High-resolution Diffraction Research Articles

Unraveling the Growth Mechanism of Chiral Inorganic Nanocrystals via High-Resolution Electron Microscopy.

Chiral inorganic nanomaterials have attracted broad interest due to their intriguing chirality-dependent performances. However, there is a lack of experimental studies and atomic-level evidence on their growth mechanism. Herein, high-crystalline chiral tellurium nanowires were synthesized in an alkali solution by using tellurium oxide as an inorganic source and hydrazine hydrate as a reductant. The evolution of the nucleus and crystalline domains was manifested using high-resolution electron microscopy and electron diffraction, demonstrating a nonclassical growth path, that is, from monomers to nanowires of clusters and then nanocrystals. Furthermore, chiral inducers, d/l-penicillamine, were used at different stages to study their effects on the bias of two enantiomorphic structures with different chiral space groups. A similar nonclassical growth mechanism was also found in the synthesis of chiral terbium phosphate nanowires, demonstrating a common growth phenomenon in chiral inorganic nanomaterials. This work provides novel insights into the formation of chiral nanomaterials, benefiting the further controllable synthesis of various chiral nanomaterials.

Towards measuring absolute residual stress by HR-EBSD with simulated reference patterns

The High-Resolution Electron Backscatter Diffraction (HR-EBSD) technique has drawn attention in recent years, mainly thanks to its ability to assess the elastic strain/stress state with a sub-micron spatial resolution. Each diffraction pattern is correlated with a reference one, and the strain level relative to the reference is retrieved in the procedure. Several studies have attempted to use dynamically simulated diffraction patterns as references to access absolute strain/stress states to circumvent the difficulty of finding a strain-free reference pattern, which is often inaccessible. Numerous factors need to be considered and corrected to register better experimental and simulated diffraction patterns, such as the accurate positioning of the projection center, Kikuchi band (K-band) brightness asymmetry, K-band gray level reversal, optical distortion, or non-uniform electron energy. Here, an integrated digital image correlation method is proposed to register experimental patterns to a master pattern defined on a sphere, where the difficulties with experimental patterns are, for the most part, corrected efficiently. Due to the shallow inspection depth of EBSD, the free-surface property (vanishing stress vector at the observation surface) is also adopted to reduce the degrees of freedom and enhance precision. Through several tests on high-quality experimental patterns, the proposed method proves robust and precise. Both the systematic and random errors of the residual strain results are several 10−4. The method also allows the simultaneous determination of residual stress and the projection center coordinates.

High Resolution X-ray Diffraction Studies of the Natural Minerals of Gas Hydrates and Occurrence of Mixed Phases

The types and concentrations of gas hydrates collected from four different geological sites were analyzed using high-resolution angular dispersive X-ray powder diffraction, with synchrotron radiation as the source. Measurements were taken across a temperature range of 80 to 300 K and a pressure range of 0.1 to 80 MPa. All four gas hydrate samples showed the presence of three mixed crystal structures: structures I, II, and H. Additionally, the ice Ih structure was inherently present in all the natural gas hydrate minerals. The variation in the types and concentrations of gas hydrates can be attributed to the diversity of natural gases at different geographic locations.

Quantifying the Hydration-Dependent Dynamics of Cu Migration and Activity in Zeolite Omega for the Partial Oxidation of Methane.

Copper-exchanged zeolite omega (Cu-omega) is a potent material for the selective conversion of methane-to-methanol (MtM) via the oxygen looping approach. However, its performance exhibits substantial variation depending on the operational conditions. Under an isothermal temperature regime, Cu-omega demonstrates subdued activity below 230 °C, but experiences a remarkable increase in activity at 290 °C. Applying a high-temperature activation protocol at 450 °C causes a rapid deactivation of the material. This behavioral divergence is investigated by combining reactivity studies, neutron diffraction and in situ high-resolution anomalous X-ray powder diffraction (HR-AXRPD), as well as electron paramagnetic resonance spectroscopy, to reveal that the migration of Cu throughout the framework is the primary cause of these behaviors, which in turn is predominantly governed by the degree of hydration of the system. This work suggests that control over the Cu migration throughout the zeolite framework may be harnessed to significantly increase the activity of Cu-omega by generating more active sites for the MtM conversion. These results underscore the power of in situ HR-AXRPD for unraveling the behavior of materials under reaction conditions and suggest that a re-evaluation of Cu-zeolites priorly deemed inactive for the MtM conversion across a broader range of conditions and looping protocols may be warranted.

