I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[20893, 20094]
Open Access
Abstract: In situ electrochemical cycling combined with total scattering measurements can provide valuable structural information on crystalline, semi-crystalline and amorphous phases present during (dis)charging of batteries. In situ measurements are particularly challenging for total scattering experiments due to the requirement for low, constant and reproducible backgrounds. Poor cell design can introduce artefacts into the total scattering data or cause inhomogeneous electrochemical cycling, leading to poor data quality or misleading results. This work presents a new cell design optimized to provide good electrochemical performance while performing bulk multi-scale characterizations based on total scattering and pair distribution function methods, and with potential for techniques such as X-ray Raman spectroscopy. As an example, the structural changes of a nanostructured high-capacity cathode with a disordered rock-salt structure and composition Li4Mn2O5 are demonstrated. The results show that there is no contribution to the recorded signal from other cell components, and a very low and consistent contribution from the cell background.
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Sep 2020
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B18-Core EXAFS
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Diamond Proposal Number(s):
[14239]
Abstract: Defects of various types in crystalline and nanocrystalline materials govern a range of electrical, optical and mechanical properties. In particular, they are at the heart of translational ion dynamics in solid electrolytes. One of the most prominent examples revealing a drastic increase in ionic conductivity σDC by several orders of magnitude when going from an ordered crystalline matrix to a structurally disordered one is lithium tantalate. Here, structurally disordered, nanocrystalline LiTaO3 served as a model substance to shed light on the question to what extent the degree of disorder decreases upon annealing an originally defect-rich oxide. Disorder can be introduced by high-energy ball milling of LiTaO3 crystallites with diameters in the μm range. Broadband conductivity spectroscopy, EXAFS and positron annihilation lifetime spectroscopy were used to correlate ion transport properties with interatomic distances, bond distortions and positron lifetimes. It turned out that milling times of only 30 min are sufficient to generate a highly defective oxide. Upon annealing at temperatures of T = 200 °C the defects can almost be preserved. Annealing at 750 °C for 1 h is needed to induce healing of the defects. Although we observe a recovery of the original interatomic distances and an increase in activation energy Ea for ionic transport from 0.75 eV to 0.81 eV, the initial transport properties of the unmilled sample (0.97 eV) cannot be fully restored. Most interestingly, the change in Ea is accompanied by a change of the entropy-controlled Arrhenius pre-factor governing the temperature dependence of σDCT. Moreover, positron lifetimes remain high in the annealed samples. Hence, our results point to samples with fewer distortions but still rich in vacancy-type defects. Altogether, the combination of ball milling and annealing helps adjust ionic conductivities in LiTaO3 to vary over 4 to 5 orders of magnitude.
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Sep 2020
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I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[21742]
Open Access
Abstract: Amorphous tin-gallium oxide (a-SGO) grown with atomic layer deposition was evaluated as a buffer layer in (Ag,Cu)(In,Ga)Se2 thin-film solar cells in search for a new material that is compatible with a variety of absorber band gaps. Hard and soft X-ray photoelectron spectroscopy on absorber/a-SGO stacks combined with J–V characterization of solar cells that were fabricated, showed that the conduction band alignment at the absorber/a-SGO interface can be tuned by varying the cation composition and/or growth temperature. Here, the surface band gap was 1.1 eV for the absorber. However, optical band gap data for a-SGO indicate that a suitable conduction band alignment can most likely be achieved even for wider absorber band gaps relevant for tandem top cells. A best efficiency of 17.0% was achieved for (Ag,Cu)(In,Ga)Se2/a-SGO devices, compared to η = 18.6% for the best corresponding CdS reference. Lower fill factor and open-circuit voltage values were responsible for lower cell efficiencies. The reduced fill factor is explained by a larger series resistance, seemingly related to interface properties, which are yet to be optimized. Some layer constellations resulted in degradation in fill factor during light soaking as well. This may partly be explained by light-induced changes in the electrical properties of a-SGO, according to analysis of Al/SGO/n-Si metal-oxide-semiconductor capacitors that were fabricated and characterized with J–V and C–V. Moreover, the introduction of a 1 nm thick Ga2O3 interlayer between the absorber and a-SGO improved the open-circuit voltage, which further indicates that the absorber/a-SGO interface can be improved.
