Cold Field-emission Scanning Electron Microscopy Research Articles

An experimental investigation on the damage mechanisms of red glutenite in the Mount Wuyi cultural and natural heritage site subject to acid rain and wet-dry cycles: a macro-to-micro approach

The safety of rock landscapes in Mount Wuyi is significantly impacted by acid rain and wet-dry cycles. In this paper, the decay characteristics of the physical–mechanical properties of red glutenite were investigated under acidic wet-dry cycles. A systematic approach, including cold field emission scanning electron microscopy (CFE-SEM), image processing techniques, and X-ray diffraction (XRD), was proposed to investigate the damage mechanism of red glutenite under acidic wet-dry cycles. The results indicate that with increasing solution acidity and wet-dry cycles, dry density (DD), longitudinal wave velocity (LWV), uniaxial compressive strength (UCS), and elastic modulus (EM) of red glutenite significantly decrease. Under different acidic conditions, DD, LWV, and UCS exhibit exponential decay with wet-dry cycles, while EM exhibits linear decay. A regression fitting was employed to establish a prediction model for UCS, which exhibited a better capability in predicting the correlation between UCS, pH, and the number of wet-dry cycles. Microscopic comprehensive analysis reveals that the interaction between rock dissolution and desiccation is the primary factor leading to changes in the microstructure and mineral composition of red glutenite, culminating in the decay of its physical–mechanical properties. This study holds significant guidance implications for the preservation of cultural and natural heritage in Mount Wuyi.

Two methods for constructing ZIF-8 nanomaterials with good bio compatibility and robust antibacterial applied to biomedical

Metal-organic framework materials not only possess porous structures, but also have excellent antibacterial properties. It is of great practical significance to prepare new antibacterial materials with excellent antibacterial effect by metal-organic framework materials. In our study, Zeolitic Imidazolate Framework-8 (ZIF-8) nanomaterials with antibacterial properties were prepared via the solvent method and diethanolamine template method. The materials were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), cold field-emission scanning electron microscope (SEM), transmission electron microscopy (TEM), N2 adsorption-desorption experiment, antibacterial experiment, and biocompatibility experiment. Results showed that ZIF-8 prepared by solvent method has a more typical hexagonal structure, larger specific surface area, and smaller pore size, and the values are 1812.07 m2g-1 and 2.2412 nm, respectively. At the same time, the materials prepared by the two methods have excellent antibacterial properties, and exhibit good biocompatibility at low concentrations, the antibacterial activity against Escherichia coli and Staphylococcus aureus are higher than 95%, and the cell viabilities of the selected five material concentrations of 12.5 µg mL-1, 25 µg mL-1, 50 µg mL-1, 100 µg mL-1 and 200 µg mL-1 are more than 70%. Therefore, this study provides a feasible method for preparing Nano-scale antibacterial functional particles, and it is of great significance to broaden the application field of ZIF-8 materials and prepare ZIF-8 drug-delivery functional materials.

Internal cavity amplification of shell-like ferritin regulated with the change of the secondary and tertiary structure induced by PEF technology

In this study, the effect of pulsed electric field (PEF) on apparent morphology and molecular structure of shell-like ferritin obtained from horse spleen was determined by circular dichroic (CD), fluorescence spectroscopy, Raman spectroscopy, cold field emission scanning electron microscopy (CF-SEM) and transmission electron microscopy (TEM), and verified by molecule dynamics (MD) simulation. After PEF treatment, the α-helix content of the samples reached a minimum value at 10 kV/cm, which indicated that the ferritin structure has been partially unfolded. However, the α-helix content peaked again after resting for 2 h at 25 ± 1 °C. This indicated that the PEF-treated ferritin tended to restore its original spherical morphology probably owing to the reversible assembly characteristic of ferritin. In addition, microstructure analysis revealed that ferritin particles aggregated after PEF treatment. Therefore, PEF treatment could induce the “exposure” of hydrophobic amino acids and conversion of disulfide bond configuration, and consequently, regulate the internal cavity stability of ferritin. The research will be beneficial to expand the application of PEF treatment in the modification of protein structure, and provide a theoretical basis for the application of ferritin as a carrier of bioactive molecules in food.