Surface patterning for multi-scale strain analysis of in-situ SEM mechanical experiments

Scanning electron microscopy (SEM) enables microstructure characterization at multi-scale, having potential to quantify strain distribution across multiple fields of view (FOVs) and exploring coordinated relationships among the deformations of multi-scale microstructures. Optimizing distribution of multi-scale speckles is crucial for achieving high precision and efficiency in digital image correlation (DIC) computations. In this work, a multi-scale strain measurement method is proposed for in-situ SEM mechanical experiments, which relies on an uncomplicated multi-scale speckle preparation method. Multi-scale speckle preparation can be achieved by the combination of spin-coating and magnetron sputtering. By using micro- and macro-speckle, multi-scale strain calculations can be achieved during the in-situ SEM mechanical loading. The InSn macro-speckle is composed of controllable-sized InSn nanoscale speckles, ensuring that the accuracy of DIC measurements in the microscopic regions are not compromised by the coverage of macro-speckles in the testing region. In regions covered exclusively by SiO2 nano-speckles, in-situ SEM mechanical loading allows for the acquisition of high-resolution DIC (HR-DIC) and electron backscatter diffraction (EBSD) data from the same region and under the same deformation state. Experiments are conducted to illustrate the functionality and utility of the multi-scale speckles. Such experimental analyses offer an opportunity to further explore multi-scale strain heterogeneity in some advanced structural materials and provide reliable experimental verification for material mechanics simulations.

Multifunctional N-fused fluorescent probes for detection of iron ions and nitro explosives

In this work, two novel probes 4a and 4b were synthesized through Suzuki-Miyaura coupling reaction, whose structures were further confirmed by 1H NMR, 13C NMR, high-resolution mass spectrometry (HRMS) and X-ray single crystal diffraction. The optical properties of the obtained molecules were investigated accordingly. Owing to different bridging fluorophores, there are certain differences in optical performance and detection ability between the two synthesized compounds. Especially, due to the subtle difference in orbitals energy and electron distribution displayed by the DFT calculations, 4a possesses the characteristics of dual-state emission (DSE) molecule, while 4b is an aggregation-induced emission (AIE) molecule. Interestingly, these two molecules can be developed into multifunctional detection probes, successfully applied for the fluorescence recognition of iron ions and common nitroaromatic compounds (NACs). At the same time, the probe molecules can also be applied to the detection of NACs in aqueous environment. What’s more, they can also be loaded on test strips and thin-films for fluorescence identification of NACs, thus being expected to be developed into portable detection tools for NACs.

Fracture behaviors and crack propagation anisotropy in multi-ions modified bismuth titanate ferroelectrics

Bismuth titanate (BIT) is widely considered a promising lead-free piezoelectric material for advanced high-temperature applications. Despite significant advances in high-performance BIT ferroelectrics, there remains little understanding of mechanical properties including fracture failure and crack propagation behaviors, hindering the optimization of stability and reliability for next-generation high-temperature ferroelectrics. In this work, we investigated mechanical fracture and crack propagation behaviors of a type of high-performance bismuth titanate-based ceramic (Bi3.96Ce0.04Ti3–2xWxNbxO12, BCTWN) with different doping contents and electric poling states. High-resolution transmission electron microscopy (HRTEM) and electron backscatter diffraction (EBSD) results reveal that the BCTWN ceramics possess a single ferroelectric phase and exhibit layered crystal structures characterized by periodic fringe features. In addition, the striped domain structures are observed on the surface of plate-like grains. Mechanical measurements indicate that fracture behaviors of BCTWN ceramics are significantly affected by doping contents. The ceramics with the largest grain size present inferior microstructure with more defects, endowing the lowest bending strength and fracture toughness. For the samples with different poling states, strong anisotropy in crack propagation and fracture toughness is observed, attributed to the different domain switching mechanisms driven by local incompatible stress fields, which is experimentally validated by the intriguing evolutions of striped domain structures around crack tips. This work advances our understanding of the fracture and crack propagation mechanisms of BIT-based ceramics and provides insight into tailoring the mechanical behaviors through doping and poling strategies.

