Recent Developments of Crystallographic Analysis Methods in the Scanning Electron Microscope for Applications in Metallurgy

The field of metallurgy has greatly benefited from the development of electron microscopy over the last two decades. Scanning electron microscopy (SEM) has become a powerful tool for the investigation of nano- and microstructures. This article reviews the complete set of tools for crystallographic analysis in the SEM, i.e., electron backscatter diffraction (EBSD), transmission Kikuchi diffraction (TKD), and electron channeling contrast imaging (ECCI). We describe recent relevant developments in electron microscopy, and discuss the state-of-the-art of the techniques and their use for analyses in metallurgy. EBSD orientation measurements provide better angular resolution than spot diffraction in TEM but slightly lower than Kikuchi diffraction in TEM, however, its statistical significance is superior to TEM techniques. Although spatial resolution is slightly lower than in TEM/STEM techniques, EBSD is often a preferred tool for quantitative phase characterization in bulk metals. Moreover, EBSD enables the measurement of lattice strain/rotation at the sub-micron scale, and dislocation density. TKD enables the transmitted electron diffraction analysis of thin-foil specimens. The small interaction volume between the sample and the electron beam enhances considerably the spatial resolution as compared to EBSD, allowing the characterization of ultra-fine-grained metals in the SEM. ECCI is a useful technique to image near-surface lattice defects without the necessity to expose two free surfaces as in TEM. Its relevant contributions to metallography include deformation characterization of metals, including defect visualization, and dislocation density measurements. EBSD and ECCI are mature techniques, still undergoing a continuous expansion in research and industry. Upcoming technical developments in electron sources and optics, as well as detector instrumentation and software, will likely push the border of performance in terms of spatial resolution and acquisition speed. The potential of TKD, combined with EDS, to provide crystallographic, chemical, and morphologic characterizations of nano-structured metals will surely be a valuable asset in metallurgy.     

Electron back scattered diffraction study of SmCo magnets

The remanence and energy product of permanent magnets is a strong function of their crystallographic texture. Electron back scattered diffraction (EBSD) is a tool for texture analysis providing information about the atomic layers up to 50 nm below the surface of the material. This paper discusses experimental requirements for performing EBSD measurements on rare-earth permanent magnets and presents results on commercial SmCo magnet material. EBSD measurements proved to be very sensitive to misaligned grains and were sensitive to texture in good agreement with information provided by X-ray diffraction scans. Results for nanostructured Sm(CoFeCuZr)_z magnets are also discussed.     

Crystal plasticity study on stress and strain partitioning in a measured 3D dual phase steel microstructure

Dual phase steels are advanced high strength alloys typically used for structural parts and reinforcements in car bodies. Their good combination of strength and ductility and their lean composition render them an economically competitive option for realizing multiple lightweight design options in automotive engineering. The mechanical response of dual phase steels is the result of the strain and stress partitioning among the ferritic and martensitic phases and the individual crystallographic grains and subgrains of these phases. Therefore, understanding how these microstructural features influence the global and local mechanical properties is of utmost importance for the design of improved dual phase steel grades. While multiple corresponding simulation studies have been dedicated to the investigation of dual phase steel micromechanics, numerical tools and experiment techniques for characterizing and simulating real 3D microstructures of such complex materials have been emerged only recently. Here we present a crystal plasticity simulation study based on a 3D dual phase microstructure which is obtained by EBSD tomography, also referred to as 3D EBSD (EBSD—electron backscatter diffraction). In the present case we utilized a 3D EBSD serial sectioning approach based on mechanical polishing. Moreover, sections of the 3D microstructure are used as 2D models to study the effect of this simplification on the stress and strain distribution. The simulations are conducted using a phenomenological crystal plasticity model and a spectral method approach implemented in the Düsseldorf Advanced Material Simulation Kit (DAMASK).     

Studies on molluscan shells: Contributions from microscopic and analytical methods

Molluscan shells have always attracted the interest of researchers, from biologists to physicists, from paleontologists to materials scientists. Much information is available at present, on the elaborate architecture of the shell, regarding the various Mollusc classes. The crystallographic characterization of the different shell layers, as well as their physical and chemical properties have been the subject of several investigations. In addition, many researches have addressed the characterization of the biological component of the shell and the role it plays in the hard exoskeleton assembly, that is, the biomineralization process. All these topics have seen great advances in the last two or three decades, expanding our knowledge on the shell properties, in terms of structure, functions and composition. This involved the use of a range of specialized and modern techniques, integrating microscopic methods with biochemistry, molecular biology procedures and spectroscopy. However, the factors governing synthesis of a specific crystalline carbonate phase in any particular layer of the shell and the interplay between organic and inorganic components during the biomineral assembly are still not widely known.This present survey deals with microstructural aspects of molluscan shells, as disclosed through use of scanning electron microscopy and related analytical methods (microanalysis, X-ray diffraction, electron diffraction and infrared spectroscopy). These already published data provide relevant information on shells and also contribute for better understanding the biomineralization process.     

