Synchrotron X-ray Diffractometry Research Articles

Suppression of Ferroelectric Transitions by Symmetry Trapping in Dion-Jacobson-Layered Perovskites Cs(La,Nd)Nb2O7.

CsNdNb2O7 is a hybrid improper ferroelectric (HIF) where oxygen octahedral rotation modes induce spontaneous polarization. While CsLaNb2O7 is also believed to be an HIF, its polar structure and ferroelectric properties remain poorly understood. This study investigates their solid solution, CsLa1-xNdxNb2O7, by constructing a temperature-composition phase diagram using synchrotron X-ray diffractometry, first-principles calculations, and dielectric measurements. Upon cooling, the Nd-rich compositions (x = 0.5, 0.75, and 1) undergo phase transitions from a P4/mmm to a C2/m and then to a polar P21am phase. Both transition temperatures decrease as x decreases. The polar P21am phase, accompanied by ferroelectric polarization switching, is stabilized at room temperature only when x = 0.75 and 1. For La-rich compositions, the nonpolar C2/m phase remains down to room temperature without exhibiting any indication of transformation into the polar P21am phase. Theoretical calculations suggest that a symmetry trapping effect hinders the nonpolar (C2/m)-to-polar (P21am) phase transition.

Influence of Quenching and Subsequent Artificial Aging on Tensile Strength of Laser-Welded Joints of Al–Cu–Li Alloy

The research aim was to optimize post-weld heat-treatment (PWHT) modes for a laser-welded joint of the Al–Cu–Li alloy and improve their respective strength properties. As a result, the ultimate tensile strength, yield point, and elongation of the joint were enhanced up to 95%, 94%, and 38%, respectively, of those inherent in the base metal. Before and after PWHT, both microstructures and phase compositions have been examined by optical and scanning electron microscopy, as well as synchrotron X-ray diffractometry. In the as-welded metal, the α-Al and T1(Al2CuLi) phases were found, along with the θ′(Al2Cu) and S′(Al2CuMg) phases localized at the grain boundaries, significantly reducing the mechanical properties of the joint. Upon quenching, the agglomerates dissolved at the grain boundaries, the solid solution was homogenized, and both Guinier–Preston zones and precipitates of the intermediate metastable θ″ phase were formed. After subsequent optimal artificial aging, the (predominant) hardening θ′ and (partial) T1(Al2CuLi) phases were observed in the weld metal, which contributed to the improvement of the strength properties of the joint.

Role of Poloxamer 188 in Preventing Ice-Surface-Induced Protein Destabilization during Freeze-Thawing.

The phase behavior of poloxamer 188 (P188) in aqueous solutions, characterized by differential scanning calorimetry (DSC) and synchrotron X-ray diffractometry, revealed solute crystallization during both freezing and thawing. Sucrose and trehalose inhibited P188 crystallization during freeze-thawing (FT). While trehalose inhibited P188 crystallization only during cooling, sucrose completely suppressed P188 crystallization during both cooling and heating. Lactate dehydrogenase (LDH) served as a model protein to evaluate the stabilizing effect of P188. The ability of P188, over a concentration range of 0.003-0.800% w/v, to prevent LDH (10 μg/mL) destabilization was evaluated. After five FT cycles, the aggregation behavior (by dynamic light scattering) and activity recovery were evaluated. While LDH alone was sensitive to interfacial stress, P188 at concentrations of ≥0.100% w/v stabilized the protein. However, as the surfactant concentration decreased, protein aggregation after FT increased. The addition of sugar (1.0% w/v; sucrose or trehalose) improved the stabilizing function of P188 at lower concentrations (≤0.010% w/v), possibly due to the inhibition of surfactant crystallization. Based on a comparison with the stabilization effect of polysorbate (both 20 and 80), it was evident that P188 could be a promising alternative surfactant in frozen protein formulations. However, when the surfactant concentration is low, the potential for P188 crystallization and the consequent compromise in its functionality warrant careful consideration.

Understanding the Effect of Nucleation in Amorphous Solid Dispersions through Time-Temperature Transformation.

