Precession Electron Diffraction Research Articles

A novel grain refinement of Ce-Fe-B magnets induced by magnetic field annealing

Magnetic field annealing-induced grain refinement usually occurs during the crystallization process of amorphous alloys. This work investigates the effects of magnetic field annealing on the microstructure and magnetic properties of crystalline Ce17Fe76Co1Zr0.5B6Mo0.5 alloys. The results indicate that magnetic field annealing below the Curie temperature (TC) of the Ce2Fe14B phase in the alloys reduces the alloy’s grain size. At an annealing temperature of 433 K, the average grain size of alloys decreased from 48.0 nm in the as-spun sample to 27.2 nm in the magnetic field annealing sample. Moreover, magnetic field annealing can effectively reduce the volume fraction of the CeFe2 phase in the alloy. After magnetic field annealing at 433 K, the alloy obtained the optimal comprehensive magnetic properties: the intrinsic coercivity (Hci = 441.1 kA/m), remanence (Br = 0.49 T), squareness (Hk/Hci = 0.53), and maximum energy product ((BH)max) = 35.5 kJ/m3), which were 0.2 %, 16.7 %, 6 %, and 29.1 % higher than the values of the as-spun sample, respectively. Precession electron diffraction (PED) analysis revealed that magnetic field annealing increased strain at grain and phase boundaries and a more uniform grain orientation spread (GOS), promoting recrystallization and grain refinement. This study provides new insights into the grain refinement mechanism of crystalline alloys under magnetic field annealing, contributing to further improving the magnetic properties of Ce-Fe-B magnets.

Development of ultrafast four-dimensional precession electron diffraction

Ultrafast electron diffraction/microscopy technique enables us to investigate the nonequilibrium dynamics of crystal structures in the femtosecond-nanosecond time domain. However, the electron diffraction intensities are in general extremely sensitive to the excitation errors (i.e., deviation from the Bragg condition) and the dynamical effects, which had prevented us from quantitatively discussing the crystal structure dynamics particularly in thick samples. Here, we develop a four-dimensional precession electron diffraction (4D-PED) system by which time (t) and electron-incident-angle (ϕ) dependences of electron diffraction patterns (qx,qy) are recorded. Nonequilibrium crystal structure refinement on VTe2 demonstrates that the ultrafast change in the crystal structure can be quantitatively determined from 4D-PED. We further perform the analysis of the ϕ dependence, from which we can qualitatively estimate the change in the reciprocal lattice vector parallel to the optical axis. These results show the capability of the 4D-PED method for the quantitative investigation of ultrafast crystal structural dynamics.

Unsupervised Learning for the Automatic Counting of Grains in Nanocrystals and Image Segmentation at the Atomic Resolution.

Identifying the grain distribution and grain boundaries of nanoparticles is important for predicting their properties. Experimental methods for identifying the crystallographic distribution, such as precession electron diffraction, are limited by their probe size. In this study, we developed an unsupervised learning method by applying a Gabor filter to HAADF-STEM images at the atomic level for image segmentation and automatic counting of grains in polycrystalline nanoparticles. The methodology comprises a Gabor filter for feature extraction, non-negative matrix factorization for dimension reduction, and K-means clustering. We set the threshold distance and angle between the clusters required for the number of clusters to converge so as to automatically determine the optimal number of grains. This approach can shed new light on the nature of polycrystalline nanoparticles and their structure-property relationships.

Determination of five-parameter grain boundary characteristics in nanocrystalline Ni-W by scanning precession electron diffraction tomography

