Quantitative statistical analysis, optimization and noise reduction of atomic resolved electron energy loss spectrum images

In this work we investigate methods of statistical processing and background fitting of atomic resolution electron energy loss spectrum image (SI) data. Application of principal component analysis to SI data has been analyzed in terms of the spectral signal-to-noise ratio (SNR) and was found to improve both the spectral SNR and its standard deviation over the SI, though only the latter was found to improve significantly and consistently across all data sets analyzed. The influence of the number of principal components used in the reconstructed data set on the SNR and resultant elemental maps has been analyzed and the experimental results are compared to theoretical calculations.     

Toward automatic evaluation of defect detectability in infrared images of composites and honeycomb structures

Non-destructive testing (NDT) refers to inspection methods employed to assess a material specimen without impairing its future usefulness. An important type of these methods is infrared (IR) for NDT (IRNDT), which employs the heat emitted by bodies/objects to rapidly and noninvasively inspect wide surfaces and to find specific defects such as delaminations, cracks, voids, and discontinuities in materials. Current advancements in sensor technology for IRNDT generate great amounts of image sequences. These data require further processing to determine the integrity of objects. Processing techniques for IRNDT data implicitly looks for defect visibility enhancement. Commonly, IRNDT community employs signal to noise ratio (SNR) to measure defect visibility. Nonetheless, current applications of SNR are local, thereby overseeing spatial information, and depend on a-priori knowledge of defect’s location. In this paper, we present a general framework to assess defect detectability based on SNR maps derived from processed IR images. The joint use of image segmentation procedures along with algorithms for filling regions of interest (ROI) estimates a reference background to compute SNR maps. Our main contributions are: (i) a method to compute SNR maps that takes into account spatial variation and are independent of a-priori knowledge of defect location in the sample, (ii) spatial background analysis in processed images, and (iii) semi-automatic calculation of segmentation algorithm parameters. We test our approach in carbon fiber and honeycomb samples with complex geometries and defects with different sizes and depths.     

光谱相似性制图(SSM)用于成像光谱图像处理的研究

将光谱相似性制图(SSM)用于成像光谱图像的处理,通过对真假叶片以及混合在一起的藻类的成像光谱图像的SSM处理,证明了SSM方法在甄别光学伪装和藻类鉴别及计数两方面具有很高的有效性,从而证明了SSM方法用于处理成像光谱图像上的优越性。同时,该方法还可用于其他方面成像光谱数据的处理,对扩展成像光谱的应用范围具有重要的意义。     

Valence state mapping of cobalt and manganese using near-edge fine structures

The properties of transition metal oxides are related to the presence of elements with mixed valences. The spectroscopy analysis of the valence states is feasible experimentally, but a spatial mapping of valence states of transition metal elements is a challenge to existing microscopy techniques. In this paper, with the use of valence state information provided by the white lines and near-edge fine structures observed using the electron energy-loss spectroscopy (EELS) in a transmission electron microscope (TEM), a novel experimental approach is demonstrated to map the valence state distributions of Mn and Co using the ratio of white lines in the energy-filtered TEM. The valence state map is almost independent of specimen thickness in the thickness range adequate for quantitative EELS microanalysis. An optimum spatial resolution of approximately 2 nm has been achieved for a two-phase Co oxides.     

Raman spectral detection and assessment of thin organic layers on metal substrates: systematic approach from substrate preparation to map evaluation

Raman spectral mapping of thin organic layers on metal substrates is an important analytical tool to characterize these systems. Surface‐enhanced Raman scattering (SERS) spectroscopy is a suitable technique for analysis of such layers. Development of new SERS‐active surfaces with repeatable properties and without disturbing adsorbed species is one of the important steps for reliable assessment of the thin organic layers designed. This paper presents new SERS‐active substrates suitable for both macro (millimeter scale) and microscopic (micrometer scale) spectral mapping, which allow easy regeneration for repetitive experiments. Both gold and silver SERS‐active surfaces prepared by electrochemical deposition were tested. Complete map data evaluation utilities were newly designed and applied, using both ordinarily used and newly modified mathematical algorithms and chemometric procedures. Evaluation of data starts with finite impulse response (FIR) filtration algorithms to eliminate spectral interferences in individual spectra. Principal component analysis was used for transformation of multidimensional data to understandable dimensions. Various mathematical/statistical techniques were then used for data visualization as spectral maps and for similarity testing. Copyright © 2008 John Wiley & Sons, Ltd.     

