Microstructure characterization of advanced protective Cr/CrN+a‐C:H/a‐C:H:Cr multilayer coatings on carbon fibre composite (CFC)

Studies of advanced protective chromium‐based coatings on the carbon fibre composite (CFC) were performed. Multidisciplinary examinations were carried out comprising: microstructure transmission electron microscopy (TEM, HREM) studies, micromechanical analysis and wear resistance. Coatings were prepared using a magnetron sputtering technique with application of high‐purity chromium and carbon (graphite) targets deposited on the CFC substrate. Selection of the CFC for surface modification in respect to irregularities on the surface making the CFC surface more smooth was performed. Deposited coatings consisted of two parts. The inner part was responsible for the residual stress compensation and cracking initiation as well as resistance at elevated temperatures occurring namely during surgical tools sterilization process. The outer part was responsible for wear resistance properties and biocompatibility. Experimental studies revealed that irregularities on the substrate surface had a negative influence on the crystallites growth direction. Chromium implanted into the a‐C:H structure reacted with carbon forming the cubic nanocrystal chromium carbides of the Cr₂₃C₆ type. The cracking was initiated at the coating/substrate interface and the energy of brittle cracking was reduced because of the plastic deformation at each Cr interlayer interface. The wear mechanism and cracking process was described in micro‐ and nanoscale by means of transmission electron microscope studies. Examined materials of coated CFC type would find applications in advanced surgical tools.     

Characterising the surface and interior chemistry of core-shell nanoparticles using scanning transmission electron microscopy

A method for extracting core and shell spectra from core-shell particles with varying core to shell volume fractions is described. The method extracts the information from a single EELS spectrum image of the particle. The distribution of O and N was correctly reproduced for a nanoparticle with a TiN core and Ti-oxide shell. In addition, the O distribution from a nanoparticle with a Cu core and a Cu-oxide shell was obtained, and the extracted Cu L_2,3-core and shell spectra showed the required change in EELS near edge fine structure. The extracted spectra can be used for multiple linear least squares fitting to the raw data in the spectrum image. The effect of certain approximations on numerical accuracy, such as treating the nanoparticle as a perfect sphere, as well as the intrinsic detection limits of the technique have also been explored. The technique is most suitable for qualitative, rather than quantitative, work.     

A new analytical method for characterising the bonding environment at rough interfaces in high-k gate stacks using electron energy loss spectroscopy

Determining the bonding environment at a rough interface, using for example the near-edge fine structure in electron energy loss spectroscopy (EELS), is problematic since the measurement contains information from the interface and surrounding matrix phase. Here we present a novel analytical method for determining the interfacial EELS difference spectrum (with respect to the matrix phase) from a rough interface of unknown geometry, which, unlike multiple linear least squares (MLLS) fitting, does not require the use of reference spectra from suitable standards. The method is based on analysing a series of EELS spectra with variable interface to matrix volume fraction and, as an example, is applied to a TiN/poly-Si interface containing oxygen in a HfO₂-based, high-k dielectric gate stack. A silicon oxynitride layer was detected at the interface consistent with previous results based on MLLS fitting.     

Specimen thickness dependence of hydrogen evolution during cryo‐transmission electron microscopy of hydrated soft materials

The evolution of hydrogen from many hydrated cryo‐preserved soft materials under electron irradiation in the transmission electron microscope can be observed at doses of the order of 1000 e nm^?2 and above. Such hydrogen causes artefacts in conventional transmission electron microscope or scanning transmission electron microscopy (STEM) imaging as well as in analyses by electron energy‐loss spectroscopy. Here we show that the evolution of hydrogen depends on specimen thickness. Using wedge‐shaped specimens of frozen‐hydrated Nafion, a perfluorinated ionomer, saturated with the organic solvent DMMP together with both thin and thick sections of frozen‐hydrated porcine skin, we show that there is a thickness below which hydrogen evolution is not detected either by bubble observation in transmission electron microscope image mode or by spectroscopic analysis in STEM electron energy‐loss spectroscopy mode. We suggest that this effect is due to the diffusion of hydrogen, whose diffusivity remains significant even at liquid nitrogen temperature over the length scales and time scales relevant to transmission electron microscopy analysis of thin specimens. In short, we speculate that sufficient hydrogen can diffuse to the specimen surface in thin sections so that concentrations are too low for bubbling or for spectroscopic detection. Significantly, this finding indicates that higher electron doses can be used during the imaging of radiation‐sensitive hydrated soft materials and, consequently, higher spatial resolution can be achieved, if sufficiently thin specimens are used in order to avoid the evolution of hydrogen‐based artefacts.     

