EBSD and TKD analyses using inverted contrast Kikuchi diffraction patterns and alternative measurement geometries.

Electron backscatter diffraction (EBSD) patterns can exhibit Kikuchi bands with inverted contrast due to anomalous absorption. This can be observed, for example, on samples with nanoscale topography, in case of a low tilt backscattering geometry, or for transmission Kikuchi diffraction (TKD) on thicker samples. Three examples are discussed where contrast-inverted physics-based simulated master patterns have been applied to find the correct crystal orientation. As first EBSD example, self-assembled gold nanostructures made of Au fcc and Au hcp phases on single-crystal germanium were investigated. Gold covered about 12% of the mapped area, with only two thirds being successfully interpreted using standard Hough-based indexing. The remaining third was solved by brute force indexing using a contrast-inverted master pattern. The second EBSD example deals with maps collected at a non-tilted surface instead of the commonly used 70° tilted one. As TKD example, a jet-polished foil made of duplex stainless steel 2205 was examined. The thin part close to the hole edge producing normal-contrast patterns were standard indexed. The areas of the foil that become thicker with increasing distance from the edge of the hole produce contrast-inverted patterns. They covered three times the evaluable area and were successfully processed using the contrast-inverted master pattern. In the last example, inverted patterns collected at a non-tiled sample were mathematically inverted to normal contrast, and Hough/Radon-based indexing was successfully applied.

Melt Pool Changes Characterization in Laser-Processed H11 Hot Work Tool Steel Using Point-by-Point Scanning Mode towards LPBF Process Optimization.

Additive manufacturing techniques employing laser-based metal melting have garnered significant attention within the scientific community. Despite a decade of comprehensive research on the fundamentals of these techniques, there still remain unexplored facets related to heat flux impact on metallic alloys' properties. Particularly, the effects of point-by-point laser operation on melt pool formation in metallic materials still remain unclear. Thus, this study focuses on the implications of laser metal melting, particularly investigating a point-by-point laser mode operation's influence on melt pool formation and its geometry in the phase-transformation-sensitive material H11 hot work tool steel. To examine the melt pool, singular laser tracks with various laser parameters were scanned across H11 sheet metal, which allowed for the elimination of layer-by-layer heat cycles' influence on the melt pool's microstructure. Samples were examined by means of metallography, revealing significant differences in the melt pool's depth, influenced mostly by exposure time rather than volumetric energy density. Heat-affected zone effects were found to have a limited range and thus potentially marginal effects in layer-by-layer manufacturing conditions. At the same time, retained austenite concentrations near fusion lines have been found within melt pools, suggesting potential micro-segregation of the alloying additions. The results present guidelines towards laser melting processes optimization.

Synthesis and Characterization of Boron Carbide Nanoparticles as Potential Boron-Rich Therapeutic Carriers.

Boron carbide is one of the hardest materials in the world which can be synthesized by various methods. The most common one is a carbothermic or magnesiothermic reduction of B2O3 performed at high temperatures, where the obtained powder still requires grinding and purification. The goal of this research is to present the possibility of synthesizing B4C nanoparticles from elements via vapor deposition and modifying the morphology of the obtained powders, particularly those synthesized at high temperatures. B4C nanoparticles were synthesized in the process of direct synthesis from boron and carbon powders heated at the temperature of 1650 °C for 2 h under argon and characterized by using scanning electron microscopy, transmission electron microscopy, atomic force microscopy, X-ray diffraction analysis, and dynamic light scattering measurements. The physicochemical characteristics of B4C nanoparticles were determined, including the diffusion coefficients, hydrodynamic diameter, electrophoretic mobilities, and zeta potentials. An evaluation of the obtained B4C nanoparticles was performed on several human and mouse cell lines, showing the relation between the cytotoxicity effect and the size of the synthesized nanoparticles. Assessing the suitability of the synthesized B4C for further modifications in terms of its applicability in boron neutron capture therapy was the overarching goal of this research.

Mapping of lattice distortion in martensitic steel-Comparison of different evaluation methods of EBSD patterns.