Microstructure and mechanical properties of additively manufactured Ti–6Al–4V alloy based on large area, high-resolution EBSD mapping

The laser direct energy deposition (L-DED) is well-suited for metal manufacturing, offering advantages of excellent performance, high precision, intricate structures and material flexibility, etc. In this study, the microstructure and mechanical property of Ti–6Al–4V alloy were investigated using L-DED under various printing parameters. A large-area, high-resolution Electron Backscatter Diffraction (EBSD) mapping technique, enabling to characterize the coarse columnar β-grains with individual crystals up to a centimeter along the building direction, and the sub-grain acicular α′ phase down to 50 nm in the same image, was utilized to analyze the crystalline phases and their lattice orientations in additively manufactured Ti–6Al–4V parts. The microstructure evolution, involving the high temperature β grain structures, β+α phase transformation, as well as acicular α′ martensitic phases, were studied during the periodically attenuated thermal cycles of L-DED. The formation of the “fish-scale” morphology results primarily from the radically different α phase in size between the interior and edges of the “fish-scale” morphology. Additionally, the effect of processing parameters, i.e., scanning speed and laser power, on microstructures and mechanical properties is discussed in detail.

Fatigue mechanisms at 450°C of a highly twined (>70%) and HIP-densified IN718 superalloy additively manufactured by laser beam powder bed fusion

Fatigue resistance at elevated temperatures is crucial for certifying aerospace structures additively manufactured by the laser beam powder bed fusion (PBF-LB) method with IN718 superalloy. This study employed a multi-step, supersolvus heat treatment process with hot isostatic pressing (HIP), called RHSA, to minimize pores and brittle phases. Stress intensity factor (△K) calculations using data from X-ray computed tomography and shape factors referencing finite element analysis (FEA) studies confirmed the suppression of △K below the threshold of conventional IN718 (∼5 MPa√m), shifting fatigue behavior to grain-structure-dominated. Despite a very high twin boundary (TB) fraction (>70%), fatigue tests at 450°C and R = 0.1 demonstrated low scatter. Slip trace analysis and high-resolution electron backscatter diffraction (EBSD) revealed that TB-induced strain concentration became prominent only at high △K, causing cracking at 45⁰ to the loading direction. The randomly oriented TBs with higher angles (60⁰) compared to high-angle grain boundaries (HAGBs) (30–40⁰) likely enhanced slip resistance and provided a net strengthening effect, which can explain the lower-than-average TB% along fracture paths. These insights suggest that a high TB fraction is not detrimental if fatigue stress is not excessive, alleviating concerns about annealing twins during defect minimization in AM IN718, allowing novel processes to improve fatigue resistance in PBF-LB IN718.

Damage-tolerant oxides by imprint of an ultra-high dislocation density

Dislocations in ductile ceramics offer the potential for robust mechanical performance while unlocking versatile functional properties. Previous studies have been limited by small volumes with dislocations and/or low dislocation densities in ceramics. Here, we use Brinell ball scratching to create crack-free, large plastic zones, offering a simple and effective method for dislocation engineering at room temperature. Using MgO, we tailor high dislocation densities up to ∼1015 m−2. We characterise the plastic zones by chemical etching, electron channelling contrast imaging, and scanning transmission electron microscopy, and further demonstrate that crack initiation and propagation in the plastic zones with high-density dislocations can be completely suppressed. The residual stresses in the plastic zones were analysed using high-resolution electron backscatter diffraction. With the residual stress being subsequently relieved via thermal annealing while retaining the high-density dislocations, we observe the cracks are no longer completely suppressed, but the pure toughening effect of the dislocations remains evident.

