Physicochemical properties of transition metal oxides are directly determined by the oxidation state of the metallic cations. To address the increasing need to accurately evaluate the oxidation states of transition metal oxide systems at the nanoscale, here we present “Oxide Wizard.” This script for Digital Micrograph characterizes the energy-loss near-edge structure and the position of the transition metal edges in the electron energy-loss spectrum. These characteristics of the edges can be linked to the oxidation states of transition metals with high spatial resolution. The power of the script is demonstrated by mapping manganese oxidation states in Fe3O4/Mn3O4 core/shell nanoparticles with sub-nanometer resolution in real space.

Drug release from oral pharmaceutical formulations can be modified by applying a polymeric coating film with controlled mass transport properties. Interaction of the coating film with water may crucially influence its composition and permeability to both water and drug. Understanding this interaction between film microstructure, wetting, and mass transport is important for the development of new coatings. We present a novel method for controlled wetting of polymer coating films in an environmental scanning electron microscope, providing direct visual information about the processes occurring as the film goes from dry to wet. Free films made of phase-separated blends of water-insoluble ethyl cellulose (EC) and water-soluble hydroxypropyl cellulose (HPC) were used as a model system, and the blend ratio was varied to study the effect on the water transport properties. Local variations in water transport through the EC/HPC films were directly observed, enabling the immediate analysis of the structure–mass transport relationships. The leaching of HPC could be studied by evaporating water from the films in situ. Significant differences were observed between films of varying composition. The method provides a valuable complement to the current approach of making distinct diffusion and microscopy experiments for studying the dynamic interaction of polymer films with water.

Energy filtered transmission electron microscopy techniques are regularly used to build elemental maps of spatially distributed nanoparticles in materials and biological specimens. When working with thick biological sections, electron energy loss spectroscopy techniques involving core-loss electrons often require exposures exceeding several minutes to provide sufficient signal to noise. Image quality with these long exposures is often compromised by specimen drift, which results in blurring and reduced resolution. To mitigate drift artifacts, a series of short exposure images can be acquired, aligned, and merged to form a single image. For samples where the target elements have extremely low signal yields, the use of charge coupled device (CCD)-based detectors for this purpose can be problematic. At short acquisition times, the images produced by CCDs can be noisy and may contain fixed pattern artifacts that impact subsequent correlative alignment. Here we report on the use of direct electron detection devices (DDD’s) to increase the signal to noise as compared with CCD’s. A 3× improvement in signal is reported with a DDD versus a comparably formatted CCD, with equivalent dose on each detector. With the fast rolling-readout design of the DDD, the duty cycle provides a major benefit, as there is no dead time between successive frames.

According to treatises on 15th and 16th century paintings, artists dedicated particular attention to the sizing layer—consisting mainly of animal glue applied onto the wood support before further application of the ground layer. The stability of a painting mainly depends on the presence of a very cohesive sizing layer. However, the study of these layers has not received special attention from researchers. In this article we present a methodology for characterization of the sizing layer both chemically, by IR spectroscopy (Fourier transform infrared spectroscopy), and morphologically, by scanning electron microscopy (SEM). Secondary electron images obtained by SEM allow precise characterization of such layers. Painting reconstructions were used as references in development of the method to study the sizing layer in real painting samples. Presented herein are examples of this study on 15th and 16th century Portuguese paintings, particularly on the Triptych of S. Simão, from the Aveiro Museum, and S. Pedro, belonging to the Mercy of Tavira.

We have studied the influence of experimental factors and specimen geometry on the quality of the mass spectra in copper (Cu) during pulsed-laser atom-probe tomography. We have evaluated the effects of laser pulse energy, laser pulse frequency, specimen base temperature, specimen tip radius, and specimen tip shank half-angle on the effects of mass resolving power, (m/Δm), at full-width at half-maximum and at full-width at tenth-maximum, the tail size after the major mass-to-charge state (m/n) ratio peaks, and the mass spectra. Our results indicate that mass resolving power improves with decreasing pulse energy between 40 and 80 pJ and decreasing base temperature between 20 and 80 K. The mass resolving power also improves with increasing tip radius and shank half-angle. A pulse frequency of 250 kHz slightly improves the mass resolving power relative to 100 or 500 kHz. The tail size decreases with increasing pulse energy. The mass resolving power improves when the cooling time is reduced, which is influenced by the thermal diffusivity of Cu and the specimen base temperature.

The in vitro effect of cadmium (Cd) on apical segments of Pterocladiella capillacea was examined. Over a period of 7 days, the segments were cultivated with the combination of different salinities (25, 35, and 45 practical salinity units) and Cd concentrations, ranging from 0.17 to 0.70 ppm. The effects of Cd on growth rates and content of photosynthetic pigments were analyzed. In addition, metabolic profiling was performed, and samples were processed for microscopy. Serious damage to physiological performance and ultrastructure was observed under different combinations of Cd concentrations and salinity values. Elementary infrared spectroscopy revealed toxic effects registered on growth rate, photosynthetic pigments, chloroplast, and mitochondria organization, as well as changes in lipids and carbohydrates. These alterations in physiology and ultrastructure were, however, coupled to activation of such defense mechanisms as cell wall thickness, reduction of photosynthetic harvesting complex, and flavonoid. In conclusion, P. capillacea is especially sensitive to Cd stress when intermediate concentrations of this pollutant are associated with low salinity values. Such conditions resulted in metabolic compromise, reduction of primary productivity, i.e., photosynthesis, and carbohydrate accumulation in the form of starch granules. Taken together, these findings improve our understanding of the potential impact of this metal in the natural environment.