Determining the full five-parameter grain boundary characteristics from experiments is essential for understanding grain boundaries impact on material properties, improving related models, and designing advanced alloys. However, achieving this is generally challenging, in particular at nanoscale, due to their 3D nature. In our study, we successfully determined the grain boundary characteristics of an annealed nickel-tungsten alloy (NiW) nanocrystalline needle-shaped specimen (tip) containing twins using Scanning Precession Electron Diffraction (SPED) Tomography. The presence of annealing twins in this face-centered cubic (fcc) material gives rise to common reflections in the SPED diffraction patterns, which challenges the reconstruction of orientation-specific virtual dark field (VDF) images required for tomographic reconstruction of the 3D grain shapes. To address this, an automated post-processing step identifies and deselects these shared reflections prior to the reconstruction of the VDF images. Combined with appropriate intensity normalization and projection alignment procedures, this approach enables high-fidelity 3D reconstruction of the individual grains contained in the needle-shaped sample volume. To probe the accuracy of the resulting boundary characteristics, the twin boundary surface normal directions were extracted from the 3D voxelated grain boundary map using a 3D Hough transform. For the sub-set of coherent Σ3 boundaries, the expected {111} grain boundary plane normals were obtained with an angular error of <3° for boundary sizes down to 400 nm². This work advances our ability to precisely characterize and understand the complex grain boundaries that govern material properties.

Applying Precession Electron Diffraction to Cepstral Analysis to Investigate Polarity in Ferroelastically Tilted Specimens

Applying Precession Electron Diffraction to Cepstral Analysis to Investigate Polarity in Ferroelastically Tilted Specimens

Elastic strain mapping of plastically deformed materials by TEM

A method for mapping elastic strains by TEM in plastically deformed materials is presented. A characteristic feature of plastically deformed materials, which cannot be handled by standard strain measurement method, is the presence of orientation gradients. To circumvent this issue, we couple orientation and strain maps obtained from scanning precession electron diffraction datasets. More specifically, orientation gradients are taken into account by 1) identifying the diffraction spot positions in a reference pattern, 2) measuring the disorientation between the diffraction patterns in the map and the reference pattern, 3) rotating the coordinate system following the measured disorientation at each position in the map, 4) calculating strains in the rotated coordinate system. At present, only azimuthal rotations of the crystal are handled. The method is illustrated on a Cr2AlC monocrystal micropilar deformed in near simple flexion during a nanomechanical test. After plastic deformation, the sample contains dislocations arranged in pile-ups and walls. The strain-field around each dislocation is consistent with theory, and a clear difference is observed between the strain fields around pile-ups and walls. It is further remarked that strain maps allow for the orientation of the Burgers vector to be identified. Since the loading undergone by the sample is known, this also allows for the position of the dislocation sources to be estimated. Perspectives for the study of deformed materials are finally discussed.

Synthesis and in-depth structure determination of a novel metastable high-pressure CrTe3 phase

This study reports the synthesis and crystal structure determination of a novel CrTe3 phase using various experimental and theoretical methods. The average stoichiometry and local phase separation of this quenched high-pressure phase were characterized by ex situ synchrotron powder X-ray diffraction and total scattering. Several structural models were obtained using simulated annealing, but all suffered from an imperfect Rietveld refinement, especially at higher diffraction angles. Finally, a novel stoichiometrically correct crystal structure model was proposed on the basis of electron diffraction data and refined against powder diffraction data using the Rietveld method. Scanning electron microscopy–energy-dispersive X-ray spectrometry (EDX) measurements verified the targeted 1:3 (Cr:Te) average stoichiometry for the starting compound and for the quenched high-pressure phase within experimental errors. Scanning transmission electron microscopy (STEM)–EDX was used to examine minute variations of the Cr-to-Te ratio at the nanoscale. Precession electron diffraction (PED) experiments were applied for the nanoscale structure analysis of the quenched high-pressure phase. The proposed monoclinic model from PED experiments provided an improved fit to the X-ray patterns, especially after introducing atomic anisotropic displacement parameters and partial occupancy of Cr atoms. Atomic resolution STEM and simulations were conducted to identify variations in the Cr-atom site-occupancy factor. No significant variations were observed experimentally for several zone axes. The magnetic properties of the novel CrTe3 phase were investigated through temperature- and field-dependent magnetization measurements. In order to understand these properties, auxiliary theoretical investigations have been performed by first-principles electronic structure calculations and Monte Carlo simulations. The obtained results allow the observed magnetization behavior to be interpreted as the consequence of competition between the applied magnetic field and the Cr–Cr exchange interactions, leading to a decrease of the magnetization towards T = 0 K typical for antiferromagnetic systems, as well as a field-induced enhanced magnetization around the critical temperature due to the high magnetic susceptibility in this region.

