Polymorphism of garnet solid electrolytes and its implications for grain-level chemo-mechanics.

Understanding and mitigating filament formation, short-circuit and solid electrolyte fracture is necessary for advanced all-solid-state batteries. Here, we employ a coupled far-field high-energy diffraction microscopy and tomography approach for assessing the chemo-mechanical behaviour for dense, polycrystalline garnet (Li7La3Zr2O12) solid electrolytes with grain-level resolution. In situ monitoring of grain-level stress responses reveals that the failure mechanism is stochastic and affected by local microstructural heterogeneity. Coupling high-energy X-ray diffraction and far-field high-energy diffraction microscopy measurements reveals the presence of phase heterogeneity that can alter local chemo-mechanics within the bulk solid electrolyte. These local regions are proposed to be regions with the presence of a cubic polymorph of LLZO, potentially arising from local dopant concentration variation. The coupled tomography and FF-HEDM experiments are combined with transport and mechanics modelling to illustrate the degradation of polycrystalline garnet solid electrolytes. The results showcase the pathways for processing high-performing solid-state batteries.

Structural changes across thermodynamic maxima in supercooled liquid tellurium: A water-like scenario.

Liquid polymorphism is an intriguing phenomenon that has been found in a few single-component systems, the most famous being water. By supercooling liquid Te to more than 130 K below its melting point and performing simultaneous small-angle and wide-angle X-ray scattering measurements, we observe clear maxima in its thermodynamic response functions around 615 K, suggesting the possible existence of liquid polymorphism. A close look at the underlying structural evolution shows the development of intermediate-range order upon cooling, most strongly around the thermodynamic maxima, which we attribute to bond-orientational ordering. The striking similarities between our results and those of water, despite the lack of hydrogen-bonding and tetrahedrality in Te, indicate that water-like anomalies may be a general phenomenon among liquid systems with competing bond- and density-ordering.

BraggNN: fast X-ray Bragg peak analysis using deep learning.

X-ray diffraction based microscopy techniques such as high-energy diffraction microscopy (HEDM) rely on knowledge of the position of diffraction peaks with high precision. These positions are typically computed by fitting the observed intensities in detector data to a theoretical peak shape such as pseudo-Voigt. As experiments become more complex and detector technologies evolve, the computational cost of such peak-shape fitting becomes the biggest hurdle to the rapid analysis required for real-time feedback in experiments. To this end, we propose BraggNN, a deep-learning based method that can determine peak positions much more rapidly than conventional pseudo-Voigt peak fitting. When applied to a test dataset, peak center-of-mass positions obtained from BraggNN deviate less than 0.29 and 0.57 pixels for 75 and 95% of the peaks, respectively, from positions obtained using conventional pseudo-Voigt fitting (Euclidean distance). When applied to a real experimental dataset and using grain positions from near-field HEDM reconstruction as ground-truth, grain positions using BraggNN result in 15% smaller errors compared with those calculated using pseudo-Voigt. Recent advances in deep-learning method implementations and special-purpose model inference accelerators allow BraggNN to deliver enormous performance improvements relative to the conventional method, running, for example, more than 200 times faster on a consumer-class GPU card with out-of-the-box software.

Method for conducting in situ high-temperature digital image correlation with simultaneous synchrotron measurements under thermomechanical conditions.

This work presents a novel method of obtaining in situ strain measurements at high temperature by simultaneous digital image correlation (DIC), which provides the total strain on the specimen surface, and synchrotron x-ray diffraction (XRD), which provides lattice strains of crystalline materials. DIC at high temperature requires specialized techniques to overcome the effects of increased blackbody radiation that would otherwise overexpose the images. The technique presented herein is unique in that it can be used with a sample enclosed in an infrared heater, remotely and simultaneously with synchrotron XRD measurements. The heater included a window for camera access, and the light of the heater lamps is used as illumination. High-temperature paint is used to apply a random speckle pattern to the sample to allow the tracking of displacements and the calculation of the DIC strains. An inexpensive blue theatrical gel filter is used to block interfering visible and infrared light at high temperatures. This technique successfully produces properly exposed images at 870 °C and is expected to perform similarly at higher temperatures. The average strains measured by DIC were validated by an analytical calculation of the theoretical strain. Simultaneous DIC and XRD strain measurements of Inconel 718 (IN718) tensile test specimens were performed under thermal and mechanical loads and evaluated. This approach uses the fact that with DIC, the total strain is measured, including plastic strain, while with XRD, only elastic strain is captured. The observed differences were discussed with respect to the effective deformation mechanisms.

iRadMat: A thermo-mechanical testing system for in situ high-energy X-ray characterization of radioactive specimens.

