Microspectroscopic soft X-ray analysis of keratin based biofibers

Scanning soft X-ray transmission microspectroscopy (STXM) and transmission electron microscopy (TEM) have been employed for a high-resolution morphological and chemical analysis of hair fibers from human, sheep and alpaca. STXM allows optimum contrast imaging of the main hair building blocks due to tuneable photon energy. Chemical similarities and deviations for the human hair building blocks as well as for the three investigated species are discussed on the basis of the local near-edge X-ray absorption fine structure (NEXAFS). The spectra of melanosomes corroborate the state-of-the-art model for the chemical structure of eumelanin. Complementary TEM micrographs reveal the occurrence of cortex sectioning in alpaca hair to some extent. A spectroscopic analysis for human hair cortex indicates low mass loss upon soft X-ray irradiation, but transformation of chemical species with decreasing amount of peptide bonds and increasing NEXAFS signal for unsaturated carbon–carbon bonds.     

A scanning transmission X‐ray microscope at the Pohang Light Source

A scanning transmission X‐ray microscope is operational at the 10A beamline at the Pohang Light Source. The 10A beamline provides soft X‐rays in the photon energy range 100–2000 eV using an elliptically polarized undulator. The practically usable photon energy range of the scanning transmission X‐ray microscopy (STXM) setup is from ～150 to ～1600 eV. With a zone plate of 25 nm outermost zone width, the diffraction‐limited space resolution, ～30 nm, is achieved in the photon energy range up to ～850 eV. In transmission mode for thin samples, STXM provides the element, chemical state and magnetic moment specific distributions, based on absorption spectroscopy. A soft X‐ray fluorescence measurement setup has been implemented in order to provide the elemental distribution of thicker samples as well as chemical state information with a space resolution of ～50 nm. A ptychography setup has been implemented in order to improve the space resolution down to 10 nm. Hardware setups and application activities of the STXM are presented.     

SSRL Workshop on STXM and X-ray Nanoprobe Capabilities and Needs in the Environmental,Geological, and Biomedical Sciences

Scanning transmission X-ray microscopy (STXM) has emerged as an important technique for chemical imaging and spectromicroscopy on the <100nm spatial scale in the environmental, geological, and biomedical sciences. Much has transpired technologically and scientifically in the 20-plus year interval that zone-plate STXM technology has been in development. Yet STXM/nanoprobe facilities are few in number, beam time remains exceedingly tight, and numerous scientific, technical, and infrastructure challenges continue to present significant barriers to the widespread use of these techniques in these three areas of science.     

Humidity dependence of tribocharging of electrophotographic carriers coated with poly(vinylidene fluoride)-poly(methyl methacrylate) blends

In this study, the effect of humidity on the work function of ferrite carrier particles coated with blends of poly(vinylidene fluoride) and poly(methyl methacrylate) was investigated. Charging measurements made as a function of humidity using toner surface treated with hydrophobic and hydrophilic silica were analyzed using an extension of the surface state model of tribocharging. The carrier work function is a linear function of the ratio of poly(vinylidene fluoride) and poly(methyl methacrylate) in the carrier coating. In contrast to the work function of the surface treated toners used, the carrier work function is independent of humidity. The density of states of the charging sites on the carrier is large enough that the term containing it is much less than 1.0. Thus, unlike the toner, the carrier is in the so-called high density of states limit.     

X-ray and electron microscopy of actinide materials

Actinide materials demonstrate a wide variety of interesting physical properties in both bulk and nanoscale form. To better understand these materials, a broad array of microscopy techniques have been employed, including transmission electron microscopy (TEM), electron energy-loss spectroscopy (EELS), energy dispersive X-ray spectroscopy (EDXS), high-angle annular dark-field imaging (HAADF), scanning electron microscopy (SEM), wavelength dispersive X-ray spectroscopy (WDXS), electron back scattered diffraction (EBSD), scanning tunneling microscopy (STM), atomic force microscopy (AFM), and scanning transmission X-ray microscopy (STXM). Here these techniques will be reviewed, highlighting advances made in the physics, materials science, chemistry, and biology of actinide materials through microscopy. Construction of a spin-polarized TEM will be discussed, considering its potential for examining the nanoscale magnetic structure of actinides as well as broader materials and devices, such as those for computational magnetic memory.     