Preparation and characterization of nano-Fe3O4/paraffin encapsulated isocyanate microcapsule by electromagnetic controlled rupture for self-healing cementitious materials

In this paper, a novel electromagnetic controlled rupture microcapsule (ECRM) with ultrahigh self-healing capability was prepared by melt condensation method, whose shell was constructed by nano-Fe3O4 and paraffin, and whose core was toluene-di-isocyanate (TDI). Effect of paraffin/TDI mass ratio on core fraction of ECRM was investigated. The morphology, particle size distribution and component identification of ECRM were characterized by cold field emission scanning electron microscope (CFE-SEM), laser particle analyzer and Fourier transform infrared spectrometer (FTIR), respectively. Subsequently, the effects of ECRM on mechanical propertyand self-healing ability of mortars were evaluated. The results showed that the paraffin/TDI mass ratio delivered a major impact on core fraction of ECRM. The core fraction of ECRM was 65.3% when the mass ratio of paraffin/TDI was 1:2. The particle size distribution of ECRM mainly ranged from 60 μm to 1258 μm with 600 rpm agitation rate. The ECRM exhibited ellipsoidal with a rough surface. FTIR confirmed the successfully encapsulation of TDI in the shell of paraffin and nano-Fe3O4. In addition, ECRM containing 10 wt% nano-Fe3O4 can be heated to higher than 60 ℃ under electromagnetic field (output voltage: 600 V, field frequency: 124 kHz) for 500 s. Compared to the control mortar, the compressive strength and the flexural strength of mortar showed positive correlation with the ECRM dosage increasing (0 to 4 wt%). The reserved ratio of compressive strength of damaged mortar containing 6% ECRM with 60% compressive strength preload was 91.4% after self-healing for 30 min under electromagnetic field and curing for 24 h at room temperature. This work is anticipated to afford new insights for solving rupture problems of microcapsules in self-healing cementitious materials.

Green synthesis of ZnO hierarchical microstructures by Cordia myxa and their antibacterial activity.

In this study, the leaves extract of Cordia myxa, has been used for the first time to synthesize zinc oxide (ZnO) hierarchical microstructures. The solution combustion method was employed as a self-sustaining reaction between zinc nitrate and the leaves extract. The surface properties of leaves mediated ZnO microstructures were determined by UV–Visible spectral analysis, Fourier transform infrared (FT-IR), Cold field emission-scanning electron microscopy (CFE-SEM), Energy dispersive X-ray (EDX), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). In addition, the effect of the leaves extract concentration on ZnO structures, size and surface properties was also studied. ZnO structures synthesized employing C. myxa were found to be hexagonal, triangular and round in shape which was determined using CFE-SEM. X-ray diffraction (XRD) analysis confirmed the crystalline nature of compounds. Furthermore, C. myxa mediated ZnO microstructures shows good bactericidal activity against Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria.

Electron energy-loss spectroscopy (EELS) with a cold-field emission scanning electron microscope at low accelerating voltage in transmission mode

A commercial electron energy-loss spectrometer (EELS) attached to a high-resolution cold-field emission scanning electron microscope in transmission mode (STEM) is evaluated and its potential for characterizing materials science thin specimens at low accelerating voltage is reviewed. Despite the increased beam radiation damage at SEM voltages on sensitive compounds, we describe some potential applications which benefit from lowering the primary electrons voltage on less-sensitive specimens. We report bandgap measurements on several dielectrics which were facilitated by the lack of Cherenkov radiation losses at 30 kV. The possibility of volume plasmon imaging to probe local composition changes in complex materials was demonstrated using energy-filtered STEM, either via spectrum imaging or elemental mapping using the “three-windows” method. As plasmonic materials are increasing used for energy, electronics or biomedical applications, the ability of reliably evaluate their properties at low accelerating voltage in a SEM is very appealing and is demonstrated. The energy resolution of the spectrometer, taken as the full width at half maximum of the zero-loss peak, was routinely measured at around 0.55 eV and it is demonstrated that t/λ ratios up to 1.5 allowed practical EEL spectroscopy at 30 kV.

Optimization study of direct morphology observation by cold field emission SEM without gold coating

Gold coating is a general operation that is generally applied on non-conductive or low conductive materials, during which the morphology of the materials can be examined by scanning electron microscopy (SEM). However, fatal deficiencies in the materials can result in irreversible distortion and damage. The present study directly characterized different low conductive materials such as hydroxyapatite, modified poly(vinylidene fluoride) (PVDF) fiber, and zinc oxide nanopillar by cold field emission scanning electron microscopy (FE-SEM) without a gold coating. According to the characteristics of the low conductive materials, various test conditions, such as different working signal modes, accelerating voltages, electron beam spots, and working distances, were characterized to determine the best morphological observations of each sample.

