I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[23975]
Abstract: The strength and fracture toughness of Additively Manufactured (AM) components are significantly influenced by the concentration and size of oxides and precipitate inclusions within the build powders. These features are highly sensitive to powder production parameters, as well as the number of times a powder has been reused. In this study synchrotron X-ray powder diffraction was performed in an inert atmosphere at room temperature and during in-situ heating, providing crucial insights into growth rates and distribution of oxides and precipitates as a function of temperature. From the high angular resolution data collected, the structural refinement showed that plasma wire arc atomisation shows lower residual strain than gas atomised powder samples at room temperature after atomisation likely due to lower temperatures achieved during the production process. Additionally, the results from the diffraction patterns collected during in-situ heating provide key insights to the four metal powders considered in this study, Ti-6Al-4 V, Ni718, AlSi10Mg, and Scalmalloy. This paper also highlights the potential that using synchrotron X-ray diffraction to study AM parts and constituent AM powder has to gain crucial insight into material properties and the build reliability of end use production quality parts from AM.
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Jun 2023
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[24845]
Open Access
Abstract: W-type hexaferrites with varied Co/Zn ratios were synthesized and the magnetic order was investigated using neutron powder diffraction. In SrCo2Fe16O27 and SrCoZnFe16O27 a planar (Cm′cm′) magnetic ordering was found, rather than the uniaxial ordering (P63/mm′c′) found in SrZn2Fe16O27 which is common in most W-type hexaferrites. In all three studied samples, non-collinear terms were present in the magnetic ordering. One of the non-collinear terms is common to the planar ordering in SrCoZnFe16O27 and uniaxial ordering in SrZn2Fe16O27, which could be a sign of an imminent transition in the magnetic structure. The thermomagnetic measurements revealed magnetic transitions at 520 and 360 K for SrCo2Fe16O27 and SrCoZnFe16O27, and Curie temperatures of 780 and 680 K, respectively, while SrZn2Fe16O27 showed no transition but a Curie temperature at 590 K. This leads to the conclusion that the magnetic transition can be adjusted by fine-tuning the Co/Zn stoichiometry in the sample.
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Jun 2023
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B18-Core EXAFS
I11-High Resolution Powder Diffraction
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Shunsuke
Sasaki
,
Souvik
Giri
,
Simon J.
Cassidy
,
Sunita
Dey
,
Maria
Batuk
,
Daphne
Vandemeulebroucke
,
Giannantonio
Cibin
,
Ronald I.
Smith
,
Philip
Holdship
,
Clare P.
Grey
,
Joke
Hadermann
,
Simon J.
Clarke
Diamond Proposal Number(s):
[25166, 14239]
Open Access
Abstract: Topochemistry enables step-by-step conversions of solid-state materials often leading to metastable structures that retain initial structural motifs. Recent advances in this field revealed many examples where relatively bulky anionic constituents were actively involved in redox reactions during (de)intercalation processes. Such reactions are often accompanied by anion-anion bond formation, which heralds possibilities to design novel structure types disparate from known precursors, in a controlled manner. Here we present the multistep conversion of layered oxychalcogenides Sr2MnO2Cu1.5Ch2 (Ch = S, Se) into Cu-deintercalated phases where antifluorite type [Cu1.5Ch2]2.5- slabs collapsed into two-dimensional arrays of chalcogen dimers. The collapse of the chalcogenide layers on deintercalation led to various stacking types of Sr2MnO2Ch2 slabs, which formed polychalcogenide structures unattainable by conventional high-temperature syntheses. Anion-redox topochemistry is demonstrated to be of interest not only for electrochemical applications but also as a means to design complex layered architectures.
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May 2023
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I11-High Resolution Powder Diffraction
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F.
Duarte Martinez
,
A.
Syed
,
K.
Dawson
,
G. J.
Tatlock
,
N. I.
Morar
,
M.
Kothari
,
C.
Tang
,
J.
Leggett
,
J. C.
Mason-Flucke
,
G.
Gibson
,
J.r.
Nicholls
,
S.
Gray
,
G. M.
Castelluccio
Open Access
Abstract: In the pursuit of more efficient gas turbine engines, components are required to operate for longer times at elevated temperatures. This increased time in service, together with a complex loading regime, can expose the material to environmental attack. This work has demonstrated that the interaction of stress, NaCl and a sulphur-containing environment is critical to cause crack initiation in the early stages of the exposure and accelerated corrosion rates in CMSX-4 at 550°C. The effect of having small concentrations of moisture in the gaseous environment or as water crystallisation in the salt is still to be investigated. A working hypothesis is that the interaction of alkali chlorides with a sulphur-containing atmosphere is the trigger to a self-sustaining cycle where metal chloride formation, vaporisation and oxidation lead to high amounts of hydrogen injection in a rapid manner and, therefore, hydrogen embrittlement.
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May 2023
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I11-High Resolution Powder Diffraction
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Aizhamal
Subanbekova
,
Varvara I.
