I15-Extreme Conditions
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Diamond Proposal Number(s):
[22477]
Open Access
Abstract: Defects are emerging as a key tool for fine-tuning the stimuli-responsive behavior of coordination polymers and metal–organic frameworks. Here, we study the ramifications of defects on the mechanical properties of the molecular perovskite [C(NH2)3]MnII(HCOO)3 and its defective analogue [C(NH2)3]Fe2/3III□1/3(HCOO)3, where □ = vacancy. Defects reduce the bulk modulus by 30% and give rise to a temperature-driven phase transition not observed in the nondefective system. The results highlight the opportunities that come with defect-engineering approaches to alter the mechanical properties and underlying thermodynamics, with important implications for the research on stimuli-responsive materials.
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Jan 2021
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I15-Extreme Conditions
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Diamond Proposal Number(s):
[4631, 6707]
Abstract: High-pressure studies have been performed on the ε-form of the powerful explosive CL-20. Hydrostatic compression over the pressure range 0–12 GPa has been monitored using synchrotron X-ray powder diffraction. The potential effects of X-ray radiation damage were observed and circumvented through a follow-up compression study over the pressure range 0–7 GPa using neutron powder diffraction. This second study revealed smooth compression behavior, and the absence of any phase transitions. Intermolecular interaction energies as obtained using PIXEL calculations did not show any discontinuity upon the application of pressure. An isothermal equation of state has been determined, and the high-pressure response is supported by dispersion-corrected density functional theory calculations. Inelastic neutron scattering (experimental and simulated) spectra for the ε-form are in excellent agreement.
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Dec 2020
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I15-Extreme Conditions
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Diamond Proposal Number(s):
[17412]
Abstract: A melt-extracted HoErCo medium-entropy alloy (MEA) with large magnetic entropy change and excellent magnetic refrigerant capacity is successfully designed in this study. The microstructure evolution of these microwires near room temperature is studied by an in-situ high energy synchrotron X-ray diffraction (HEXRD). The wires show typical amorphous characteristics during room temperature to 250 K. For a field change of 5 T, the maximum magnetic entropy change (-ΔSMmax) of the microwires reaches a maximum value of 15.0 J•kg−1 K−1. Magnetization measurements revealed a paramagnetic to ferromagnetic phase transition at TC~16 K. The refrigerant capacity (RC) and relative cooling power (RCP) are 527 J•kg−1 and 600 J•kg−1, respectively. This investigation highlights the potential of HoErCo MEA microwires as promising magnetocaloric effect materials for cryogenic applications of magnetic cooling.
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Dec 2020
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I15-Extreme Conditions
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Diamond Proposal Number(s):
[26782]
Abstract: X-ray diffraction measurements performed in a diamond anvil cell under quasihydrostatic conditions up to 142 GPa at 300 K evidence an
α
-Zr
→
(17 GPa)
ω
-Zr
→
(35 GPa)
β
-Zr phase transitions sequence. Ab initio molecular dynamics calculations performed on the body-centered cubic
β
-Zr at 300 and 1000 K and between 0 and 100 GPa produced an equation of state in excellent agreement with the experiments. The stability of
β
-Zr under pressure has been verified by numerical heating-quenching experiments, and the anharmonicity of the thermal vibrations has been evaluated. No dynamical instability due to a soft mode is evidenced between 25 and 100 GPa, in line with the experimental finding of a wide stability range for
β
-Zr.
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Nov 2020
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I15-Extreme Conditions
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Diamond Proposal Number(s):
[20613]
Abstract: The mechanical behavior of different microstructural constituents in SAE 52100 bearing steel has been studied at room temperature in relation to quenching and partitioning (QP) and bainitization (B) process parameters, and compared to the standard quenched and tempered (QT) microstructure using high-energy synchrotron X-ray diffraction in situ during tensile loading. Owing to a larger degree of carbon entrapment in its body-centered cubic lattice and associated lattice distortion, martensite in the QT microstructure showed a larger lattice parameter and broadened diffraction peaks as compared to lower bainitic ferrite or partitioned martensite. A reduction in diffraction peak broadness in tempered martensite occurs at a true stress value of ∼1800 MPa, and preserves its peak broadness even after subsequent unloading. In contrast, an equivalent effect in peak broadness is detected at ∼1500 MPa in the lower bainitic ferrite or mixed bainitic/martensitic matrix characteristic of the B and QP microstructures. In all studied microstructures, the metastable austenite phase transforms when a critical stress is reached, the value of which increases with the bainitic ferrite/martensite fraction and with the carbon content in austenite, but remains lower in the QP and B microstructures compared to the standard QT steel. These results suggest that the carbon solid solution strengthening and associated lattice distortion in bainitic ferrite or martensite are key in determining the mechanical performance of the constituent phases in the steel, with the phase fraction and local carbon content playing an additional role on the austenite mechanical stability.
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Nov 2020
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I15-Extreme Conditions
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Diamond Proposal Number(s):
[21610]
Open Access
Abstract: We report on high-pressure synchrotron X-ray diffraction measurements on Ni3V2O8 at room-temperature up to 23 GPa. According to this study, the ambient-pressure orthorhombic structure remains stable up to the highest pressure reached in the experiments. We have also obtained the pressure dependence of the unit-cell parameters, which reveals an anisotropic compression behavior. In addition, a room-temperature pressure–volume third-order Birch–Murnaghan equation of state has been obtained with parameters: V0 = 555.7(2) Å3, K0 = 139(3) GPa, and K0′ = 4.4(3). According to this result, Ni3V2O8 is the least compressible kagome-type vanadate. The changes of the crystal structure under compression have been related to the presence of a chain of edge-sharing NiO6 octahedral units forming kagome staircases interconnected by VO4 rigid tetrahedral units. The reported results are discussed in comparison with high-pressure X-ray diffraction results from isostructural Zn3V2O8 and density-functional theory calculations on several isostructural vanadates.
