Characterisation and analysis of micro-contaminants in industrial polymers

Analysis of very small particles can present problems. This paper describes the application of temperature programmed solid insertion probe mass spectrometry (TP-SIP-MS), scanning electron microscopy and SEM X-ray microanalysis to the identification of foreign particles present in an industrial product. The relative advantages and limitations of the techniques are discussed. It is shown that TP-SIP-MS is a powerful tool for such work and complements the use of more conventional microanalytical methods.     

Physico-chemical characterization of crystalline phases in fly ashes

Fuel oil combustion in power plants, domestic heating systems and diesel engines, causes the emission in the environment of particles with a typical structure and composition: the cenospheres.These particles are produced during the microdrop fuel oil combustion, when air and fuel are injected into the combustion chamber; they have a spheroidal morphology and a spongy structure.Cenospheres are constituted by an amorphous component rich in C, S, Si, Fe and Al; phases composed by microcrystals of sulphates, oxides and pure metallic elements or their alloys, are frequently present in the cenospheres.These crystalline phases are important from environmental and toxicological points of view both because they are composed of heavy metals, and because they can play an important role in heterogeneous catalysis.We started to study these crystalline phases by analytical electron microscopy techniques and electron energy loss spectrometry to define and characterise their structure and composition.     

Modeling of scattering on the residual gas in an electron diffraction experiment

The scattering on the residual gas in an electron diffraction chamber is modeled. A comparison with experimental data reveals that is this scattering that may make a major contribution to the extraneous signal inevitably present in the recorded diffraction pattern. Practical recommendations on the development of the electron diffraction apparatus design are given.     

Study of the formation of biodegradable polycaprolactone particles using solvent evaporation method

Poly(ε-caprolactone) (PCL), an aliphatic polyester paved the way in the formation of biodegradable and biocompatible polymer particles in tissue engineering and drug delivery applications. The factors affecting in the preparation of PCL particles such as influences of the concentration of PCL, molecular weight and concentration of poly(vinylpyrrolidone) (PVP) stabilizer, and the reaction time on the characteristics of PCL particles were investigated. In the fabrication of PCL particles, size, morphology and stability of the polymer particles were tailored by varying the type and concentration of the stabilizer to the polymer, reaction time and stirring speed of the reaction. Additionally, formation of particles was also related to the amount of PCL and PVP concentration. The PCL particles possessed a spherical shape with the size ranges of 5-20 micron and stability increases with higher concentration of PVP while coagulation observed when PCL particles prepared with the low concentration of PVP. The change in the morphology and sizes of the PCL particle at different reaction conditions were evaluated by scanning electron microscopy (SEM) analysis.     

Study of PVB aggregation process by electron microscopy

The structure of aggregates formed from poly(vinyl butyral) (PVB) in tetrahydrofuran (THF) was studied by transmission electron microscopy (TEM). We have found that the primary associated particles are nearly spherical and, as the association advances, the particles lengthen. Eventually aggregates branch to form a three-dimensional network. The bulk PVB was investigated by scanning electron microscopy (SEM). We have found that the bulk PVB grains are aggregates of the particles the shape and dimension of which are similar to those of the primary associated particles formed in PVB solution. © 1994 John Wiley & Sons. Inc.     

Local and surface analysis within an analytical electron microscope

Analytical transmission electron microscopes have the ability to display at very high spatial resolution both the structural information of solid specimens prepared as thin films and the spectroscopic information related either to electronic properties or to the elemental composition. An example of study, by electron energy loss spectroscopy, of small spherical silicon particles is given as an illustration of the performances of the technique.     

Nanoscopic Porous Iridium/Iridium Dioxide Superstructures (15 nm): Synthesis and Thermal Conversion by In Situ Transmission Electron Microscopy

Porous particle superstructures of about 15 nm diameter, consisting of ultrasmall nanoparticles of iridium and iridium dioxide, are prepared through the reduction of sodium hexachloridoiridate(+IV) with sodium citrate/sodium borohydride in water. The water-dispersible porous particles contain about 20 wt % poly(N-vinylpyrrolidone) (PVP), which was added for colloidal stabilization. High-resolution transmission electron microscopy confirms the presence of both iridium and iridium dioxide primary particles (1–2 nm) in each porous superstructure. The internal porosity (≈58 vol%) is demonstrated by electron tomography. In situ transmission electron microscopy up to 1000 °C under oxygen, nitrogen, argon/hydrogen (all at 1 bar), and vacuum shows that the porous particles undergo sintering and subsequent compaction upon heating, a process that starts at around 250 °C and is completed at around 800 °C. Finally, well-crystalline iridium dioxide is obtained under all four environments. The catalytic activity of the as-prepared porous superstructures in electrochemical water splitting (oxygen evolution reaction; OER) is reduced considerably upon heating owing to sintering of the pores and loss of internal surface area.     