On the magnetic and crystal structures of NiO and MnO.

The magnetic and crystal structures of manganese and nickel monoxides have been studied using high-resolution neutron diffraction. The known 1k-structures based on the single propagation vector [½ ½ ½] for the parent paramagnetic space group Fm3m are forced to have monoclinic magnetic symmetry and are not possible in rhombohedral symmetry. However, the monoclinic distortions from the rhombohedral crystal metric allowed by symmetry are very small, and the explicit monoclinic splittings of the diffraction peaks have not been experimentally observed. We analyse the magnetic crystallographic models metrically compatible with our experimental data in full detail by using isotropy subgroup representation approach, including rhombohedral solutions based on the propagation vector star {[½ ½ ½], [-½ ½ ½], [½-½ ½], [½ ½ -½]}. Although the full star rhombohedral RI3c structure can equally well fit our diffraction data for NiO, we conclude that the best solution for the crystal and magnetic structures for NiO and MnO is the 1k monoclinic model with the magnetic space group Cc2/c (Belov-Neronova-Smirnova No. 15.90, UNI symbol C2/c.1'c[C2/m]).

Automated analysis framework of strain partitioning and deformation mechanisms via multimodal fusion and computer vision

Simultaneously investigating strain partitioning and the underlying deformation mechanisms for both the grain interior and the grain boundary (GB) is essential for understanding the complex plastic deformation of hexagonal close-packed metals. To this end, an automated analysis framework based on high-resolution digital image correlation (HRDIC) and electron backscatter diffraction (EBSD) data fusion and computer vision, integrating nanoscale resolution and a large field of view, is proposed. This framework consists of: (1) HRDIC-EBSD data fusion; (2) Segmenting the strain field into individual grains each with a core and a mantle; (3) Data clustering of the Matrix and slip bands (SBs) for each grain; (4) Full slip system (SS) identification and SS assignment to the SBs. The capabilities of this framework were demonstrated on Mg-10Y during compression. The strain field data, which was segmented into different clusters, including grain mantle, grain core, Matrix, and SBs, was analyzed statistically and quantitatively. The pixel-based slip activity, which considers the SB morphology, was obtained from a statistical perspective. Inter-granular accommodating mechanisms, including GB strain, slip transfer, and GB sliding, were quantitatively analyzed. Overall, this analysis framework, which can be applied to other materials, can automatically and statistically evaluate both nanoscale strain fields and underlying intra- and inter-granular deformation mechanisms grain-by-grain. This work provides valuable experimental insights into plastic deformation and accommodation mechanisms for polycrystals.

Mapping of Microscopic and Local Stress-Strain Curve Information by Combination of Digital Image Correlation and High-Resolution Electron Backscatter Diffraction Methods

Mapping of Microscopic and Local Stress-Strain Curve Information by Combination of Digital Image Correlation and High-Resolution Electron Backscatter Diffraction Methods

Dynamic recrystallisation: A quantitative study on grain boundary characteristics and dependence on temperature and strain rate in an aluminium alloy

