Trace Analysis of Nanoscale Materials by Analytical Electron Microscopy

1994 ◽  
Vol 332 ◽  
Author(s):  
Dale E. Newbury ◽  
Richard D. Leapman

ABSTRACTTrace analysis of nanometer-scale objects can be performed with parallel-detection electron energy loss spectrometry in the analytical electron microscope. Spectra are collected in the second difference mode with the beam current chosen to maximize the spectral count rate. Numerous elements can be detected at trace levels below 100 parts per million atomic, including transition metal, alkali metal, alkaline earth, and rare earth elements, provided they have a “white line” resonance structure at the ionization edge. Trace nanoanalysis by AEM/PEELS permits direct examination of the microscopic distribution of trace constituents.

Author(s):  
N. D. Evans ◽  
J. Bentley ◽  
S. J. Zinkle

Magnesium aluminate spinel (MgAl2O4) is a candidate material for specialized applications in proposed fusion reactors, and previously, has been irradiated with Al+ or Mg+ ions to assess the effects of high-dose irradiation. Electron energy-loss spectrometry (EELS) has been used to confirm the identity of metallic aluminum colloids located in the ion-implanted region of the spinel because electron diffraction experiments were inconclusive for phase identification. In the present study, energy-filtered plasmon images of the ionimplanted region have been obtained to reveal this colloid distribution.Following implantation with 2 MeV Al+ ions to a fluence of 3.8 × 1021 ions/m2 at 923 K, or with 2.4 MeV Mg+ to a fluence of 2.8 × 1021 ions/m2 at room temperature, spinel specimens were prepared in cross-section for analytical electron microscopy. Energy-filtered images were obtained using a Philips CM30 microscope with an attached Gatan Imaging Filter. Acquired images were 512 × 512 pixels in size and gain normalized.


Author(s):  
Dale E. Newbury ◽  
Richard D. Leapman

The measurement of trace level constituents, arbitrarily defined for this study as concentration levels below 1 atom percent, has always been considered problematic for analytical electron microscopy (AEM) with energy dispersive x-ray spectrometry (EDS) and electron energy loss spectrometry (EELS). In a landmark study of various microanalysis techniques, Wittry evaluated the influence of various instrumental factors (source brightness, detection efficiency, accumulation time) and physical factors (cross section, peak-to-background) upon detection limits. Although the ionization cross section, fluorescence yield, and collection efficiency favor EELS over EDS, the peak-to-background ratio of EELS spectra is much lower than that of EDS spectra, leading Wittry to suggest that the limit of detection should be 0.1 percent for EDS and 1 percent for EELS for practical measurement conditions. Recent developments in parallel detection EELS (PEELS) indicate that a re-evaluation of the situation for trace constituent determination is needed for those elements characterized by "white line" resonance structures at the ionization edge.


1994 ◽  
Vol 373 ◽  
Author(s):  
N. D. Evans ◽  
S. J. Zinkle ◽  
J. Bentley

AbstractAnalytical electron microscopy (AEM) has been used to investigate precipitates in MgAl2O4 spinel implantated with Al+, Mg+, or Fe2+ ions. Experiments combining diffraction, energy dispersive X-ray spectrometry (EDS), electron energy-loss spectrometry (EELS), and energy-filtered imaging were employed to identify and characterize precipitates observed in the implanted ion region. Diffraction studies suggested these are metallic aluminum colloids, although EELS and energy-filtered images revealed this to be so only for the Al+ and Mg+ implantations, but not for Fe2+ ion implantations. Multiple-least-squares (MLS) fitting of EELS plasmon spectra was employed to quantify the volume fraction of metallic aluminum in the implanted ion region. Energy-filtered plasmon images of the implanted ion region clearly show the colloid distribution in the Al+ and Mg+ implanted spinel. Energy-filtered images from the Fe2+ ion implanted spinel indicate that the features visible in diffraction contrast cannot be associated with either metallic aluminum or iron-rich precipitates.


