% at intervals of 10% for DSC and 20% for XRD. Based on XRD, two different ordered structures were identified in pure the PEs. The structure designated as PEx was truly crystalline and needed a very high degree of supercooling for its nucleation from the melt. The structure designated PEy formed without supercooling and showed long-range order with multiple reflections at small angles but only one broad reflection at high angle, typical of liquid crystalline samples. Furthermore, PEy had a high tolerance for molecules of different chemical nature. In the PE-PO blends no other ordered structures were formed other than the ones observed in the pure PEs and PO. The peaks in the DSC runs of the PE-PO blends were linked to transitions of the different polymorphic forms. All structural information of the binary blends as a function of concentration and temperature was collected in morphology maps. The binary blends exhibited eutectic characteristics visualized in the morphology maps with a eutectic point at 40% PEs.

A 4D view on the evolution of metamorphic dehydration reactions

Metamorphic reactions influence the evolution of the Earth’s crust in a range of tectonic settings. For example hydrous mineral dehydration in a subducting slab can produce fluid overpressures which may trigger seismicity. During reaction the mechanisms of chemical transport, including water expulsion, will dictate the rate of transformation and hence the evolution of physical properties such as fluid pressure. Despite the importance of such processes, direct observation of mineral changes due to chemical transport during metamorphism has been previously impossible both in nature and in experiment. Using time-resolved (4D) synchrotron X-ray microtomography we have imaged a complete metamorphic reaction and show how chemical transport evolves during reaction. We analyse the dehydration of gypsum to form bassanite and H2O which, like most dehydration reactions, produces a solid volume reduction leading to the formation of pore space. This porosity surrounds new bassanite grains producing fluid-filled moats, across which transport of dissolved ions to the growing grains occurs via diffusion. As moats grow in width, diffusion and hence reaction rate slow down. Our results demonstrate how, with new insights into the chemical transport mechanisms, we can move towards a more fundamental understanding of the hydraulic and chemical evolution of natural dehydrating systems.

Formation of intermetallic δ phase in Al-10Si-0.3Fe alloy investigated by in-situ 4D X-ray synchrotron tomography

During solidification of Fe-containing Al-Si casting alloys, various different intermetallic phases are formed. As this can have an impact on mechanical properties we investigated phase formation by applying in-situ time resolved synchrotron X-ray tomography. For a commercially pure Al-10Si-0.3 wt.% Fe alloy, phase morphology and spatial arrangement during solidification was revealed with 1 °C temperature resolution. We find that many of the intermetallic phases that have been identified as β-AlFeSi phases in previous studies are in fact δ phases. It was found that δ plates mainly nucleate on the eutectic Al and Si. δ phase formation terminates almost simultaneously with the final solidification of eutectic phases. Features of δ phase growth such as impingement, branching and deformation of plates are discussed. The phase separation sequence during solidification is described and explained by the existence of “cells” of residual liquid in which δ phase formation progresses rapidly due to the supersaturation of solute atoms.

From Rate Measurements to Mechanistic Data for Condensed Matter Reactions: A Case Study Using the Crystallization of [Zn(OH2)6][ZnCl4

The kinetics of crystallization of the R = 3 hydrate of zinc chloride, [Zn(OH2)6][ZnCl4], is measured by time-resolved synchrotron x-ray diffraction, time-resolved neutron diffraction, and by differential scanning calorimetry. It is shown that analysis of the rate data using the classic Kolmogorov, Johnson, Mehl, Avrami (KJMA) kinetic model affords radically different rate constants for equivalent reaction conditions. Reintroducing the amount of sample measured by each method into the kinetic model, using our recently developed modified-KJMA model (M-KJMA), it is shown that each of these diverse rate measurement techniques can give the intrinsic, material specific rate constant, the velocity of the phase boundary, vpb. These data are then compared to the velocity of the crystallization front directly measured optically. The time-resolved diffraction methods uniquely monitor the loss of the liquid reactant and formation of the crystalline product demonstrating that the crystallization of this hydrate phase proceeds through no intermediate phases. The temperature dependent vpb data are then well fit to transition zone theory to extract activation parameters. These demonstrate that the rate-limiting component to this crystallization reaction is the ordering of the waters (or protons) of hydration into restricted positions of the crystalline lattice resulting in large negative entropy of activation.

A kinetic analysis of the transformation from akaganeite to hematite: An in situ time-resolved X-ray diffraction study

The nucleation and growth of akaganeite and its transformation to hematite under hydrothermal conditions were monitored over a temperature range of 80 to 200°C using time-resolved synchrotron X-ray diffraction. In each experiment, akaganeite was the first phase to form and hematite was the final phase. No intermediate phases were identified. The induction time to akaganeite nucleation was ~5525s and 537s at 80°C and 100°C, respectively, yielding an activation energy of 129±15kJ/mol. However, akaganeite nucleated at a constant temperature of 123±5°C when the heater set point was 150°C or higher, suggesting an activation energy for akaganeite nucleation of 0kJ/mol between 150 and 200°C. Hematite nucleation induction times decreased with increasing temperature from 1723s to 110s between 150 and 200°C. Based on a JMAK analysis, the activation energies for the crystal growth and dissolution of akaganeite were 74±8kJ/mol and 125±7kJ/mol, respectively. Our calculated activation energies for hematite nucleation and crystal growth were 80±13kJ/mol and 110±21kJ/mol, respectively.