Tensile Properties of a Non-Equiatomic Ni–Co–V Medium Entropy Alloy at Cryogenic Temperature

The development of strong and ductile alloys for application in cryogenic temperatures has long been sought after. In this work, we have developed a face-centered cubic Ni10Co56.5V33.5 multi-principal element alloy (MPEA) that exhibits a balanced combination of high strength and good ductility at 77 K, based on the considerations of large local lattice distortion (LLD) and low stacking fault energy. The small-grained Ni10Co56.5V33.5 MPEA exhibits a yield strength of 1400 MPa and an ultimate tensile strength of 1890 MPa, while preserving a good ductility of 23%. Moreover, precession electron diffraction and transmission electron microscopy revealed multiple deformation mechanisms, including wavy dislocations, atypically severely twisted dislocation bands, hierarchical stacking faults, and deformation twins, which are implicated in the alloy’s outstanding mechanical performance. These insights offer a strategic guide for the design of strong and ductile alloys, particularly for utilization in extreme environments.

From microstructural changes to electrochemical behavior: decoding the corrosion mechanism in Zr-Sn-Nb-Fe-Cr-Mo-O-V alloys

The oxide formed on a Zr-0.4Sn-0.7Nb-0.3Fe-0.1Cr-0.15Mo-0.12O-0.05V, wt% alloy, after exposure for 300 d in 360°C/20 MPa (water with 0 ppb, 300 ppb, and 1000 ppb), was characterized by transmission electron microscope (TEM), precession electron diffraction (PED) and electrochemical impedance spectroscopy (EIS). Results showed that DO accelerated the corrosion of the alloy, and this effect was enhanced with the increase of the DO concentrations. A mechanism of the correlation between electrochemical behavior evolution and microstructural changes of oxide film was proposed, which provided theoretical guidance for the selection of fuel cladding materials for small nuclear reactors.

Microstructure evolution of ATI718 plus alloy during high-speed machining: Experiments and a combined FE-CA approach

Excellent surface integrity is an eternal pursuit in high performance manufacturing, with microstructure being a crucial component of the surface integrity dataset and a key factor controlling surface properties such as fatigue and creep. The multi-physical fields generated by thermo-mechanical loads during high-speed machining act on the processed surface layer, influencing the evolution of microstructures. To investigate the microstructural evolution mechanisms of ATI718 plus during high-speed machining, cutting experiments and techniques such as Electron back scatter diffraction (EBSD), Transmission Kikuchi diffraction (TKD), and Precession electron diffraction (PED) is conducted to quantitatively analyze the microstructures in the chip shear zone and the machined surface. Subsequently, a combined finite element (FE) and cellular automata (CA) model is developed to simulate the microstructure evolution during the cutting process. The discontinuous dynamic recrystallization (DDRX) mechanism is employed to demonstrate the nucleation and growth of grains under the influence of multiple physical fields. The simulation and experimental results show similar dynamic recrystallization (DRX) grain sizes, indicating acceptable accuracy of the CA model in terms of DRX grain size. The comparison between experimental and simulation results confirms the occurrence of both continuous dynamic recrystallization (CDRX) and DDRX during the cutting process. The synergistic competition between CDRX induced grain lamellar refinement and DDRX induced grain growth emerge as the primary mechanism driving microstructural evolution. A layer of ultrafine grains, with a thickness within 20 μm, is formed on the machined surface. Results under different parameters demonstrate that the temperature has a more significant impact on the thickness of the ultrafine grain layer and the diameter of grains within the layer compared to the strain rate.