Assessment of collagen fibril spacing in relation to selected region of interest (ROI) on electron micrographs--application to the mammalian corneal stroma

AIMS: To evaluate measurements of collagen fibril spacing using different shaped regions of interest (ROI) on transmission electron micrograph (TEM) images of rabbit corneal stroma. METHODS: Following glutaraldehyde fixation and phosphotungstic acid staining, TEM images of collagen fibrils in cross section were projected at a final magnification close to 250,000 × to obtain overlays. Interfibril distances (IFDs; center‐to‐center spacing) were measured within different ROIs of the same nominal area (0.25 μm²) but different shape (with the length to width, L:W, ratio from 1:1 to 6:1). The IFD distribution was analyzed, and the 2D organization assessed using a radial distribution analysis. RESULTS: The fibrils had an average diameter of 35.3 ± 3.8 (SD) nm, packing density of 393 ± 4 fibrils / μm² and a fibril volume fraction of 0.39 ± 0.02. IFDs ranged from 29 to 1400 nm depending on the shape of the ROI, with average values ranging from 263 to 443 nm. By artificially selecting IFD data only to a radial distance of 250 nm, the average IFDs were just 145–157 nm. The radial distributions, to 250 nm, all showed a nearest neighbors first peak which shifted slightly from predominantly at 45–54 nm with more rectangular ROIs. The radial distribution profiles could be shown to be statistically different if the ROI L:W ratio was 2:1 or greater. CONCLUSION: Selection of an ROI for assessment of packing density and interfibril distances should be standardized for comparative assessments of TEMs of collagen fibrils. Microsc. Res. Tech., 2011. © 2011 Wiley‐Liss, Inc.     

The importance of microscopy in studying the wear behaviour of ceramic surfaces

This paper demonstrates how careful microscopy of worn ceramic surfaces can be used to provide information on the mechanisms of material removal. This information is necessary as a critical complement to wear-rate data obtainable from simple wear tests alone (e.g. lapping with diamond grits). Scanning electron microscopy has been extensively used to investigate the changing appearance of worn surfaces as plasticity and fracture processes compete as materials removal and redistribution mechanisms. Examples of the use of secondary electron imaging at different surface tilts, back-scattered electron imaging and stereo imaging are shown. Further, transmission electron microscopy of samples specially prepared to contain the worn surface layer can reveal the presence of phase changes accompanying wear. Furthermore, observations have been made of instances whereby brittle fracture has unexpectedly occurred as a result of repeated plastic deformation of surfaces at low contact severities. Some conclusions are drawn regarding the influence of specimen microstructure, abrasive grit size and environment of the wear of glass-bonded (debased) alumina and titania materials.     

Microscopy and microanalysis of complex nanosized strengthening precipitates in new generation commercial Al–Cu–Li alloys

Precipitates (ppts) in new generation aluminum–lithium alloys (AA2099 and AA2199) were characterised using scanning and transmission electron microscopy and atom probe tomography. Results obtained on the following ppts are reported: Guinier–Preston zones, T₁ (Al₂CuLi), β’ (Al₃Zr) and δ’ (Al₃Li). The focus was placed on their composition and the presence of minor elements. X‐ray energy‐dispersive spectrometry in the electron microscopes and mass spectrometry in the atom probe microscope showed that T₁ ppts were enriched in zinc (Zn) and magnesium up to about 1.9 and 3.5 at.%, respectively. A concentration of 2.5 at.% Zn in the δ’ ppts was also measured. Unlike Li and copper, Zn in the T₁ ppts could not be detected using electron energy‐loss spectroscopy in the transmission electron microscope because of its too low concentration and the small sizes of these ppts. Indeed, Monte Carlo simulations of EEL spectra for the Zn L_2,3 edge showed that the signal‐to‐noise ratio was not high enough and that the detection limit was at least 2.5 at.%, depending on the probe current. Also, the simulation of X‐ray spectra confirmed that the detection limit was exceeded for the Zn K_α X‐ray line because the signal‐to‐noise ratio was high enough in that case, which is in agreement with our observations.     