Investigating the role of microbes in mineral weathering: Nanometre-scale characterisation of the cell–mineral interface using FIB and TEM

Focused ion beam (FIB) sample preparation in combination with subsequent transmission electron microscopy (TEM) analysis are powerful tools for nanometre-scale examination of the cell–mineral interface in bio-geological samples. In this study, we used FIB-TEM to investigate the interaction between a cyanobacterium (Hassallia byssoidea) and a common sheet silicate mineral (biotite) following a laboratory-based bioweathering, incubation experiment. We discuss the FIB preparation of cross-sections of the cell mineral interface for TEM investigation. We also establish an electron fluence threshold (at 200 keV) in biotite for the transition from scanning (S)TEM electron beam induced contamination build up on the surface of biotite thin sections to mass loss, or hole-drilling within the sections. Working below this threshold fluence nanometre-scale structural and elemental information has been obtained from biotite directly underneath cyanobacterial cells incubated on the biotite for 3 months. No physical alteration of the biotite was detected by TEM imaging and diffraction with little or no elemental alteration detected by STEM–energy dispersive X-ray (EDX) elemental line-scanning or by energy filtered TEM (EF-TEM) jump ratio elemental mapping. As such we present evidence that the cyanobacterial strain of H. byssoidea did not cause any measurable alteration of biotite, within the resolution limits of the analysis techniques used, after 3 months of incubation on its surface.     

Monte Carlo modeling of gold nanoparticles detection limits of benchtop three-dimensional L- and K-shell X-ray fluorescence mapping systems

This study aims to investigate the detection limits of gold nanoparticle (GNP) concentrations by Monte Carlo (MC) modeling of benchtop polychromatic K- and L-shell X-ray fluorescence mapping system. In Monte Carlo N-Particle (MCNP version 6.1) simulations, a 0.25-cm-diameter cylinder containing GNPs of various concentrations (i.e., 0.005%–1.0% gold by weight, wt%) was assumed to be located at the center of a cylindrical water phantom of various diameters (1.0–10 cm). Two different sets of incident pencil beam X-rays and detectors were modeled to stimulate X-ray fluorescence (XRF) of GNPs: (1) 62 kVp and silicon drift detector for L-XRF, (2) 105 kVp and cadmium telluride detector for K-XRF. The detection limits were calculated for given radiation doses to the center of phantom (375–1500 mGy). When the diameter of the phantom was 1 cm, the detection limits for L-XRF and K-XRF were an order of 0.001 wt% and of 0.01 wt%, respectively. The detectability of K-XRF turned out to be superior to that of L-XRF for the phantoms greater than or equal to 3 cm in diameter. The MC results will provide a guide for developing an optimal benchtop XRF imaging system for in vivo preclinical imaging, depending on the sizes of GNP-loaded objects, GNP concentrations, and radiation doses.     

Elemental quantitation of natural organic matter by CPMAS 13C NMR spectroscopy

Cross-polarized magic-angle-spinning NMR (CPMAS-NMR) techniques are assumed to be only semi-quantitative in the assessment of carbon distribution in humic substances or natural organic matter, due to a number of interferences such as spinning side bands (SSB) in spectra, paramagnetic species in samples, and low or remote protonation of aromatic carbons. Fast rotor spin rates or direct polarization NMR techniques are normally applied to improve quantitative signal detectability. Variable contact time pulse sequences were used here to obtain CPMAS-NMR spectra of organic compounds of known structure and different humic substances. Integration of spectral areas, previously subtracted of SSB, and relative stoichiometric factors were used for mathematical elaboration to calculate the elemental content in samples. These values did not significantly differ from those obtained by direct determination of elemental content with quantitative elemental analysis. Our results showed that the carbon observed CPMAS-NMR provides a quantitative representation of the whole carbon content in humic substances.     