Applications of the electron backscatter diffraction technique to ceramic materials

A technique with a relatively high spatial resolution is required for an effective analysis of the microstructure of ceramic materials. The recently developed electron backscatter diffraction (EBSD) technique, which works within a scanning electron microscope, enables a spatially highly resolved study of crystallographic orientations while recording Kikuchi patterns on a user-defined grid. However, such an EBSD texture analysis was until now not often performed on ceramic materials – in contrary, the technique is widely employed in the analysis of metallic materials, including the investigation of various types of steels. The use of ceramics possesses a variety of problems for EBSD investigations like: (i) complicated crystal structure, (ii) difficult surface preparation, and (iii) problems arising from a low conductivity of the ceramic materials. Here, we discuss these problems and present solutions in order to obtain high-quality Kikuchi patterns from such ceramics.     

Microstructure,crystallography and diagenetic alteration in fossil ostrich eggshells from Upper Palaeolithic sites of Indian peninsular region

Biominerals studies are of importance as they provide an understanding of natural evolutionary processes. In this study we have investigated the fossil ostrich eggshells using Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD) and Electron Backscatter Diffraction (EBSD). SEM studies demonstrated the ultrastructure of fossil eggshells and formation of calcified cuticular layer. The presence of calcified cuticle layer in eggshell is the basis for ancient DNA studies as it contains preserved biomolecules.EBSD accentuates the crystallographic structure of the ostrich eggshells with sub-micrometer resolution. It is a non-destructive tool for evaluating the extent of diagenesis in a biomineral. EBSD analysis revealed the presence of dolomite in the eggshells. This research resulted in the complete recognition of the structure of ostrich eggshells as well as the nature and extent of diagenesis in these eggshells which is vital for genetic and paleoenvironmental studies.     

EBSD analysis of electroplated magnetite thin films

By means of electron backscatter diffraction (EBSD), we analyse the crystallographic orientation of electroplated magnetite thin films on Si/copper substrates. Varying the voltage during the electroplating procedure, the resulting surface properties are differing considerably. While a high voltage produces larger but individual grains on the surface, the surfaces become smoother on decreasing voltage. Good quality Kikuchi patterns could be obtained from all samples; even on individual grains, where the surface and the edges could be measured. The spatial resolution of the EBSD measurement could be increased to about 10 nm; thus enabling a detailed analysis of single magnetite grains. The thin film samples are polycrystalline and do not exhibit a preferred orientation. EBSD reveals that the grain size changes depending on the processing conditions, while the detected misorientation angles stay similar.     

Advanced microstructural analysis of ferrite materials by means of electron backscatter diffraction (EBSD)

The analysis of the achieved texture is of great importance for the performance of ferrite materials, either bulk or thin films. The recently developed electron backscatter diffraction (EBSD) technique enables a spatially resolved study of the crystallographic orientations by means of recording of Kikuchi patterns. To our knowledge, such a thorough EBSD analysis was not yet performed in any oxidic magnetic material, and only very recently on magnetite thin films by us. A good surface polishing/cleaning is essential for this analysis, as the method requires an undisturbed surface area for a high image quality (IQ). This information is recorded to each measured Kikuchi pattern, together with a parameter describing the quality of indexation. Here, the spatially highly resolved EBSD mappings provide additional information as compared to the standard analysis techniques, which can contribute to an optimization of the growth process. Furthermore, an analysis of the grain aspect ratio is possible which provides further insight to the microstructural dependence of the magnetic properties of ferrites.     

Orientation sensitivity of focused ion beam damage in pure zirconium: direct experimental observations and molecular dynamics simulations

A high-purity predominantly single crystalline zirconium was subjected to controlled focused ion beam (FIB) damage. Damage estimates were obtained from electron backscattered diffraction (EBSD) and nano-indentation measurements on exactly the same area/orientation. The damage kinetics, between different crystallographic orientations, differed by one order of magnitude and a clear hierarchy of orientation sensitive ion damage emerged. Use of a simple geometric approach, linear density of atoms and corresponding scattering cross-sections to impinging gallium ions, could differentiate between extreme damage kinetics; but failed when such differences were relatively minor. Numerically intensive molecular dynamics (MD) simulations, on the other hand, were more effective. However, MD simulations or direct EBSD observations failed to justify anisotropic irradiation hardening (AIH): 3–8 times more hardening for near basal. Though explanation for AIH is indirect, evidence and rationalization for orientation-sensitive radiation damage appears clear and statistically reproducible.     