We present an in situ Radiated Materials (iRadMat) experimental module designed to interface with a servo-hydraulic load frame for X-ray measurements at beamline 1-ID at the Advanced Photon Source. This new capability allows in situ studies of radioactive specimens subject to thermo-mechanical loading using a suite of high-energy X-ray scattering and imaging techniques. The iRadMat is a radiation-shielded vacuum heating system with the sample rotation-under-load capability. We describe the design features and performances of the iRadMat and present a dataset from a 300 °C uniaxial tensile test of a neutron-irradiated pure Fe specimen to demonstrate its capabilities.

HBM Mice Have Altered Bone Matrix Composition and Improved Material Toughness.

The G171V mutation in the low-density lipoprotein receptor-related protein 5 (LRP5) leads to a high bone mass (HBM) phenotype. Studies using HBM transgenic mouse models have consistently found increased bone mass and whole-bone strength, but little attention has been paid to the composition of the bone matrix. The current study sought to determine if the cortical bone matrix composition differs in HBM and wild-type mice and to determine how much of the variance in bone material properties is explained by variance in matrix composition. Consistent with previous studies, HBM mice had greater cortical area, moment of inertia, ultimate force, bending stiffness, and energy to failure than wild-type animals. The increased energy to failure was primarily caused by a large increase in post-yield behavior, with no difference in pre-yield behavior. The HBM mice had increased mineral-to-matrix and collagen cross-link ratios, and decreased crystallinity, carbonate, and acid phosphate substitution as measured by Fourier transform infrared microspectroscopy, but no differences in crystal length, intra-fibular strains, and mineral spacing compared to wild-type controls, as measured by X-ray scattering. The largest between genotype difference in material properties was a twofold increase in the modulus of toughness in HBM mice. Step-wise regression analyses showed that the specific matrix compositional parameters most closely associated with material properties varied between the wild-type and HBM genotypes. Although the mechanisms controlling the paradoxical combination of more mineralized yet tougher bone in HBM mice remain to be fully explained, the findings suggest that LRP5 represents a target to not only build bone mass but also to improve bone quality.

Effect of water on nanomechanics of bone is different between tension and compression.

Water, an important constituent in bone, resides in different compartments in bone matrix and may impose significant effects on its bulk mechanical properties. However, a clear understanding of the mechanistic role of water in toughening bone is yet to emerge. To address this issue, this study used a progressive loading protocol, coupled with measurements of in situ mineral and collagen fibril deformations using synchrotron X-ray diffraction techniques. Using this unique approach, the contribution of water to the ultrastructural behavior of bone was examined by testing bone specimens in different loading modes (tension and compression) and hydration states (wet and dehydrated). The results indicated that the effect of water on the mechanical behavior of mineral and collagen phases at the ultrastructural level was loading-mode dependent and correlated with the bulk behavior of bone. Tensile loading elicited a transitional drop followed by an increase in load bearing by the mineral phase at the ultrastructural level, which was correlated with a strain hardening behavior of bone at the bulk level. Compression loading caused a continuous loss of load bearing by the mineral phase, which was reflected at the bulk level as a strain softening behavior. In addition, viscous strain relaxation and pre-strain reduction were observed in the mineral phase in the presence of water. Taken together, the results of this study suggest that water dictates the bulk behavior of bone by altering the interaction between mineral crystals and their surrounding matrix.

Investigation of High-Energy Ion-Irradiated MA957 Using Synchrotron Radiation under In-Situ Tension.

