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At least 991 records · Page 55

Synchrotron Microbeam Diffraction Studies on the Alignment within 3D-Printed Smectic-A Liquid Crystal Elastomer Filaments during Extrusion

3D printing of novel and smart materials has received considerable attention due to its applications within biological and medical fields, mostly as they can be used to print complex architectures and particular designs. However, the internal structure during 3D printing can be problematic to resolve. We present here how time-resolved synchrotron microbeam Small-Angle X-ray Diffraction (μ-SAXD) allows us to elucidate the local orientational structure of a liquid crystal elastomer-based printed scaffold. Most reported 3D-printed liquid crystal elastomers are mainly nematic; here, we present a Smectic-A 3D-printed liquid crystal elastomer that has previously been reported to promote cell proliferation and alignment. The data obtained on the 3D-printed filaments will provide insights into the internal structure of the liquid crystal elastomer for the future fabrication of liquid crystal elastomers as responsive and anisotropic 3D cell scaffolds.

36 MATERIALS SCIENCE↗

Can Cr( iii ) substitute for Al( iii ) in the structure of boehmite?

The dissolution of boehmite is a technical issue for the Al industry because of its recalcitrant nature. In fact, a similar problem exists with boehmite in nuclear waste sludge at the Hanford site in eastern Washington State, USA. Dissolution of Al phases is required to reduce the waste loadings in the final borosilicate glass waste form. Although not the most common Al-bearing species in the sludge, boehmite may become a rate limiting step in the processing of the wastes. Hanford boehmite is an order of magnitude more resistant to dissolution in hot caustic solutions than expected from surface-normalized rates. We are exploring potential intrinsic and extrinsic effects that may limit boehmite reactivity; one clue comes from microstructural analyses that indicate an association of Cr with Al in the Hanford nuclear waste. Hence, in this first paper, we investigated the potential role of chromium on the reactivity of boehmite in caustic solution. An important finding was that irrespective of the synthesis pathway, amount of Cr(III), or the resultant morphology, there was no evidence for Cr incorporation in the bulk structure, in agreement with QM calculations. In fact, electron microscopic (EM) and spectroscopic analyses showed that Cr was enriched at the (101) edges of the boehmite. However, Cr had no measurable effect on the morphology during the synthesis step. In contrast, comparison of the morphologies of the synthetic Cr-doped and pure boehmite samples after exposure to caustic solutions provided evidence that Cr inhibited the corrosion. TEM showed that Cr was not homogeneously distributed at the surface. Consequently, Cr may have partially passivated the surface by blocking discrete energetic sites on the lateral surfaces of boehmite.

1-Cra and 1-Crb↗

Synthesis and X-ray diffraction study of (Cs{sub 0.5}Ba{sub 0.25})[UO{sub 2}(CH{sub 3}COO){sub 3}] and Ba{sub 0.5}[UO{sub 2}(CH{sub 3}COO){sub 3}]

Uranyl triacetate complexes (Cs{sub 0.5}Ba{sub 0.25})[UO{sub 2}(CH{sub 3}COO){sub 3}] (I) and Ba{sub 0.5}[UO{sub 2}(CH{sub 3}COO){sub 3}] (II) are synthesized for the first time and their structures are determined by X-ray diffraction. Both compounds crystallize in the cubic crystal system. The crystal data are as follows: a = 17.3289(7) Angstrom-Sign , V = 5203.7(4) Angstrom-Sign {sup 3}, space group I2{sub 1}3 and Z = 16 (I); a = 17.0515(8) Angstrom-Sign , V = 4957.8(4) Angstrom-Sign {sup 3}, space group I 4 bar 3d, and Z = 16 (II). In I and II, as in all uranyl triacetates studied earlier, the coordination polyhedron of the uranium atom is a hexagonal bipyramid whose vertices are occupied by the oxygen atoms of the uranyl and three acetate groups. The uranium-containing group belongs to the AB{sub 3}{sup 01} (A = UO{sub 2}{sup 2+}, B{sup 01} = CH{sub 3}COO{sup -}) crystal chemical group of uranyl complexes. It was found that compound II is isostructural to the (Rb{sub 0.50}Ba{sub 0.25})[UO{sub 2}(CH{sub 3}COO){sub 3}] studied earlier.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Isolation, structural modification of macrophin from endophytic fungus Phoma macrostoma and their cytotoxic potential