Determination of Na+ Cation Locations in Nanozeolite ECR-1 Using a 3D ED Method

Until now, the comprehensive structural analysis of single crystals of zeolite ECR-1, an aluminosilicate with the EON topology, has been hindered owing to the submicron dimensions of the obtained crystals. Additionally, this zeolite, which is characterized by a topology comprising alternating periodic building units of MAZ and MOR layers, exhibits stacking faults that impede accurate refinement through the Rietveld method. In this report, we present, for the first time, the structure of ECR-1 elucidated by studying a nanocrystal with a significantly reduced number of stacking faults. The sample used was synthesized hydrothermally using trioxane as the organic structure-directing agent. The structure determination was conducted using precession electron diffraction (PED) at 103 K. Partial dehydration occurred owing to the high vacuum conditions in the TEM sample chamber. From the dynamical refinement (Robs = 0.097), 8.16 Na+ compensating cations were localized on six distinct crystallographic sites, along with approximately four water molecules per unit cell. Furthermore, a canonical Monte Carlo computational study was conducted to compare the experimental cationic distribution and location of water molecules with the simulation.

Study of the epitaxy between ɛ-Fe2O3, hematite and spinel in brown-glazed Chinese ceramics using electron diffraction mapping techniques

Black-to-brown Chinese ceramics have sparked the interest of material scientists since the widespread discovery of complex dendritic structures containing mainly the rare ɛ-Fe2O3 polymorph in their glazes. This study proposes to tackle this issue using two electron diffraction mapping techniques, transmission Kikuchi diffraction and automated crystal orientation mapping–precession electron diffraction, which have not been fully exploited despite their relevance for studying these structures at the scales of interest. It first demonstrates the efficiency of applying these techniques to characterize the structures at the nanoscale and discusses some limitations that may be encountered, in particular due to the specificity of heritage samples. It then focuses on the crystalline orientations obtained with these techniques, which highlight epitaxial relationships among the crystalline planes (001) of the ɛ-Fe2O3 phase, (0001) of the hematite and (111) of the spinel. Finally, it discusses the growth of such complex multi-phase structures by proposing two possible mechanisms, one based on the transformation of ɛ-Fe2O3 into hematite and spinel, and the other based on the growth of hematite and spinel on already crystallized ɛ-Fe2O3 dendrites. It also compares the dendritic structures of the two modern samples with those found in an ancient sample of Jian ware.

Dynamical refinement with multipolar electron scattering factors.

Dynamical refinement is a well established method for refining crystal structures against 3D electron diffraction (ED) data and its benefits have been discussed in the literature [Palatinus, Petříček & Corrêa, (2015). Acta Cryst. A71, 235-244; Palatinus, Corrêa et al. (2015). Acta Cryst. B71, 740-751]. However, until now, dynamical refinements have only been conducted using the independent atom model (IAM). Recent research has shown that a more accurate description can be achieved by applying the transferable aspherical atom model (TAAM), but this has been limited only to kinematical refinements [Gruza et al. (2020). Acta Cryst. A76, 92-109; Jha et al. (2021). J. Appl. Cryst. 54, 1234-1243]. In this study, we combine dynamical refinement with TAAM for the crystal structure of 1-methyluracil, using data from precession ED. Our results show that this approach improves the residual Fourier electrostatic potential and refinement figures of merit. Furthermore, it leads to systematic changes in the atomic displacement parameters of all atoms and the positions of hydrogen atoms. We found that the refinement results are sensitive to the parameters used in the TAAM modelling process. Though our results show that TAAM offers superior performance compared with IAM in all cases, they also show that TAAM parameters obtained by periodic DFT calculations on the refined structure are superior to the TAAM parameters from the UBDB/MATTS database. It appears that multipolar parameters transferred from the database may not be sufficiently accurate to provide a satisfactory description of all details of the electrostatic potential probed by the 3D ED experiment.