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Sep 2020
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Open Access
Abstract: The CD8 T cell response to the HLA-A2-restricted epitope LLWNGPMAV (LLW) of the non-structural protein 4b of Yellow Fever Virus (YFV) is remarkably immunodominant, highly prevalent and powerful in YFV-vaccinated humans. Here we used a combinatorial peptide library screening in the context of an A2/LLW-specific CD8 T cell clone to identify a superagonist that features a methionine to isoleucine substitution at position 7. Based on in silico modeling, the functional enhancement of this LLW-7I mutation was associated with alterations in the structural dynamics of the peptide in the major histocompatibility complex (pMHC) binding with the T cell receptor (TCR). While the TCR off-rate of LLW-7I pMHC is comparable to the wild type peptide, the rigidity of the 7I peptide seems to confer less entropy loss upon TCR binding. This LLW-7I superagonist is an example of improved functionality in human CD8 T cells associated with optimized ligand rigidity for TCR binding and not with changes in TCR:pMHC off-rate kinetics.
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Sep 2020
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Open Access
Abstract: Conventional battery cathodes are limited by the redox capacity of the transition metal components. For example, the delithiation of LiCoO2 involves the formal oxidation from Co(III) to Co(IV). Enhanced capacities can be achieved if the anion also contributes to reversible oxidation. The origins of redox activity in crystals are difficult to quantify from experimental measurements or first-principles materials modelling. We present practical procedures to describe the electrostatic (Madelung potential) and electronic (integrated density of states) contributions, which are applied to the LiMO2 and Li2 MO3 (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt, Au) model systems. We discuss how such descriptors could be integrated in a materials design workflow.
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Sep 2020
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I13-1-Coherence
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Frank
Seiboth
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Dennis
Brückner
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Maik
Kahnt
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Mikhail
Lyubomirskiy
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Felix
Wittwer
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Dmitry
Dzhigaev
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Tobias
Ullsperger
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Stefan
Nolte
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Frieder
Koch
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Christian
David
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Jan
Garrevoet
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Gerald
Falkenberg
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Christian G.
Schroer
Diamond Proposal Number(s):
[19906]
Open Access
Abstract: Modern subtractive and additive manufacturing techniques present new avenues for X-ray optics with complex shapes and patterns. Refractive phase plates acting as glasses for X-ray optics have been fabricated, and spherical aberration in refractive X-ray lenses made from beryllium has been successfully corrected. A diamond phase plate made by femtosecond laser ablation was found to improve the Strehl ratio of a lens stack with a numerical aperture (NA) of 0.88 × 10−3 at 8.2 keV from 0.1 to 0.7. A polymer phase plate made by additive printing achieved an increase in the Strehl ratio of a lens stack at 35 keV with NA of 0.18 × 10−3 from 0.15 to 0.89, demonstrating diffraction-limited nanofocusing at high X-ray energies.
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Sep 2020
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Herbert J.
Bernstein
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Andreas
Forster
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Asmit
Bhowmick
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Aaron S.
Brewster
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Sandor
Brockhauser
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Luca
Gelisio
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David R.
Hall
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Filip
Leonarski
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Valerio
Mariani
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Gianluca
Santoni
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Clemens
Vonrhein
,
Graeme
Winter
Open Access
Abstract: Macromolecular crystallography (MX) is the dominant means of determining the three-dimensional structures of biological macromolecules. Over the last few decades, most MX data have been collected at synchrotron beamlines using a large number of different detectors produced by various manufacturers and taking advantage of various protocols and goniometries. These data came in their own formats: sometimes proprietary, sometimes open. The associated metadata rarely reached the degree of completeness required for data management according to Findability, Accessibility, Interoperability and Reusability (FAIR) principles. Efforts to reuse old data by other investigators or even by the original investigators some time later were often frustrated. In the culmination of an effort dating back more than two decades, a large portion of the research community concerned with high data-rate macromolecular crystallography (HDRMX) has now agreed to an updated specification of data and metadata for diffraction images produced at synchrotron light sources and X-ray free-electron lasers (XFELs). This `Gold Standard' will facilitate the processing of data sets independent of the facility at which they were collected and enable data archiving according to FAIR principles, with a particular focus on interoperability and reusability. This agreed standard builds on the NeXus/HDF5 NXmx application definition and the International Union of Crystallography (IUCr) imgCIF/CBF dictionary, and it is compatible with major data-processing programs and pipelines. Just as with the IUCr CBF/imgCIF standard from which it arose and to which it is tied, the NeXus/HDF5 NXmx Gold Standard application definition is intended to be applicable to all detectors used for crystallography, and all hardware and software developers in the field are encouraged to adopt and contribute to the standard.