In this study, an MA957 oxide dispersion-strengthened (ODS) alloy was irradiated with high-energy ions in the Argonne Tandem Linac Accelerator System. Fe ions at an energy of 84 MeV bombarded MA957 tensile specimens, creating a damage region ~7.5 µm in depth; the peak damage (~40 dpa) was estimated to be at ~7 µm from the surface. Following the irradiation, in-situ high-energy X-ray diffraction measurements were performed at the Advanced Photon Source in order to study the dynamic deformation behavior of the specimens after ion irradiation damage. In-situ X-ray measurements taken during tensile testing of the ion-irradiated MA957 revealed a difference in loading behavior between the irradiated and un-irradiated regions of the specimen. At equivalent applied stresses, lower lattice strains were found in the radiation-damaged region than those in the un-irradiated region. This might be associated with a higher level of Type II stresses as a result of radiation hardening. The study has demonstrated the feasibility of combining high-energy ion radiation and high-energy synchrotron X-ray diffraction to study materials' radiation damage in a dynamic manner.

A rotational and axial motion system load frame insert for in situ high energy x-ray studies.

High energy x-ray characterization methods hold great potential for gaining insight into the behavior of materials and providing comparison datasets for the validation and development of mesoscale modeling tools. A suite of techniques have been developed by the x-ray community for characterizing the 3D structure and micromechanical state of polycrystalline materials; however, combining these techniques with in situ mechanical testing under well characterized and controlled boundary conditions has been challenging due to experimental design requirements, which demand new high-precision hardware as well as access to high-energy x-ray beamlines. We describe the design and performance of a load frame insert with a rotational and axial motion system that has been developed to meet these requirements. An example dataset from a deforming titanium alloy demonstrates the new capability.

Maximum a posteriori estimation of crystallographic phases in X-ray diffraction tomography.

A maximum a posteriori approach is proposed for X-ray diffraction tomography for reconstructing three-dimensional spatial distribution of crystallographic phases and orientations of polycrystalline materials. The approach maximizes the a posteriori density which includes a Poisson log-likelihood and an a priori term that reinforces expected solution properties such as smoothness or local continuity. The reconstruction method is validated with experimental data acquired from a section of the spinous process of a porcine vertebra collected at the 1-ID-C beamline of the Advanced Photon Source, at Argonne National Laboratory. The reconstruction results show significant improvement in the reduction of aliasing and streaking artefacts, and improved robustness to noise and undersampling compared to conventional analytical inversion approaches. The approach has the potential to reduce data acquisition times, and significantly improve beamtime efficiency.

Strain response of thermal barrier coatings captured under extreme engine environments through synchrotron X-ray diffraction.

The mechanical behaviour of thermal barrier coatings in operation holds the key to understanding durability of jet engine turbine blades. Here we report the results from experiments that monitor strains in the layers of a coating subjected to thermal gradients and mechanical loads representing extreme engine environments. Hollow cylindrical specimens, with electron beam physical vapour deposited coatings, were tested with internal cooling and external heating under various controlled conditions. High-energy synchrotron X-ray measurements captured the in situ strain response through the depth of each layer, revealing the link between these conditions and the evolution of local strains. Results of this study demonstrate that variations in these conditions create corresponding trends in depth-resolved strains with the largest effects displayed at or near the interface with the bond coat. With larger temperature drops across the coating, significant strain gradients are seen, which can contribute to failure modes occurring within the layer adjacent to the interface.

Calcite orientations and composition ranges within teeth across Echinoidea.

Sea urchin's teeth from four families of order Echinoida and from orders Temnopleuroida, Arbacioida and Cidaroida were studied with synchrotron X-ray diffraction. The high and very high Mg calcite phases of the teeth, i.e. the first and second stage mineral constituents, respectively, have the same crystallographic orientations. The co-orientation of first and second stage mineral, which the authors attribute to epitaxy, extends across the phylogenic width of the extant regular sea urchins and demonstrates that this is a primitive character of this group. The range of compositions Δx for the two phases of Ca1-xMgxCO3 is about 0.20 or greater and is consistent with a common biomineralization process.