Development of In-Situ/Operando Sample Cells for Soft X-ray Transmission Spectromicroscopy at UVSOR-III Synchrotron

In-situ/operando techniques have been developed for spectromicroscopic studies of heavy elements using hard X-rays with high transmittance in samples and long focal length of optical elements (i.e., long working distance) at photon energies >4 keV. On the other hand, in-situ measurements in the soft X-ray region for spectromicroscopic studies of light elements at deep inner shells and heavy elements at shallow inner shells face significant technical challenges due to several difficulties, including low transmittance and short focal lengths of optical elements. Scanning transmission X-ray microscopy (STXM) in the soft X-ray region is a promising technique for in-situ observation in comparison with other microscopic techniques using electrons and ions, considering its characteristics, such as high resolving power in energy and in space, low radiation damage, and two-dimensional (and three-dimensional) chemical state analysis using near-edge X-ray absorption fine structure.     

Preparation and Characterization of Acrylic Resin/Hindered Phenolic Antioxidant (AO80)-modified Carbon Black Nanocomposite

To improve the dispersion stability of carbon black (CB) in an acrylic resin coating, a hindered phenolic antioxidant (AO80) was chosen to modify the CB by a solid state method based on the blending of CB and AO80 in an internal mixer. The modified CB (m-CB) was directly introduced into the acrylic resin with 50% solid content in butyl acetate by ball milling without any other treatment. That the majority of the m-CB particles were nanosized in ethanol was proven by a particle size analyzer. Transmission electron microscopy (TEM) and field emission scanning electron microscope (FESEM) micrographs indicated that the m-CB particles were also dispersed in the acrylic resin as nanoscale particles. Compared with the unmodified CB, the modification of CB can decrease the viscosity of the acrylic resin/m-CB nanocomposite and improve its flow property. The adhesion and gloss of the acrylic resin/m-CB nanocomposite were also improved. More importantly, the UV shielding and stability of the acrylic resin/m-CB nanocomposite were enhanced.     

红外显微观测被俘获吸光性颗粒

光镊技术被广泛应用在俘获和操纵微纳米尺寸颗粒, 目前被研究学者普遍接受的俘获吸光性颗粒的机理为光泳力. 本文实现了对空气中被俘获的吸光性颗粒的红外显微观测. 当激光器功率为1.0 W时, 成功观测到被俘获墨粉颗粒(直径约7 μm)和甲苯胺蓝颗粒(直径约为1–20 μm)的温升约为14 K, 为光泳力理论提供了强有力的证据. 另外, 首次用可见光显微镜和红外显微镜同时观测到被俘获颗粒的周期振荡现象, 并分析了振荡现象的产生机理. 关键词： 光镊 光俘获 红外显微     

High-resolution electron microscopy for heterogeneous catalysis research

Heterogeneous catalysts are the most important catalysts in industrial reactions. Nanocatalysts, with size ranging from hundreds of nanometers to the atomic scale, possess activities that are closely connected to their structural characteristics such as particle size, surface morphology, and three-dimensional topography. Recently, the development of advanced analytical transmission electron microscopy(TEM) techniques, especially quantitative high-angle annular darkfield(HAADF) imaging and high-energy resolution spectroscopy analysis in scanning transmission electron microscopy(STEM) at the atomic scale, strengthens the power of(S)TEM in analyzing the structural/chemical information of heterogeneous catalysts. Three-dimensional reconstruction from two-dimensional projected images and the real-time recording of structural evolution during catalytic reactions using in-situ(S)TEM methods further broaden the scope of(S)TEM observation. The atomic-scale structural information obtained from high-resolution(S)TEM has proven to be of significance for better understanding and designing of new catalysts with enhanced performance.     