Four known metabolites, macrophin (1), rosellisin (2), 2-(2-hydroxy-5-6-methoxy-3-methylene-1,4-benzodioxin-2(3H)-one (3), and methoxyphenoxyacrylic acid (4) were isolated, for the first time, from an endophytic fungus, Phoma macrostoma inhabiting the inner tissue of medicinal plant Glycyrrhiza glabra Linn. Their structures were characterized by comparison of their NMR data with literature data, and X-ray diffraction data of macrophin (1) as described herein for the first time. The compounds (1–4) were evaluated for their growth-inhibitory activities against a panel of cancer cell lines. Of these substances, macrophin (1) showed prominent cytotoxic activity against the MDA-MB-231, T47D, MCF-7, and MIAPaCa-2 cancer-cell lines with IC{sub 50} values of 14.8, 8.12, 13.0, and 0.9 μM, respectively. This biological significance has prompted us to generate a series of five acylated analogs (1a–1e) of 1 to conduct structure–activity relationship (SAR) study. The result illustrates all the analogues (1a–1e) were more potent than 1 against MDMB-231 and MIAPaCa-2 cancer cell lines. The compound 1d, an n-butanoyl substituent, has been proven to be three-fold more potent than 1 with IC{sub 50} values of 0.3 and 3.7 µM against MIAPaCa-2 and MDMB-231 cell lines, respectively.

60 APPLIED LIFE SCIENCES↗

Towards a Counting Point Detector for Nanosecond Coherent X-ray Science

We present the technical realization of a high-speed hard X-ray single-photon counting-detection scheme based on a commercial avalanche silicon photodiode and high-speed oscilloscope. The development is motivated by the need to perform pulse-resolved photon-correlation and pump-probe studies at synchrotron sources with densely packed pulse patterns that result in high repetition rate pulses on the order of hundreds of MHz. Commissioning experiments are performed at the 1C PAL-KRISS beamline at PLS-II of South Korea operating at a burst mode maximum repetition rate of 500 MHz. In such a high count-rate measurement, detector dead-time can lead to a distortion of counting statistics. We are able to model the counting behavior of our detector under these conditions with a detector dead-time comparable to time between X-ray pulses, implying that nanosecond X-ray photon correlation spectroscopy should be possible at diffraction-limited light sources.

36 MATERIALS SCIENCE↗

Monitoring non-pseudomorphic epitaxial growth of spinel/perovskite oxide heterostructures by reflection high-energy electron diffraction

Pulsed laser deposition of spinel γ-Al{sub 2}O{sub 3} thin films on bulk perovskite SrTiO{sub 3} is monitored by high-pressure reflection high-energy electron diffraction (RHEED). The heteroepitaxial combination of two materials with different crystal structures is found to be inherently accompanied by a strong intensity modulation of bulk diffraction patterns from inelastically scattered electrons, which impedes the observation of RHEED intensity oscillations. Avoiding such electron surface-wave resonance enhancement by de-tuning the RHEED geometry allows for the separate observation of the surface-diffracted specular RHEED signal and thus the real-time monitoring of sub-unit cell two-dimensional layer-by-layer growth. Since these challenges are essentially rooted in the difference between film and substrate crystal structure, our findings are of relevance for the growth of any heterostructure combining oxides with different crystal symmetry and may thus facilitate the search for novel oxide heterointerfaces.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Nanoscale strain wave generation by a piezoelectric grating from polar vortices

Nanostructures formed by spontaneously broken symmetry have provided new ways to manipulate quantum states. Specifically, topological structures with periodic spatial ordering, such as polar vortices and skyrmions, can be ideal hosts for creating engineered responses in both spatial and frequency domains. So far, however, only a few examples of such hierarchical engineering have been reported in the literature. Here we demonstrate that the spatially modulated piezoelectric response of a polar vortex structure can create strain waves with a characteristic nanoscale wavefront. Using time-resolved pump–probe resonant X-ray scattering and diffraction measurements, coupled with dynamical phase-field simulations, we show that the piezoelectric modulation of the spontaneously formed polar vortex crystal functions as an acoustic diffraction grating. This system converts incoming laterally uniform strain waves into outgoing waves with a characteristic sub-terahertz frequency, driven by an intrinsic excitation of the polar vortex crystal. Moreover, our phase-field simulations suggest that the dynamic mechanical displacements exhibiting vortex textures are generated from both space- and time-varying piezoelectric responses. Our findings illustrate a new method for generating nanoscale strain waves with unique spatial textures by tuning the hierarchical order of polar topologies to engineer new collective modes, allowing for a wide range of control through the topological lattice.