Fish otolith trace element maps: new approaches with synchrotron microbeam x‐ray fluorescence

Otoliths, the carbonate earstones of fishes, take up minor and trace amounts of elements as they accrete through a fish's life. We apply synchrotron microbeam x‐ray fluorescence methods to establish a breakthrough in high‐resolution, simultaneous area mapping of multiple trace elements in otoliths, with spatial resolution down to 20 µm and trace element detection down into the part per million range for multiple elements. Concentration maps of Ca, Sr, Zn and, for the first time, Ba, Mn, and Se are obtained simultaneously. Combinations of these elemental maps provide new insights into the environmental history of fishes and their lifetime movements, illustrated by several case studies. This method helps pave the way toward improved spatial analysis of otolith microchemistry. Copyright © 2007 John Wiley & Sons, Ltd.     

Synchrotron-based X-ray fluorescence,imaging and elemental mapping from biological samples

The present study utilized the new hard X-ray microspectroscopy beamline facility, X27A, available at NSLS, BNL, USA, for elemental mapping. This facility provided the primary beam in a small spot of the order of ∼10 μm, for focussing. With this spatial resolution and high flux throughput, the synchrotron-based X-ray fluorescent intensities for Mn, Fe, Zn, Cr, Ti and Cu were measured using a liquid-nitrogen-cooled 13-element energy-dispersive high-purity germanium detector. The sample is scanned in a ‘step-and-repeat’ mode for fast elemental mapping measurements and generated elemental maps at 8, 10 and 12 keV, from a small animal shell (snail). The accumulated trace elements, from these biological samples, in small areas have been identified. Analysis of the small areas will be better suited to establish the physiology of metals in specific structures like small animal shell and the distribution of other elements.     

Image quality of microns-thick specimens in the ultra-high voltage electron microscope

Image quality of MeV transmission electrons is an important factor for both observation and electron tomography of microns-thick specimens with the high voltage electron microscope (HVEM) and the ultra-HVEM. In this work, we have investigated image quality of a tilted thick specimen by experiment and analysis. In a 3 MV ultra-HVEM, we obtained transmission electron images in amplitude contrast of 100 nm gold particles on the top surface of a tilted 5 μm thick amorphous epoxy-resin film. From line profiles of the images, we then measured and evaluated image blurring, contrast, and the signal-to-noise ratio (SNR) under different effective thicknesses of the tilted specimen and accelerating voltages of electrons. The variation of imaging blurring was consistent with the analysis based on multiple elastic scattering. When the effective thickness almost tripled, image blurring increased from ～3 to ～20 nm at the accelerating voltage of 3 MV. For the increase of accelerating voltage from 1 to 3 MV in the condition of the 14.6 μm effective thickness, due to the reduction of multiple scattering effects, image blurring decreased from ～54 to ～20 nm, and image contrast and SNR were both obviously enhanced by a factor of ～3 to preferable values. The specimen thickness was shown to influence image quality more than the accelerating voltage. Moreover, improvement on image quality of thick specimens due to increasing the accelerating voltage would become less when it was further increased from 2 to 3 MV in this work.     

Using transmission Kikuchi diffraction to study intergranular stress corrosion cracking in type 316 stainless steels

Transmission Kikuchi diffraction (TKD), also known as transmission-electron backscatter diffraction (t-EBSD) is a novel method for orientation mapping of electron transparent transmission electron microscopy specimen in the scanning electron microscope and has been utilized for stress corrosion cracking characterization of type 316 stainless steels. The main advantage of TKD is a significantly higher spatial resolution compared to the conventional EBSD due to the smaller interaction volume of the incident beam with the specimen.Two 316 stainless steel specimen, tested for stress corrosion cracking in hydrogenated and oxygenated pressurized water reactor chemistry, were characterized via TKD. The results include inverse pole figure (IPFZ) maps, image quality maps and misorientation maps, all acquired in very short time (<60 min) and with remarkable spatial resolution (up to 5 nm step size possible). They have been used in order to determine the location of the open crack with respect to the grain boundary, deformation bands, twinning and slip. Furthermore, TKD has been used to measure the grain boundary misorientation and establish a gauge for quantifying plastic deformation at the crack tip and other regions in the surrounding matrix. Both grain boundary migration and slip transfer have been detected as well.     