Quantitative microbeam analysis of particles

The ability to characterize individual microscopic particles is important in many areas of science and technology. A variety of microbeam analysis methods are capable of providing information on microscopic particles. With electron probe X-ray microanalysis quantitative analysis is possible under well controlled conditions. Using computer controlled electron microscopes it is feasible to characterize a large number of individual particles. The application of this technique requires the use of multivariate data analysis procedures for the interpretation of the large amount of data obtained.     

Cryogenic Correlative Single-Particle Photoluminescence Spectroscopy and Electron Tomography for Investigation of Nanomaterials

Cryogenic single-particle photoluminescence (PL) spectroscopy has been used with great success to directly observe the heterogeneous photophysical states present in a population of luminescent particles. Cryogenic electron tomography provides complementary nanometer scale structural information to PL spectroscopy, but the two techniques have not been correlated due to technical challenges. Here, we present a method for correlating single-particle information from these two powerful microscopy modalities. We simultaneously observe PL brightness, emission spectrum, and in-plane excitation dipole orientation of CdSSe/ZnS quantum dots suspended in vitreous ice. Stable and fluctuating emitters were observed, as well as a surprising splitting of the PL spectrum into two bands with an average energy separation of 80 meV. In some cases, the onset of the splitting corresponded to changes in the in-plane excitation dipole orientation. These dynamics were assigned to structures of individual quantum dots and the excitation dipoles were visualized in the context of structural features.     

Cryogenic Correlative Single‐Particle Photoluminescence Spectroscopy and Electron Tomography for Investigation of Nanomaterials

Cryogenic single‐particle photoluminescence (PL) spectroscopy has been used with great success to directly observe the heterogeneous photophysical states present in a population of luminescent particles. Cryogenic electron tomography provides complementary nanometer scale structural information to PL spectroscopy, but the two techniques have not been correlated due to technical challenges. Here, we present a method for correlating single‐particle information from these two powerful microscopy modalities. We simultaneously observe PL brightness, emission spectrum, and in‐plane excitation dipole orientation of CdSSe/ZnS quantum dots suspended in vitreous ice. Stable and fluctuating emitters were observed, as well as a surprising splitting of the PL spectrum into two bands with an average energy separation of 80 meV. In some cases, the onset of the splitting corresponded to changes in the in‐plane excitation dipole orientation. These dynamics were assigned to structures of individual quantum dots and the excitation dipoles were visualized in the context of structural features.     

Probing the Different Life Stages of a Fluid Catalytic Cracking Particle with Integrated Laser and Electron Microscopy

While cycling through a fluid catalytic cracking (FCC) unit, the structure and performance of FCC catalyst particles are severely affected. In this study, we set out to characterize the damage to commercial equilibrium catalyst particles, further denoted as ECat samples, and map the different pathways involved in their deactivation in a practical unit. The degradation was studied on a structural and a functional level. Transmission electron microscopy (TEM) of ECat samples revealed several structural features; including zeolite crystals that were partly or fully severed, mesoporous, macroporous, and/or amorphous. These defects were then correlated to structural features observed in FCC particles that were treated with different levels of hydrothermal deactivation. This allowed us not only to identify which features observed in ECat samples were a result of hydrothermal deactivation, but also to determine the severity of treatments resulting in these defects. For functional characterization of the ECat sample, the Brønsted acidity within individual FCC particles was studied by a selective fluorescent probe reaction with 4‐fluorostyrene. Integrated laser and electron microscopy (iLEM) allowed correlating this Brønsted acidity to structural features by combining a fluorescence and a transmission electron microscope in a single set‐up. Together, these analyses allowed us to postulate a plausible model for the degradation of zeolite crystals in FCC particles in the ECat sample. Furthermore, the distribution of the various deactivation processes within particles of different ages was studied. A rim of completely deactivated zeolites surrounding each particle in the ECat sample was identified by using iLEM. These zeolites, which were never observed in fresh or steam‐deactivated samples, contained clots of dense structures. The structures are proposed to be carbonaceous deposits formed during the cracking process, and seem resistant towards burning off during catalyst regeneration.     