Research on Quantitative Analysis for Nanopore Structure Characteristics of Shale Based on NMR and NMR Cryoporometry

Shale gas is a key natural gas resource of very great significance in China. On the basis of the differences in pore structure characteristics between marine and continental shale in China, the Weiyuan marine shale (sample #1), Jiao Shiba marine shale (sample #2), and Yaoqu continental shale (samples #5 and #6) were selected to study the pore structure characteristics and controlling factors using cold field-emission scanning electron microscopy and nuclear magnetic resonance (NMR). NMR cryoporometry (NMRC) was employed to determine the nanoscale pore structure. This method can be extended to micron measurements combining NMR relaxation analysis to detect in detail the pore structure of shales on different aperture scales. The smaller the test temperature gradient is, the finer is the pore distribution result. The test results show decreasing porosity in going from sample #5 to samples #2, #6, and #1 to #4. NMRC, low-field NMR (LFNMR), mercury intrusion porosimetry (MIP), and gas adsorption (GA) methods show good agreement for the pore distribution in their respective scopes of application. The NMR methods result in a much better estimate for the total pore volume than the more common MIP and GA methods. Hence, the pore structure of the reservoir shale can be evaluated more accurately by combining NMRC and LFNMR with GA and MIP. Thus, the nanopores of continental shale (sample #5, Yaoqu shale) are clearly better developed and will more likely have a higher commercial exploitation value than marine shale.

Graphene-supporting films and low-voltage STEM in SEM toward imaging nanobio materials without staining: Observation of insulin amyloid fibrils

Utilization of graphene-supporting films and low-voltage scanning transmission electron microscopy (LV-STEM) in scanning electron microscopy (SEM) is shown to be an effective means of observing unstained nanobio materials. Insulin amyloid fibrils, which are implicated as a cause of type II diabetes, are formed in vitro and observed without staining at room temperature. An in-lens cold field-emission SEM, equipped with an additional homemade STEM detector, provides dark field (DF)-STEM images in the low energy range of 5–30keV, together with secondary electron (SE) images. Analysis based on Lenz’s theory is used to interpret the experimental results. Graphene films, where the fibrils are deposited, reduce the background level of the STEM images compared with instances when conventional amorphous carbon films are used. Using 30keV, which is lower than that for conventional TEM (100–300keV), together with low detection angles (15–55mrad) enhances the signals from the fibrils. These factors improve image quality, which enables observation of thin fibrils with widths of 7–8nm. STEM imaging clearly reveals a twisted-ribbon structure of a fibril, and SE imaging shows an emphasized striped pattern of the fibril. The LV-STEM in SEM enables acquisition of two types of images of an identical fibril in a single instrument, which is useful for understanding the structure. This study expands the application of SEM to other systems of interest, which is beneficial to a large number of users. The method in this study can be applied to the observation of various nanobio materials and analysis of their native structures, thus contributing to research in materials and life sciences.

Rotation contour contrast reconstruction using electron backscatter diffraction in a scanning electron microscope

The microstructure of a deformed Mg–Al–Ca alloy was imaged using an electron-beam energy of 20 keV in a cold field-emission scanning electron microscope. The backscattered electron (BSE) micrographs showed a non-uniform contrast, the simplest being in the form of parallel contours inside a number of grains. This contrast is described as rotation contour contrast (RCC) and is attributed to local rotation of the crystal during the deformation of the grain. A model is presented to relate the rotation of crystal planes about one rotation axis to the channeling contrast in the channeling pattern and, consequently, to RCC in the BSE micrograph. This model was validated with the electron backscatter diffraction technique such that the RCCs in the BSE micrograph were reconstructed using the electron backscatter diffraction pattern intensities. The appearance of the RCCs was attributed to the change in the electron-beam position across a Kikuchi band due to local crystal rotation.

Rotation axes analysis of deformed magnesium based on rotation contour contrast in a scanning electron microscope

A crystallographic orientation contrast in the form of cross-shaped and intersecting contours was observed in a backscattered electron (BSE) micrograph of deformed magnesium (Mg) grains in a cold field emission scanning electron microscope (CFE-SEM). This contrast was identified as rotation contour contrast (RCC). A model is presented to link the RCC in the BSE micrograph to the channeling contrast in the corresponding channeling pattern. Based on this model, the appearance of the cross-shaped RCC in the BSE micrograph was attributed to the rotation of the crystal about two rotation axes and the RCC was related to a two dimensional angular scan of the corresponding channeling pattern. This model was experimentally validated using the selected area channeling pattern (SACP) technique. The crystallographic directions of the rotation axes were identified using the electron backscatter diffraction (EBSD) technique.