To visualize the varying tetragonal distortions in high carbon martensitic steels by EBSD, two different approaches have been applied on backscattered Kikuchi diffraction (BKD) patterns. A band-edge refinement technique called Refined Accuracy (RA) (Oxford Instruments) is compared with a technique called Pattern Matching (PM), which optimizes the fit to a simulated BKD signal. RA distinguishes between hypothetical phases of different fixed c/a, while PM determines a best fitting continuous c/a by projective transformation of a master pattern. Both techniques require stored BKD patterns. The sensitivity of the c/a-determination was tested by investigating the microstructure of a ferritic steel with an expected c/a=1. The influence of the Kikuchi pattern noise on c/a was compared for a single or 40 averaged frames per measuring point, and turned out to be not significant. The application of RA and PM on the martensitic microstructure delivered qualitatively similar maps of c/a. The comparison of RA and PM shows that RA is suitably fast and precise during mapping the martensite c/a ratio in analyses of high carbon martensite, especially for fast initial surveys. As RA leads quantitatively to higher noise in c/a, the PM analysis can be used for higher precision results.

Influence of polyvinylpyrrolidone (PVP) in the synthesis of luminescent NaYF4:Yb,Er upconversion nanoparticles.

Polyvinylpyrrolidone (PVP) can be used to produce upconversion nanoparticles (UCNPs) in an advantageous manner, i.e. at modest temperatures in open-to-air conditions with simple hotplate and flask apparatus. However, the influence of PVP parameters on the formation of UCNPs has not been previously investigated. In this exploratory study, we establish that PVP molecular weight and relative amount of PVP can greatly influence the morphology and diameter of NaYF4:Yb,Er UCNPs produced via the PVP-assisted route. At nominal amounts of PVP, varying the molecular weight of PVP in synthesis between 10,000 g mol-1(PVP10), 40,000 g mol-1(PVP40), and 55,000 g mol-1(PVP55), had minimal effect on UCNP morphology, whereas reducing the quantity of PVP10 and PVP40 in the reaction to 10% of the nominal amount resulted in two notable effects: (1) the generation of a greater range of UCNP diameters and (2) the production of an unexpected sub-population of rhombus-shaped UCNPs. Bulk and individual nanoparticle analysis indicates that all UCNP morphologies were cubic (α-phase) crystal structure and consisted of NaYF4:Yb,Er. Optical emission properties exhibited only modest green and red luminescence emission ratio when PVP parameters were varied. However, separately produced PVP40 NaYF4:Yb,Tm UCNPs exhibited a much more intense and dual-band blue/red emission. This exploratory work demonstrates that tailoring PVP content in synthesis of UCNPs can greatly alter morphology of UCNPs produced and should be carefully considered in experimental design. However, the underlying mechanisms of action of the role PVP plays in this synthesis remain unclear. Ultimately, significant further work is still required to fully elucidate the relevant chemistry to achieve full control of PVP-UCNP synthesis.

Aerogels based on cationically modified chitosan and poly(vinyl alcohol) for efficient capturing of viruses.

In this study, we developed a new filtering bioaerogel based on linear polyvinyl alcohol (PVA) and the cationic derivative of chitosan (N-[(2-hydroxy-3-trimethylamine) propyl] chitosan chloride, HTCC) with a potential antiviral application. A strong intermolecular network architecture was formed thanks to the introduction of linear PVA chains, which can efficiently interpenetrate the glutaraldehyde(GA)-crosslinked HTCC chains. The morphology of the obtained structures was examined using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The aerogels and modified polymers' elemental composition (including the chemical environment) was determined using X-ray photoelectron spectroscopy (XPS). New aerogels with more than twice as much developed micro- and mesopore space and BET-specific surface area were obtained concerning the starting sample chitosan aerogel crosslinked by glutaraldehyde (Chit/GA). The results obtained from the XPS analysis showed the presence of cationic 3-trimethylammonium groups on the surface of the aerogel, which can interact with viral capsid proteins. No cytotoxic effect of HTCC/GA/PVA aerogel was also observed on fibroblast cells of the NIH3T3 line. Furthermore, the HTCC/GA/PVA aerogel has been shown that efficiently traps mouse hepatitis virus (MHV) from suspension. The presented concept of aerogel filters for virus capture based on modified chitosan and polyvinyl alcohol has a high application potential.

Correlative Analysis of the Dimensional Properties of Bipyramidal Titania Nanoparticles by Complementing Electron Microscopy with Other Methods.