Nikolayenko
,
Andrey A.
Bezrukov
,
Debobroto
Sensharma
,
Naveen
Kumar
,
Daniel J.
O'Hearn
,
Volodymyr
Bon
,
Shi-Qiang
Wang
,
Kyriaki
Koupepidou
,
Shaza
Darwish
,
Stefan
Kaskel
,
Michael J.
Zaworotko
Diamond Proposal Number(s):
[30456]
Open Access
Abstract: In this work, we report the synthesis, structural characterisation and sorption properties of an 8-fold interpenetrated diamondoid (dia) metal–organic framework (MOF) that is sustained by a new extended linker ligand, [Cd(Imibz)2], X-dia-2-Cd, HImibz or 2 = 4-((4-(1H-imidazol-1-yl)phenylimino)methyl)benzoic acid. X-dia-2-Cd was found to exhibit reversible single-crystal-to-single-crystal (SC–SC) transformations between four distinct phases: an as-synthesised (from N,N-dimethylformamide) wide-pore phase, X-dia-2-Cd-α; a narrow-pore phase, X-dia-2-Cd-β, formed upon exposure to water; a narrow-pore phase obtained by activation, X-dia-2-Cd-γ; a medium-pore CO2-loaded phase X-dia-2-Cd-δ. While the space group remained constant in the four phases, the cell volumes and calculated void space ranged from 4988.7 Å3 and 47% (X-dia-2-Cd-α), respectively, to 3200.8 Å3 and 9.1% (X-dia-2-Cd-γ), respectively. X-dia-2-Cd-γ also exhibited a water vapour-induced structural transformation to the water-loaded X-dia-2-Cd-β phase, resulting in an S-shaped sorption isotherm. The inflection point occurred at 18% RH with negligible hysteresis on the desorption profile. Water vapour temperature-humidity swing cycling (60% RH, 300 K to 0% RH, 333 K) indicated hydrolytic stability of X-dia-2-Cd and working capacity was retained after 128 cycles of sorbent regeneration. CO2 (at 195 K) was also observed to induce a structural transformation in X-dia-2-Cd-γ and in situ PXRD studies at 1 bar of CO2, 195 K revealed the formation of X-dia-2-Cd-δ, which exhibited 31% larger unit cell volume than X-dia-2-Cd-γ.
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May 2023
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I11-High Resolution Powder Diffraction
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Aleksandra
Mielewczyk-Gryń
,
Shuhao
Yang
,
Maria
Balaguer
,
Ragnar
Strandbakke
,
Magnus H.
Sørby
,
Iga
Szpunar
,
Agnieszka
Witkowska
,
Sebastian
Wachowski
,
Jose M.
Serra
,
Alexandra
Navrotsky
,
Maria
Gazda
Abstract: This study concerns energetics of formation and the stability in high water partial pressure of BaLnCo2O6−δ, (Ln = La, Pr, Nd, and Gd) (BLnC) and BaGd1−xLaxCo2O6−δ, where x = 0.2, 0.5, and 0.7 (BGLC) double perovskite cobaltites. Those materials are extensively studied due to their potential applications as a positrode in electrochemical devices. Therefore, their stability under such conditions is a key issue. All investigated materials are thermodynamically stable relative to binary oxides and exhibit strongly exothermic enthalpies of formation. Moreover, BaGd0.3La0.7Co2O6−δ and BaGd0.8La0.2Co2O6−δ remain the main perovskite structure up to 3 bars of water vapor at 400 °C. At higher steam pressure, reaching 10 bar at 300 °C, the partial decomposition to constituent oxides and hydroxides was observed. The BGLC compounds exhibit higher negative formation enthalpies in comparison to single-Ln compositions, which does not translate into higher chemical stability under high steam pressures since the BLnC series retained the main perovskite structure at higher temperatures as well as in higher water vapor pressures.
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Apr 2023
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[20894]
Open Access
Abstract: Phase transitions in crystalline molecular solids have important implications in the fundamental understanding of materials properties and in the development of materials applications. Herein, we report the solid-state phase transition behavior of 1-iodoadamantane (1-IA) investigated using a multi-technique strategy [synchrotron powder X-ray diffraction (XRD), single-crystal XRD, solid-state NMR, and differential scanning calorimetry (DSC)], which reveals complex phase transition behavior on cooling from ambient temperature to ca. 123 K and on subsequent heating to the melting temperature (348 K). Starting from the known phase of 1-IA at ambient temperature (phase A), three low-temperature phases are identified (phases B, C, and D); the crystal structures of phases B and C are reported, together with a re-determination of the structure of phase A. Remarkably, single-crystal XRD shows that some individual crystals of phase A transform to phase B, while other crystals of phase A transform instead to phase C. Results (from powder XRD and DSC) on cooling a powder sample of phase A are fully consistent with this behavior while also revealing an additional transformation pathway from phase A to phase D. Thus, on cooling, a powder sample of phase A transforms partially to phase C (at 229 K), partially to phase D (at 226 K) and partially to phase B (at 211 K). During the cooling process, each of the phases B, C, and D is formed directly from phase A, and no transformations are observed between phases B, C, and D. On heating the resulting triphasic powder sample of phases B, C, and D from 123 K, phase B transforms to phase D (at 211 K), followed by the transformation of phase D to phase C (at 255 K), and finally, phase C transforms to phase A (at 284 K). From these observations, it is apparent that different crystals of phase A, which are ostensibly identical at the level of information revealed by XRD, must actually differ in other aspects that significantly influence their low-temperature phase transition pathways. This unusual behavior will stimulate future studies to gain deeper insights into the specific properties that control the phase transition pathways in individual crystals of this material.