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Oct 2020
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B18-Core EXAFS
I15-Extreme Conditions
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Diamond Proposal Number(s):
[22856, 22930]
Abstract: For magnesium ion batteries (MIBs) to be used commercially, new cathodes must be developed that show stable reversible Mg intercalation. VS4 is one such promising material, with vanadium and disulfide anions [S2]2– forming one-dimensional linear chains, with a large interchain spacing (5.83 Å) enabling reversible Mg insertion. However, little is known about the details of the redox processes and structural transformations that occur upon Mg intercalation and deintercalation. Here, employing a suite of local structure characterization methods including X-ray photoelectron spectroscopy (XPS), V and S X-ray absorption near-edge spectroscopy (XANES), and 51V Hahn echo and magic-angle turning with phase-adjusted sideband separation (MATPASS) NMR, we show that the reaction proceeds via internal electron transfer from V4+ to [S2]2–, resulting in the simultaneous and coupled oxidation of V4+ to V5+ and reduction of [S2]2– to S2–. We report the formation of a previously unknown intermediate in the Mg–V–S compositional space, Mg3V2S8, comprising [VS4]3– tetrahedral units, identified by using density functional theory coupled with an evolutionary structure-predicting algorithm. The structure is verified experimentally via X-ray pair distribution function analysis. The voltage associated with the competing conversion reaction to form MgS plus V metal directly is similar to that of intermediate formation, resulting in two competing reaction pathways. Partial reversibility is seen to re-form the V5+ and S2– containing intermediate on charging instead of VS4. This work showcases the possibility of developing a family of transition metal polychalcogenides functioning via coupled cationic–anionic redox processes as a potential way of achieving higher capacities for MIBs.
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Oct 2020
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B16-Test Beamline
I15-Extreme Conditions
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Diamond Proposal Number(s):
[17704, 17707]
Open Access
Abstract: Purpose: Photon-counting silicon strip detectors are attracting interest for use in next-generation CT scanners. For CT detectors in a clinical environment, it is desirable to have a low power consumption. However, decreasing the power consumption leads to higher noise. This is particularly detrimental for silicon detectors, which require a low noise floor to obtain a good dose efficiency. The increase in noise can be mitigated using a longer shaping time in the readout electronics. This also results in longer pulses, which requires an increased deadtime, thereby degrading the count-rate performance. However, as the photon flux varies greatly during a typical CT scan, not all projection lines require a high count-rate capability. We propose adjusting the shaping time to counteract the increased noise that results from decreasing the power consumption.
Approach: To show the potential of increasing the shaping time to decrease the noise level, synchrotron measurements were performed using a detector prototype with two shaping time settings. From the measurements, a simulation model was developed and used to predict the performance of a future channel design.
Results: Based on the synchrotron measurements, we show that increasing the shaping time from 28.1 to 39.4 ns decreases the noise and increases the signal-to-noise ratio with 6.5% at low count rates. With the developed simulation model, we predict that a 50% decrease in power can be attained in a proposed future detector design by increasing the shaping time with a factor of 1.875.
Conclusion: Our results show that the shaping time can be an important tool to adapt the pulse length and noise level to the photon flux and thereby optimize the dose efficiency of photon-counting silicon detectors.
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Oct 2020
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I15-Extreme Conditions
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Diamond Proposal Number(s):
[19776]
Open Access
Abstract: The spin state of the Prussian blue analogue FeIIPtIV(CN)6 is investigated in response to temperature, pressure, and X-ray irradiation. While cooling to 10 K maintains the high-spin state of FeII, compression at ambient temperature induces a first-order spin-crossover (SCO) transition with a small hysteresis loop (p↑ = 0.8 GPa, p↓ = 0.6 GPa). In addition, the high-spin to low-spin transition can be initiated at lower pressure through increased X-ray irradiation. Our study highlights a cooperative SCO with moderate pressure in a porous Prussian blue analogue.
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Sep 2020
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I15-Extreme Conditions
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Zhilun
Lu
,
Weichao
Bao
,
Ge
Wang
,
Shikuan
Sun
,
Linhao
Li
,
Jinglei
Li
,
Huijing
Yang
,
Hongfen
Ji
,
Antonio
Feteira
,
Dejun
Li
,
Fangfang
Xu
,
Annette K.
Kleppe
,
Dawei
Wang
,
Shi-yu
Liu
,
Ian M.
Reaney
Diamond Proposal Number(s):
[21714]
Open Access
Abstract: The mechanisms underpinning high energy storage in lead-free Ag1-3xNdxTayNb1-yO3 antiferroelectric (AFE) ceramics have been investigated. Rietveld refinements of in-situ synchrotron X-ray data reveal that the structure remains quadrupled and orthorhombic under electric field (E) but adopts a non-centrosymmetric space group, Pmc21, in which the cations exhibit a ferrielectric configuration. Nd and Ta doping both stabilise the AFE structure, thereby increasing the AFE-ferrielectric switching field from 150 to 350 kV cm-1. Domain size and correlation length of AFE/ferrielectric coupling reduce with Nd doping, leading to slimmer hysteresis loops. Pmax is optimised through A-site aliovalent doping which also decreases electrical conductivity, permitting the application of a larger E. These effects combine to enhance energy storage density to give Wrec = 6.5 J cm-3 for Ag0.97Nd0.01Ta0.20Nb0.80O3.
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Sep 2020
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