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Liquid phase electron microscopy is a new analytical method that has opened up a rapidly emerging field of research during the past decade. This article discusses this new microscopy modality within the context of imaging eukaryotic cells, bacteria, proteins, viruses, and biomineralization processes. The obtained resolution is typically not a function of the instrument, rather it is limited by the available electron dose within the limit of radiation damage. Therefore, different types of samples are best imaged with different electron microscopy (EM) modalities. The obtained information differs from that acquired with conventional EM as well as cryo-electron microscopy. This article gives an overview of achievements thus far in this area and the unique information that has been obtained. A discussion on potential future developments in the field, and technological advancements required to reach those goals conclude the article.
Insights into the dynamics of electrochemical processes are critically needed to improve our fundamental understanding of electron, charge, and mass transfer mechanisms and reaction kinetics that influence a broad range of applications, from the functionality of electrical energy-storage and conversion devices (e.g., batteries, fuel cells, and supercapacitors), to materials degradation issues (e.g., corrosion and oxidation), and materials synthesis (e.g., electrodeposition). To unravel these processes, in situ electrochemical scanning/transmission electron microscopy (ec-S/TEM) was developed to permit detailed site-specific characterization of evolving electrochemical processes that occur at electrode–electrolyte interfaces in their native electrolyte environment, in real time and at high-spatial resolution. This approach utilizes “closed-form” microfabricated electrochemical cells that couple the capability for quantitative electrochemical measurements with high spatial and temporal resolution imaging, spectroscopy, and diffraction. In this article, we review the state-of-the-art instrumentation for in situ ec-S/TEM and how this approach has resulted in new observations of electrochemical processes.
Liquid phase (or liquid cell) transmission electron microscopy (LP-TEM) has been established as a powerful tool for observing dynamic processes in liquids at nanometer to atomic length scales. However, the simple act of observation using electrons irreversibly alters the nature of the sample. A clear understanding of electron-beam-driven processes during LP-TEM is required to interpret in situ observations and utilize the electron beam as a stimulus to drive nanoscale dynamic processes. In this article, we discuss recent advances toward understanding, quantifying, mitigating, and harnessing electron-beam-driven chemical processes occurring during LP-TEM. We highlight progress in several research areas, including modeling electron-beam-induced radiolysis near interfaces, electron-beam-induced nanocrystal formation, and radiation damage of soft materials and biomolecules.
Liquid phase (also called “liquid cell”) transmission electron microscopy (TEM) is a powerful platform for nanoscale imaging and characterization of physical and chemical processes of materials in liquids. It is a direct approach to address critical scientific questions on how materials form or transform in response to external stimuli, such as changes in chemical potential, applied electric bias, and interactions with other materials or their environment. Answers to these questions are essential for understanding and controlling nanoscale materials properties and advancing their applications. With the recent technical advances in TEM, such as the development of sample stages, detectors, and image processing toolkits, liquid phase TEM is transforming our ability to characterize materials and revolutionizing our understanding of many fundamental processes in materials science and other fields. In this article, we briefly review the current status, challenges, and opportunities in liquid phase TEM. More details of the development and applications of liquid cell TEM are discussed in the articles in this issue of MRS Bulletin.
Ammonia can supplement hydrogen gas as a clean fuel to combat climate change. It overcomes hindrances that currently impede the realization of the full potential of hydrogen gas, including economical storage, political commitment, and safety concerns.
Liquid cell transmission electron microscopy (TEM) has become an essential tool for studying the structure and properties of both hard and soft condensed-matter samples, as well as liquids themselves. Liquid cell sample holders, often consisting of two thin window layers separating the liquid sample from the high vacuum of the microscope column, have been designed to control in situ conditions, including temperature, voltage/current, or flow through the window region. While high-resolution and time-resolved TEM imaging probes the structure, shape, and dynamics of liquid cell samples, information about the chemical composition and spatially resolved bonding is often difficult to obtain due to the liquid thickness, the window layers, the holder configuration, or beam-induced radiolysis. In this article, we review different approaches to quantitative liquid cell electron microscopy, including recent developments to perform energy-dispersive x-ray and electron energy-loss spectroscopy experiments on samples in a liquid environment or the liquid itself. We also cover graphene liquid cells and other ultrathin window layer holders.
The corrosion behavior of uncoated, nickel (Ni) and nickel–phosphorous (Ni–P)-coated AISI 430 alloy was investigated in Ar–3%H2 and Ar–3%H2–3%H2O atmosphere at 800 °C for 100 h. Microstructure, chemical composition, and reaction products were analyzed by scanning electron microscopy, energy-dispersive spectroscopy, and X-ray diffraction techniques. The corrosion extent of Ni–P-coated AISI 430 is higher than Ni-coated AISI 430. Oxidation promotes corrosion in the uncoated and coated alloy. The oxidation rate of Ni-coated alloy is the lowest in Ar–3%H2 but Ni–P-coated alloy in Ar–3%H2–3%H2O for initial 20 h. The oxidation rate of the Ni–P-coated sample is ~14 times higher in 20–100 h in Ar–3%H2–3%H2O. External growth of Cr2O3 is observed for Ni-coated alloy in Ar–3%H2 and for Ni–P-coated alloy in both the atmospheres. Inward growth of Cr2O3 by AISI 430 alloy consumption attributes to the lowest oxidation rate and the corrosion extent of Ni-coated sample in Ar–3%H2–3%H2O.
Molecular weight (Mw) effects in poly(vinylidene fluoride) (PVDF) influence both processability and combustion behavior in energetic Al–PVDF filaments. Results show decreased viscosity in unloaded and fuel-lean (i.e., 15 wt% Al) filaments. In highly loaded filaments (i.e., 30 wt% Al), reduced viscosity is minimal due to higher electrostatic interaction between Al particles and low Mw chains as confirmed by Fourier-transform infrared spectroscopy. Thermal and combustion analysis further corroborates this story as exothermic activity decreases in PVDF with smaller Mw chains. Differential scanning calorimetry and Thermogravimetric analysis show reduced reaction enthalpy and lower char yield in low Mw PVDF. Enthalpy reduction trends continued in nonequilibrium burn rate studies, which confirm that burn rate decreases in the presence of low Mw PVDF. Furthermore, powder X-ray patterns of post-burn products suggest that low Mw PVDF decomposition creates a diffusion barrier near the Al particle surface resulting in negligible AlF3 formation in fuel-rich filaments.