Mesoscale strain measurement in deformed crystals: A comparison of X-ray microdiffraction with electron backscatter diffraction

Mapping of residual stresses at the mesoscale is increasingly practical thanks to technological developments in electron backscatter diffraction (EBSD) and X-ray microdiffraction using high brilliance synchrotron sources. An analysis is presented of a Cu single crystal deformed in compression to about 10% macroscopic strain. Local orientation measurements were made on sectioned and polished specimens using EBSD and X-ray microdiffraction. In broad strokes, the results are similar to each other with orientations being observed that are on the order of 5° misoriented from that of the original crystallite. At the fine scale it is apparent that the X-ray technique can distinguish features in the structure that are much finer in detail than those observed using EBSD even though the spatial resolution of EBSD is superior to that of X-ray diffraction by approximately two orders of magnitude. The results are explained by the sensitivity of the EBSD technique to the specimen surface condition. Dislocation dynamics simulations show that there is a relaxation of the dislocation structure near the free surface of the specimen that extends approximately 650 Å into the specimen. The high spatial resolution of the EBSD technique is detrimental in this respect as the information volume extends only 200 Å or so into the specimen. The X-rays probe a volume on the order of 2 µm in diameter, thus measuring the structure that is relatively unaffected by the near-surface relaxation.     

Preferential crystallographic alignment in polycrystalline MnP

The existence of preferential crystallographic alignment in hot pressed and die upset manganese phosphide (MnP) was investigated using magnetic measurements and electron backscatter diffraction (EBSD). Pole figures calculated from the EBSD data show that die upsetting causes the 〈1 1 0〉 directions to align preferentially along the die upset (DU) direction with the 〈0 0 1〉 direction preferentially perpendicular to the DU direction. Magnetic measurements show that the die upsetting can reduce the saturation field relative to that of a similar sample with randomly oriented grains. Since the low-field magnetocaloric effect in single crystals of MnP has been shown to be greatest along the 〈0 1 0〉 direction and smallest along the 〈1 0 0〉 direction, this technique offers a means to achieve the advantages of single crystal alignment with the economy of using bulk processing techniques on polycrystalline material. The peak magnetic entropy change measured with the field applied along the DU direction in the DU sample was 3%, 5%, and 8% greater than the peak entropy change of a randomly oriented powder at fields of 2.0, 1.0, and 0.5 T, respectively.     

Detection of recrystallized structure by means of automatic analysis of electron backscattered diffraction patterns

The possibility of applying the automatic analysis of electron backscattered diffraction (EBSD) patterns to reveal the recrystallized structure in the partially recrystallized material has been discussed. The analysis has been performed based on new experimental results. It has been shown that the EBSD method can be successfully used to investigate the recrystallization process.     

Ultramicrotomy reveals crystallographic information on a sectioned surface of a metallic block specimen

Ultramicrotomy is widely regarded as a thin section preparation method for transmission electron microscopy (TEM) investigations. It is shown that ultramicrotomy can also provide a simple path for microstructure analysis and assessment of mechanical properties for a sectioned block-face. Furthermore, electron backscatter diffraction (EBSD) analysis can be applied directly on ultramicrotomed surfaces without any additional polishing or etching. EBSD analysis relates the inherent cutting artefacts to the crystallographic orientations of the grains, hence delivering a rough assessment of their deformation resistance. TEM investigations revealed that crystallographic-related cutting artefacts, which exhibit a wave-like pattern, are the result of the dislocation pile-ups close to the knife–specimen interface. This technique is considered suitable to be coupled with EBSD for three-dimensional microstructure reconstructions when used for serial sectioning of large volumes.     

Competitive effects of metal dissolution and passivation modulated by surface structure: An AFM and EBSD study of the corrosion of alloy 22

Electron backscatter diffraction (EBSD) and atomic force microscopy (AFM) are used to correlate crystallographic grain orientation with corrosion rates of polycrystalline alloy 22 following immersion in 1 and 3 molar (M) hydrochloric acid. For each acid concentration, relative corrosion rates are simultaneously characterized for approximately 50 unique grain orientations. The results demonstrate that the corrosion rate anisotropies are markedly different in the two acid concentrations. In very aggressive acidic environments (3M HCl), where electrochemical impedance spectroscopy and spectroscopic ellipsometry data demonstrate that the passive oxide film of alloy 22 is completely dissolved, alloy dissolution rates scale inversely with the average coordination number of surface atoms for a given grain orientation, where highly correlated surfaces dissolve the slowest. Thus, similar to simple metallic systems, the corrosion rates scale with the surface plane-normal crystallographic orientations as {1 1 1} < {1 0 0} < {1 1 0}. Less intuitively, in milder corrosive environments (1M HCl), where the passive film of the alloy is still intact, the dissolution does not scale inversely with surface atomic density. Rather, corrosion rates scale with crystallographic orientations as {1 1 1} < {1 1 0} < {1 0 0}. This is attributed to the fact that facets most susceptible to corrosion (least coordinated) are also the most able to form protective oxides, so that the dissolution anisotropy is a result of the delicate balance between metal dissolution and oxide growth.     