Extended energy-loss fine structure spectroscopy of structural modifications in Nd2CuO4−δ at the oxygen K edge

The discovery of the superconducting electron-doped compound Nd₁₈₅Ce₀₁₅CuO_4?δ has stimulated great interest in its micro- and crystal structure, since the superconducting properties depend on parameters such as nonstoichiometry, phase composition, heat treatment and microstructure. The work presented herein is focused on the determination of the oxygen environment in the undoped parent compound Nd₂CuO₄ and in the structural modification Nd₂CuO₃₅ The analysis of the oxygen K (O 1s) edge extended electron energy-loss fine structure (EXELFS) of the tetragonal parent compound Nd₂CuO₄ and of the orthorhombic modification Nd₂CuO₃₅ is reported by using electron energy-loss spectroscopy in combination with transmission electron microscopy. Nd₂CuO₃₅ is produced by in situ heating and reduction of Nd₂CuO₄ in the transmission electron microscope. The EXELFS of the O 1s electron energy-loss edges is analysed with the classical extended X-ray absorption fine structure (EXAFS) treatment and compared with ab initio multiple scattering EXAFS calculations for both structural modifications. Highly accurate information on the local atomic environment of the oxygen atoms in Nd₂CuO₃₅ is obtained from EXELFS analysis using Nd₂CuO₄ as a standard. The results are in accordance with the structural data gained from X-ray diffraction analysis. This applies especially to the more complicated structure of Nd₂CuO₃₅ determined recently.     

Application of recording and processing of energy-filtered image sequences for the elemental mapping of biological specimens: Imaging-Spectrum

Computerized energy-filtered transmission electron microscope (EFTEM) permits the recording and the processing of energy-filtered images, allowing a part of an electron energy-loss spectrum for each picture element to be obtained. This method, called ‘Imaging-Spectrum’, uses a Zeiss CEM902 coupled to several image analysis systems. The actual configuration records sequences of 48 images, 256 × 256 pixels, in steps of the energy loss, ΔE. Processing these sequences results in part of a core-loss EELS-spectrum for each pixel. This approach produces elemental maps with a short processing time. We have implemented three kinds of background calculation for the image subtraction. The influence of the irradiation dose and of the energy selecting slit width on the quality of the spectra is investigated. The method is applied to the analysis of some biological specimens (pericellular coat behaviour during adhesion between macrophages and red blood cells and location of calcite microcrystals in dental pulp cells). The Imaging-Spectrum method appears to be suitable for the analysis of large areas.     

Quantitative study of spurious X-ray production in thin film microanalysis

When X-ray microanalysis is performed in a TEM on a thin area of a specimen, some a priori indistinguishable spurious photons produced in other zones of this specimen are always recorded. Several mechanisms contribute to this production. For instance, some Bremsstrahlung and characteristic photons are generated by secondary and Auger electrons; a conservative upper bound to this particular contribution is calculated for several materials, and the present approach is compared to the Monte Carlo simulation. It is then shown that, in special test-specimens, the total extraneous contribution of the thick parts of the specimen to the spectra recorded in a thin zone can be measured; different instruments may now be compared in this respect. In the HB5 STEM, this total contribution remains low; its main cause is beam scattering in the specimen, not before it. Finally, an experimental procedure for estimating this bulk contribution in any specimen of interest is proposed. Calculations and experiments are illustrated for the case of gallium arsenide.     