Soft X-ray spectromicroscopy of phase-change microcapsules

A synchrotron-based scanning transmission X-ray microscope (STXM) is used to investigate Micronal^® phase-change microcapsules. Prolonged X-ray illumination of the specimen leads to the breaking of the microcapsules’ protective polymer shell and a partial separation of the core–shell species occurs. The paraffin wax and acrylic polymer components are characterized by carbon K-edge near X-ray edge absorption fine structure (NEXAFS) spectroscopy and components distribution mapping of the beam-damaged specimen is performed.     

Humic acid metal cation interaction studied by spectromicroscopy techniques in combination with quantum chemical calculations

Humic acids (HA) have a high binding capacity towards traces of toxic metal cations, thus affecting their transport in aquatic systems. Eu(III)–HA aggregates are studied by synchrotron‐based scanning transmission X‐ray microscopy (STXM) at the carbon K‐edge and laser scanning luminescence microscopy (LSLM) at the ⁵D₀→⁷F_1,2 fluorescence emission lines. Both methods provide the necessary spatial resolution in the sub‐micrometre range to resolve characteristic aggregate morphologies: optically dense zones embedded in a matrix of less dense material in STXM images correspond to areas with increased Eu(III) luminescence yield in the LSLM micrographs. In the C 1s‐NEXAFS of metal‐loaded polyacrylic acid (PAA), used as a HA model compound, a distinct complexation effect is identified. This effect is similar to trends observed in the dense fraction of HA/metal cation aggregates. The strongest complexation effect is observed for the Zr(IV)–HA/PAA system. This effect is confirmed by quantum chemical calculations performed at the ab initio level for model complexes with different metal centres and complex geometries. Without the high spatial resolution of STXM and LSLM and without the combination of molecular modelling with experimental results, the different zones indicating a `pseudo'‐phase separation into strong complexing domains and weaker complexing domains of HA would never have been identified. This type of strategy can be used to study metal interaction with other organic material.     

NEXAFS microscopy studies of the association of hydrocarbon thin films with fine clay particles

The nature of organic species associated with clay minerals plays a significant role in several processes, from hydrocarbon recovery in oil sands to contaminated soil remediation and water treatment. In this work, we address the use of scanning transmission X-ray microscopy (STXM) in conjunction with near edge X-ray absorption fine structure (NEXAFS) spectroscopy to study the microstructure and chemistry of organic–clay associations in situ. A model system based on methylene blue and illite is used to explore the sensitivity of NEXAFS microscopy to these interactions, and to identify and resolve experimental challenges in these measurements. We find that sample contamination from X-ray induced photodeposition is a significant problem in STXM microscopy, but also that this problem can be substantially reduced with a liquid nitrogen cooled anticontaminator. With appropriate sample preparation and experimental procedures, we find that STXM microscopy is sensitive to thin carbon adsorbates on clay surfaces.     

Radiation damage in soft X-ray microscopy

The rates of chemical transformation by radiation damage of polystyrene (PS), poly(methyl methacrylate) (PMMA), and fibrinogen (Fg) in a X-ray photoemission electron microscope (X-PEEM) and in a scanning transmission X-ray microscope (STXM) have been measured quantitatively using synchrotron radiation. As part of the method of dose evaluation in X-PEEM, the characteristic (1/e) sampling depth of X-PEEM for polystyrene in the C 1s region was measured to be 4 ± 1 nm. Critical doses for chemical change as monitored by changes in the X-ray absorption spectra are 80 (12), 280 (40) and 1230 (180) MGy (1 MGy = 6.242*ρ eV/nm³, where ρ is the polymer density in g/cm³) at 300 eV photon energy for PMMA, Fg and PS, respectively. The critical dose for each material is comparable in X-PEEM and STXM and the values cited are thus the mean of the values determined by X-PEEM and STXM. C 1s, N 1s and O 1s spectroscopy of the damaged materials is used to gain insight into the chemical changes that soft X-rays induce in these materials.     