Microstructural Characterization of Mg–0.3Al–0.2Ca Alloy Using Ion Milling Surface Preparation Technique

The Vickers microindentation and spherical nanoindentation tests were carried out on a polycrystalline Mg–0.3Al–0.2Ca alloy specimen. Specimens were prepared with chemical polishing and ion milling techniques. The electron channeling contrast imaging (ECCI) and electron backscattered diffraction (EBSD) were used to study the plastic deformation inside and around the indents with a cold-field emission scanning electron microscope. The distribution of strain fields, slip lines, and twins was imaged on an indented surface. A crystallographic orientation mapping was performed to map the local crystallographic misorientation associated with channeling contrast variations. The chemical polishing technique was used to remove the material from the surface and allow the study of deformed microstructure at a maximum depth of the indent. The combination of ECCI and EBSD with chemical polishing and ion milling surface preparation techniques proved to be beneficial to study the indentation-induced plastic deformation in a polycrystalline Mg–0.3Al–0.2Ca alloy specimen.

Application of Low Energy STEM with the In-lens Cold FE-SEM

We have developed a high resolution STEM imaging method using accelerating beam voltages of 30 kV and less. In this study, we examined and determined the low accelerating voltage parameters necessary for obtaining lattice resolution in STEM images, using the cold field emission scanning electron microscope (CFE-SEM), Hitachi SU9000. We also investigated and optimized the objective lens conditions for optimum lattice fringe imaging. The STEM images and associated Fourier transform image obtained at 30 kV show the Si (222) lattice fringes and reflection spots, corresponding to the d-lattice spacing of 0.157 nm. The STEM images and associated Fourier transform image at 15 kV show the Si (111) lattice fringes and reflection spot, corresponding to the d-lattice spacing of 0.314 nm.

Electron channelling contrast observations in deformed Mg alloys prepared with ion milling

Electron channelling contrast imaging (ECCI) was used in the cold-field emission scanning electron microscope (CFE-SEM) to image the microstructure on deformed bulk specimen. Imaging was conducted with a pole-piece mounted silicon photodiode detector at 5 keV to collect backscattered electrons generated from a low-tilted (0 – 3 degrees) specimen. Broad ion beam milling surface preparation technique was used to remove surface layers and reveal near-surface deformation features. The uniaxial hot-compression tests were conducted on Mg-0.3 wt% Al-0.2 wt% Ca alloy. ECCI observations on deformed bulk specimen showed irregular and complex channelling contrast variations inside parent grains and low angle grain boundaries originated from parent grain boundaries. ECCI on an ion milled prepared surface provides non-destructive and rapid visualisation and characterisation of strain fields along with near-surface deformation substructures in CFE-SEM.

Lattice imaging at an accelerating voltage of 30kV using an in-lens type cold field-emission scanning electron microscope

We reported investigation of lattice resolution imaging using a Hitachi SU9000 conventional in-lens type cold field emission scanning electron microscope without an aberration corrector at an accelerating voltage of 30kV and discuss the electron optics and optimization of observation conditions for obtaining lattice resolution. It is possible to visualize lattice spacings that are much smaller than the diameter of the incident electron beam through the influence of the superior coherent performance of the cold field emission electron source. The defocus difference between STEM imaging and lattice imaging is found to increase with spherical aberration but it is possible to reduce the spherical aberration by reducing the focal length (f) of the objective lens combined with an experimental sample stage enabling a shorter distance between the objective lens pre-field and the sample. We demonstrate that it is possible to observe the STEM image and crystalline lattice simultaneously. STEM and Fourier transform images are detected for Si{222} lattice fringes and reflection spots, corresponding to 0.157nm. These results reveal the potential and possibility for a measuring technique with excellent precision as a theoretically exact dimension and established the ability to perform high precision measurements of crystal lattices for the structural characterization of semiconductor materials with minimal radiation beam damage.

Multi‐walled carbon nanotubes decorated by platinum catalyst nanoparticles—Examination and microanalysis using scanning and transmission electron microscopies

Carbon nanotubes (CNTs) decorated with platinum (Pt) nanoparticles (NPs) have been characterized using a cold field-emission scanning electron microscope (SEM) and a high resolution field-emission transmission electron microscope (TEM). With this particular composite material, the complementary nature of the two instruments was demonstrated. Although the long CNTs were found to be mostly bent and defective in some parts, the nucleation of Pt occurred randomly and uniformly covered the CNTs. The NPs displayed a large variation in size, were sometimes defective with twins and stacking faults, and were found to be faceted with the presence of surface steps. The shape and size of the NPs and the presence of defects may have significant consequences on the activity of the Pt catalyst material. Also, thin layers of platinum oxide were identified on the surface of some NPs.