窄带傅里叶变换光谱仪中平稳高斯噪声的理论分析

在本文所研究的空间调制型傅里叶变换光谱仪中, 在窄的光谱带宽内进行探测可以有效提高光谱的分辨率. 为了研究光源辐射噪声对系统的影响, 本文将辐射噪声归纳为一种高斯窄带的平稳随机过程, 利用线性系统分析方法, 根据统计学原理推导了辐射噪声作为随机变量通过干涉系统前后的输入信噪比与输出信噪比. 然后, 对于一个具有窄带矩形光谱的系统进行了计算仿真, 得出了信噪比增益随着光程差在不同自相关度和互相关度取值时的变化情况. 仿真结果表明, 不同光程差下的信噪比增益在相关度空间是一单调的平滑曲面, 增益极值始终沿着相关度圆的半径和周线移动, 并且经过一个光程差又回到初始的位置. 根据对信噪比增益的分析, 可以将噪声的相关度取值控制在某一范围之内, 并作为系统光源设计与测试的依据.     

Impact of graphene nanoplatelet concentration and film thickness on vapor detection for polymer based chemiresistive sensors

Chemiresistive gas sensors utilizing graphene nanoplatelet (GNP)-polymer film coated electrodes have great promise for electronic nose applications. In this study GNP-polycaprolactone (PCL) based sensors fabricated using airbrush deposition are exposed to ethanol as an example target analyte to investigate ideal parameters for sensing performance maximization. The ratio of GNP to PCL was investigated from 3 to 21 wt% with sensing response maximized at 15 wt% and signal to noise ratio (SNR) maximized at 18 wt%. The effect of average coating thickness on the sensing performance was investigated by depositing 50–250 μL of 18 wt% GNP solution (852–2030 nm). The response was maximized at 150 μL (1370 nm) and the SNR was maximized at 200 μL (1680 nm). The results are consistent with previous studies of vapor sensors that employ carbon black-polymer films as sensing materials. The fabricated devices were robust and repeatable with respect to initial resistance, depth, roughness, sensor response, and SNR. Overall the results elucidate important parameters for fabrication and development of GNP-polymer gas sensors for detection and discrimination of target analytes with electronic nose systems.     

A tilting procedure to enhance compositional contrast and reduce residual diffraction contrast in energy-filtered TEM imaging of planar interfaces

This paper systematically demonstrates that energy-filtered transmission electron microscope (EFTEM) images of a planar interface between two single crystals have increased compositional contrast and decreased residual diffraction contrast when the sample is oriented so that the electron beam is parallel to the interface, but not directly on a zone axis. This off-axis orientation reduces diffraction contrast in the unfiltered (and zero-loss) image, which in turn, reduces residual diffraction contrast in single energy-filtered TEM (EFTEM) images, thickness maps, jump-ratio images, and elemental maps. Most importantly, this procedure produces EFTEM images that are more directly interpretable and, in most cases, possess superior spatial resolution compared to EFTEM images acquired directly on a zone axis.     

Evaluation of plasma produced by first and second harmonic nano-second laser for enhancing the capability of laser induced breakdown spectroscopy technique

Evaluation of plasmas produced and optimized for improving the capability of convenential laser induced breakdown spectroscopy (LIBS) for analytical purposes of solid samples is the main goal of the present work. The plasma produced in the present study was generated by focusing a single nano-second Nd:YAG laser at the fundamental wavelength of 1064 nm and at the second harmonic wavelength of 532 nm on an Al target in air at atmospheric pressure. The emission spectrum was recorded time resolved over the whole UV-NIR (200–1000 nm) spectral range. This work describes an extension of previously reported studies and focuses now on the determination of the plasma parameters at the optimum condition – highest signal-to-noise ratio (SNR) and minimum limit of detection (LOD) — of the LIBS technique, which is now widely applied to the elemental analysis of materials in atmospheric air. Parameters of the produced plasma in the time interval from 0 to 10 μs are determined for to further understanding the LIBS plasma dynamics. O I and Mn I spectral lines are used in the present work as thermometric lines for the determination of the plasma temperature based on Boltzmann plots. Stark broadening of lines yields the electron density. The widths of the H _α -line at 656.27 nm, of the O I line at 844.65 nm, of Al II lines at 281.65 nm and 466.30 nm and of the Si I line at 288.15 nm has been utilized for that. The plasma temperature ranged from 0.73 eV to around 1 eV for the different laser energies with both laser wavelengths for the optimized plasma used for LIBS analysis. This temperature is very close to that well known for the other spectrochemical analytical techniques or in excitation sources such as inductively coupled plasma-optical emission spectrometry (ICP-OES).     