Specimen transfer under controlled environment conditions, such as temperature, pressure, and gas composition, is necessary to conduct successive complementary in situ characterization of materials sensitive to ambient conditions. The in situ transfer concept is introduced by linking an environmental transmission electron microscope to an in situ X-ray diffractometer through a dedicated transmission electron microscope specimen transfer holder, capable of sealing the specimen in a gaseous environment at elevated temperatures. Two catalyst material systems have been investigated; Cu/ZnO/Al2O3 catalyst for methanol synthesis and a Co/Al2O3 catalyst for Fischer–Tropsch synthesis. Both systems are sensitive to ambient atmosphere as they will oxidize after relatively short air exposure. The Cu/ZnO/Al2O3 catalyst, was reduced in the in situ X-ray diffractometer set-up, and subsequently, successfully transferred in a reactive environment to the environmental transmission electron microscope where further analysis on the local scale were conducted. The Co/Al2O3 catalyst was reduced in the environmental microscope and successfully kept reduced outside the microscope in a reactive environment. The in situ transfer holder facilitates complimentary in situ experiments of the same specimen without changing the specimen state during transfer.

Dried leaves of Satureja khuzestanica Jamzad are a popular herbal medicine and dental anesthetic among the nomadic inhabitants of southwestern Iran. The present study establishes criteria for identification of S. khuzestanica dried whole, fragmented and powdered leaves for specification as a herbal substance using macroscopic and microscopic characterization. Quantitative microscopy techniques were also considered. Macroscopically leaves exhibit a grayish-green color, are broadly ovate in shape with an acute apex, attenuate base, and ciliate margin and have a surface covered by an indumentum of glandular and non-glandular trichomes. Microscopically leaves have an isobilateral amphistomatic structure containing peltate glandular trichomes consisting of a multiseriate stalk (five cells) and an enlarged secretory head composed of 12 cells, capitate glandular trichomes of variable morphology together with two types of non-glandular trichomes. Oval-shaped hygromorphic diacytic stomata with an adaxial stomatal index of 13.54, collateral vascular bundles consisting of xylem, and three layers of sclerenchymatous tissue close to phloem together with cluster, prismatic and raphide calcium oxalate crystals were also identified as useful pharmacognostic parameters for identification of S. khuzestanica dried leaves.

The origin of the condensation of water begins at the nanoscale, a length-scale that is challenging to probe for liquids. In this work we directly image heterogeneous nucleation of water nanodroplets by in situ transmission electron microscopy. Using gold nanoparticles bound to a flat surface as heterogeneous nucleation sites, we observe nucleation and growth of water nanodroplets. The growth of nanodroplet radii follows the power law: R(t)~(t−t0)β, where β~0.2−0.3.

Nanoimpedance measurements, using the dynamic impedance spectroscopy technique, were carried out during loading and unloading force of a probe on three kinds of materials of different resistivity. These materials were: gold, boron-doped diamond, and AISI 304 stainless steel. Changes of impedance spectra versus applied force were registered and differences in the tip-to-sample contact character on each material were revealed. To enable comparison between materials and phases, a new standardization method is proposed, which simulates conditions of initial contact.

It is demonstrated that energy-filtered transmission electron microscope enables following of in situ changes of the Ca-L2,3 edge which can originate from variations in both local symmetry and bond lengths. Low accelerating voltages of 20 and 40 kV slow down radiation damage effects and enable study of the start and finish of phase transformations. We observed electron beam-induced phase transformation of single crystalline calcite (CaCO3) to polycrystalline calcium oxide (CaO) which occurs in different stages. The coordination of Ca in calcite is close to an octahedral one streched along the <111> direction. Changes during phase transformation to an octahedral coordination of Ca in CaO go along with a bond length increase by 5 pm, where oxygen is preserved as a binding partner. Electron loss near-edge structure of the Ca-L2,3 edge show four separated peaks, which all shift toward lower energies during phase transformation at the same time the energy level splitting increases. We suggest that these changes can be mainly addressed to the change of the bond length on the order of picometers. An important pre-condition for such studies is stability of the energy drift in the range of meV over at least 1 h, which is achieved with the sub-Ångström low-voltage transmission electron microscope I prototype microscope.

The composition of co-precipitated and collocated NbC carbide precipitates, Fe3C iron carbide (cementite), and Cu-rich precipitates are studied experimentally by atom-probe tomography (APT). The Cu-rich precipitates located at a grain boundary (GB) are also studied. The APT results for the carbides are supplemented with computational thermodynamics predictions of composition at thermodynamic equilibrium. Two types of NbC carbide precipitates are distinguished based on their stoichiometric ratio and size. The Cu-rich precipitates at the periphery of the iron carbide and at the GB are larger than those distributed in the α-Fe (body-centered cubic) matrix, which is attributed to short-circuit diffusion of Cu along the GB. Manganese segregation is not observed at the heterophase interfaces of the Cu-rich precipitates that are located at the periphery of the iron carbide or at the GB, which is unlike those located at the edge of the NbC carbide precipitates or distributed in the α-Fe matrix. This suggests the presence of two populations of NiAl-type (B2 structure) phases at the heterophase interfaces in multicomponent Fe–Cu steels.

A newly designed, 100 mm2, silicon drift detector has been installed on an aberration-corrected scanning transmission electron microscope equipped with an ultra-high resolution pole piece, without requiring column modifications. With its unique, windowless design, the detector’s active region is in close proximity to the sample, resulting in a dramatic increase in count rate, while demonstrating an increased sensitivity to low energy X-rays and a muted tilt dependence. Numerous examples of X-ray energy dispersive spectrometry are presented on relevant materials such as AlxGa1−xN nanowires, perovskite oxides, and polycrystalline CdTe thin films, across both varying length scales and accelerating voltages.