Misorientation/local plastic strain manifestations in chemical etching color

Cold plastic deformation produces misorientations inside the crystal grains, and the distribution of the misorientation is quite crucial to understand the deformation behavior of the metals or alloys. The misorientation manifestations in chemical etching contrast are investigated in this study in the case of cold-deformed iron. The chemical etching is performed by using nital, while the crystal orientation is determined by electron backscatter diffraction (EBSD). The correlation between the chemical etching contrast and crystal orientation have been studied in both cold-deformed and undeformed iron. The results clearly show that the chemical etching contrast strongly reflects the crystallographic orientation. The gradual change in chemical etching contrast inside the individual deformed grains gives information of both the misorientation and local plastic strain within the grains. This method can provide an easy and alternative way to qualitatively understand the misorientation and local plastic strain distributions in the microstructures.     

Polarized Raman and photoluminescence studies of a sub‐micron sized hexagonal AlGaN crystallite for structural and optical properties

The polarized Raman spectroscopy is capable of giving confirmation regarding the crystalline phase as well as the crystallographic orientation of the sample. In this context, apart from crystallographic X‐ray and electron diffraction tools, polarized Raman spectroscopy and corresponding spectral imaging can be a promising crystallographic tool for determining both crystalline phase and orientation. Sub‐micron sized hexagonal AlGaN crystallites are grown by a simple atmospheric pressure chemical vapor deposition technique using the self catalytic vapor–solid process under N‐rich condition. The crystallites are used for the polarized Raman spectra in different crystalline orientations along with spectral imaging studies. The results obtained from the polarized Raman spectral studies show single crystalline nature of sub‐micron sized hexagonal AlGaN crystallites. Optical properties of the crystallites for different crystalline orientations are also studied using polarized photoluminescence measurements. The influence of internal crystal field to the photoluminescence spectra is proposed to explain the distinctive observation of splitting of emission intensity reported, for the first time, in case of c‐plane oriented single crystalline AlGaN crystallite as compared with that of m‐plane oriented crystallite. Copyright © 2016 John Wiley & Sons, Ltd.     

Crystallographic analysis of lightly facetted cylindrical crystals

A method is described for determining the crystallographic orientation of cylindrical crystals from the geometry of surface facets. The method is applied to individual grains in polycrystalline wire samples having a bamboo structure, where classical methods of orientation determination, such as electron and X-ray diffraction, are inapplicable. In addition to providing information on the orientation of grains, the methods identifies the crystallographic orientation of the facets, which is of potential importance in studies of facet formation.     

Structure and orientation of an intermetallic phase in a W-Ni-Co alloy

The aim of this investigation is crystal structure determination of an intermetallic phase formed in a W-Ni-Co alloy during a heat-treatment carried out at a temperature of 800°C. This intermetallic phase is expected to play a critical role on the final microstructure (fine tungsten particles in an FCC matrix that is present in between large tungsten grains) and thereby, on the properties of the alloy. 92W-5.3Ni-2.7Co alloy was prepared through powder metallurgy route (liquid phase sintering) followed by heat-treatment at 800°C for 5?h. The intermetallic phase formed at this temperature was characterised using transmission and scanning electron microscopes. The intermetallic phase was found to have orthorhombic crystal structure with Pnam (62) space group as determined using automated diffraction tomography along with precession electron diffraction. Chemical analysis in TEM suggested that the intermetallic phase is based on stoichiometry (Co,Ni)₂W. Orientation imaging of the phase was also carried out in TEM and EBSD to understand its evolution. Equiaxed or lath morphology of the intermetallic phase was found to depend on the crystallographic orientation relationship of the phase with the tungsten grains and the matrix phase.     

Evidence of registry at the interface during inorganic nucleation at an organic template

In situ synchrotron x-ray diffraction studies of the nucleation of barium fluoride from supersaturated solutions, at fatty-acid monolayer templates, reveal a commensurate relationship between the interfacial lattices of the organic molecules and the inorganic atoms. At the onset of growth, the barium fluoride layer is very thin and the lateral unit cell is contracted by as much as 4%; at the same time the organic molecules tilt, expanding the organic unit cell. This flexibility is what allows the lattice parameters to be commensurate. Such registry is expected to play an important precursor role in controlled biomineralization and organic-matrix-mediated materials synthesis.