Bone cell-independent benefits of raloxifene on the skeleton: a novel mechanism for improving bone material properties.

Raloxifene is an FDA approved agent used to treat bone loss and decrease fracture risk. In clinical trials and animal studies, raloxifene reduces fracture risk and improves bone mechanical properties, but the mechanisms of action remain unclear because these benefits occur largely independent of changes to bone mass. Using a novel experimental approach, machined bone beams, both from mature male canine and human male donors, were depleted of living cells and then exposed to raloxifene ex vivo. Our data show that ex vivo exposure of non-viable bone to raloxifene improves intrinsic toughness, both in canine and human cortical bone beams tested by 4-point bending. These effects are cell-independent and appear to be mediated by an increase in matrix bound water, assessed using basic gravimetric weighing and sophisticated ultrashort echo time magnetic resonance imaging. The hydroxyl groups (OH) on raloxifene were shown to be important in both the water and toughness increases. Wide and small angle X-ray scattering patterns during 4-pt bending show that raloxifene alters the transfer of load between the collagen matrix and the mineral crystals, placing lower strains on the mineral, and allowing greater overall deformation prior to failure. Collectively, these findings provide a possible mechanistic explanation for the therapeutic effect of raloxifene and more importantly identify a cell-independent mechanism that can be utilized for novel pharmacological approaches for enhancing bone strength.

In operando spatiotemporal study of Li(2)O(2) grain growth and its distribution inside operating Li-O(2) batteries.

Nanocrystalline lithium peroxide (Li2 O2 ) is considered to play a critical role in the redox chemistry during the discharge-charge cycling of the Li-O2 batteries. In this report, a spatially resolved, real-time synchrotron X-ray diffraction technique was applied to study the cyclic formation/decomposition of Li2 O2 crystallites in an operating Li-O2 cell. The evaluation of Li2 O2 grain size, concentration, and spatial distribution inside the cathode is demonstrated under the actual cycling conditions. The study not only unambiguously proved the reversibility of the Li2 O2 redox reaction during reduction and evolution of O2 , but also allowed for the concentration and dimension growths of the peroxide nanocrystallites to be accurately measured at different regions within the cathode. The results provide important insights for future investigation on mass and charge transport properties in Li2 O2 and improvement in cathode structure and material design.

Effect of cyclic loading on the nanoscale deformation of hydroxyapatite and collagen fibrils in bovine bone.

Cyclic compressive loading tests were carried out on bovine femoral bones at body temperature (37 °C), with varying mean stresses (-55 to -80 MPa) and loading frequencies (0.5-5 Hz). At various times, the cyclic loading was interrupted to carry out high-energy X-ray scattering measurements of the internal strains developing in the hydroxyapatite (HAP) platelets and the collagen fibrils. The residual strains upon unloading were always tensile in the HAP and compressive in the fibrils, and each increases in magnitude with loading cycles, which can be explained from damage at the HAP­collagen interface and accumulation of plastic deformation within the collagen phase. The samples tested at a higher mean stress and stress amplitude, and at lower loading frequencies exhibit greater plastic deformation and damage accumulation, which is attributed to greater contribution of creep. Synchrotron microcomputed tomography of some of the specimens showed that cracks are produced during cyclic loading and that they mostly occur concentric with Haversian canals.

Quantitative determination of fragmentation kinetics and thermodynamics of colloidal silver nanowires by in situ high-energy synchrotron X-ray diffraction.

Colloidal silver nanowires become instable and tend to fragment into shortened nanorods and nanoparticles at elevated temperatures. Such morphological variations are associated with the transformation of crystalline structures from the body-centered tetragonal (b.c.t.) lattices into the face-centered cubic (f.c.c.) ones. The crystalline phase transformation has been probed in real time with an in situ technique based on time-resolved high-energy synchrotron X-ray diffraction. Comprehensive analysis of the in situ measurements provides, for the first time, the quantitative understanding of kinetics and thermodynamics involved in the fragmentation of the colloidal silver nanowires.

Synchrotron X-ray measurement techniques for thermal barrier coated cylindrical samples under thermal gradients.