应用分析电子显微镜考察铂锡催化剂上的积炭

在高分散铂锡催化剂上分别以正丁烷,正己烷及长链烷烃为反应物经催化剂脱氢表面积炭。从电子显微镜图像观察到积炭有多种结构,最小的炭粒呈条纹排列,炭粒集聚形成球状炭黑及不同形状的石墨结晶。选区电子衍射分析炭(002)晶面间距有3.35～4.13A变化表明石墨化程度不同。三种积炭样品的电子能量损失谱相应地亦展示明显的差别。     

Electron Diffraction with the Transmission Electron Microscope as a Phase-Determining Diffractometer—From Spatial Frequency Filtering to the Three-Dimensional Structure Analysis of Ribosomes

Chemists recognize X-ray crystal structure analysis and electron microscopy as powerful methods of analysis. In the last 20 years the basic ideas of X-ray diffraction analysis have been extended to the field of electron microscopy, whereby an image-forming apparatus is converted into an electron diffractometer, and through which an old dream of crystallographers can be realized—the measurement of the phase shift of scattered waves, a prerequisite for the direct calculation of structures. Its most important area of application, like that of the X-ray diffractometer, is in three-dimensional structure analysis—in all fields of science. However, beyond crystallography, aperiodic structures (comparable to crystals with a single unit cell) can also be analyzed three-dimensionally. In this progress report, the development of the first idea (spatial frequency filtering) to the analysis of ribosomal particles is outlined. Attention will be focused primarily on quantitative methods for the measurement of scattered rays, which are also usable beyond the conventional limit of resolution, down to atomic resolution. In the course of this work in 1968, the principle of the three-dimensional analysis of native biological crystal structures using the electron microscope, as worked with today in many laboratories, was developed. In Munich, however, further research focused on the three-dimensional analysis of aperiodic and individual (especially biological) objects. The analysis of 50S-subunits of the procaryotic ribosome of E. coli showed surprisingly good reproducibility of the results (although only within the same orientation), allowing the deduction of almost ideal average model structures from a limited number of particles.     

Al2O3纳米粒子在TEM测试中分散性的研究

对自制不同粒径范围的球形和纤维状Ａｌ２Ｏ３纳米粉在电镜（ＴＥＭ）测试中颗粒的分散性进行了研究。以卵磷脂、油酸为表面活性剂，无水乙醇为溶剂进行试验，结果表明：当卵磷脂浓度为０．５％时，能得到颗粒之间无聚集、分散性良好的ＴＥＭ照片。文中给出了可能的分散机理     

金属基复合材料的界面分析

用透射电镜、扫描电镜、Ｘ射线能谱仪和电子探针研究了碳化硅颗粒（ＳｉＣｐ）增强Ａｌ２０１４复合材料的微观结构和界面。鉴定了界面上和基体中三种主要的沉淀相：ＣｕＡｌ２、Ｃｕ２Ｍｇ８Ｓｉ６Ａｌ５、（Ｍｎ，Ｆｅ）３ＳｉＡｌ１２和高温下形成的条状Ａｌ４Ｃ３。试验指出，碳化硅和基体间的界面上没有Ｓｉ和Ａｌ的相互扩散，并观察分析了ＳｉＣｐ／Ａｌ２０１４界面周围的无析出带和高密度位错     

Structural Study of Micro and Nanotubes Synthesized by Rapid Thermal Chemical Vapor Deposition

The structures of micro and nanotubes obtained by pyrolysis of hydrocarbons, hold onto silicon (Si) substrates, are reported in this work. The tubes fabrication experiments were carried out by Rapid Thermal Chemical Vapor Deposition (RTCVD) using propane (C₃H₈) as carbon (C) precursor. Selection of parameters such as temperature of deposition, vacuum conditions or surface cleaning leads to the creation of tubular structures. Transmission electron microscopy (TEM), scanning electron microscopy (SEM), selected area electron diffraction (SAED) and energy dispersive X-ray measurements (EDX) are the microbeam techniques that allow to characterize the tubes found in the studied specimens. Different tube configurations such as isolated nanorods, Y-type junctions or fiber-like layers are evidenced. Metallic catalysis seems to be the mechanism involved in the wires formation since Fe particles are present inside the CNT tubes. Other poly-crystalline inclusions are also evidenced by SAED. The composition of the nanotubes changes from tip to tail in an amorphous matrix. The growth mechanisms leading to tube formation are described.     