In this paper, the accurate determination of the size and size distribution of bipyramidal anatase nanoparticles (NPs) after deposition as single particles on a silicon substrate by correlative Scanning Electron Microscopy (SEM) with Atomic Force Microscopy (AFM) analysis is described as a new measurement procedure for metrological purposes. The knowledge of the exact orientation of the NPs is a crucial step in extracting the real 3D dimensions of the particles. Two approaches are proposed to determine the geometrical orientation of individual nano-bipyramides: (i) AFM profiling along the long bipyramid axis and (ii) stage tilting followed by SEM imaging. Furthermore, a recently developed method, Transmission Kikuchi Diffraction (TKD), which needs preparation of the crystalline NPs on electron-transparent substrates such as TEM grids, has been tested with respect to its capability of identifying the geometrical orientation of the individual NPs. With the NPs prepared homogeneously on a TEM grid, the transmission mode in a SEM, i.e., STEM-in-SEM (or T-SEM), can be also applied to extract accurate projection dimensions of the nanoparticles from the same sample area as that analysed by SEM, TKD and possibly AFM. Finally, Small Angle X-ray Scattering (SAXS) can be used as an ensemble technique able to measure the NPs in liquid suspension and, with ab-initio knowledge of the NP shape from the descriptive imaging techniques, to provide traceable NP size distribution and particle concentration.

Application of Nanosilicon to the Sintering of Mg-Mg2Si Interpenetrating Phases Composite.

The new in situ fabrication process for Mg-Mg2Si composites composed of interpenetrating metal/intermetallic phases via powder metallurgy was characterized. To obtain the designed composite microstructure, variable nanosilicon ((n)Si) (i.e., 2, 4, and 6 vol.% (n)Si) concentrations were mixed with magnesium powders. The mixture was ordered using a sonic method. The powder mixture morphologies were characterized using scanning electron microscopy (SEM), and heating and cooling-induced thermal effects were characterized using differential scanning calorimetry (DSC). Composite sinters were fabricated by hot-pressing the powders under a vacuum of 2.8 Pa. Shifts in the sintering temperature resulted in two observable microstructures: (1) the presence of Mg2Si and MgO intermetallic phases in α-Mg (580 °C); and (2) Mg2Si intermetallic phases in the α-Mg matrix enriched with bands of refined MgO (640 °C). Materials were characterized by light microscopy (LM) with quantitative metallography, X-ray diffraction (XRD), open porosity measurements, hardness testing, microhardness testing, and nanoindentation. The results revealed that (n)Si in applied sintering conditions ensured the formation of globular and very fine Mg2Si particles. The particles bonded with each other to form an intermetallic network. The volume fraction of this network increased with (n)Si concentration but was dependent on sintering temperature. Increasing sintering temperature intensified magnesium vaporization, affecting the composite formation mechanism and increasing the volume fraction of silicide.

Transmission Kikuchi diffraction: The impact of the signal-to-noise ratio.

Signal optimization for transmission Kikuchi diffraction (TKD) measurements in the scanning electron microscope is investigated by a comparison of different sample holder designs. An optimized design is presented, which uses a metal shield to efficiently trap the electron beam after transmission through the sample. For comparison, a second holder configuration allows a significant number of the transmitted electrons to scatter back from the surface of the sample holder onto the diffraction camera screen. It is shown that the secondary interaction with the sample holder leads to a significant increase in the background level, as well as to additional noise in the final Kikuchi diffraction signal. The clean TKD signal of the optimized holder design with reduced background scattering makes it possible to use small signal changes in the range of 2% of the camera full dynamic range. As is shown by an analysis of the power spectrum, the signal-to-noise ratio in the processed Kikuchi diffraction patterns is improved by an order of magnitude. As a result, the optimized design allows an increase in pattern signal to noise ratio which may lead to increase in measurement speed and indexing reliability.

Effect of a Sulfur Precursor on the Hydrothermal Synthesis of Cu2MnSnS4.

Cu2MnSnS4 (CMTS) is acknowledged as an alternative to traditional semiconductors. The structure and microstructure of synthetic CMTS depend on, among other things, the types of sulfur sources used. Traditionally obtained CMTS mostly has a tetragonal structure. In this study, the effect of using thiourea (Tu) or Na2S as a sulfur source on the product structure was compared using hydrothermal synthesis at 190 °C for 7 days (ethylene glycol with water in the presence of poly(vinylpyrollidone) was used as a solvent). When Tu was used, CMTS precipitated in the form of concentric microspheres, 1-1.5 µm in size, consisting of hexagonal (in the cores) and tetragonal (the rims) forms. Most probably, the rapidly formed hexagonal nucleus was later surrounded by a slower-forming rim with a tetragonal structure. In contrast, when Na2S was used as a precursor, microspheres were not formed and a fine crystalline material with a homogeneous tetragonal structure was obtained. This allowed for the choice of micromorphology and product structure during synthesis.