ferroelectrics↗

Structural Characterization and Magnetic Properties of SrCo{sub 2}Fe{sub 16}O{sub 27} Hexaferrite Synthesized by Citric Acid Sol-Gel Method

The W -type SrCo{sub 2}Fe{sub 16}O{sub 27} (SCFO) hexagonal ferrite samples were prepared by the sol-gel method using metal nitrate as raw material, citric acid as complexing agent, and water as solvent. The effects of different sintering temperatures and holding times on the phase composition and morphology properties were explored in detail by using the X-ray diffractometer and field emission scanning electron microscope. The X-ray diffraction, microstructure, and magnetic performance of most optimum sintering temperature and holding time of preparing single-phase SCFO hexagonal ferrite were investigated. The experimental results indicate that the best optimum sintering temperature and holding time of SCFO hexagonal ferrite are 1280 °C and 4 h, respectively. Field emission scanning electron microscopy results indicate that the size of the particles is about 5–10 μ m. The result of magnetic measurement shows that SCFO hexagonal ferrite exhibits the soft magnetic property and the Curie temperature (T{sub C}) is ∼ 850 K. Furthermore, by analyzing the Arrott plot, the phase transition near the T{sub C} is a secondary phase transition.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Quantification of Metabolic Products from Microbial Hosts in Complex Media Using Optically Diffracting Hydrogels

In this work, we herein describe a highly versatile platform approach for the in situ and real-time screening of microbial biocatalysts for enhanced production of bioproducts using photonic crystal hydrogels. This approach was demonstrated by preparing optically diffracting films based on polymerized N-isopropylacrylamide that contracted in the presence of alcohols and organic acids. The hydrogel films were prepared in a microwell plate format, which allows for high-throughput screening, and characterized optically using a microwell plate reader. While demonstrating the ability to detect a broad range of relevant alcohols and organic acids, we showed that the response of the films correlated strongly with the octanol-water partition coefficient (log P) of the analyte. Differences in the secretion of ethanol and succinic acid from strains of Zymomonas mobilis and Actinobacillus succinogenes, respectively, were further detected via optical characterization of the films. These differences, which in some cases were as low as ~3 g/L, were confirmed by high-performance liquid chromatography, thereby demonstrating the sensitivity of this approach. Our findings highlight the potential utility of this multiplexed approach for the detection of small organic analytes in complex biological media, which overcomes a major challenge in conventional optical sensing methods.

09 BIOMASS FUELS↗

Real-time observation of rotational twin formation during molecular-beam epitaxial growth of GaAs on Si (111) by x-ray diffraction

The formation and evolution of rotational twin (TW) domains introduced by a stacking fault during molecular-beam epitaxial growth of GaAs on Si (111) substrates were studied by in situ x-ray diffraction. To modify the volume ratio of TW to total GaAs domains, GaAs was deposited under high and low group V/group III (V/III) flux ratios. For low V/III, there was less nucleation of TW than normal growth (NG) domains, although the NG and TW growth rates were similar. For high V/III, the NG and TW growth rates varied until a few GaAs monolayers were deposited; the mean TW domain size was smaller for all film thicknesses.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Recombination and bandgap engineering in CdSeTe/CdTe solar cells

Selenium compositional grading in CdTe-based thin-film solar cells substantively improves carrier lifetime and performance. However, where and how recombination lifetime improves has not been studied significantly. Here, we deposit a CdSe x Te 1-x /CdTe bilayer on MgZnO/SnO 2 /glass, which achieves a short-circuit current density greater than 28 mA/cm 2 and carrier lifetimes as long as 10-20 ns. We analyze the grain structure, composition, and recombination through the thickness of the absorber using electron backscatter diffraction, Auger-electron spectroscopy, cathodoluminescence spectrum imaging, and time-resolved photoluminescence microscopy. Despite small CdSeTe grains near the pn-junction and significantly larger CdTe grains in the rest of the film, both time-resolved photoluminescence and cathodoluminescence reveal that the carrier lifetime in CdSeTe alloy regions is longer than in CdTe regions. The results indicate that Se both passivates grain boundaries and improves grain-interior carrier lifetime. However, these effects occur only where there is significant alloying, which is important for bandgap engineering.