In an earlier investigation, the critical cooling rate to prevent drug crystallization (CRcrit) during the preparation of nifedipine (NIF) amorphous solid dispersions (ASDs) was determined through a time-temperature transformation (TTT) diagram (Lalge et al. Mol. Pharmaceutics 2023, 20 (3), 1806-1817). The current study aims to use the TTT diagram to determine the critical cooling rate to prevent drug nucleation (CRcritN) during the preparation of ASDs. ASDs were prepared with each polyvinylpyrrolidone (PVP) and hydroxypropyl methylcellulose acetate succinate (HPMCAS). The dispersions were first stored under conditions promoting nucleation and then heated to the temperature that favors crystallization. The crystallization onset time (tC) was determined by differential scanning calorimetry and synchrotron X-ray diffractometry. TTT diagrams for nucleation were generated, which provided the critical nucleation temperature (50 °C) and the critical cooling rate to avoid nucleation (CRcritN). The strength of the drug-polymer interactions as well as the polymer concentration affected the CRcritN, with PVP having a stronger interaction than HPMCAS. The CRcrit of amorphous NIF was ∼17.5 °C/min. The addition of a 20% w/w polymer resulted in CRcrit of ∼0.05 and 0.2 °C/min and CRcritN of ∼4.1 and 8.1 °C/min for the dispersions prepared with PVP and HPMCAS, respectively.

Low-temperature thermal expansion behavior of the entropy-stabilized oxide (MgCoNiCuZn)O

The coefficient of thermal expansion (CTE) of entropy-stabilized oxide (MgCoNiCuZn)O has been firstly experimentally measured and studied at low temperatures below room temperature. The temperature-dependent lattice parameters of (MgCoNiCuZn)O were determined by synchrotron X-ray diffractometry. A CTE value of α = 2.2780x10-5 K−1 at 113 K for (MgCoNiCuZn)O was calculated using a second-degree polynomial fitting. The quenched homogeneous NaCl-type (MgCoNiCuZn)O structure has the highest CTE value below 133 K among all its constituent oxides. An unquenched (MgCoNiCuZn)O was also investigated, and the homogeneity was found to affect CTE values. Finally, the anisotropic behavior of the constituent oxides and (MgCoNiCuZn)O were also compared.

Implications of Drug-Polymer Interactions on Time-Temperature-Transformation: A Tool to Assess the Crystallization Propensity in Amorphous Solid Dispersions.

The critical cooling rate (CRcrit) to prevent drug crystallization during the preparation of nifedipine amorphous solid dispersions (ASDs) was determined through the time-temperature-transformation (TTT) diagram. ASDs were prepared with polyvinylpyrrolidone, hydroxypropylmethyl cellulose acetate succinate, and poly(acrylic acid). ASDs were subjected to isothermal crystallization over a wide temperature range, and the time and temperature dependence of nifedipine crystallization onset time (tC) was determined by differential scanning calorimetry (DSC) and synchrotron X-ray diffractometry. TTT diagrams were generated for ASDs, which provided the CRcrit for the dispersions prepared with each polymer. The observed differences in CRcrit could be explained in terms of differences in the strength of interactions. Stronger drug-polymer interactions led to longer tC and decreased CRcrit. The effect of polymer concentrations (4-20% w/w) was also influenced by the strength of the interaction. The CRcrit of amorphous NIF was ∼17.5 °C/min. Addition of 20% w/w polymer resulted in a CRcrit of ∼0.05, 0.2, and 11 °C/min for the dispersions prepared with PVP, HPMCAS, and PAA, respectively.

Cold consolidation and coercivity enhancement in Sm2Fe17N3 magnets by high-pressure torsion

Sm2Fe17N3 coarse powder was directly consolidated into a disc magnet by the high-pressure torsion technique. The huge superimposed hydrostatic pressure (10 GPa) made it possible to apply a large amount of plastic deformation to the disc as well as the powder particles of the brittle Sm2Fe17N3 compound at room temperature. This large deformation brought about grain subdivision inside powder particles and enabled to produce a bulk magnet having the coercivity of 5.7 kOe from the coarse powder having the coercivity of 1 kOe without reducing the particle size. It was clarified that those grain subdivision events are accompanied by the motion of dislocations confined in non-basal planes. Synchrotron X-ray diffractometry was also performed and revealed that too large strain, however, results in the disappearance of the hard magnetic Sm2Fe17N3 phase and the eventual loss of the coercivity.