Kikuchi pattern simulations of backscattered and transmitted electrons.

We discuss a refined simulation approach which treats Kikuchi diffraction patterns in electron backscatter diffraction (EBSD) and transmission Kikuchi diffraction (TKD). The model considers the result of two combined mechanisms: (a) the dynamical diffraction of electrons emitted coherently from point sources in a crystal and (b) diffraction effects on incoherent diffuse intensity distributions. Using suitable parameter settings, the refined simulation model allows to reproduce various thickness- and energy-dependent features which are observed in experimental Kikuchi diffraction patterns. Excess-deficiency features are treated by the effect of gradients in the incoherent background intensity. Based on the analytical two-beam approximation to dynamical electron diffraction, a phenomenological model of excess-deficiency features is derived, which can be used for pattern matching applications. The model allows to approximate the effect of the incident beam geometry as a correction signal for template patterns which can be reprojected from pre-calculated reference data. As an application, we find that the accuracy of fitted projection centre coordinates in EBSD and TKD can be affected by changes in the order of 10 - 3 - 10 - 2 if excess-deficiency features are not considered in the theoretical model underlying a best-fit pattern matching approach. Correspondingly, the absolute accuracy of simulation-based EBSD strain determination can suffer from biases of a similar order of magnitude if excess-deficiency effects are neglected in the simulation model.

Crystallographic analysis of the lattice metric (CALM) from single electron backscatter diffraction or transmission Kikuchi diffraction patterns.

A new software is presented for the determination of crystal lattice parameters from the positions and widths of Kikuchi bands in a diffraction pattern. Starting with a single wide-angle Kikuchi pattern of arbitrary resolution and unknown phase, the traces of all visibly diffracting lattice planes are manually derived from four initial Kikuchi band traces via an intuitive graphical user interface. A single Kikuchi bandwidth is then used as reference to scale all reciprocal lattice point distances. Kikuchi band detection, via a filtered Funk transformation, and simultaneous display of the band intensity profile helps users to select band positions and widths. Bandwidths are calculated using the first derivative of the band profiles as excess-deficiency effects have minimal influence. From the reciprocal lattice, the metrics of possible Bravais lattice types are derived for all crystal systems. The measured lattice parameters achieve a precision of <1%, even for good quality Kikuchi diffraction patterns of 400 × 300 pixels. This band-edge detection approach has been validated on several hundred experimental diffraction patterns from phases of different symmetries and random orientations. It produces a systematic lattice parameter offset of up to ±4%, which appears to scale with the mean atomic number or the backscatter coefficient.

Assignment of enantiomorphs for the chiral allotrope ß-Mn by diffraction methods.

The assignment of enantiomorphs by diffraction methods shows fundamental differences for x-rays and electrons. This is particularly evident for the chiral allotrope of ß-Mn. While it is not possible to determine the sense of chirality of ß-Mn with established x-ray diffraction methods, Kikuchi pattern simulation of the enantiomorphs reveals differences, if dynamical electron diffraction is considered. Quantitative comparison between experimental and simulated Kikuchi patterns allows the spatially resolved assignment of the enantiomorph in polycrystalline materials of ß-Mn, as well as the structurally strongly related phase Pt2Cu3B. On the basis of enantiomorph distribution maps, crystals were extracted from enantiopure domains by micropreparation techniques. The x-ray diffraction analyses confirm the assignment of the Kikuchi pattern evaluations for Pt2Cu3B and do not allow to distinguish between the enantiomorphs of ß-Mn.

Numerical Study on the Dependency of Microstructure Morphologies of Pulsed Laser Deposited TiN Thin Films and the Strain Heterogeneities during Mechanical Testing.

Numerical study of the influence of pulsed laser deposited TiN thin films' microstructure morphologies on strain heterogeneities during loading was the goal of this research. The investigation was based on the digital material representation (DMR) concept applied to replicate an investigated thin film's microstructure morphology. The physically based pulsed laser deposited model was implemented to recreate characteristic features of a thin film microstructure. The kinetic Monte Carlo (kMC) approach was the basis of the model in the first part of the work. The developed kMC algorithm was used to generate thin film's three-dimensional representation with its columnar morphology. Such a digital model was then validated with the experimental data from metallographic analysis of laboratory deposited TiN(100)/Si. In the second part of the research, the kMC generated DMR model of thin film was incorporated into the finite element (FE) simulation. The 3D film's morphology was discretized with conforming finite element mesh, and then incorporated as a microscale model into the macroscale finite element simulation of nanoindentation test. Such a multiscale model was finally used to evaluate the development of local deformation heterogeneities associated with the underlying microstructure morphology. In this part, the capabilities of the proposed approach were clearly highlighted.