Intracellular localization of samarium in the lactating mammary gland cells: ultrastructural and microanalytical study

The frequent use of some rare earths in the medical and industrial domains make us worry about their intracellular behavior into the body. Reason for which we have investigated the subcellular localization of one of these elements, the samarium, in the mammary gland of lactating female wistar rats using two very sensitive methods of observation and microanalysis, the transmission electron microscopy and the secondary ion mass spectrometry. The ultrastructural study showed the presence of electron dense deposits in the lactating mammary glandular epithelial cell lysosomes of the samarium-treated rats, but no loaded lysosomes were observed in those of control rats. The microanalytical study allowed both the identification of the chemical species present in those deposits as samarium isotopes ((152) Sm(+)) and the cartography of its distribution. Our results confirm the previous ones showing that lysosomes of the glandular epithelial cells are the site of the intracellular concentration of foreign elements such as gallium. The intralysosomal deposits observed in the mammary glandular cells of the samarium-treated rats are similar in their form and density to those observed with the same element in other varieties of cells, such as liver, bone marrow, and spleen cells. Our ultrastructural and microanalytical results and those obtained in previous studies allow deducing that the intralysosomal deposits are very probably composed of an insoluble samarium phosphate salt.     

Adsorption properties of aqueous methylene blue on mesocellular foam silica: Equilibrium,kinetic, isotherm,and thermodynamic characterization

Abstract

Mesocellular foam silica was prepared by a hydrothermal synthesis protocol. The surface and pore structure of mesocellular foam silica were characterized by low temperature nitrogen adsorption isotherms, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared (FT-IR) spectroscopy. The methylene blue was adsorbed by the synthetic mesocellular foam silica; the optimized adsorption conditions were evaluated and the maximum adsorption capacity of methylene blue by mesocellular foam silica was determined to be 215.5?mg g^?1. The kinetics of the adsorption of methylene blue by mesocellular foam silica were in accordance with a quasi-second-order kinetic equation. The results were analyzed by Langmuir and Freundlich adsorption isotherm models. The adsorption of methylene blue on mesocellular foam silica was shown to follow the Freundlich adsorption isotherm model. The Gibbs free energy change during adsorption showed that this process was spontaneous. The enthalpy change in the process was –28.868?J·mol^?1 K^?1, indicating that the adsorption is exothermic. The negative value of entropy –49.296?J·mol^?1 K^-1 shows that the system disorder decreases due to adsorption.     

Microstructural characterization of Ti‐6Al‐4V alloy subjected to the duplex SMAT/plasma nitriding

In this study, microstructural characterization of Ti‐6Al‐4V alloy, subjected to the duplex surface mechanical attrition treatment (SMAT)/nitriding treatment, leading to improve its mechanical properties, was carried out through novel and original samples preparation methods. Instead of acid etching which is limited for morphological characterization by scanning electron microscopy (SEM), an original ion polishing method was developed. Moreover, for structural characterization by transmission electron microscopy (TEM), an ion milling method based with the use of two ions guns was also carried out for cross‐section preparation. To demonstrate the efficiency of the two developed methods, morphological investigations were done by traditional SEM and field emission gun SEM. This was followed by structural investigations through selected area electron diffraction (SAED) coupled with TEM and X‐ray diffraction techniques. The results demonstrated that ionic polishing allowed to reveal a variation of the microstructure according to the surface treatment that could not be observed by acid etching preparation. TEM associated to SAED and X‐ray diffraction provided information regarding the nanostructure compositional changes induced by the duplex SMAT/nitriding process. Microsc. Res. Tech. 76:897–903, 2013. © 2013 Wiley Periodicals, Inc.     

Hydrothermal synthesis of a lamellar zinc dimolybdate hydroxide with application as the anode for lithium-ion batteries

Abstract

A lamellar zinc dimolybdate hydroxide Zn₃Mo₂O₈(OH)₂ was prepared for the first time by a facile hydrothermal synthesis. The electrochemical properties of the lamellar Zn₃Mo₂O₈(OH)₂ as an anode material were investigated by cyclic voltammetry (CV), reversible capacity, cycling stability and rate capability for lithium ion batteries (LIB). The lamellar zinc dimolybdate hydroxide exhibits a reversible capacity of 404.6 mAh g^?1 at a current density of 100?mA g^?1 after 200 cycles. The reversible capacity of the lamellar Zn₃Mo₂O₈(OH)₂ remained at 60 mAh g^?1 even at a current density of 3000?mA g^?1. When the current density was returned to 100?mA g^?1, a discharge capacity of 380 mAh g^?1 was maintained after 200 discharge/charge cycles. The excellent electrochemical performance may be due to its unique lamellar structure, which buffers the volume change during the Li⁺ intercalation/de-intercalation and provides the electrode with convenient lithium ions and electron transport pathways. These results suggest the promising potential application of the lamellar zinc dimolybdate hydroxide in lithium-ion batteries.     