Author(s):  
J. Bentley ◽  
E. A. Kenik

Common artifacts on analytical electron microscope (AEM) specimens prepared from bulk materials are surface films with altered structure and composition that result from electropolishing, oxidation, hydrocarbon contamination, or ion milling (preferential sputtering or deposition of sputtered specimen or support material). Of course, the best solution for surface films is to avoid them by improved specimen preparation and handling procedures or to remove them by low energy ion sputter cleaning, a capability that already exists on some specialized AEMs and one that is likely to become increasingly common. However, the problem remains and it is surprising that surface films have not received more attention with respect to composition determination by energy dispersive X-ray spectrometry (EDS) and electron energy loss spectrometry (EELS).For EDS, an effective first-order correction to remove the contribution of surface films on wedge shaped specimens is to subtract from the spectrum of interest a spectrum obtained under identical conditions (probe current, diffracting conditions, acquisition live time) from a thinner region of the specimen.


1999 ◽  
Vol 5 (S2) ◽  
pp. 664-665
Author(s):  
A.J. Craven ◽  
M. MacKenzie

The performance of many materials systems depends on our ability to control the distribution of atoms on a nanometre or sub-nanometre scale within those systems. This is as true for steels as it is for semiconductors. A key requirement for improving their performance is the ability to determine the distribution of the elements resulting from processing the material under a given set of conditions. Analytical electron microscopy (AEM) provides a range of powerful techniques with which to investigate this distribution. By combining information from different techniques, many of the ambiguities of interpretation of the data from an individual technique can be eliminated. The electron energy loss near edge structure (ELNES) present on an ionisation edge in the electron energy loss spectrum reflects the local structural and chemical environments in which the particular atomic species occurs. Thus it is a useful contribution to the information available. Since a similar local environment frequently results in a similar shape, ELNES is useful as a “fingerprint”.


2010 ◽  
Vol 135 (2) ◽  
pp. 95-101
Author(s):  
Holger Weichert ◽  
Stefanie Peschel ◽  
Moritz Knoche ◽  
Dieter Neumann

Recent studies established that some ferric salts, including FeCl3, decrease water permeability of the sweet cherry (Prunus avium L.) fruit exocarp and fruit cracking, presumably by a pH-dependent precipitation reaction that blocks high-flux pathways across the fruit surface. The objectives of our study were the following: to establish the effect of receiver pH on penetration of 55FeCl3 through excised exocarp segments (ES) and isolated cuticular membranes (CM) and to localize any Fe precipitates in the epidermal system of mature sweet cherry fruit. Penetration was studied using an infinite dose diffusion system where 55Fe penetrated from donor solutions of ferric salts (10 mm, pH 2.2–2.6) or EDTA-Na-Fe(III) (10 mm, pH 5.0) across an interfacing ES or CM into aqueous receiver solutions of pH values ranging from 2.0 to 6.0. For receiver pH 2.0, 55Fe penetration of the ES from a 10 mm FeCl3 donor (pH 2.6) was linear with time, but for receiver pH ≥ 3.0, penetration was low and insignificant. Increasing the pH of the water receiver from 2.0 to 6.0 in the course of an experiment resulted in an immediate halt of penetration regardless of whether 55Fe penetration occurred from FeCl3 (pH 2.6), Fe(NO3)3 (pH 2.6), or Fe2(SO4)3 (pH 2.4) as donor solutions (all at 10 mm). Only from EDTA-Na-Fe(III) (pH 5.0) 55Fe penetration continued to occur albeit at a decreased rate (−30%). At receiver pH 2.0, the 55FeCl3 flux through stomatous ‘Sam’ ES averaged 10.4 ± 2.3 pmol·m−2·s−1 and was positively correlated to stomatal density. Conventional and analytical electron microscopy (energy dispersive X-ray analysis, electron spectroscopic imaging, and electron energy loss spectroscopy) identified ferric precipitates in periclinal and anticlinal cell walls of epidermal cells underlying the cuticle, but not within the cuticle. These data indicate that the lack of 55Fe penetration from donor solutions of ferric salts through the ES into a receiver solution at pH ≥ 3 and the previously reported decrease in water uptake and cracking as a response to immersing fruit in solutions of ferric salts are the result of a precipitation reaction at the cuticle/cell wall interface in the sweet cherry exocarp. Although spray application of ferric salts is prohibitive for ecotoxicological reasons, understanding their mechanism in decreasing water uptake and fruit cracking may be helpful in the search for alternate compounds that are effective and ecotoxicologically acceptable.