Dynamic recrystallisation (DRX) usually occurs during hot forming of metallic materials, significantly impacting the mechanical properties of the final parts. Although DRX has been studied for decades, the types of DRX that occurs in high stacking fault energy (SFE) materials like aluminium alloys are still controversial, and their dependence on both temperature and strain rate is surprisingly missing. To fill these gaps, in the present study, uniaxial compression tests on an aluminium alloy AA6061 were carried out at different temperatures from 250 to 475 °C and strain rates from 0.01 to 1 s-1. The grain orientation and misorientation before and after the hot deformation were quantitively characterised using high-resolution Electron Backscatter Diffraction (EBSD) with a misorientation resolution of 0.05°, enabling high-angle grain boundaries (HAGBs), low-angle grain boundaries (LAGBs) and geometrically necessary dislocations (GNDs) to be accurately quantified and correlated against temperature and strain rate. Results reveal that both continuous dynamic recrystallisation (CDRX) and geometric dynamic recrystallisation (GDRX) occurred concurrently, resulting in the formation of discontinuous HAGBs and fine equiaxed grains, respectively. The misorientation angle distributions of the discontinuous HAGBs exhibit an opposite trend compared to those of the fine grains’ HAGBs. Both temperature and strain rate significantly affect the density of HAGBs formed by DRX, but have little effect on their misorientation angle distributions. This study sheds light on the fundamental understanding of DRX and provides comprehensive experimental data for future modelling of DRX processes in high SFE materials.

Chirality Determination of Nanocrystals by Electron Crystallography.

Chirality is a common phenomenon in nature and plays an important role in the properties of matter. The rational synthesis of chiral compounds and exploration of their applications in various fields require an unambiguous determination of their handedness. However, in many cases, determinations of the chiral crystal structure and chiral morphology have been a challenging task due to the lack of proper characterization methods, especially for nanosized crystals. Therefore, it is crucial to develop novel and efficient characterization methods. Owing to the strong interactions between matter and electrons, electron crystallography has become a powerful tool for structural analysis of nanomaterials. In recent years, methods based on electron crystallography, such as high-resolution electron microscopy imaging and electron diffraction, have been developed to unravel the chirality of nanomaterials. This brings new opportunities to the design, synthesis, and applications of versatile chiral nanomaterials. In this perspective, we summarize the recent methodology developments and ongoing research of electron crystallography for chiral structure and morphology determination of nanocrystals, including inorganic and organic materials, as well as highlight the potential and further improvement of these methods in the future.

Automated pipeline processing X-ray diffraction data from dynamic compression experiments on the Extreme Conditions Beamline of PETRAIII.

Presented and discussed here is the implementation of a software solution that provides prompt X-ray diffraction data analysis during fast dynamic compression experiments conducted within the dynamic diamond anvil cell technique. It includes efficient data collection, streaming of data and metadata to a high-performance cluster (HPC), fast azimuthal data integration on the cluster, and tools for controlling the data processing steps and visualizing the data using the DIOPTAS software package. This data processing pipeline is invaluable for a great number of studies. The potential of the pipeline is illustrated with two examples of data collected on ammonia-water mixtures and multiphase mineral assemblies under high pressure. The pipeline is designed to be generic in nature and could be readily adapted to provide rapid feedback for many other X-ray diffraction techniques, e.g. large-volume press studies, in situ stress/strain studies, phase transformation studies, chemical reactions studied with high-resolution diffraction etc.

Unraveling factors affecting the reversibility of martensitic phase transformation in FeNiCoAlTi shape memory alloys: Insights from HR-EBSD and acoustic emission analysis

The reversibility of the martensitic phase transformation is crucial for the functionality of shape memory alloys. The easier the martensite is pinned, the faster occurs the degradation of the shape memory effect during cyclic loading. This study investigates various factors influencing the stabilization of martensite during deformation of single-crystalline states of the FeNiCoAlTi system. In order to investigate early pinning mechanisms in more detail a 〈011〉 single crystal with expected lower reversibility of the martensitic phase transformation and, consequently, lower superelasticity was chosen. Complementary in situ methods, such as digital image correlation and acoustic emission, were used to characterize the evolution of the martensitic phase transformation and the role of dislocations during deformation. Thereby, experimental evidence was elaborated pointing at mechanisms that so far have been underrated in terms of functional degradation. Beside interaction of martensitic variants and dislocation activity, detwinning, associated with high acoustic energy, was identified as an additional significant factor contributing to reduced reversibility and superelasticity. In addition, high-resolution electron backscatter diffraction measurements were applied for the first time to identify residual stresses in the austenitic matrix, which significantly contribute to the reverse transformation. Micro-mechanical experiments using pillar compression tests were carried out to study the influence of residual back stresses of the austenitic matrix on the reversibility of the martensitic phase transformation. A reduced reversibility was found in the case of the absence of back stresses. The findings from this study foster the understanding of pinning mechanisms during loading of the FeNiCoAlTi shape memory alloy eventually enabling targeted optimization for enhanced superelastic material behavior.

