Synchrotron Diffraction Measurements Research Articles

A New High-Valent Fe Redox Couple in Intercalation Electrodes

The overwhelming majority of layered oxide cathode materials are based on the redox activity of expensive and scarce transition metals like Co and Ni. While the Fe-redox based material LiFePO4 has become increasingly attractive due to its low cost, its low gravimetric energy density and relatively low operating voltage limit its use cases. A high-voltage Fe-based layered oxide cathode would provide high energy density utilizing the redox-activity of the most abundant transition metal in Earth’s crust, but such a material that provides stable and reversible electrochemical performance remains elusive. Indeed, high-voltage Fe-redox in oxides is plagued by cation disorder and oxygen dimerization, which leads to capacity fading and large voltage hysteresis (> 1 V).[1]In contrast, the layered oxide cathode Li4FeSbO6 (equivalently, Li[Li1/3Fe1/3Sb1/3]O2, abbreviated LFSO) exhibits <0.2 V of hysteresis, and a discharge plateau at 4.2 V versus Li/Li+ with two-electron capacity.[2] Both the exceptional electrochemical reversibility of this material and its phase separating nature upon (de)intercalation raise questions about the origin of these properties that are unusual for layered Fe oxide cathodes. In this work, we will discuss our efforts to probe the electronic structure of LFSO with Fe L–edge x–ray absorption (XAS) and 57Fe Mössbauer spectroscopy, as well as O K–edge resonant inelastic x–ray scattering spectroscopy (RIXS). The combination of these element-specific and valence-state sensitive techniques, in conjunction with charge-transfer multiplet and density functional theory calculations, allows us to reveal the electronic structure changes at Fe and O as a function of state of charge for the first time. Correlating these electronic structure changes with synchrotron diffraction measurements, we reveal a unique redox compensation mechanism that readily rationalizes the exceptional electrochemical reversibility, unlocking a new direction for high-voltage, Fe-based redox systems.

Chemical pressure induced spin reorientation in the magnetic structure of Ca3Mn2−xSnxO7 ( x=0,0.03,0.05 )

The effect of partially substituting Tin (Sn) at the Manganese (Mn) site of Ca3Mn2O7 , viz. Ca3Mn2−xSnxO7 with x=0.03,0.05 , on its structural and magnetic properties have been investigated using synchrotron diffraction, neutron diffraction, and bulk magnetization measurements. It is observed that with a substitution of x=0.03 , the minor (≈8%) tetragonal ( I4/mmm ) structural phase that is present in the predominantly orthorhombic ( Cmc21 ) undoped Ca3Mn2O7 , completely disappears. The compounds order antiferromagnetically, the ordering temperature decreases with increasing Sn-content, indicating a weakening of the antiferromagnetic exchange interactions. Interestingly, in the ordered state, the spin magnetic moments which were aligned along the a-axis of the unit cell in the undoped compound, are observed to have reoriented with their major components lying in the b − c plane in the Sn-doped compounds. The above influence of Sn-doping is seen to be stemming from a significant modification of the octahedral rotation and tilt mode geometry in the unit cell, that is known to be responsible for driving ferroelectricity in these compounds.

To Freeze or Not to Freeze: Questioning the Origin of the Deep Eutectic in the Zinc Chloride Hydrate System

Zinc chloride is one of the most soluble salts in aqueous solutions, with an ambient temperature solubility of over 430 g per 100 g of water (ZnCl2·R H2O, R = 1.8). It also exhibits a deep eutectic, at R = 7.25 and -60 °C between pure water and the most water-rich crystalline hydrate, R = 4.5 (see Figure). We previously demonstrated that the molecular ions of the crystalline R = 3 hydrate persist into the melt (Tm = 5 °C) resulting in the ionic liquid [Zn(OH2)6][ZnCl4]. Results from an extensive series of Raman spectroscopy and synchrotron diffraction measurements will be shown to demonstrate that the [ZnCl4]2- anion persists to high dilution. These data further provide evidence for a complex hydration structure beyond the first neighbor water of the hexaaquo zinc cation. Notably the complex speciation/hydration structure directly correlates with the concentration-dependent differential scanning calorimetry of this system and will be shown to be the origin of the system’s deep eutectic. Evaluating the concentration dependence of the temperature and heat of the liquidus reveals that this salt solution exists as an ionic liquid up to a concentration of about 98 mole percent water, beyond which it follows more traditional electrolyte descriptions. The principles derived from this structural and spectroscopic analysis can be applied to more generally explain the freezing point depression in diverse systems. In particular, this analysis demonstrates how the phase diagrams and liquidus heat and temperature can reveal the nature of speciation within aqueous salt solutions. Figure 1