Omega Phase Formation in Ti-3wt.%Nb Alloy Induced by High-Pressure Torsion.

It is well known that severe plastic deformation not only leads to strong grain refinement and material strengthening but also can drive phase transformations. A study of the fundamentals of α → ω phase transformations induced by high-pressure torsion (HPT) in Ti-Nb-based alloys is presented in the current work. Before HPT, a Ti-3wt.%Nb alloy was annealed at two different temperatures in order to obtain the α-phase state with different amounts of niobium. X-ray diffraction analysis, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were applied for the characterisation of phase transitions and evolution of the microstructure. A small amount of the ß-phase was found in the initial states, which completely transformed into the ω-phase during the HPT process. During HPT, strong grain refinement in the α-phase took place, as did partial transformation of the α- into the ω-phase. Therefore, two kinds of ω-phase, each with different chemical composition, were obtained after HPT. The first one was formed from the ß-phase, enriched in Nb, and the second one from the α-phase. It was also found that the transformation of the α-phase into the ω-phase depended on the Nb concentration in the α-Ti phase. The less Nb there was in the α-phase, the more of the α-phase was transformed into the ω-phase.

Synthesis and Characterization of Cu2FeSnS4-Cu2MnSnS4 Solid Solution Microspheres.

In this study, we used a hydrothermal method to synthesize microspheres of Cu2(Mn1-xFex)SnS4 solid solution (X = 1, 0.8, 0.6, 0.4, 0.2, 0). The process was optimized to improve the crystallinity, morphology, and purity of the obtained materials. All samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), Raman spectroscopy, and Fourier transform infrared (FTIR) spectroscopy. The following conditions were optimized: A mixture of water and ethylene glycol at the ratio of 1:7 as the reaction medium, polyvinylpyrrolidone (PVP) as the surface ligand, and reaction temperature of 195 °C for 7 days. The product of synthesis precipitated in the form of aggregates of nanocrystals, which form homogeneous, often concentric microspheres with a diameter of 1-1.5 µm. The chemical composition of the product can be well controlled by the chemical composition of the reactants. The compound Cu2(Mn1-xFex)SnS4 forms a continuous series of solid solutions.

Approximant-based orientation determination of quasicrystals using electron backscatter diffraction.

Orientation mapping of quasicrystalline materials is demonstrated using crystalline approximant structures in the technique of electron backscatter diffraction (EBSD). The approximant-based orientations are symmetrised according to the rotational point group of the quasicrystal, including the visualization of orientation maps using proper colour keys for quasicrystal symmetries. Alternatively, approximant-based orientation data can also be treated using pseudosymmetry post-processing options in the EBSD system software, which enables basic grain size estimations. Approximant-based orientation analyses are demonstrated for icosahedral and decagonal quasicrystals.

Refined Calibration Model for Improving the Orientation Precision of Electron Backscatter Diffraction Maps.

For the precise determination of orientations in polycrystalline materials, electron backscatter diffraction (EBSD) requires a consistent calibration of the diffraction geometry in the scanning electron microscope (SEM). In the present paper, the variation of the projection center for the Kikuchi diffraction patterns which are measured by EBSD is calibrated using a projective transformation model for the SEM beam scan positions on the sample. Based on a full pattern matching approach between simulated and experimental Kikuchi patterns, individual projection center estimates are determined on a subgrid of the EBSD map, from which least-square fits to affine and projective transformations can be obtained. Reference measurements on single-crystalline silicon are used to quantify the orientation errors which result from different calibration models for the variation of the projection center.

Manual measurement of angles in backscattered and transmission Kikuchi diffraction patterns.

A historical tool for crystallographic analysis is provided by the Hilton net, which can be used for manually surveying the crystal lattice as it is manifested by the Kikuchi bands in a gnomonic projection. For a quantitative analysis using the Hilton net, the projection centre as the relative position of the signal source with respect to the detector plane needs to be known. Interplanar angles are accessible with a precision and accuracy which is estimated to be ≤0.3°. Angles between any directions, e.g. zone axes, are directly readable. Finally, for the rare case of an unknown projection-centre position, its determination is demonstrated by adapting an old approach developed for photogrammetric applications. It requires the indexing of four zone axes [uvw] i in a backscattered Kikuchi diffraction pattern of a known phase collected under comparable geometric conditions.