Crystal structures, microtopography, morphologies, elemental compositions, and ionic conductivity have been investigated for Li5-xLa3(Nb,Ta)O12-y using X-ray diffraction (XRD), field-emission analytical scanning and transmission electron microscopies (S/TEM), and electrochemical impedance spectroscopy. Using Rietveld refinements with powder XRD patterns, we determined that the number of Li atoms in the formula is less than 5 and that Li5-xLa3(NbTa)O12-y crystallizes in the cubic garnet structure with a space group Ia-3d. Sintering at varying temperatures (750–1000 °C) for 5 h in an ambient atmosphere produced distinct outcomes. Rietveld refinements disclosed that the sample sintered at 1000 °C (Li3.43(2)La3Nb1.07(2)Ta0.93(2)O12-y, a = 12.8361(7) Å, V = 2114.96(3) Å3) exhibited the highest ionic conductivity, while the 850 °C sample had the lowest conductivity, characterized by lower Li concentration and impurity phases (Li(Nb,Ta)3O88, Li2CO3). Analyses, including XRD and electron microscopy, confirmed the 1000 °C sample as a relatively phase pure with enhanced Li content (Li/La = 1.2), larger grains (15 μm), and uniform crystallinity. The 1000 °C sample introduced additional partially filled Li3 (96h) sites, promoting Li migration, and enhancing ionic conductivity. The resulting XRD pattern at 1000 °C has been submitted to the Powder Diffraction File as a reference.

The crystallochemical features of Co in Co-substituted goethite solid-solutions prepared by two different procedures have been studied using infrared, X-ray photoelectron and electron energy loss spectroscopies. It was found that the path followed for the synthesis of Co-substituted goethite determines the oxidation state of Co in the goethite structure. Thus, in the solid-solution prepared by precipitation with Na2CO3 of an Fe(II) aqueous solution containing Co(II) cations, followed by the aerial oxidation of the precipitate, the Co cations were found to be divalent, whereas trivalent Co was incorporated into the goethite obtained by ageing a solution containing Fe(III) and Co(II) cations precipitated by the addition of KOH. This different behavior is explained by the higher pH of goethite formation in the latter case, which favors the oxidation of the Co(II) cations.

The Weches Formation of the Claiborne Group (Eocene) in northeast Texas consists of clayey sandstones and mudrocks, both with variable proportions of dark green to brown clay peloids deposited in a marginal to open marine setting on the Gulf Coast margin. The composition of the dark green peloids, from two localities, has been investigated using X-ray diffraction, back-scattered electron microscopy with X-ray analysis, electron energy-loss spectroscopy (EELS), Mössbauer spectroscopy, chemical analysis and Fourier transform infrared spectroscopy. These peloids were previously described on the basis of their color as glauconite (Yancey and Davidoff, 1994); our results, however, show that the dark green indurated pellets are predominantly composed of mixed-layer clays with a high proportion of Fe-rich 7 Å serpentine layers coexisting with a mixed-layer phase containing glauconite, nontronite and vermiculite layers, in addition to discrete illite and kaolinte. Analyses by EELS of single particles with a chemical composition consistent with them being the Fe-rich clay indicate that the Fe is >95% ferric, while Mössbauer analyses of the bulk magnetically separated fraction for the same samples indicates a ferric iron content of ∼60–70%, despite the variable relative proportions of expandable and 7 Å layers. Taking into account that there is a significant amount of 2:1 layers containing ferric Fe, we interpret these data as indicating that the Fe in the 7 Å layers has a significant amount of Fe2+ even taking into account the high ferric Fe ratio from the EELS analysis when the coexisting 2:1 layers are considered. Thus, these 1:1 layers are closer to berthierine in composition than to odinite. The vermiculite layers in the Texas clay may indicate partial ‘verdinization’ of expandable 2:1 clay. A possible reaction is smectite → vermiculite → berthierine-like phase. We estimate a temperature of 20°C for the seawater in which the Texas clay formed, the lower end of the range for modern occurrences of odinite.