Frustration, strain and phase co-existence in the mixed valent hexagonal iridate Ba3NaIr2O9

Using detailed synchrotron diffraction, magnetization, thermodynamic and transport measurements, we investigate the relationship between the mixed valence of Ir, lattice strain and the resultant structural and magnetic ground states in the geometrically frustrated triple perovskite iridate Ba3NaIr2O9. We observe a complex interplay between lattice strain and structural phase co-existence, which is typically not observed in this family of compounds. The low temperature magnetic ground state is characterized by the absence of long-range magnetic order, and points towards the condensation of a cluster glass state from an extended regime of short range magnetic correlations.

Numerical modeling and synchrotron diffraction measurements of residual stresses in laser powder bed fusion manufactured alloy 625

Residual stresses in metal additive manufactured components are a well-known problem. It causes distortion of the samples when removing them from the build plate, as well as acting detrimental with regard to fatigue. The understanding of how residual stresses in a printed sample are affected by process parameters is crucial to allow manufacturers to tune their process parameters, or the design of their component, to limit the negative influence of residual stresses. In this paper, residual stresses in additive manufactured samples are simulated using a thermo-mechanical finite element model. The elasto-plastic behavior of the material is described by a mechanism-based material model that accounts for microstructural and relaxation effects. The heat source in the finite element model is calibrated by fitting the model to experimental data. The residual stress field from the finite element model is compared with experimental results attained from synchrotron X-ray diffraction measurements. The results from the model and measurement give the same trend in the residual stress field. In addition, it is shown that there is no significant difference in trend and magnitude of the resulting residual stresses for an alternation in laser power and scanning speed.

Structure and stability of 2Ha−MoS2 at high pressure and low temperatures

X-ray synchrotron diffraction (XRD) measurements of single-crystal and powder molybdenum disulfide $\mathrm{Mo}{\mathrm{S}}_{2}$ are performed at pressures (P) up to 78 GPa and temperatures (T) of 20 to 298 K in diamond-anvil cells. The results on single crystals demonstrate a sharp pressure induced isosymmetric phase transition of $2{H}_{c}$ to $2{H}_{a}$ modification at 23 GPa at 40 and 300 K. The structure of the high-pressure $2{H}_{a}$ phase previously inferred theoretically and from powder XRD data is confirmed by our single-crystal XRD data solution, which also definitively determines the atomic potions as a function of pressure. No additional periodicity (commensurate or incommensurate) or distortion is found in the whole P-T range of this study. These results suggest that a previously proposed hypothetic charge-density-wave phase does not host pressure induced superconductivity experimentally found above 90 GPa.

Microstructural Changes Influencing the Magnetoresistive Behavior of Bulk Nanocrystalline Materials

Bulk nanocrystalline materials of small and medium ferromagnetic content were produced using severe plastic deformation by high-pressure torsion at room temperature. Giant magnetoresistive behavior was found for as-deformed materials, which was further improved by adjusting the microstructure with thermal treatments. The adequate range of annealing temperatures was assessed with in-situ synchrotron diffraction measurements. Thermally treated Cu–Co materials show larger giant magnetoresistance after annealing for 1 h at 300 °C, while for Cu-Fe this annealing temperature is too high and decreases the magnetoresistive properties. The improvement of magnetoresistivity by thermal treatments is discussed with respect to the microstructural evolution as observed by electron microscopy and ex-situ synchrotron diffraction measurements.