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Sep 2020
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I12-JEEP: Joint Engineering, Environmental and Processing
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Diamond Proposal Number(s):
[12606]
Abstract: Effects of plastic constraint on the fracture of materials have been studied extensively. Often in such studies, the plastic constraint is divided into in-plane and out-of-plane directions and each treated separately. Such a separation adds considerable complexity to the engineering structural integrity assessment analyses. Despite previous suggestions for unifying the effects of constraint in a single parameter, the current engineering assessments have not been updated due to lack of direct experimental validation of such parameters. In this study, we directly measured the effects of in-plane and out-of-plane constraints, for the first time, in the form of plastic zone around the crack using advanced experimental techniques. The measurement of constraints in four specimens with different levels of in and out of plane constraints, allowed us to show and relate the interdependency of in and out of plane constraints. The tests were carried out using synchrotron X-ray tomography with in-situ loading. Attenuation contrast between the constituents of the metal matrix composite material used allowed the tomograms to be analysed using digital volume correlation which calculated the full-field displacement within the samples. The displacement fields were used via a finite element framework to calculate the energy release rate in the form of the J-integral along the crack fronts. The measured plastic zone sizes, dependant on the combined level of in plane and out of plane constraints, were used successfully to rank the J-Integral at fracture of the samples. It was therefore proved the level of plastic constraint can be quantified by using the size of the plastic zone as without separating it into two components thus simplifying the treatment of constraint in structural analyses significantly.
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Aug 2020
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I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[20494]
Abstract: This research provides a thorough study of the mechanical response of PCL scaffolds and determines their deformation micromechanisms at different scales by a combination of experimental techniques (mechanical tests, scanning electron microscopy, wide angle X-ray diffraction and small-angle X-ray scattering). Scaffolds with different fibre orientation distribution functions were manufactured and subjected to tensile loading. The macromechanical properties were dictated the by the fibre deformation and interaction in terms of fibre straightening, rotation and stretching. The stiffness and the yield strength were directly proportional to the percentage of fibres oriented with the loading direction. The gradual deformation induced a progressive fibre rotation, uncurling and stretching, showing different impact at molecular level for each configuration. The fibres aligned with the loading direction presented a homogeneous plasticity with an inherent loss of the crystal phase, meanwhile the misaligned fibres exhibited a negligible loss of crystallinity due to a predominance of the fibre rotation. The fibre plasticity triggered the macromechanical yielding of the scaffold and for high levels of plastic deformation the fibres developed macromolecular fibrils and microvoids. These findings provide the fundamental observations to develop engineering tissues with highly tunable and tailored mechanical properties for site specific in vivo applications.
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Aug 2020
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I15-Extreme Conditions
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Diamond Proposal Number(s):
[18643]
Abstract: Alkali-silica reaction (ASR) causes severe degradation of concrete. The mechanical property of the ASR product is fundamental to the multiscale modeling of concrete behavior over the long term. Despite years of study, there is a lack of consensus regarding the structure and elastic modulus of the ASR product. Here, ASR products from both degraded field infrastructures and laboratory synthesis were investigated using high-pressure X-ray diffraction. The results unveiled the multiphase and metastable nature of ASR products from the field. The dominant phase undergoes permanent phase change via collapsing of the interlayer region and in-planar glide of the main layer, under pressure >2 GPa. The bulk moduli of the low- and high-pressure polymorphs are 27±3 and 46±3 GPa, respectively. The laboratory-synthesized sample and the minor phase in the field samples undergo no changes of phase during compression. Their bulk moduli are 35±2 and 76±4 GPa, respectively. The results provide the first atomistic-scale measurement of the mechanical property of crystalline ASR products.
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Aug 2020
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