The electron energy-loss near-edge structure (ELNES) on the N K-edges from the transition metal mononitrides with the rock-salt structure and its comparison with that on the C K-edges from the corresponding transition metal monocarbides

This paper presents the shapes of the electron energy-loss near-edges structure (ELNES) on the N K-edge of the group IV_A (Ti, Zr, Hf) and group V_A (V, Nb, Ta) transition metal mononitrides close to stoichiometry. With the exceptions of NbN and TaN, these compounds have the rock-salt (B1) structure when close to stoichiometry. NbN exists with both the rock-salt structure and a hexagonal structure. Two distinct ELNES shapes were observed from it, one of which corresponds closely with previously published data from the rock-salt structure. Under normal conditions, TaN is considered to exist only in the hexagonal form, the rock-salt form being a high-temperature/high-pressure phase although it has been reported as the result of plasma jet heating of the hexagonal form. Again two distinct ELNES shapes were observed, one of which appeared to fit into the pattern of the shapes from the other compounds with the rock-salt structure. The systematic changes of shape observed are very similar to those observed in the equivalent carbides and qualitatively follow the behaviour expected from theoretical band structures. The change in the chemical shift of the N K-edge on going from a group IV_A nitride to a group V_A nitride is ～-0·8 eV while that on going from a group IV_A carbide to a group V_A carbide is ～+0·8 eV. This difference in behaviour is explained as the result of differences in the densities of states at the Fermi levels of the compounds. The position of the first peak in the ELNES also shows a systematic change in its energy relative to the core state as the number of valence electrons in the compound increases and also as the transition series of the metal species changes. The energies, E_r, of the peaks in the ELNES relative to the threshold follow a relationship similar to that predicted by Natoli, i.e. (E_r - V)a = const. where V is the ‘muffin tin’ potential and a is the lattice parameter. The first peak gives a negative constant in the relationship. The value of constant increases for each subsequent peak up to the sixth becoming positive for the fourth and higher peaks but drops slightly on going from the sixth to the seventh peak. Each peak gives a different value of V in the relationship. The data sets for the carbides and the nitrides are systematically different in a similar way for each peak and there are deviations from linearity within each set. The systematic difference is minimized and the linearity significantly improved if the difference in the energies of two prominent peaks is used instead of E_r. This systematic variation of peak energy with lattice parameter can be used to predict the lattice parameter. If both the nitride and the carbide data for the energy of a prominent peak relative to the threshold are used, this results in a maximum deviation of 4% (or ～0·02 nm). However, if the differences in the energies of two prominent peaks are used and the data for the carbides and the nitrides are treated independently, the maximum deviation drops to 0·4% (or ～0·002 nm). At this level, uncertainties in the lattice parameters themselves come into play and better characterized materials are required to set true limits to the accuracy of the predictions. Finally some applications in the microanalysis of materials are outlined briefly.     

Microstructure analysis of Nd-Fe-B sintered magnets improved by Tb-metal vapour sorption

Behaviours of constituent elements in the Nd-Fe-B sintered magnets improved by Tb-metal vapour sorption have been investigated by using an analytical transmission microscopy. It was found that a triple junction of the grain boundaries consists of fine Nd-O crystalline and amorphous phase. The energy dispersive X-ray spectroscopy (EDS) analysis showed that the amorphous phase mainly consists of Co, Nd and Tb. The Tb-treatment causes the formation of the amorphous Co-Nd(Tb) wetting-layer phase which wraps each Nd₂Fe₁₄B grain. The results suggest that the wrapped structure prevents the nucleation of magnetic reversed domains and then improves significantly the coercivity of the magnet.     