Retrieving the configuration of grain boundary structure in polycrystalline materials by extraordinary X-ray reflection analysis

The development of materials is strongly related to our capability of understanding thermal, mechanical and chemical processing on the nanoscale. Unravelling the interface structure is crucial for opening new regimes in property–performance space. Interface arrangements have been characterized by statistically limited microscopy techniques. In this work, a large-angular-range detector was used for synchrotron diffraction measurements on commercially pure Mg. Long acquisitions allowed the retrieval of preferred interface configurations through the observation of extraordinary diffraction peaks located close to the Mg 102, 200, 204 and 300 fundamental reflections. A kinematical simulation scanning possible interface structures established the correspondence of the non-bulk peaks to the interfacial organization of atoms that may be responsible for their appearance. Simulated interfaces were probed for a wide range of angular displacements with respect to the main cleavage planes. The results indicate configurations that allow the observation of X-ray diffraction, representing a long-range-ordered pattern of atomic distributions in Mg. The introduced methodology allows for nondestructive monitoring of systems that undergo processes that modify grain sizes and grain-interface orientation.

Redox Chemistry and Reversible Structural Changes in Rhombohedral VO2F Cathode during Li Intercalation.

Metal oxyfluorides are currently attracting much attention for next-generation rechargeable batteries because of their high theoretical capacity and resulting high energy density. Rhombohedral VO2F is promising because it allows two-electron transfer during electrochemical lithium cycling, with a theoretical capacity of 526 mAh g-1. However, the chemical changes it undergoes during operation are not clearly understood. In this work, a combination of synchrotron X-ray and neutron diffraction was employed to accurately describe the crystal structure of both pristine and lithiated VO2F, using samples with high crystallinity to overcome challenges in previous studies. The mechanism and reversibility of the lithium insertion was monitored in real time by high angular synchrotron diffraction measurements, performed in operando on a lithium battery in the high-voltage range: 3.9-2.3 V vs Li+/Li. Insertion of up to one lithium ion proceeds through a solid-solution reaction, while Rietveld refinements of neutron powder diffraction data revealed that the lithiated states adopt the noncentrosymmetric R3c framework, uncovering an octahedral Li-(O/F)6 coordination with reasonable Li-O/F bond lengths. This work further evaluates the redox changes of VO2F upon Li intercalation. By a comparison of changes in electronic states of all the elements in the compound, it clarifies the critical role of both anions, O and F, in the charge compensation through their covalent interactions with the 3d states of V. The clear evidence of participation of F challenges existing assumptions that its high electronegativity renders this anion largely a spectator in the redox reaction.

The origin of discontinuous yielding in Mg alloys under slip-dominated condition studied by in-situ synchrotron diffraction and elastic-viscoplastic self-consistent modeling

A discontinuous yielding was observed in the as-extruded Mg-7Gd-2Y-1Zn-0.6Zr (wt. %) alloy under uniaxial tension along the extrusion direction, which was eliminated by the peak-aging treatment. The deformation mechanisms of the as-extruded and peak-aged alloys were studied by in-situ synchrotron diffraction measurement and elastic-viscoplastic self-consistent (EVPSC) modeling. The in-situ synchrotron diffraction results suggest that the unpinning of basal dislocations from solute atmospheres causes the stress relaxation in the basal slip favored grains. The EVPSC modeling results indicate that the discontinuous yielding in the as-extruded alloy is associated with the interaction between basal dislocations and solute atmospheres. After peak-aging treatment, the interaction between basal dislocations and solute atmospheres is weakened due to the consumption of a number of solute atoms. Consequently, the discontinuous yielding is eliminated in the peak-aged alloy.

In-situ visualizing atomic structural evolution during crystallization in ternary Zr[sbnd]Cu[sbnd]Al bulk metallic glasses

A well-designed experimental method has been presented to in-situ visualize the amorphous-to-crystalline phase transformation of two glass formers at the atomic-length scale in the supercooled liquid region using a high voltage electron microscopy (HVEM). Analysis of the HVEM high-resolution images, supported by the in-situ synchrotron diffraction, further confirms previous observations of distinctively different crystallization pathways in the two ZrCuAl alloys. Moreover, the HVEM results illustrate that isolated distributed nanocrystals with mutual orientation easily grew up from the Zr56Cu36Al8, an average glass former, which follows a classical crystallization pathway; while density population poorly ordered atomic clusters with large misorientation suspended the growth in the Zr46Cu46Al8, a good glass former, which might follow an unusual crystallization pathway. In addition, in-situ synchrotron diffraction measurements confirm that the Zr56Cu36Al8 alloy finally crystallized into an extended structure, in contrast, the final crystalline product of Zr46Cu46Al8 alloy possesses a damped structure. Our study provides a detailed microscopic understanding of the crystallization behaviors in the supercooled liquids, showing that the density population nucleation site with large misorientation and the confined final crystalline structure contribute to the stability of ZrCuAl supercooled liquids.