A device for X‐Ray elemental mapping using annular radioisotope source

An energy‐dispersive system is described for elemental mapping by X‐ray fluorescence spectrometry. The present study describes the design of an X‐ray fluorescence spectrometer and presents its performance in elemental mapping applications. The spectrometer is based on a new ring‐shaped collimator with a pinhole in the center of it and a ring‐shaped Am‐241 isotope mounted in the collimator as a source for excitation of X‐ray fluorescence. The photons were detected by high‐resolution Si (Li) detector coupled to a multi‐channel analyser and cooled by liquid nitrogen. In this study, we used two samples; one of them was made from pure elemental powders, and the second one was a piece of a stone and three types of maps were plotted. In the maps type one, the areas of the elements were shown with a single color. These maps only show the location of the elements in the sample. In the maps type two, the area of each element was shown with different colors because of the count (intensity) related to the area. In the third type of the maps for each element, depending on the elements' position on the sample, the counts were plotted in three dimensions. The areas with higher intensity have greater height, and areas with lower intensity have lower altitude. These two last types of maps provide information about the homogeneity or heterogeneity of the elemental distribution in the samples. The spectrometer can perform non‐destructive analyses of samples and objects in the air. Copyright © 2017 John Wiley & Sons, Ltd.     

Analytical solution to the Lipari-Szabo model based on the reduced spectral density approximation offers a novel protocol for extracting motional parameters.

An analytical solution to the Lipari-Szabo model is derived for isotropic overall tumbling. The parameters of the original Lipari-Szabo model, the order parameter S2 and the effective internal correlation time tau(e), are calculated from two values of the spectral density function. If additionally the spectral density value J(0) is known, the exchange contribution R(ex) term can also be determined. The overall tumbling time tau(c) must be determined in advance, for example, from T1/T2 ratios. The required spectral density values are obtained by reduced spectral density mapping from T1, T2, and NOE measurements. Our computer simulations show that the reduced spectral density mapping is a very good approximation in almost all cases in which the Lipari-Szabo model is applicable. The robustness of the analytical formula to experimental errors is also investigated by extensive computer simulations and is found to be similar to that of the fitting procedures. The derived formulas were applied to the experimental 15N relaxation data of ubiquitin. Our results agree well with the published parameter values of S2 and tau(e), which were obtained from standard fitting procedures. The analytical approach to extract parameters of molecular motions may be more robust than standard analyses and provides a safeguard against spurious fitting results, especially for determining the exchange contribution R(ex).     

Unsteady loading on an airfoil of arbitrary thickness

The unsteady loading on an airfoil of arbitrary thickness is evaluated by using the generalized form of Blasius theorem and a conformal mapping that maps the airfoil surface onto a circle. For a blade vortex interaction the results show that the time history of the unsteady loading is determined by the passage of the vortex relative to the leading edge singularity in the circle plane. The singularity lies inside the circle and moves to a smaller radius as the thickness is increased, causing the unsteady loading pulse to be smoothed. The effect of angle of attack is to move the stagnation point relative to the leading edge singularity and this significantly increases the unsteady lift if the vortex passes on the suction side of the airfoil. These characteristics are different for a step upwash gust, which is considered as a simplified model of a large scale turbulent gust. It is shown that the time history of the magnitude of the unsteady loading is almost completely unaltered by angle of attack for the step gust, but it's direction of action rotates forward by an angle equal to the angle of attack, extending an earlier result by Howe for a flat plate in a turbulent flow to airfoils of arbitrary thickness. However spectral analysis of the gust shows that the high frequency blade response is reduced as the thickness of the airfoil is increased.     

用智能波长校正的扫描式ICP光谱仪测定铬铁矿中六种元素成分

本文利用作者所在实研究室开发的扫描式ＩＣＰ光谱仪的智能波长校正装置取代传统的ＩＣＰ光谱仪的局部恒温系统，测定了铬铁矿及铬酸盐中的Ｃｒ，Ｓｉ，Ａｌ，Ｆｅ，Ｍｎ和Ｍｇ六种元素成分。测定结果与铬矿标样的鉴定值基本一致，测量的相对标准偏差（ＲＳＤ）为１．０％，智能波和工校正装置的波长校正结果与谱线峰值描迹结果的比较表明，该智能波长校正装置是有效的，具有省时，安全，结构简单的特点，有广泛的应用的前景。