Alteration of basalt is a ubiquitous process on the vast oceanic crust surface and results in the formation of secondary-phase minerals that include clay minerals and Fe-(oxyhydr)oxides. Thus, this process is a significant consequence of water/rock interactions that could reveal the (bio)geochemical conditions of formation. Core samples at the basalt/sediment interface from a depth of 74.79 m below sea floor (mbsf) were recovered during the International Ocean Discovery Program (IODP) expedition 329 (2010.10.10–2010.12.13) in the South Pacific Gyre (SPG). Two distinct regions of yellow- and red-colored sediment were observed. The mineralogy, elemental composition, Fe oxidation state, and mineral structure of the altered basalt samples were analyzed using transmission electron microscopy (TEM) with selected area electron diffraction (SAED) patterns, energy dispersive spectroscopy (EDS), electron energy loss spectroscopy (EELS), and micro X-ray fluorescence (μ-XRF). In the yellow sediment, K-nontronite and feroxyhyte (δ’-FeO(OH)) were the dominant mineral phases, while Mg-rich smectite (saponite), chlorite, and hematite were found predominantly in the reddish sediment. The appearance of K-nontronite and feroxyhyte mineral assemblages in altered sediment indicated that oxidative conditions prevailed during basalt alteration. Variation in the Fe-oxidation states in the K-nontronite structure, however, may indicate that local reducing conditions persisted throughout the biogeochemical reactions.

Aberration correction in the analytical transmission electron microscope is most closely associated with improvements in high-resolution imaging. In this paper, the combination of that technology with new system designs, which optimize both electron optics and x-ray detection, is shown to provide more than a tenfold increase in performance over the last 25 years.

A direct comparison between electron transparent transmission electron microscope (TEM) samples prepared with gallium (Ga) and xenon (Xe) focused ion beams (FIBs) is performed to determine if equivalent quality samples can be prepared with both ion species. We prepared samples using Ga FIB and Xe plasma focused ion beam (PFIB) while altering a variety of different deposition and milling parameters. The samples’ final thicknesses were evaluated using STEM-EELS t/λ data. Using the Ga FIB sample as a standard, we compared the Xe PFIB samples to the standard and to each other. We show that although the Xe PFIB sample preparation technique is quite different from the Ga FIB technique, it is possible to produce high-quality, large area TEM samples with Xe PFIB. We also describe best practices for a Xe PFIB TEM sample preparation workflow to enable consistent success for any thoughtful FIB operator. For Xe PFIB, we show that a decision must be made between the ultimate sample thickness and the size of the electron transparent region.

Hierarchical density-based spatial clustering of applications with noise (HDBSCAN) and uniform manifold approximation and projection (UMAP), two new state-of-the-art algorithms for clustering analysis, and dimensionality reduction, respectively, are proposed for the segmentation of core-loss electron energy loss spectroscopy (EELS) spectrum images. The performances of UMAP and HDBSCAN are systematically compared to the other clustering analysis approaches used in EELS in the literature using a known synthetic dataset. Better results are found for these new approaches. Furthermore, UMAP and HDBSCAN are showcased in a real experimental dataset from a core–shell nanoparticle of iron and manganese oxides, as well as the triple combination nonnegative matrix factorization–UMAP–HDBSCAN. The results obtained indicate how the complementary use of different combinations may be beneficial in a real-case scenario to attain a complete picture, as different algorithms highlight different aspects of the dataset studied.

Previous studies of nickel hydroxide (Ni(OH)2) powders have shown that either heating or mechanical grinding can result in complete de-hydroxylation, leading to conversion to nickel oxide (NiO). In both cases, this process appears to occur in one stage, without evidence for any intermediate compounds being formed. During studies of Ni(OH)2 powders for applications in the positive electrodes of Ni metal hydride (NiMH) rechargeable batteries, using transmission electron microscopy (TEM), we have observed significant changes caused by exposure to the highly energetic electron beam used for imaging and analysis. It is shown here, using electron energy-loss spectroscopy (EELS), that de-hydroxylation under electron irradiation occurs in two stages, with nickel oxy-hydroxide (NiOOH) being formed at the intermediate stage.

Transmission electron microscopy (TEM) offers significant potential for studying chemical changes that occur in a battery electrode at a spatial resolution approaching atomic dimensions, provided a representative specimen can be prepared. The purpose of this paper is to show that it is possible to examine an electrode in the charged condition using TEM, while avoiding major changes in chemistry from specimen preparation. We also demonstrate the power of electron energy-loss spectroscopy (EELS) for phase identification at high spatial resolution. The origin of “fading” of an electrode after repeated charge-discharge cycling is also discussed.

The authors discuss the dipole vibrational modes that predominate in the energy-loss spectra of ionic materials below 1 eV, concentrating on thin-film specimens of typical transmission electron microscopy (TEM) thickness. The thickness dependence of the intensity is shown to be a useful guide to the bulk or surface character of vibrational peaks. The lateral and depth resolution of the energy-loss signal is investigated with the aid of finite-element calculations.