14 SOLAR ENERGY↗

A study of thermal properties of sodium titanate nanotubes synthesized by microwave-assisted hydrothermal method

Highlights: • The microwave-assisted hydrothermal route was used for titanate nanotubes synthesis. • Conversion to single-phase nanotube morphology completes after 8 h reaction time. • The nanotube morphology is stable up to 600 °C, as determined by in-situ XRD and SEM. • Sodium ions migrate to the surface due to thermal motion and structure condensation. - Abstract: Sodium titanate nanotubes (NaTiNTs) were synthesized by microwave-assisted hydrothermal treatment of commercial TiO{sub 2}, at constant temperature (135 °C) and different irradiation times (15 min, 1, 4, 8 and 16 h). The products were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, differential scanning calorimetry and specific surface area measurements. The irradiation time turned out to be the key parameter for morphological control of the material. Nanotubes were observed already after 15 min of microwave irradiation. The analyses of the products irradiated for 8 and 16 h confirm the complete transformation of the starting TiO{sub 2} powder to NaTiNTs. The nanotubes are open ended with multi-wall structures, with the average outer diameter of 8 nm and specific surface area up to 210 m{sup 2}/g. The morphology, surface area and crystal structure of the sodium titanate nanotubes synthesized by microwave-assisted hydrothermal method were similar to those obtained by conventional hydrothermal method.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Shortening x-ray pulses for pump-probe experiments at synchrotrons

We implemented an experimental scheme for ultrafast x-ray diffraction at storage rings based on a laser-driven Bragg-switch that shortens the x-ray pulses emitted from an undulator. The increased time-resolution is demonstrated by observing changes of intensity, position and width of the diffraction peaks of a La{sub 0.7}Sr{sub 0.3}MnO{sub 3}/SrTiO{sub 3} superlattice sample after optical excitation, i.e., by quantitatively measuring the propagation of an expansion wave through the sample. These experimental transients with timescales of 35 to 60 ps evidence a reduction of the x-ray pulse duration by a factor of two.

36 MATERIALS SCIENCE↗

Double-shot MeV electron diffraction and microscopy

Here in this paper, we study by numerical simulations a time-resolved MeV electron scattering mode where two consecutive electron pulses are used to capture the evolution of a material sample on 10 ps time scales. The two electron pulses are generated by illuminating a photocathode in a radiofrequency photogun by two short laser pulses with adjustable delay. A streak camera/deflecting cavity is used after the sample to project the two electron bunches on two well separated regions of the detector screen. By using sufficiently short pulses, the 2D spatial information from each snapshot can be preserved. This “double-shot” technique enables the efficient capture of irreversible dynamics in both diffraction and imaging modes. Finally, in this work, we demonstrate both modes in start-to-end simulations of the UCLA Pegasus MeV microscope column.

36 MATERIALS SCIENCE↗

Blocking Losses With a Photon Counter

It was not known how to assess accurately losses in a communications link due to photodetector blocking, a phenomenon wherein a detector is rendered inactive for a short time after the detection of a photon. When used to detect a communications signal, blocking leads to losses relative to an ideal detector, which may be measured as a reduction in the communications rate for a given received signal power, or an increase in the signal power required to support the same communications rate. This work involved characterizing blocking losses for single detectors and arrays of detectors. Blocking may be mitigated by spreading the signal intensity over an array of detectors, reducing the count rate on any one detector. A simple approximation was made to the blocking loss as a function of the probability that a detector is unblocked at a given time, essentially treating the blocking probability as a scaling of the detection efficiency. An exact statistical characterization was derived for a single detector, and an approximation for multiple detectors. This allowed derivation of several accurate approximations to the loss. Methods were also derived to account for a rise time in recovery, and non-uniform illumination due to diffraction and atmospheric distortion of the phase front. It was assumed that the communications signal is intensity modulated and received by an array of photon-counting photodetectors. For the purpose of this analysis, it was assumed that the detectors are ideal, in that they produce a signal that allows one to reproduce the arrival times of electrons, produced either as photoelectrons or from dark noise, exactly. For single detectors, the performance of the maximum-likelihood (ML) receiver in blocking is illustrated, as well as a maximum-count (MC) receiver, that, when receiving a pulse-position-modulated (PPM) signal, selects the symbol corresponding to the slot with the largest electron count. Whereas the MC receiver saturates at high count rates, the ML receiver may not. The loss in capacity, symbol-error-rate (SER), and count-rate were numerically computed. It was shown that the capacity and symbol-error-rate losses track, whereas the count-rate loss does not generally reflect the SER or capacity loss, as the slot-statistics at the detector output are no longer Poisson. It is also shown that the MC receiver loss may be accurately predicted for dead times on the order of a slot.