NbC thin films via reactive DC sputtering in a CH4/Ar atmosphere

We have demonstrated the growth of NbC-Amorphous C films that manifest a well-known nanocomposite structure (Klages and Memming, 1990; Nedfors et al., 2011; Sala et al., 2021). The films were deposited using reactive DC sputtering in a CH4/Ar atmosphere using an insulating substrate near room temperature. A metallic Nb sputtering target was sputtered in an argon/CH4 atmosphere with a pressure range of 5.9 to 8.5 mTorr as the CH4 flow was also varied. Crystalline NbC films were deposited at room temperature at the lowest CH4 flow rate. The films exhibited ohmic electrical response at room temperature. The DC electrical resistivity scaled almost 4 orders of magnitude from 4.39 × 10−4 Ω-cm to 1.08 × 10−1 Ω-cm through changes in CH4 flow rates and the resultant C content of the films. The large variation in resistivity cannot be attributed to the changes in sample composition, e.g. volumetric mixing. It is postulated from XRD and TEM results that the large change in resistivity is due to the decreasing NbC crystallite size with increasing CH4. This leads to additional three-dimensional nanoscale intragranular interfaces and results in increased resistivity. X-ray reflectivity measurements were conducted, and the modelled film density was found to match the expected density for the film compositions as measured using X-ray photoelectron spectroscopy. Elastic recoil detection analysis (ERDA) was used to quantify H content of the films. The H content increased from 5.5 to 22 atomic percent with corresponding increase in CH4 flow. Transmission electron microscopy utilizing precession electron diffraction (PED) was conducted and showed a strong dependence of crystallinity on CH4 flow. A multilayer layer sample with varying CH4 flowrates was examined with TEM and showed that films were amorphous in nature for flow rates above 10 SCCM CH4; in agreement with XRD results.

Diffraction-Based Multiscale Residual Strain Measurements.

Modern analytical tools, from microfocus X-ray diffraction (XRD) to electron microscopy-based microtexture measurements, offer exciting possibilities of diffraction-based multiscale residual strain measurements. The different techniques differ in scale and resolution, but may also yield significantly different strain values. This study, for example, clearly established that high-resolution electron backscattered diffraction (HR-EBSD) and high-resolution transmission Kikuchi diffraction (HR-TKD) [sensitive to changes in interplanar angle (Δθθ)], provide quantitatively higher residual strains than micro-Laue XRD and transmission electron microscope (TEM) based precession electron diffraction (PED) [sensitive to changes in interplanar spacing (Δdd)]. Even after correcting key known factors affecting the accuracy of HR-EBSD strain measurements, a scaling factor of ∼1.57 (between HR-EBSD and micro-Laue) emerged. We have then conducted "virtual" experiments by systematically deforming an ideal lattice by either changing an interplanar angle (α) or a lattice parameter (a). The patterns were kinematically and dynamically simulated, and corresponding strains were measured by HR-EBSD. These strains showed consistently higher values for lattice(s) distorted by α, than those altered by a. The differences in strain measurements were further emphasized by mapping identical location with HR-TKD and TEM-PED. These measurements exhibited different spatial resolution, but when scaled (with ∼1.57) provided similar lattice distortions numerically.

Structural and magnetic properties of Ni cluster embedded (111)NiO layers grown on (0001)GaN films

(111) NiO epitaxial layers embedded with crystallographically oriented Ni-clusters are grown on c-GaN/Sapphire templates using the pulsed laser deposition technique. Structural and magnetic properties of the films are examined by a variety of techniques including high-resolution x-ray diffraction, precession-electron diffraction, and superconducting quantum interference device magnetometry. It has been found that Ni-clusters are formed in the NiO matrix only at sufficiently low oxygen pressures during the growth. The study further reveals that the orientation, shape, size, density, and magnetic properties of these clusters depend strongly on the growth temperature (TG). Although most of the Ni-clusters are found to be obtained crystallographically aligned with the NiO matrix with Ni(111) ∥NiO(111), clusters with other orientations also exist, especially in samples grown at lower temperatures. The average size and density of the clusters increase with TG. The proportion of the Ni(111) ∥ NiO(111)-oriented clusters also improves as TG is increased. All cluster embedded films show ferromagnetic behavior even at room temperature. Easy-axis is found to be oriented in the layer plane in samples grown at relatively lower temperatures. However, it turns perpendicular to the layer plane for samples grown at sufficiently high temperatures. This reversal of easy-axis has been attributed to the size dependent competition between the shape and magnetoelastic and the surface anisotropies of the clusters. This composite material thus has great potential to serve as a spin-injector and spin-storage medium in GaN-based spintronics of the future.

A method for crystallographic mapping of an alpha-beta titanium alloy with nanometre resolution using scanning precession electron diffraction and open-source software libraries.