Surface effects of monolayer-protected gold nanoparticles on the redox reactions between ferricyanide and thiosulfate

The intense research interest in nanosized particle materials is mainly fueled by their unique physical, chemical, electronic, and magnetic properties[1]. Among these, they have shown great application po-tentialities in the catalytic regulation of elec-t…     

Electron and positron pair emission by low energy positron impact on surfaces

The emission of electron pairs from surfaces has the power to reveal details about the electron–electron interaction in condensed matter. This process, stimulated by a primary electron or photon beam, has been studied both in experiment and theory over the last two decades. An additional pathway, namely positron–electron pair emission, holds the promise to provide additional information. It is based on the notion that the Pauli exclusion principle does not need to be considered for this process.We have commissioned a laboratory based positron source and performed a systematic study on a variety of solid surfaces. In a symmetric emission geometry we can explore the fact that positron and electron are distinguishable particles. Following fundamental symmetry arguments we have to expect that the available energy is shared unequally among positron and electron. Experimentally we observe such a behavior for all materials studied. We find an universal feature for all materials in the sense that on average the positron carries a larger fraction of the available energy. This is qualitatively accounted for by a simplified scattering model. Numerical results, which we obtained by a microscopic theory of positron–electron emission from surfaces, reveal however that there are also cases in which the electron carries more energy. Whether the positron or the electron is more energetic depends on details of the bound electron state and of the emission geometry. The coincidence intensity is strongly material dependent and there exists an almost monotonic relation between the singles and coincidence intensity. These results resemble the findings obtained in electron and photon stimulated electron pair emission. An additional reaction channel is the emission of an electron pair upon positron impact. We will discuss the energy distributions and the material dependence of the coincidence signal which shows similar features as those for positron–electron pairs.     

Cu + Au alloy particles formed in the underpotential deposition region of copper in acid solutions

Cu + Au alloy particles electrodeposited on an amorphous carbon electrode at the underpotential region of Cu in both perchloric acid and sulfuric acid solutions were investigated by means of transmission electron microscopy. The fraction of Cu in the Cu + Au alloy particles grown in both acid solutions with a concentration of 1 mM Au ion increased while the underpotential deposition (UPD) potential was decreased. However, it was independent of the concentration of Cu ion in solution. It is inferred that the composition of the Cu + Au alloy particles is dependent on the UPD potential. The fraction of Cu in the Cu + Au alloy particles grown at around the reversible Nernst potential of Cu in 0.1 mM HAuCl₄ + 50 mM Cu(ClO₄)₂ containing perchloric acid solution was 505. This result suggests a layer-by-layer formation of the Cu + Au alloy particles. The fraction of Cu in the Cu + Au alloy particles formed in the presence of sulfate was lower than that in the perchloric acid solution as the UPD potential and the concentration of Cu ion were the same. This is attributed to an influence of coadsorbed sulfate ions.     

Imaging Nanocarbon Materials: Soot Particles in Flames are Not Structurally Homogeneous

For the first time, nascent soot particles are probed by using helium‐ion microscopy (HIM). HIM is a technique that is similar to scanning electron microscopy (SEM) but it can achieve higher contrast and improved surface sensitivity, especially for carbonaceous materials. The HIM microscope yields images with a high contrast, which allows for the unambiguous recognition of smaller nascent soot particles than those observed in previous transmission electron microscopy studies. The results indicate that HIM is ideal for rapid and reliable probing of the morphology of nascent soot, with surface details visible down to approximately 5 nm, and particles as small as 2 nm are detectable. The results also show that nascent soot is structurally and chemically inhomogeneous, and even the smallest particles can have shapes that deviate from a perfect sphere.