An in situ synchrotron X-ray study of reverse austenitic transformation in a metastable FeMnCo alloy

This study concerns reverse austenitic transformation of plastic strain-induced hexagonal close-packed martensite. With the aid of in situ synchrotron X-ray diffractometry, the kinetic features of the transformation and the defect content evolution in a metastable (Fe60Mn40)85Co15 alloy are quantitatively examined using 5, 20, and 100 °C/min heating rates. It is found that the reverse austenitic transformation can be activated below 200 °C and completes within a short time scale. Through a Kissinger-style kinetic analysis, the activation energy of the reverse austenitic transformation is determined as 171.38 kJ/mol, confirming its displacive nature. Although exponential attenuation is observed in both stacking fault probability and dislocation density upon the initiation of the transformation, the resulting microstructure (single-phase face-centered cubic structure) remains highly defected, exhibiting high Vickers hardness, but still preserving somewhat strain hardenability. Atomistic mechanisms for the reverse austenitic transformation are further conceived according to the crystallographic theory of martensitic transformation.Graphical abstract

Topochemical Synthesis of LiCoF3 with a High-Temperature LiNbO3-Type Structure.

A novel perovskite fluoride, LixCoF3, which has an exceptionally low tolerance factor (0.81), has been synthesized via low-temperature lithium intercalation into a distorted ReO3-type fluoride CoF3 using organolithium reagents. Interestingly, this reaction is completed within 15 min at room temperature. Synchrotron X-ray diffractometry and optical second harmonic generation at room temperature have revealed that this compound shows a high-temperature LiNbO3-type structure (space group: R3̅c) involving Li-Co antisite defects and A-site splitting along the c direction. A-site splitting is consistent with the prediction based on hybrid Hartree-Fock density functional theory calculations. Co-L2,3 edge X-ray absorption spectroscopy, as well as bond valence sum analysis, has verified the divalent oxidation state of Co ions in the lithiated phase, suggesting that its composition is close to LiCoF3 (x ≈ 1). This compound exhibits a paramagnetic-to-antiferromagnetic transition at 36 K on cooling, accompanied by weak ferromagnetic ordering. The synthetic route based on low-temperature lithiation of metal fluorides host paves the way for obtaining a new LiNbO3-type fluoride family.

Quantitative prediction of yield strength of highly alloyed complex steel using high energy synchrotron X-ray diffractometry

The overwhelming impact of complex-phase microstructures to mechanical response in multiphase steels requires accurate constitutive properties of the individual phases. However, precise prediction of individual phase properties to their mechanical response is critical and sophisticated, and commonly requires multiscale characterizations and numerous approximations. In this work, by employing full phase information and semi-empirical analytical models, we accurately predict the yield strength of deformed variants of Ce-modified SAF2507 super duplex stainless steel (SDSS). High energy synchrotron X-ray diffraction (HE-SXRD) reveals the phase fractions of major phases along with secondary phases of Cr2N and eutectic CexFey. Average lattice strain/crystallite size of the austenite and ferrite/martensite phases from the measured volume is estimated through the Williamson-Hall method. A unique composite strengthening type analytical model is used to estimate yield strength by taking individual strengthening contributions from all phases, their grain sizes, stored dislocation densities, solid solution, and precipitates. Close agreement between reconstructed and experimental yield strength is observed for several cold and cryogenic rolled SDSS. A combination of HE-SXRD and analytical model offers a time-effective virtual design pathway to engineer high-strength steel.

Structural identification and stabilization of the new high-temperature phases in A(III)–B(VI) systems (A = Ga, In, B = S, Se). Part 1: High-temperature phases in the Ga–S system