An approach for the crystallographic mapping of two-phase alloys on the nanoscale using a combination of scanned precession electron diffraction and open-source python libraries is introduced in this paper. This method is demonstrated using the example of a two-phaseα/β titanium alloy. The data were recorded using a direct electron detector to collect the patterns, and recently developed algorithms to perform automated indexing and analyse the crystallography from the results. Very high-quality mapping is achieved at a 3nm step size. The results show the expected Burgers orientation relationships between the α laths and β matrix, as well as the expected misorientations betweenα laths. A minor issue was found that one area was affected by 180° ambiguities in indexing occur due to this area being aligned too close to a zone axis of the α with twofold projection symmetry (not present in 3D) in the zero-order Laue Zone, and this should be avoided in data acquisition in the future. Nevertheless, this study demonstrates a good workflow for the analysis of nanocrystalline two- or multi-phase materials, which will be of widespread use in analysing two-phase titanium and other systems and how they evolve as a function of thermomechanical treatments.

Quantitative Scanning Transmission Electron Microscopy–High‐Angle‐Annular Dark‐Field Study of the Structure of Pseudo‐2D Sb2Te3 Films Grown by (Quasi) Van der Waals Epitaxy

Scanning transmission electron microscopy (STEM) techniques are used to improve the understanding of out‐of‐plane oriented Sb2Te3 thin films deposited by sputtering on SiO2 and Si substrates. Nanobeam precession electron diffraction, energy‐dispersive X‐ray spectroscopy, and high‐angle‐annular dark‐field imaging show that the presence of 1–2 atomic planes of Te on top of the substrate is a crucial factor for successful growth of such films, which can be achieved by optimizing cosputtering of Te and Sb2Te3 targets. The formation of an actual van der Waals (vdW) gap between the substrate and the first Sb2Te3 quintuple layer allows for vdW epitaxy. This gap is larger than those separating Te planes in the pseudo‐2D Sb2Te3 structure. HAADF image analysis provides detailed information on the atomic arrangement such as interplanar distances, vdW gaps, and Debye–Waller coefficients, all these with a few pm precision. For the anisotropic atomic displacements, a new methodology is introduced based on the statistical analysis of atomic column positions that provides information on the low‐frequency phonon modes. Ab initio calculations are used to support our results. Overall, this study provides quantitative STEM tools particularly well suited for nonperiodic pseudo‐2D materials, such as Sb2Te3/GeTe superlattices.

High precision orientation mapping from 4D-STEM precession electron diffraction data through quantitative analysis of diffracted intensities

The association of scanning transmission electron microscopy (STEM) and detection of a diffraction pattern at each probe position (so-called 4D-STEM) represents one of the most promising approaches to analyze structural properties of materials with nanometric resolution and low irradiation levels. This is widely used for texture analysis of materials using automated crystal orientation mapping (ACOM). Herein, we perform orientation mapping in InP nanowires exploiting precession electron diffraction (PED) patterns acquired by an axial CMOS camera. Crystal orientation is determined at each probe position by the quantitative analysis of diffracted intensities minimizing a residue comparing experiments and simulations in analogy to x-ray structural refinement. Our simulations are based on the two-beam dynamical diffraction approximation and yield a high angular precision (∼0.03°), much lower than the traditional ACOM based on pattern matching algorithms (∼1°). We anticipate that simultaneous exploration of both spot positions and high precision crystal misorientation will allow the exploration of the whole potentiality provided by PED-based 4D-STEM for the characterization of deformation fields in nanomaterials.

New insights into microstructure refinement in crack initiation region of very-high-cycle fatigue for SLM Ti-6Al-4V via precession electron diffraction

The formation mechanism of crack initiation region of selective laser melted (SLM) Ti-6Al-4V in very-high-cycle fatigue (VHCF) was investigated by using the novel approach of transmission electron microscopy (TEM) with precession electron diffraction (PED). It is the first time to reveal the microstructure details of nanograin layer in the crack banks of both main crack and sub-crack in SLM Ti-6Al-4V via TEM with PED, which is the result of the crack closure and contacting between fracture surfaces. This revelation provides new insights into the microstructural evolution in the crack initiation region for SLM titanium alloys and other metallic materials, which is helpful for further understanding the crack initiation mechanism in VHCF.