可见-近红外高光谱图像技术快速鉴别激光打印墨粉

为了使用快速、无损的方法区分激光打印文件使用的墨粉种类,利用高光谱成像技术结合化学计量法对6种激光打印墨粉的光谱数据进行建模和种类鉴别的研究。利用可见-近红外高光谱成像仪采集400~1 000 nm波段内的光谱数据,采用Savitzky Golay平滑、标准化、多元散射校正和标准正态变量变换4种方法分别对光谱数据进行预处理,而后分别建立随机森林(RF)、K最近邻(KNN)、支持向量机(SVM)、偏最小二乘判别分析(PLS-DA)和簇类独立软模式(SIMCA)模型,进而实现激光打印墨粉的种类鉴别。利用准确率、拒识率和误识率3个指标作为模型评价标准。实验结果显示,SVM和PLS-DA模型的效果最佳,准确率为100%,拒识率和误识率为0。基于可见-近红外高光谱成像技术可以实现激光打印墨粉的快速种类鉴别。     

Mössbauer effect and TEM in mineralogy

Mössbauer effect (ME) provides useful information on oxidation state, co-ordination number, co-ordination state, site occupancies, and magnetic properties of Fe-bearing phases. The information gained by ME together with the information provided by other conventional techniques is used to extract temperature, pressure, and kinetics of rockforming processes. Nevertheless, ME requires that the phases studied are homogeneous over an extremely large volume and that Fe is a major component of the system. Transmission electron microscopy (TEM), on the other hand, provides similar information over a very small volume for a system of any component. However, present TEM spectrometers do not provide sufficient resolution to detect the mixed oxidation state. A complete characterisation of phases in rocks requires, therefore, that conventional techniques be combined with TEM.     

UHV-HREM and diffraction of surfaces

Characterization of the structure of surfaces is very important in order to develop a fundamental understanding of the electronic, mechanical and chemical properties of a material. While transmission electron microscopy imaging (TEM) and diffraction (TED) techniques are capable of providing surface structural information at the atomic level, such data would be suspect if obtained under conventional vacuum conditions (10^-6–10^-8 Torr). Ultrahigh vacuum (UHV) conditions are imperative during both preparation and observation of clean surfaces/interfaces. Conventional TEM techniques are very powerful for UHV-TEM investigations; however, the marriage of surface science and conventional TEM to yield an UHV-TEM is a complex task. These complexities and some of the results obtained using UHV-TEM and UHV-TED techniques for surfaces i.e. solid-vacuum interfaces will be illustrated.     

Growth process and mechanism of a multi-walled carbon nanotube nest deposited on a silicon nanoporous pillar array

A large scale nest array of multi-walled carbon nanotubes (NACNTs) was grown on silicon nanoporous pillar array (Si-NPA) by thermal chemical vapor deposition. Through observing its macro/micromorphology and structure, ascertaining the catalyst component and its locations at different growth time by hiring field emission scanning electron microscopy, transmission electron microscopy (TEM), high-resolution TEM, and selected area electron diffraction, the growth process was deduced. Its thermal properties were also investigated by using a thermogravimetric analyzer. Our experiments demonstrated that the CNTs growth by means of root-growth mechanism at the initial growth stage, then a continuous growth process with its tip open is suggested, finally, a schematic growth model of NACNT/Si-NPA was presented.     

Scanning transmission X‐ray microscopy probe for in situ mechanism study of graphene‐oxide‐based resistive random access memory

Here, an in situ probe for scanning transmission X‐ray microscopy (STXM) has been developed and applied to the study of the bipolar resistive switching (BRS) mechanism in an Al/graphene oxide (GO)/Al resistive random access memory (RRAM) device. To perform in situ STXM studies at the C K‐ and O K‐edges, both the RRAM junctions and the I₀ junction were fabricated on a single Si₃N₄ membrane to obtain local XANES spectra at these absorption edges with more delicate I₀ normalization. Using this probe combined with the synchrotron‐based STXM technique, it was possible to observe unique chemical changes involved in the BRS process of the Al/GO/Al RRAM device. Reversible oxidation and reduction of GO induced by the externally applied bias voltages were observed at the O K‐edge XANES feature located at 538.2 eV, which strongly supported the oxygen ion drift model that was recently proposed from ex situ transmission electron microscope studies.