Measurement techniques to obtain accurate in situ synchrotron strain measurements of thermal barrier coating systems (TBCs) applied to hollow cylindrical specimens are presented in this work. The Electron Beam Physical Vapor Deposition coated specimens with internal cooling were designed to achieve realistic temperature gradients over the TBC coated material such as that occurring in the turbine blades of aeroengines. Effects of the circular cross section on the x-ray diffraction (XRD) measurements in the various layers, including the thermally grown oxide, are investigated using high-energy synchrotron x-rays. Multiple approaches for beam penetration including collection, tangential, and normal to the layers, along with variations in collection parameters are compared for their ability to attain high-resolution XRD data from the internal layers. This study displays the ability to monitor in situ, the response of the internal layers within the TBC, while implementing a thermal gradient across the thickness of the coated sample. The thermal setup maintained coating surface temperatures in the range of operating conditions, while monitoring the substrate cooling, for a controlled thermal gradient. Through variation in measurement location and beam parameters, sufficient intensities are obtained from the internal layers which can be used for depth resolved strain measurements. Results are used to establish the various techniques for obtaining XRD measurements through multi-layered coating systems and their outcomes will pave the way towards goals in achieving realistic in situ testing of these coatings.

Reversibility of anodic lithium in rechargeable lithium-oxygen batteries.

Non-aqueous lithium-air batteries represent the next-generation energy storage devices with very high theoretical capacity. The benefit of lithium-air batteries is based on the assumption that the anodic lithium is completely reversible during the discharge-charge process. Here we report our investigation on the reversibility of the anodic lithium inside of an operating lithium-air battery using spatially and temporally resolved synchrotron X-ray diffraction and three-dimensional micro-tomography technique. A combined electrochemical process is found, consisting of a partial recovery of lithium metal during the charging cycle and a constant accumulation of lithium hydroxide under both charging and discharging conditions. A lithium hydroxide layer forms on the anode separating the lithium metal from the separator. However, numerous microscopic 'tunnels' are also found within the hydroxide layer that provide a pathway to connect the metallic lithium with the electrolyte, enabling sustained ion-transport and battery operation until the total consumption of lithium.

Effect of stress and temperature on the micromechanics of creep in highly irradiated bone and dentin.

Synchrotron X-ray diffraction is used to study in situ the evolution of phase strains during compressive creep deformation in bovine bone and dentin for a range of compressive stresses and irradiation rates, at ambient and body temperatures. In all cases, compressive strains in the collagen phase increase with increasing creep time (and concomitant irradiation), reflecting macroscopic deformation of the sample. By contrast, compressive elastic strains in the hydroxyapatite (HAP) phase, created upon initial application of compressive load on the sample, decrease with increasing time (and irradiation) for all conditions; this load shedding behavior is consistent with damage at the HAP-collagen interface due to the high irradiation doses (from ~100 to ~9,000 kGy). Both the HAP and fibril strain rates increase with applied compressive stress, temperature and irradiation rate, which is indicative of greater collagen molecular sliding at the HAP-collagen interface and greater intermolecular sliding (i.e., plastic deformation) within the collagen network. The temperature sensitivity confirms that testing at body temperature, rather than ambient temperature, is necessary to assess the in vivo behavior of bone and teeth. The characteristic pattern of HAP strain evolution with time differs quantitatively between bone and dentin, and may reflect their different structural organization.

Three-dimensional distribution of polymorphs and magnesium in a calcified underwater attachment system by diffraction tomography.

Biological materials display complicated three-dimensional hierarchical structures. Determining these structures is essential in understanding the link between material design and properties. Herein, we show how diffraction tomography can be used to determine the relative placement of the calcium carbonate polymorphs calcite and aragonite in the highly mineralized holdfast system of the bivalve Anomia simplex. In addition to high fidelity and non-destructive mapping of polymorphs, we use detailed analysis of X-ray diffraction peak positions in reconstructed powder diffraction data to determine the local degree of Mg substitution in the calcite phase. These data show how diffraction tomography can provide detailed multi-length scale information on complex materials in general and of biomineralized tissues in particular.