Development of a new analytical electron microscopy technique to quantify the chemistry of planar defects and to measure accurately solute segregation to grain boundaries

A new technique of analytical transmission electron microscopy called ConceptEM has been developed for determining highly accurately small amounts of solute or dopant atoms incorporated into well‐defined planar defects such as stacking faults, grain boundaries or interfaces. The method is based on recording series of analytical spectra taken with different electron beam diameters on the same position centred above a defect that is orientated either edge‐on or slightly inclined with respect to the electron beam. It can be applied to energy‐dispersive X‐ray spectroscopy or electron energy‐loss spectroscopy and necessitates only a nano‐probe modus but no scanning unit. Reliability and accuracy have been tested numerically under various conditions using simulations for a specific geometry, as a function of specimen thickness, material, acceleration voltage, collection angle, random beam displacements and solid solubility. The accuracy has been found to be substantially better (by factors of 5–10) than that of any other current standard technique based on single measurements. Our calculations suggest an accuracy in the determination of the Gibbsian solute excess at a special grain boundary down to ±1% of a monolayer, i.e. around ±0.1 atoms nm^?2 under typical experimental conditions, with a maximum error about twice as large. The parameter limiting a straightforward analysis is found to be the solid solubility, which itself, however, can be measured accurately by the technique so that it can be taken into account quantitatively and the above‐stated precision is retained.     

Design and characteristic research of a novel electromechanical-hydraulic hybrid actuator with two transmission mechanisms

Servo-hydraulic actuators (SHAs) are widely used in mechanical equipment to drive heavy-duty mechanisms. However, their energy efficiency is low, and their motion characteristics are inevitably affected by uncertain nonlinearities. Electromechanical actuators (EMAs) possess superior energy efficiency and motion characteristics. However, they cannot easily drive heavy-duty mechanisms because of weak bearing capacity. This study proposes and designs a novel electromechanical-hydraulic hybrid actuator (EMHA) that integrates the advantages of EMA and SHA. EMHA mainly features two transmission mechanisms. The piston of the hydraulic transmission mechanism and the ball screw pair of the electromechanical transmission mechanism are mechanically fixed together through screw bolts, realizing the integration of two types of transmission mechanisms. The control scheme of the electromechanical transmission mechanism is used for motion control, and the hydraulic transmission mechanism is used for power assistance. Then, the mathematical model, structure, and parameter design of the new EMHA are studied. Finally, the EMHA prototype and test platform are manufactured. The test results prove that the EMHA has good working characteristics and high energy efficiency. Compared with the valve-controlled hydraulic cylinder system, EMHA exhibits a velocity tracking error and energy consumption reduced by 49.7% and 54%, respectively, under the same working conditions.     

The induced damage in the hepatopancreas of Orchestia species after exposure to a mixture of Cu/Zn—An ultrastructural study

The hepatopancreas of crustaceans species has been recognized as an essential target organ to assess trace elements' effects. Due to its dynamic and capability of detoxifying trace metal, this organ often indicates distinct pathological disturbances. In the present work, we intend to evaluate the bioaccumulation of trace metal in three Orchestia species (Orchestia montagui, Orchestia gammarellus, and Orchestia mediterranea) living in symmetry in the banks of Bizerte lagoon (37°13′8″N 09°55′1″E) after their exposure during 14 days to a mixture of copper and zinc, and to highlight the effect of these metals on their hepatopancreas ultrastructure using transmission electron microscopy. At the end of the experiment, results showed that the mortality and the body mass varied according to the used nominal concentrations. Significant alterations were noted in all the treatment groups. The degree of these alterations depends on the used concentration, and they are represented especially by the cells remoteness and the border lyses, the reduction of the nuclear volume, the increase in the cytoplasm density with the presence of trace metal in the nucleus as well as in the vacuole, the disorganization and the destruction of microvilli, the condensation of the majority of cellular organelles and mitochondria swelling. Through this study, Orchestia genus could be an attractive candidate for the biochemical study of trace metal toxicity in Tunisian wetlands.