This article opens a series of publications devoted to the preparation and stabilization of new high-temperature (HT) semiconductor phases A (III) – B (VI), which have a large number of vacancies and possess a number of unique properties. In this first work from the proposed series, the T-x-diagram of the Ga–S system was investigated in the composition range x = (30.0–60.7) mol% S, and then the structural identification of new HT phases was carried out. For the Ga–S system, four polymorphic (α-, α′-, β-, γ-) Ga2S3 phases of different symmetry were found and displayed on the phase diagram near the Ga2S3 composition (x ∼ 60.0 mol% S). For the first time, it became possible to obtain in-situ a reliable direct proof for the existence of equilibrium in narrow temperature range for the re-opened cubic phase γ-Ga2+δS3 (x ≈ 59.0 mol% S), which was isolated at room temperature in a fairly pure form. We also confirmed the presence of another hexagonal β(α)-Ga2S3 modification, existing at much higher temperatures than the cubic γ-Ga2+δS3 phase. It was shown that the polymorphic α-Ga2S3 and α′-Ga2S3 phases mentioned in the literature form superstructures from the parent β-Ga2S3 phase. The observed structural variants for all four Ga2S3 polymorphic phases, containing up to 1/3 of vacancies in the Ga sub-lattices, are closely related to different methods of ordering Ga vacancies. The reliability of our studies follows from the combination of the methods used: differential thermal analysis (DTA), microstructural local analysis (TEM, HREM, SAED), powder X-ray diffractometry (XRD), including high-temperature synchrotron XRD.

Synthesis of Pseudobrookite Fe2-xAlxTiO5 (0 ≤ x ≤ 0.5) Powders

Synthesis of Fe2-xAlxTiO5 (0≤x≤0.5) powders has been successfully conducted by using the solid state reaction method. The powders were made by mixing the ironstone-derived Fe2O3 and commercial TiO2 powder. Meanwhile, a commercial Al (NO3)3.9H2O precursor was used as the source of Al. The Fe2O3, TiO2, and Al(NO3)3.9H2O powders at the designated composition were mixed and then ground for 5 hours at 330 rpm in a planetary ball mill. Subsequently, the powder mixtures were calcined at 1100 °C for 1 h. Synchrotron x-ray diffractometry (SXRD) and scanning electron microscopy (SEM) techniques were used to characterize the phases and microstructures. SXRD data showed that a single-phase pseudobrookite Fe2TiO5 formed for all samples. A further quantitative analysis showed that the lattice parameter and cell volume values decreased with the increase of x which indicated the success of Al doping in the Fe2TiO5 structure. The morphology of Fe2-xAlxTiO5 grains from SEM images revealed an oval and elongated shapes, in accordance with the crystal structure of the phase.

Investigating the Influence of Excipients on the Stability of Levothyroxine Sodium Pentahydrate.

A range of tablet excipients were evaluated for their influence on the physical form and chemical stability of levothyroxine sodium pentahydrate (LSP; C15H10I4NNaO4·5H2O). LSP-excipient binary powder blends were stored under two conditions: (a) in hermetically sealed containers at 40 °C and (b) at 40 °C/75% RH. By use of synchrotron X-ray diffractometry, the disappearance of LSP could be quantified and the appearance of crystalline levothyroxine (free acid) could be identified. Under hermetically sealed conditions (40 °C) hygroscopic excipients such as povidone induced partial dehydration of LSP to form levothyroxine sodium monohydrate. When stored at 40 °C/75% RH, acidic excipients induced measurable disproportionation of LSP resulting in the formation of levothyroxine (free acid). HPLC analyses of drug-excipient mixtures revealed that lactose monohydrate, microcrystalline cellulose, and croscarmellose sodium caused pronounced chemical decomposition of LSP. On the other hand, magnesium stearate, sodium stearyl fumarate, and alkaline pH modifiers did not affect the physical and chemical stability of the API following storage at 40 °C/75% RH. HPLC, being a solution based technique, revealed chemical decomposition of the API, but the technique was insensitive to physical transformations. Excipient properties such as hygroscopicity and microenvironmental acidity were identified to be critical determinants of both physical and chemical stability of LSP in a drug product. For drugs exhibiting both physical and chemical transformations, simultaneous solid-state and solution based analyses will enable comprehensive stability evaluation.