Moision, Burce E.↗

A Facile, One-Step Synthesis for Core–Shell Perovskite Materials via Molten Salt

Core–shell La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (LSCF)–La 0.8 Sr 0.2 MnO 3 (LSM) heterostructure crystalline materials have been synthesized in a simple, one-step feeding method via a KNO 3 molten salt solvent. Two-phase perovskite composites can be synthesized in times as short as 10 minutes and is demonstrated for the first time in a molten salt. Further, a combination of X-ray diffraction and S/TEM energy dispersive X-ray spectroscopy has been utilized to confirm the formation of an LSM shell on LSCF cores in all samples when adjusting dwell time, core size, weight ratio between core and shell precursors, and weight ratio of powder to salt. Specifically, decreasing the LSCF core size increases core–shell yield. Smaller cores introduce a greater density of facets on the crystal surface and provide more favorable sites for LSM heterogeneous nucleation.

36 MATERIALS SCIENCE↗

Laue-DIALS: Open-source software for polychromatic x-ray diffraction data

Most x-ray sources are inherently polychromatic. Polychromatic (“pink”) x-rays provide an efficient way to conduct diffraction experiments as many more photons can be used and large regions of reciprocal space can be probed without sample rotation during exposure—ideal conditions for time-resolved applications. Analysis of such data is complicated, however, causing most x-ray facilities to discard >99% of x-ray photons to obtain monochromatic data. Key challenges in analyzing polychromatic diffraction data include lattice searching, indexing and wavelength assignment, correction of measured intensities for wavelength-dependent effects, and deconvolution of harmonics. We recently described an algorithm, Careless, that can perform harmonic deconvolution and correct measured intensities for variation in wavelength when presented with integrated diffraction intensities and assigned wavelengths. Here, we present Laue-DIALS, an open-source software pipeline that indexes and integrates polychromatic diffraction data. Laue-DIALS is based on the dxtbx toolbox, which supports the DIALS software commonly used to process monochromatic data. As such, Laue-DIALS provides many of the same advantages: an open-source, modular, and extensible architecture, providing a robust basis for future development. We present benchmark results showing that Laue-DIALS, together with Careless, provides a suitable approach to the analysis of polychromatic diffraction data, including for time-resolved applications.

97 MATHEMATICS AND COMPUTING↗

Crystallization Mechanism and Charge Carrier Transport in MAPLE-Deposited Conjugated Polymer Thin Films

Although spin casting and chemical surface reactions are the most common methods used for fabricating functional polymer films onto substrates, they are limited with regard to producing films of certain morphological characteristics on different wetting and nonwetting substrates. The matrix-assisted pulsed laser evaporation (MAPLE) technique offers advantages with regard to producing films of different morphologies on different types of substrates. Here, we provide a quantitative characterization, using X-ray diffraction and optical methods, to elucidate the additive growth mechanism of MAPLE-deposited poly(3-hexylthiophene) (P3HT) films on substrates that have undergone different surface treatments, enabling them to possess different wettabilities. We show that MAPLE-deposited films are composed of crystalline phases, wherein the overall P3HT aggregate size and crystallite coherence length increase with deposition time. A complete pole figure constructed from X-ray diffraction measurements reveals that in these MAPLE-deposited films, there exist two distinct crystallite populations: (i) highly oriented crystals that grow from the flat dielectric substrate and (ii) misoriented crystals that preferentially grow on top of the existing polymer layers. The growth of the highly oriented crystals is highly sensitive to the chemistry of the substrate, whereas the effect of substrate chemistry on misoriented crystal growth is weaker. The use of a self-assembled monolayer to treat the substrate greatly enhances the population and crystallite coherence length at the buried interfaces, particularly during the early stage of deposition. Furthermore, the evolution of the in-plane carrier mobilities during the course of deposition is consistent with the development of highly oriented crystals at the buried interface, suggesting that this interface plays a key role toward determining carrier transport in organic thin-film transistors.

36 MATERIALS SCIENCE↗