Adding Au to Pd nanoparticles (NPs) can impart high catalytic activity with respect to hydrogenation of a wide range of substances. These materials are often synthesized by reducing metallic precursors; hence, sonochemical and solvothermal processes are commonly used to anchor these bimetals onto thin supports, including graphene. Although similar NPs have been studied reasonably well, a clear understanding of structural characteristics relative to their synthesis parameters is lacking, due to limitations in characterization techniques, which may prevent optimization of this very promising catalyst. In this report, a strategic approach has been used to identify this structural and material synthesis correlation, starting with controlled sample preparation and followed by detailed characterization. This includes advanced scanning transmission electron microscopy and electron energy loss spectroscopy; the latter using a state-of-the-art instrumentation to map the distribution of Pd and Au, and to identify chemical state of the Pd NPs, which has not been previously reported. Results show that catalytic bimetal NP clusters were made of small zero-valent Pd NPs aggregating to form a shell around an Au core. Not only can the described characterization approach be applied to similar material systems, but the results can guide the optimization of the synthesis procedures.

A scanning and transmission electron microscopy study has been performed on Oligocene glacio-marine sediments, Devonian sandstones, and Jurassic dolerites recovered during CRP-3 drilling in the Ross Sea (Antarctica). Newly formed clay minerals occur in the rock matrices and as fillings in veins and faults which crosscut the whole sequence. Authigenic clays in sediments consist of beidellite-montmorillonite, berthierine/chlorite intergrowths and illite. Al,K-rich smectites and kaolinite occur in the Devonian sandstones. Saponite, berthierine/chlorite intergrowths, and Fe-hydroxides develop in the altered dolerites. Hence, the composition of the secondary phases depends also on the geochemistry of the rock they grow in. Within each sample, the same authigenic minerals form in the matrix and in the vein/fault. Clays precipitated from fluids, with variable fO2 values, which circulated in the system during the contemporaneous diagenetic and faulting events.

Deformed jadeite grains in the UHP jadeite-quartzites from the Dabie Mountains, eastern China show evidence (by transmission electron microscopy, TEM) of plastic deformation: free dislocations, dislocation loops, dislocation networks, dislocation arrays and regularly spaced subgrain boundaries by dislocation walls. Electron energy-loss spectroscopy and TEM studies reveal the existence of water-rich bubbles within dislocations and imply a relationship with water-defect dislocation by water weakening in the jadeites. These observations suggest that the water-rich bubbles are a major weakening effect facilitating plastic deformation of jadeite by dislocation creep.

An olivine grain from peridotite nodule 9206 (Udachnaya kimberlite) was heated in air at 700°C for 9 h. It was investigated by EMPA, by IR and UV spectroscopy and by TEM. The TEM examination reveals hexagon-like inclusions up to several hundred nm in size with a core and rim structure. The AEM data show that the inclusions contain only Mg, Fe and Si as cations. The rims have almost the same composition as the olivine matrix whereas the cores are enriched in iron and depleted in Mg. Electron diffraction data, SAED and CBED, indicate that the rims are composed of a ‘secondary’ olivine while the cores are composed of coexisting feroxyhite FeOOH, bernalite Fe(OH)3 and β-cristobalite SiO2. The presence of nm-sized inclusions in minerals is expected to influence the interpretation of spectroscopic results if spectroscopy is carried out without knowledge of the microstructure.

It is speculated that the complex microstructure of the inclusions is a result of a solid state transformation of a precursor phase, probably a hydrous magnesian silicate, during the experimental heating and oxidation.

The present study examines the micro- and nano-texture and composition of ammonium-bearing and potassium micas in very-low grade metamorphic black Silurian shales from the SE Iberian Range (NE Spain). Two organic-rich shales were studied by X-ray diffraction (XRD), infrared spectroscopy (IR), transmission electron microscopy (TEM), analytical electron microscopy (AEM) and electron energy loss spectroscopy (EELS). The XRD showed the presence of two populations of micas: pure K micas with d001 = 9.98 Å and ammonium-bearing micas with larger d001 values (10.08 Å and 10.05 Å). The latter values indicate NH4 contents between 13 and 29% in the interlayer, which was confirmed by IR. Interstratifications of smectite and mica layers in the mica packets were not detected by XRD and TEM. Mica packets with sizes ranging from 100 to 250 Å show disordered polytypes and (001) lattice fringes that reflect the presence of K- and NH4-bearing layers (9.9–10.2 Å).

The combination of AEM and EELS analyses on powdered and lamellar samples indicates that micas have typical dioctahedral compositions with highly variable K contents. This variation in K is consistent with the presence of K and NH4 in the interlayers, even though the NH4 and K are not distributed homogeneously; rather they are segregated in nm-sized domains in the mica interlayer.

