Composition and Element Distribution Mapping of γ' and γ″ Phases of Inconel 718 by High-Resolution Scanning Transmission Electron Microscopy and X-ray Energy-Dispersive Spectrometry.

The main strengthening mechanism for Inconel 718 (IN718), a Ni-based superalloy, is precipitation hardening by γ' and γ″ particles. It is thus essential, for good alloy performance, that precipitates with the desired chemical composition have adequate size and dispersion. The distribution of the γ' and γ″ phases and their chemical composition were investigated in the nickel-based Inconel 718 superalloy by taking advantage of the new capabilities of scanning transmission electron microscopy and energy-dispersive X-ray spectrometry using a windowless multiple detector, a high-brightness Schottky electron gun, and a spherical aberration corrector in the illumination probe optics. A small routine was developed to deconvolute the respective compositions of γ' and γ″ nanoprecipitates embedded in the γ matrix. Keeping the electron probe current low enough-a few hundred pA-prevented excessive irradiation damage during the acquisition of element maps and brought their spatial resolution down to the atomic column level to track their element compositions. The present results agree with and complement atomic probe tomography observations and Thermo-Calc predictions from the literature. The presence of an Al enrichment at the γ'/γ″ interface-which may control the γ″ phase coarsening-is observed in the last row of Al-Nb-Ti columns along this interface. In addition, a few columns with similar composition changes are found randomly distributed in the γ' phase.

Structure, Oxygen Content and Electric Properties of Titanium Nitride Electrodes in TiNx/La:HfO2/TiNx Stacks Grown by PEALD on SiO2/Si.

This work reports experimental results of the quantitative determination of oxygen and band gap measurement in the TiNx electrodes in planar TiNx top/La:HfO2/TiNx bottom MIM stacks obtained by plasma enhanced atomic layer deposition on SiO2. Methodological aspects of extracting structural and chemical information from (scanning) transmission electron microscopy imaging (bright field and high angular annular dark field), energy dispersive X-ray spectrometry and electron energy loss spectroscopy are thoroughly considered. The study shows that the oxygen concentration is higher in the TiNxOy bottom electrode (about 14.2 ± 0.1 at. %) compared to the TiNxOy top electrode (about 11.4 ± 0.5 at. %). The following average stoichiometric formulas are TiN0.52O0.20 top and TiN0.54O0.26 bottom for top and bottom electrodes, respectively. The amount of oxygen incorporated into TiNx during PEALD because of oxygen impurities in the plasma is minor compared to that because of diffusion from SiO2 and HfO2. This asymmetry, together with results on a sample grown on a Si substrate, shows that incorporating oxygen impurity from the plasma itself is a minor part compared to diffusion from the SiO2 substrate and HfO2 dielectric during the PEALD growth. We observe the presence of TiO2 at the interface between the Hf oxide layer and the Ti nitride electrodes as well as at the SiO2 interface. EELS analysis led to a band gap ranging from 2.2 to 2.5 eV for the bottom TiNxOy and 1.7-2.2 eV for the top TiNxOy, which is in fair agreement with results obtained on the top TiNx electrode (1.6 ± 01 eV) using optical absorption spectra. Measurement of sheet resistance, resistivity and temperature coefficient of resistance by a four-point probe on the top TiNxOy electrode from 20 to 100 °C corresponds to the typical values for semiconductors.

Transmission electron microscopy of Ca oxide nano- and microcrystals in alpha-tricalcium phosphate prepared by sintering of beta-tricalcium phosphate.

Transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to study the porous and non-porous alpha-tricalcium phosphate (alpha-Ca3(PO4)2, alpha-TCP) prepared through a sintering procedure at 1200-1400 degrees C of beta-tricalcium phosphate (beta-Ca3(PO4)2, beta-TCP). The interpretation of experimental and calculated X-ray and electron diffraction patterns showed that the final product at 1400 degrees C was primarily alpha-TCP but roughly 3.0-8.0 wt.% of the starting beta-TCP phase and up to 8.0 wt.% of CaO were in the final product. TEM images and electron diffraction patterns showed that the CaO phase--formed by decomposition of TCP--exists as micron-sized areas of various oriented nanocrystals embedded into the bulk alpha-TCP material and also as self-standing spherulite particles of a few microns in size. Surprisingly, formation of CaO from TCP decomposition occurred at temperatures below those predicted from the phase diagram of the CaO-P2O5 system.

Scanning and transmission electron microscopy for evaluation of order/disorder in bone structure.

A comparative characterization of the structure of normal and abnormal (osteoporotic) human lumbar and thoracic vertebrae samples was carried out to reveal the type of possible disorder. Samples from the bone fragments extracted during the surgery due to vertebra fractures were examined by scanning electron microscopy (SEM), conventional and high resolution transmission electron microscopy (TEM and HRTEM), and X-ray energy dispersive spectroscopy (EDS). Contrary to what might be expected in accordance with possible processes of dissolution, formation and remineralization of hard tissues, no changes in phase composition of mineral part, crystal sizes (length, width, and thickness), and arrangement of crystals on collagen fibers were detected in abnormal bones compared to the normal ones. The following sizes were determined by HRTEM for all bone samples:

Pathological mineralization of cardiac valves: causes and mechanism.

OBJECTIVE: Mechanism of calcification of cardiac valves was investigated through a comparative characterization of structure, morphology, and size of hydroxyapatite (HAP) crystals formed in mineral deposit on cardiac valves, bone tissue, and crystals synthesized from aqueous solutions under definite conditions. METHODS: All deposits on cardiac valves and bone samples were characterized by scanning electron microscopy (SEM) and energy dispersive X-ray microanalysis (EDS) in a Philips XL30 FEG microscope to evaluate their overall view and structure, to estimate the sizes of particles, and to carry out the chemical analysis. High resolution transmission electron microscopy (HRTEM) and electron micro diffraction was done for precise phase identification of individual crystals and measurements of their sizes. RESULTS: Mineral deposit on cardiac valves contained hydroxyapatite crystals (HAP) crystals with lengths from a few nanometers to a few hundred nanometers. Similar to the HAP precipitation in aqueous solutions, crystals in deposit were randomly oriented relative to each other and without the substrate effect on their orientation. Octacalcium phosphate (OCP) phase was also detected in the form of large (up to a few microns) crystals. The quantity of the OCP crystals was quite low in comparison with the amount of the HAP crystals. HAP crystals in bone samples were no more than 20 nm in length and textured in the HAP [0001] direction along collagen fibers. The HAP crystals from cardiac valves and bones were of uniform thickness comparable with the crystallographic unit cell. CONCLUSIONS: Mass crystallization model and hemodynamics in heart and arteries determine the mechanism of pathological calcification through the mediation of hydroxyapatite nanocrystals perpetually circulating with the bloodstream.

Model of the mechanism of Ca loss by bones under microgravity and earth conditions.

A comparative characterization of crystal structure, morphology, sizes, and orientation in Ca phosphate precipitation from aqueous solutions, the mineral phase in bones, and mineral deposits on cardiac valves has been performed by high-resolution transmission electron microscopy to model possible mechanisms of Ca loss by bones. Physiological changes occurring in organisms can lead to deep perturbations of the natural calcium phosphate supersaturation and its local distribution, which in turn influences the phase composition, morphology, and organization of the mineral phase. Formation of crystals with larger size or of two distinct phases instead of the single hydroxyapatite one can result in the deterioration of the Ca balance in bone and tissue destruction as well as the possible misorientation (or spread of orientation) between HAP crystals newly formed in the bone.