Effect of the structure and the phase composition on the mechanical properties of Al–Cu–Li alloy laser welds

Abstract The purpose of these investigations was to study the effect of heat treatment on the structure and the phase composition of laser welded joints of the Al-2.8Cu-1.7Li alloy (V-1461 grade), providing the maximum tensile strength. To study the phase composition of the weld metal, synchrotron radiation was applied using a ‘Mega Science’ facility. This enabled to assess the phase distribution across the weld metal before and after heat treatment. It was found using high-resolution scanning and transmission electron microscopy, energy dispersive X-ray analysis, and synchrotron X-ray diffractometry that the T1(Al2CuLi) and T2(Al6CuLi3) main phases had been formed in the weld metal and at the interfaces with the matrix. Ultimate tensile strength of the welded joints was about 341 MPa, which was 62% of that of the base metal. Subsequent heat treatment of the welded samples, included hardening and artificial aging, caused the homogenization of the Al–Cu–Li alloy solid solution, as well as the formation of the δ′(Al3Li) hardening phase. Also, the T1 and T2 phases were formed partially. After quenching, tensile strength of the welded joints improved and was about 85% of that of the base metal. After artificial aging, it was about 510 MPa and approached tensile strength of the base metal (93%).

The Influence of the Strength of Drug-Polymer Interactions on the Dissolution of Amorphous Solid Dispersions.

In an earlier report, ionic interactions between ketoconazole (KTZ), a weakly basic drug, and poly(acrylic acid) (PAA), an anionic polymer, resulted in a dramatic decrease in molecular mobility as well as reduced crystallization propensity of amorphous solid dispersion (ASD) in the solid state. On the other hand, weaker dipole-dipole interactions between KTZ and polyvinylpyrrolidone (PVP) resulted in ASDs with higher crystallization propensity (Mistry Mol Pharm., 2015, 12 (9), 3339-3350). In this work, we investigated the behavior of the ketoconazole (KTZ) solid dispersions in aqueous media. In vitro dissolution tests showed that the PAA ASD maintained the level of supersaturation for a longer duration than the PVP ASD at low polymer contents (4-20% w/w polymer). Additionally, the PAA ASDs were more resistant to drug crystallization in aqueous medium when measured with synchrotron X-ray diffractometry. Two-dimensional 1H nuclear Overhauser effect spectroscopy (NOESY) NMR cross peaks between ketoconazole and PAA confirmed the existence of drug-polymer interactions in D2O. The interaction was accompanied by a reduced drug diffusivity as monitored by 2D diffusion ordered spectroscopy (DOSY) NMR and enthalpy-driven when characterized by isothermal titration calorimetry (ITC). On the other hand, drug-polymer interactions were not detected between ketoconazole and PVP in aqueous solution, with NOESY, DOSY, or ITC. The results suggest that interactions that stabilize ASDs in the solid state can also be relevant and important in sustaining supersaturation in solution.

Structural Study on Fat Crystallization Process Heterogeneously Induced by Graphite Surfaces.

Some inorganic and organic crystals have been recently found to promote fat crystallization in thermodynamically stable polymorphs, though they lack long hydrocarbon chains. The novel promoters are talc, carbon nanotube, graphite, theobromine, ellagic acid dihydrate, and terephthalic acid, among which graphite surpasses the others in the promotion effect. To elucidate the mechanism, we investigated the influence of graphite surfaces on the crystallization manner of trilaurin in terms of crystal morphology, molecular orientation, and crystallographic features. Polarized optical microscopy, cryo-scanning electron microscopy, synchrotron X-ray diffractometry, and polarized Fourier-transform infrared spectroscopy combined with the attenuated total reflection sampling method were employed for the analyses. All the results suggested that the carbon hexagonal network plane of graphite surfaces have a high potential to facilitate the clustering of fat molecules against high thermal fluctuations in fat melt, the fat molecules form a layer structure parallel to the graphite surface, and the clusters tend to grow into thin plate crystals of the β phase at the temperatures corresponding to low supercooling. The β′ phase also has a larger chance to grow on the graphite surface as supercooling increases.