Scanning transmission electron microscopy (STEM) in combination with electron energy-loss spectroscopy (EELS) can deliver information about variations of bonding at the nm scale. This is typically performed by analyzing the electron-loss near edge structure (ELNES) of given EELS edges. The present paper demonstrates an alternative way of a bonding examination through monitoring the EELS onset positions. Two conditions are essential for their accurate measurement. One (hardware) is using the dual EELS instrumentation that provides near simultaneous acquisition of low-loss and core-loss spectra. Another (software) is the least-square fitting of observed spectra to a reference spectrum. The combination of these hardware and software techniques reveals the positions of EELS onsets with the precision sufficient for mapping tiny variations of bonding. The paper shows that the method is capable of helping to solve practical tasks of nanoscale engineering like the analysis of modern CMOS devices.

For the first time, valence electron energy-loss spectroscopy (VEELS) was applied to individual single-crystalline SnO2 nanowires to investigate the dielectric function, band gap, and optical absorption coefficient. The results are compared with data from optical techniques such as spectroscopic ellipsometry and UV-Vis, and theoretical calculations from variations of density functional theory. The data obtained agree well with the standard optical and theoretical techniques. The dielectric function and optical absorption coefficient are given up to 20 eV, which otherwise requires a synchrotron source and large single crystals via optical methods. The energy loss function is given up to 40 eV, which gives a useful comparison to previous theoretical studies in an energy range that cannot be achieved via optical measurements. The comparison gives confidence in the accuracy of this method for exploring spatially-resolved measurements in individual nanoparticles or more complex nanostructures that are otherwise difficult to measure accurately using optical techniques.

A systematic study has been carried out to compare the surface morphology, shell thickness, mechanical properties, and binding behavior of melamine–formaldehyde microcapsules of 5–30 μm diameter size with various amounts of core content by using scanning and transmission electron microscopy including electron tomography, in situ nanomechanical tensile testing, and electron energy-loss spectroscopy. It is found that porosities are present on the outside surface of the capsule shell, but not on the inner surface of the shell. Nanomechanical tensile tests on the capsule shells reveal that Young’s modulus of the shell material is higher than that of bulk melamine–formaldehyde and that the shells exhibit a larger fracture strain compared with the bulk. Core-loss elemental analysis of microcapsules embedded in epoxy indicates that during the curing process, the microcapsule-matrix interface remains uniform and the epoxy matrix penetrates into the surface micro-porosities of the capsule shells.

Poly[sulfur-random-(1,3-diisopropenylbenzene)] copolymers synthesized via inverse vulcanization represent an emerging class of electrochemically active polymers recently used in cathodes for Li–S batteries, capable of realizing enhanced capacity retention (1,005 mAh/g at 100 cycles) and lifetimes of over 500 cycles. The composite cathodes are organized in complex hierarchical three-dimensional (3D) architectures, which contain several components and are challenging to understand and characterize using any single technique. Here, multimode analytical scanning and transmission electron microscopies and energy-dispersive X-ray/electron energy-loss spectroscopies coupled with multivariate statistical analysis and tomography were applied to explore origins of the cathode-enhanced capacity retention. The surface topography, morphology, bonding, and compositions of the cathodes created by combining sulfur copolymers with varying 1,3-diisopropenylbenzene content and conductive carbons have been investigated at multiple scales in relation to the electrochemical performance and physico-mechanical stability. We demonstrate that replacing the elemental sulfur with organosulfur copolymers improves the compositional homogeneity and compatibility between carbons and sulfur-containing domains down to sub-5 nm length scales resulting in (a) intimate wetting of nanocarbons by the copolymers at interfaces; (b) the creation of 3D percolation networks of conductive pathways involving graphitic-like outer shells of aggregated carbons; (c) concomitant improvements in the stability with preserved meso- and nanoscale porosities required for efficient charge transport.

When the value of the dispersion coefficient is “greatly different from 0.5,” as is the case for “free-electron” materials such as sodium (Na), the approximate expression for the volume plasmon critical wave vector (PCV) used by Hadji stops being valid and a different, more precise, expression must be used. Here a more accurate PCV formula is used to get a more accurate expression for plasmon scattering cross-section per atom (PSCA) species. This PSCA is then employed to calculate some physical quantities for several “free-electron” materials and together with the techniques from the quoted paper to determine values for physical quantities from amorphous silicon (a-Si) experimental data. The program source used to obtain these values is supplied. Any valid formula for the PSCA species is, in fact, relevant for use together with the two quoted techniques. The PCV and the dispersion coefficient have upper limits. Negative dispersion coefficient values are allowed. A PCV-related dimensionless universal function that can represent all ideal “free-electron” materials is given. “Not greatly different from 0.5” is mathematically expressed.