Clay Minerals ◽  
2018 ◽  
Vol 53 (2) ◽  
pp. 105-116 ◽  
Author(s):  
Blanca Bauluz ◽  
Fernando Nieto

ABSTRACTThe present study examines the micro- and nano-texture and composition of ammonium-bearing and potassium micas in very-low grade metamorphic black Silurian shales from the SE Iberian Range (NE Spain). Two organic-rich shales were studied by X-ray diffraction (XRD), infrared spectroscopy (IR), transmission electron microscopy (TEM), analytical electron microscopy (AEM) and electron energy loss spectroscopy (EELS). The XRD showed the presence of two populations of micas: pure K micas with d001 = 9.98 Å and ammonium-bearing micas with larger d001 values (10.08 Å and 10.05 Å). The latter values indicate NH4 contents between 13 and 29% in the interlayer, which was confirmed by IR. Interstratifications of smectite and mica layers in the mica packets were not detected by XRD and TEM. Mica packets with sizes ranging from 100 to 250 Å show disordered polytypes and (001) lattice fringes that reflect the presence of K- and NH4-bearing layers (9.9–10.2 Å).The combination of AEM and EELS analyses on powdered and lamellar samples indicates that micas have typical dioctahedral compositions with highly variable K contents. This variation in K is consistent with the presence of K and NH4 in the interlayers, even though the NH4 and K are not distributed homogeneously; rather they are segregated in nm-sized domains in the mica interlayer.


1995 ◽  
Vol 1 (4) ◽  
pp. 143-149 ◽  
Author(s):  
J.C. Bennett ◽  
R.F. Egerton

Improvements in instrumentation for energy-dispersive X-ray microanalysis (EDX) and electron energy-loss spectroscopy (EELS) have underlined the need for suitable standards for measuring performance. We report the results from several laboratories that were supplied with a test specimen consisting of a thin film of nickel oxide supported on a molybdenum grid. The Ni-Kα/Mo-Kα count ratio was used as an indication of number of stray electrons and/or X-rays in the TEM column; the Ni-Kα peak/background ratio provided a measure of the total background in the EDX spectrum, including bremsstrahlung contributions and the effect of detector electronics. By providing values typical of current instrumentation, the results illustrate how the test specimen can be used to evaluate TEM/EDX systems prior to purchase, during installation, and (periodically) during operation. The NiO films were also used to test EELS acquisition and quantification procedures: measured Ni/O elemental ratios were all within 10% of stoichiometry.


2003 ◽  
Vol 788 ◽  
Author(s):  
Vladimir P. Oleshko ◽  
James M. Howe ◽  
Satyajit Shukla ◽  
Sudipta Seal

ABSTRACTThe mechanisms underlying stabilization of the metastable tetragonal (t)-phase in sol-gel derived, nanocrystalline ZrO2 were studied by high-resolution analytical electron microscopy, utilizing parallel electron-energy loss (PEEL) and energy-dispersive X-ray spectroscopies. The powders were synthesized by hydrolysis of Zr (IV) n-propoxide at ratios of molar concentration of water to Zr n-propoxide, R=5 and 60, respectively, followed by calcination at 400°C. Dense particles of the as-precipitated ZrO2 (R=5) revealed 4–11 nm-sized nanocrystals embedded in the amorphous matrix that may serve as nuclei for the t-phase during calcination. The calcined particles consist of 10–100 nm–sized t-crystals. For as-precipitated ZrO2 (R=60), week aggregates (50–100 nm) of largely amorphous 4–20 nm-sized particles after calcination yield a mixture of t-and monoclinic (m-) nanocrystals. PEELS fingerprints of the band structure with the intensity threshold matching the expected position of a direct bandgap at 4–5 eV allow to differentiate between the amorphous and nanocrystalline ZrO2. Stabilization of t-phase (R=5) with sizes up to 16 times larger than reported earlier is likely due to strain-induced confinement from surrounding growing grains, which suppress the volume expansion associated with the martensitic t-m transformation. For R=60, loose nanoparticle agglomerates cannot suppress the transformation. In this case, the t-phase may be partially stabilized due to a crystal size effect and /or to the presence of m-phase.


1990 ◽  
Vol 1 (5-6) ◽  
pp. 443-454 ◽  
Author(s):  
Danièle Bouchet ◽  
Christian Colliex ◽  
Parmjit Flora ◽  
Ondrej Krivanek ◽  
Claudie Mory ◽  
...  

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