Partial Dehydration of Levothyroxine Sodium Pentahydrate in a Drug Product Environment: Structural Insights into Stability

Levothyroxine sodium pentahydrate (LSP; C15H10I4NNaO4·5H2O) gradually loses one molecule of water of crystallization as the water vapor pressure is decreased from 90% to 15% RH (40 °C), a behavior characteristic of nonstoichiometric hydrates. LSP loses four molecules of water of crystallization to form levothyroxine sodium monohydrate (LSM; C15H10I4NNaO4·H2O) under realistic storage conditions (40 °C/0% RH for 3 h). The crystal structure of LSP was determined following which the specimen was partially dehydrated in situ to form LSM. The crystal structure of LSM provided insight into its potential for high reactivity. Thus, its presence in a drug product is undesirable. In LSP-oxalic acid mixtures stored in a hermetic container at 40 °C, there was moisture transfer from drug to excipient. Synchrotron X-ray diffractometry revealed dehydration of LSP resulting in LSM, while anhydrous oxalic acid transformed to its dihydrate. In formulations of LSP, chemical degradation of levothyroxine sodium may be preceded by its partial dehydration.

Multiorbital antiferromagnetic metal induced by intramolecular self-doping

The authors examine the spin and charge states in a multiorbital system through orbital selective NMR spectroscopy combined with fine-structure-resolvable synchrotron X-ray diffractometry. The results show an intramolecular electron redistribution leading to interorbital self-doping

Hybrid Ni[sbnd]Al layered double hydroxide: Characterization and in situ synchrotron XRD and vibrational spectroscopic studies under high-pressure

Anions from 2-aminoterephthalic acid (ATA), an aniline derivative, were intercalated into layered double hydroxide (LDH), and submitted to high-pressures by using a diamond anvil cell to access possible transformations of guest species in confined environment. The hybrid material, constituted by Ni2+ and Al3+ in a molar ratio equal to 2 (Ni2Al-ATA), was characterized by mass spectrometry coupled thermal analysis (TGA-DSC-MS), X-ray diffractometry (XRD) and vibrational spectroscopy (infrared and Raman) at ambient pressure. The response of Ni2Al-ATA to the pressure stimuli was monitored by in situ synchrotron XRD and in situ vibrational spectroscopies (infrared and Raman), during the compression-decompression cycle up to 14–16 GPa. XRD reflections related to (00l) stacking planes of hybrid material presented broadening and intensities decreasing, pointing out a pressure-induced amorphization. XRD profile of Ni2Al-ATA was not recovered after decompression, indicating that the structural modification promoted by the pressure to the inorganic matrix is irreversible. In-situ vibrational spectroscopy as a function of pressure revealed a minor modification in the spectrum of ATA anion confined into LDH (for example, the Raman intensity decreasing (without shift) of the 1612 cm−1 band). Spectral features were recovered after the decompression, suggesting no decomposition or reactivity of the organic guest species between the LDH layers. On the other hand, Raman spectrum of 2-aminoterephthalic acid (non-intercalated) changed expressively during the decompression step and sample become completely luminescent at 1.7 GPa and at ambient pressure. Probably LDH decreases the guest reactivity by a steric blockage imposed by ATA arrangement in the confined environment, which can improve the guest stability submitted to high-pressure stimulus.

Mechanical activation enhanced solid-state synthesis of NaCrO2 cathode material

NaCrO2 has been studied lately as a promising cathode material for Na-ion batteries. Consequently, we have conducted the first investigation on how high-energy ball milling before the high temperature reaction influences the synthesis reaction of NaCrO2 derived from the typical Na2CO3 and Cr2O3 reactants. In-situ synchrotron X-ray diffractometry is employed for the first time to provide a comprehensive understanding of the critical reaction temperatures and reaction pathway. It is found that high-energy ball milling at room temperature can result in significant changes in the synthesis reaction of NaCrO2 when compared to reactants without high-energy ball milling. These changes include a decreased onset temperature for the formation of O3–NaCrO2, an increased reaction kinetics, an alternation of the reaction pathway, and a complete reaction at 900 °C to form thermally-stable O3–NaCrO2 phase. These phenomena have been ascribed to the mechanical activation induced by high-energy ball milling before high temperature reaction. In contrast, without high-energy ball milling the reaction product at 900 °C is a highly impure NaCrO2 with a poor thermal stability. The thermally-stable O3–NaCrO2 powder produced with mechanical activation of the reactants at RT has much higher specific capacity (∼115 mAh/g) than the Na-deficient NaCrO2 powder with unreacted Cr2O3 generated without mechanical activation of the reactants at RT. Furthermore, the thermally-stable O3–NaCrO2 powder exhibits the best capacity retention among all the NaCrO2 without coatings reported so far in the literature.