Capturing the Competing Influence of Thermal and Mechanical Loads on the Strain of Turbine Blade Coatings via High Energy X-rays

This paper presents findings of synchrotron diffraction measurements on tubular specimens with a thermal barrier coating (TBC) system applied by electron beam physical vapor deposition (EB-PVD), having a thermally grown oxide (TGO) layer due to aging in hot air. The diffraction measurements were in situ while applying a thermal cycle with high temperature holds at 1000 °C and varying internal air cooling mass flow and mechanical load. It was observed that, during high temperature holds at 1000 °C, the TGO strain approached zero if no mechanical load or internal cooling was applied. When applying a mechanical load, the TGO in-plane strain (e22) changed to tensile and the out of plane TGO strain (e11) became compressive. The addition of internal cooling induced a thermal gradient, yielding a competing effect, driving the e22 strain to compressive and e11 strain to tensile. Quantifying TGO strain variations in response to competing factors will provide a path to controlling the TGO strain, and further improving the lifetime assessment and durability design strategies for TBC systems.

FITEXC – DIFFRACTION PROFILE FITTING PROGRAM RUN IN MS EXCEL

We present our custom made diffraction fitting program FitExc for the basic treatment of the 1D diffraction profiles, in particular, the Intensity(2θ) of X-ray, synchrotron or neutron diffraction measurements. In the current state, the program allows for simultaneous fitting of up to three profiles in one data set and is intended to be used mainly for precise lattice parameters determination or fitting of overlapped peaks. The entire program is built in the common MS Excel environment, it does not require any installation and is free to use.

Pressure-induced structural change in liquid GeI4

The similarity in the shape of the melting curve of GeI4 to that of SnI4 suggests that a liquid–liquid transition as observed in liquid SnI4 is also expected to occur in liquid GeI4. Because the slope of the melting curve of GeI4 abruptly changes at around 3 GPa, in situ synchrotron diffraction measurements were conducted to examine closely the structural changes upon compression at around 3 GPa. The reduced radial distribution functions of the high- and low-pressure liquid states of GeI4 share the same feature inherent in the high-pressure (high-density) and low-pressure (low-density) radial distribution functions of liquid SnI4. This feature allows us to introduce local order parameters that we may use to observe the transition. Unlike the transition in liquid SnI4, the transition from the low-pressure to the high-pressure structure seems sluggish. We speculate that the liquid–liquid critical point of GeI4 is no longer a thermodynamically stable state and is slightly located below the melting curve. As a result, the structural change is said to be a crossover rather than a transition. The behavior of the local-order parameters implies a metastable extension of the liquid–liquid phase boundary with a negative slope.

Sodium vanadium titanium phosphate electrode for symmetric sodium-ion batteries with high power and long lifespan

Sodium-ion batteries operating at ambient temperature hold great promise for use in grid energy storage owing to their significant cost advantages. However, challenges remain in the development of suitable electrode materials to enable long lifespan and high rate capability. Here we report a sodium super-ionic conductor structured electrode, sodium vanadium titanium phosphate, which delivers a high specific capacity of 147 mA h g−1 at a rate of 0.1 C and excellent capacity retentions at high rates. A symmetric sodium-ion full cell demonstrates a superior rate capability with a specific capacity of about 49 mA h g−1 at 20 C rate and ultralong lifetime over 10,000 cycles. Furthermore, in situ synchrotron diffraction and X-ray absorption spectroscopy measurement are carried out to unravel the underlying sodium storage mechanism and charge compensation behaviour. Our results suggest the potential application of symmetric batteries for electrochemical energy storage given the superior rate capability and long cycle life.