Anhydrous Calcium Oxalate Polymorphism: A Combined Computational and Synchrotron X-ray Diffraction Study

Four possible models for anhydrous calcium oxalate (COA) polymorphs have been investigated through ab initio quantum mechanical methods. Their structural properties, infrared and Raman spectra, and thermodynamic stability in the range of 0–800 K have been analyzed and compared. Along with the known β-COA structure, two models turn out to be possible candidates for the α- and γ-polymorphs that were observed during dehydration of weddellite (calcium oxalate dihydrate, COD) by Walter-Lévy and Laniepce (C. R. Acad. Sci. Paris 1964, 259, 4685). While the calculated vibrational frequencies show that the four COA models correspond to minimum energy structures, β-COA is the thermodynamically favored phase over the range of temperatures examined in the present study. Despite the fact that computed vibrational spectra and X-ray diffraction (XRD) patterns of these polymorphs exhibit some different features, a definitive assignment of the structures based on computational results is not possible due to the lack of accurate experimental data. In an effort to improve comparative experimental data, the structural evolution of whewellite (calcium oxalate monohydrate, COM) has been probed using time-resolved synchrotron X-ray diffraction, in order to correlate the calculated structures to the observed structures. The evolution has been shown to go through at least four phases identified as COM, α-COA (corresponding to one of the models proposed by computation), β-COA, and CaCO3. The reactions are predominantly two-phase reactions, and at 140 °C evidence of three-phase coexistence has been noted between COM, α-COA, and β-COA. The time-resolved XRD data allow estimation of the kinetics of the reactions; these indicate second-order reactions between COM and α-COA and zeroth-order reactions between α-COA and β-COA.

Deformation and fracture of explosion-welded Ti/Al plates: A synchrotron-based study

Explosion-welded Ti/Al plates are characterized with energy dispersive spectroscopy and x-ray computed tomography, and exhibit smooth, well-jointed, interface. We perform dynamic and quasi-static uniaxial tension experiments on Ti/Al with the loading direction either perpendicular or parallel to the Ti/Al interface, using a mini split Hopkinson tension bar and a material testing system in conjunction with time-resolved synchrotron x-ray imaging. X-ray imaging and strain-field mapping reveal different deformation mechanisms responsible for anisotropic bulk-scale responses, including yield strength, ductility and rate sensitivity. Deformation and fracture are achieved predominantly in Al layer for perpendicular loading, but both Ti and Al layers as well as the interface play a role for parallel loading. The rate sensitivity of Ti/Al follows those of the constituent metals. For perpendicular loading, single deformation band develops in Al layer under quasi-static loading, while multiple deformation bands nucleate simultaneously under dynamic loading, leading to a higher dynamic fracture strain. For parallel loading, the interface impedes the growth of deformation and results in increased ductility of Ti/Al under quasi-static loading, while interface fracture occurs under dynamic loading due to the disparity in Poisson's contraction.

Anhydrate to hydrate solid-state transformations of carbamazepine and nitrofurantoin in biorelevant media studied in situ using time-resolved synchrotron X-ray diffraction

Transformation of the solid-state form of a drug compound in the lumen of the gastrointestinal tract may alter the drug bioavailability and in extreme cases result in patient fatalities. The solution-mediated anhydrate-to-hydrate phase transformation was examined using an in vitro model with different biorelevant media, simulated fasted and fed state intestinal fluids containing bile salt and dioleoylphosphatidylcholine (DOPC) micelles, DOPC/sodium dodecyl sulfate (SDS) mixture, bile salt solution and water. Two anhydrate compounds (carbamazepine, CBZ and nitrofurantoin, NF) with different overall transformation time into hydrate form were used as model compounds. The transformations were monitored using direct structural information from time-resolved synchrotron X-ray diffraction. The kinetics of these transformations were estimated using multivariate data analysis (principal component analysis, PCA) and compared to those for nitrofurantoin (NF). The study showed that the solution-mediated phase transformation of CBZ anhydrate was remarkably faster in the DOPC/SDS medium compared to transformation in all the other aqueous dispersion media. The conversion time for CBZ anhydrate in water was shorter than for DOPC/SDS but still faster than the conversion seen in fed and fasted state micellar media. The conversion of CBZ anhydrate to hydrate was the slowest in the solution containing bile salt alone. In contrast, the solution-mediated phase transformations of NF did only show limited kinetic dependence on the dispersion media used, indicating the complexity of the nucleation process. Furthermore, when the CBZ and NF material was compacted into tablets the transformation times were remarkably slower. Results suggest that variations in the composition of the contents of the stomach/gut may affect the recrystallization kinetics, especially when investigating compounds with relatively fast overall transformation time, such as CBZ.

Spatially confined low-power optically pumped ultrafast synchrotron x-ray nanodiffraction.

The combination of ultrafast optical excitation and time-resolved synchrotron x-ray nanodiffraction provides unique insight into the photoinduced dynamics of materials, with the spatial resolution required to probe individual nanostructures or small volumes within heterogeneous materials. Optically excited x-ray nanobeam experiments are challenging because the high total optical power required for experimentally relevant optical fluences leads to mechanical instability due to heating. For a given fluence, tightly focusing the optical excitation reduces the average optical power by more than three orders of magnitude and thus ensures sufficient thermal stability for x-ray nanobeam studies. Delivering optical pulses via a scannable fiber-coupled optical objective provides a well-defined excitation geometry during rotation and translation of the sample and allows the selective excitation of isolated areas within the sample. Experimental studies of the photoinduced lattice dynamics of a 35 nm BiFeO3 thin film on a SrTiO3 substrate demonstrate the potential to excite and probe nanoscale volumes.

Novel Electrothermodynamic Power Generation

To investigate how exhaust heat from automobiles can be converted to renewable energy, an innovative electrothermodynamic cycle is presented, which is based on temporal temperature variations, the pyroelectric effect, instead of spatial temperature gradient, and the Seebeck effect. A generating mechanism is investigated using operando time-resolved synchrotron X-ray diffraction. Practical energy and true energy breakeven are achieved via real engine dynamometer experiments.