Acquisition parameters optimization of a transmission electron forward scatter diffraction system in a cold‐field emission scanning electron microscope for nanomaterials characterization

Transmission electron forward scatter diffraction (t-EFSD) is a new technique providing crystallographic information with high resolution on thin specimens by using a conventional electron backscatter diffraction (EBSD) system in a scanning electron microscope. In this study, the impact of tilt angle, working distance, and detector distance on the Kikuchi pattern quality were investigated in a cold-field emission scanning electron microscope (CFE-SEM). We demonstrated that t-EFSD is applicable for tilt angles ranging from -20° to -40°. Working distance (WD) should be optimized for each material by choosing the WD for which the EBSD camera screen illumination is the highest, as the number of detected electrons on the screen is directly dependent on the scattering angle. To take advantage of the best performances of the CFE-SEM, the EBSD camera should be close to the sample and oriented towards the bottom to increase forward scattered electron collection efficiency. However, specimen chamber cluttering and beam/mechanical drift are important limitations in the CFE-SEM used in this work. Finally, the importance of t-EFSD in materials science characterization was illustrated through three examples of phase identification and orientation mapping.

Detection of nerve agent stimulants based on photoluminescent porous silicon interferometer

Porous silicon (PSi) exhibiting dual optical properties, both Fabry-Pérot fringe and photolumincence, was developed and used as chemical sensors. PSi samples were prepared by an electrochemical etch of p-type silicon under the illumination of 300-W tungsten lamp during the etch process. The surface of PSi was characterized by cold field-emission scanning electron microscope. PSi samples exhibited a strong visible orange photoluminescence at 610 nm with an excitation wavelength of 460 nm as well as Fabry-Pérot fringe with a tungsten light source. Both reflectivity and photoluminescence were simultaneously measured under the exposure of organophosphate vapors. An increase of optical thickness and quenching photoluminescences under the exposure of various organophosphate vapors were observed.

Porous ZnO nanobelts: synthesis, mechanism, and morphological evolutions

Porous ZnO nanobelts with rough surface and poly-crystalline nature have been developed from a facile wet chemical method. The as-prepared products were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), cold field emission scanning electron microscopy (CFE-SEM), and energy dispersive analysis of X-rays (EDAX). The ZnO nanobelts were synthesized with usually 5 to 6 nm in thickness, 10 to 40 nm in width, and about several micrometers in length. A PVP promoted self-assembly mechanism is believed to be responsible for the morphology shaping process of the ZnO nanostructures. This first wet chemical synthesis of such hierarchical structures without any hard templates implies a simple and inexpensive way to prepare transition metal superstructures on a large scale for modern chemical synthesis. Optical characterization by a confocal laser Raman were also carried out to explore their optical properties; the PL and Raman results showed both good agreement with the characters of our samples and potential for future applications such as sensors and other modern technologies.

Study of the corrosion resistance of electroless Ni-P deposits in a sodium chloride medium

The corrosion resistance of electroless Ni-P deposits with phosphorous contents from 12% to 14% in sodium chloride solutions was studied. The deposits were immersed in 3.5% NaCl solutions for 29 d to obtain the electrochemical parameters and were examined in a standard salt spray test for 15 d respectively. The corrosion resistance of the deposits was studied by potentio-dynamic scan, electrochemical impedance spectroscopy (EIS), X-ray diffraction (XRD) and cold-field emission scanning electron microscopy (FE-SEM) equipped with an energy dispersive X-ray detector (EDX). The patterns of XRD and the results of FE-SEM showed that the prepared deposits were amorphous. But after a 15 d standard salt spray test, a few pinholes appeared on the surface of the deposit and the weight content of phosphorus on the surface of the deposit was higher (which was beneficial to the formation of the passivation films) than that before the standard salt spray test when the nickel content was lower because the dissolved weight of nickel was greater than that of phosphorus. The results from potentio-dynamic scan and EIS showed that passivation films formed on the Ni-P deposit after immersion in the NaCl solutions, which decreased the corrosion rate of Ni-P samples. The results of this work show their potential applications in marine corrosion.