Single crystal growth and structural evolution across the 1st order valence transition in (Pr1−yYy)1−xCaxCoO3-δ

Praseodymium-containing cobalt perovskites, such as (Pr1−yYy)1−xCaxCoO3-δ, have been argued to undergo a first-order charge shift between Pr and hybridized Co-O orbitals that leads to a metal-insulator transition at a temperature, TVT. Magnetization and x-ray absorption spectroscopy measurements on single crystals of (Pr0.85Y0.15)0.7Ca0.3CoO3-δ grown in an IR image furnace under 40–60bar of oxygen confirm the presence of this valence transition. Single crystal x-ray synchrotron diffraction measurements are consistent with an isomorphic phase transition at TVT. No evidence of charge ordering was revealed by the single crystal diffraction. Dissimilar to analytical transmission electron microscopy measurements performed on a grain from a polycrystalline sample that revealed an oxygen vacancy order-disorder transition at TVT, the present single-crystal measurements did not evidence such a transition, likely reflecting a lower density of oxygen vacancies in the high-pO2 grown single crystals.

Orthorhombic distortion and orbital order in the vanadium spinelFeV2O4

Using synchrotron and neutron diffraction measurements, we find a low-temperature orthorhombic phase in vanadium spinel ${\mathrm{FeV}}_{2}{\mathrm{O}}_{4}$. The orbital order of ${\mathrm{V}}^{3+}$ ions with tetragonal normal modes occurs at 68 K, and this leads to an appearance of the pseudotetragonal phase at a noncollinear ferrimagnetic transition temperature. Below the magnetic transition temperature, unconventional behavior of the orbital state of ${\mathrm{Fe}}^{2+}$ ions accompanied by the emergence of the orthorhombic phase was observed by using the normal mode analysis. We have also studied the structural properties of orbitally diluted materials. The orthorhombic phase, which is significantly affected by the other ions, is intrinsic in ${\mathrm{FeV}}_{2}{\mathrm{O}}_{4}$. We suggest the orthorhombic phase is strongly related with the double orbital states of ${\mathrm{Fe}}^{2+}$ and ${\mathrm{V}}^{3+}$ ions.

高角度分解能放射光X線回折によるスピネル型酸化物CoV 2 O 4 の微小格子歪み

高角度分解能放射光X線回折によるスピネル型酸化物CoV 2 O 4 の微小格子歪み

Deformation fields near a steady fatigue crack with anisotropic plasticity

In this work, from finite element simulations based on an irreversible, hysteretic cohesive interface model, a steady fatigue crack can be realized if the crack extension exceeds about twice the plastic zone size, and both the crack increment per loading cycle and the crack bridging zone size are smaller than the plastic zone size. The corresponding deformation fields develop a plastic wake behind the crack tip and a compressive residual stress field ahead of the crack tip. In addition, the Hill’s plasticity model is used to study the role of plastic anisotropy on the retardation of fatigue crack growth and the elastic strain fields. It is found that for Mode-I cyclic loading, an enhanced yield stress in directions that are inclined from the crack plane will lead to slower crack growth rate, but this retardation is insignificant for typical degrees of plastic anisotropy. These results provide key inputs for future comparisons to neutron and synchrotron diffraction measurements that provide full-field lattice strain mapping near fracture and fatigue crack tips, especially in textured materials such as wrought or rolled Mg alloys.

Removal of oxides and brittle coating constituents at the surface of coated hot-forming 22MnB5 steel for a laser welding process with aluminum alloys

Abstract The surface of a press-hardened steel 22MnB5 coated with Al-base (AlSi10Fe3) and Zn-base (ZnNi10) was conditioned by a pulse laser and by sandblasting to remove undesirable oxides and brittle phases. Oxides formed on coating surfaces counteract the wettability of welding filler during a welding or brazing process. Furthermore, welding and brazing joints of 22MnB5 coated with aluminum alloys failed along the brittle intermetallic phases in the coating under a low mechanical load. Treated 22MnB5 surfaces were analyzed microscopically, and the phase compositions were investigated by synchrotron diffraction measurements. It was found that brittle phases could be locally removed by laser ablation; however, high laser energies led to remelting and oxidation of the coating surface. In contrast, sandblasting homogenously removed oxides and brittle intermetallic phases. Surface-treated 22MnB5 steel sheets were joined to AA6016 aluminum sheets by laser welding, and the strength of the weldment was determined by tensile tests. The measured mechanical strength of the aluminum/steel joints was 210–230 MPa. Failure of the weldments under tensile loading occurred within the aluminum sheet, away from the steel surface/welding filler interface if brittle coating components and oxides were removed homogenously.