High-throughput and high-resolution powder X-ray diffractometer consisting of six sets of 2D CdTe detectors with variable sample-to-detector distance and innovative automation system.

The demand for powder X-ray diffraction analysis continues to increase in a variety of scientific fields, as the excellent beam quality of high-brightness synchrotron light sources enables the acquisition of high-quality measurement data with high intensity and angular resolution. Synchrotron powder diffraction has enabled the rapid measurement of many samples and various in situ/operando experiments in nonambient sample environments. To meet the demands for even higher throughput measurements using high-energy X-rays at SPring-8, a high-throughput and high-resolution powder diffraction system has been developed. This system is combined with six sets of two-dimensional (2D) CdTe detectors for high-energy X-rays, and various automation systems, including a system for automatic switching among large sample environmental equipment, have been developed in the third experimental hutch of the insertion device beamline BL13XU at SPring-8. In this diffractometer system, high-brilliance and high-energy X-rays ranging from 16 to 72 keV are available. The powder diffraction data measured under ambient and various nonambient conditions can be analysed using Rietveld refinement and the pair distribution function. Using the 2D CdTe detectors with variable sample-to-detector distance, three types of scan modes have been established: standard, single-step and high-resolution. A major feature is the ability to measure a whole powder pattern with millisecond resolution. Equally important, this system can measure powder diffraction data with high Q exceeding 30 Å-1 within several tens of seconds. This capability is expected to contribute significantly to new research avenues using machine learning and artificial intelligence by utilizing the large amount of data obtained from high-throughput measurements.

On the resolution of the three-axis neutron diffractometer setting optimized for some powder diffractometry studies

Presented three-axis neutron diffractometer performance documents the feasibility of using it in special cases high-resolution powder diffraction studies, namely, for elastic and plastic deformation studies of bulk polycrystalline samples when the whole powder diffraction spectrum is not required. Contrary to the conventional double-axis setting the suggested alternative consists of an unconventional three axis set-up employing a bent perfect crystal (BPC) monochromator and analyzer with a polycrystalline sample in between. The analysis of the profile of the beam diffracted by a sample is carried out by rocking the BPC-analyzer and the neutron signal is registered by a point detector. Though the diffractometer alternative is, for measurements, much more time consuming, its resolution is, however, substantially higher and permits also plastic deformation studies on the basis of analysis of the sample diffraction profiles. The so-called analyzer rocking curve then provides a sample diffraction profile and could reflect the lattice or structural changes. Moreover, much larger widths (up to 10 mm) of the irradiated gauge volumes can be investigated when just slightly affecting the resolution of the experimental setting.

Composition Dictates Octahedral Tilt and Photostability in Halide Perovskites.

Halide perovskites are excellent candidate materials for use in solar cell, LED, and detector devices, in part because their composition can be tuned to achieve ideal optoelectronic properties. Empirical efficiency optimization has led the field toward compositions rich in FA (formamidinium) on the A-site and I on the X-site, with additional small amounts of MA (methylammonium) or Cs A-site cations and Br X-site anions. However, it is not clear how and why the specific compositions of alloyed, that is, mixed component, halide perovskites relate to photo-stability of the materials. Here, this work combines synchrotron grazing incidence wide-angle X-ray scattering, photoluminescence, high-resolution scanning electron diffraction measurements and theoretical modelling to reveal the links between material structure and photostability. Namely, this work finds that increased octahedral titling leads to improved photo-stability that is correlated with lower densities of performance-harming hexagonal polytype impurities. These results uncover the structural signatures underpinning photo-stability and can therefore be used to make targeted changes to halide perovskites, bettering the commercial prospects of technologies based on these materials.