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Apr 2023
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I11-High Resolution Powder Diffraction
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Zi
Wang
,
Alena M.
Sheveleva
,
Daniel
Lee
,
Yinlin
Chen
,
Dinu
Iuga
,
W. Trent
Franks
,
Yujie
Ma
,
Jiangnan
Li
,
Lei
Li
,
Yongqiang
Cheng
,
Luke L.
Daemen
,
Sarah J.
Day
,
Anibal J.
Ramirez-Cuesta
,
Bing
Han
,
Alexander S.
Eggeman
,
Eric J. L.
Mcinnes
,
Floriana
Tuna
,
Sihai
Yang
,
Martin
Schroeder
Abstract: We report the modulation of reactivity of nitrogen dioxide (NO2) in a charged metal-organic framework (MOF) material, MFM-305-CH3 in which unbound N-centres are methylated and the cationic charge counter-balanced by Cl− ions in the pores. Uptake of NO2 into MFM-305-CH3 leads to reaction between NO2 and Cl– to give nitrosyl chloride (NOCl) and NO3− anions. A high dynamic uptake of 6.58 mmol g−1 at 298 K is observed for MFM-305-CH3 as measured using a flow of 500 ppm NO2 in He. In contrast, the analogous neutral material, MFM-305, shows a much lower uptake of 2.38 mmol g−1. The binding domains and reactivity of adsorbed NO2 molecules within MFM-305-CH3 and MFM-305 have been probed using in situ synchrotron X-ray diffraction, inelastic neutron scattering and by electron paramagnetic resonance, high-field solid-state nuclear magnetic resonance and UV-vis spectroscopies. The design of charged porous sorbents provides a new platform to control the reactivity of corrosive air pollutants.
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Apr 2023
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[18786]
Open Access
Abstract: The crystallization of a new series of A-site substituted lanthanum ferrite materials (La1–xREx)FeO3 was explored by the hydrothermal method at 240 °C, for rare earth (RE) = Nd, Sm, Gd, Ho, Er, Yb, and Y, with 0 ≤ x ≤ 1. The effect of elemental substitution on the morphological, structural, and magnetic properties of the materials was studied using high-resolution powder X-ray diffraction, energy dispersive spectroscopy (EDS) on the scanning electron microscope, Raman spectroscopy, and SQUID magnetometry. If the radius of the La3+ and the substituent ions is similar, such as for Nd3+, Sm3+, and Gd3+, homogeneous solid solutions are formed, with the orthorhombic GdFeO3-type structure, and a continuous evolution of Raman spectra with composition and distinct magnetic behavior from the end members. When the radius difference between substituents and La3+ is large, such as for Ho3+, Er3+, Yb3+, and Y3+, then instead of forming solid solutions, crystallization in separate phases is found. However, low levels of element mixing are found and intergrowths of segregated regions give composite particles. In this case, the Raman spectra and magnetic behavior are characteristic of mixtures of phases, while EDS shows distinctive elemental segregation. A-site replacement induces an evolution in the crystallite shape with an increasing amount of substituent ions and this is most evident for RE = Y from cube-shaped crystals seen for LaFeO3 to multipodal crystals for (La1–xYx)FeO3, providing evidence for a phase-separation-driven evolution of morphology.
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Mar 2023
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[18786, 25166]
Open Access
Abstract: Two new phases derived from the layered ternary chalcogenide Ta2PdS6 have been successfully synthesised via the intercalation of sodium or potassium. MTa2PdS6 (M = Na, K) crystallise in monoclinic space group I2/m (No. 12), Z = 2, with lattice parameters a = 8.1366(7) Å, b = 3.2876(1) Å, c = 15.3279(3) Å, β = 97.407(2)° for NaTa2PdS6, and a = 8.3845(3) Å, b = 3.2955(1) Å, c = 16.7416(8) Å, β = 86.339(3)° in the case of KTa2PdS6. The general structure of the parent phase is retained upon intercalation, with increased unit cell volumes of 17.3% and 33.2% for the Na and K intercalates respectively. SQUID magnetometry shows that both intercalates are net diamagnets, but shows a significant reduction of magnetic susceptibility from Ta2PdS6 due to the increase in a Pauli paramagnetic component due to partial band filling.
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Mar 2023
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