Chemical vapor deposition and composition-depth profiling of a graded coating by Auger electron spectroscopy used in conjunction with taper polishing

A graded TiC_xN_1−x coating with x varying parabolically in the range 0-1 was grown by chemical vapor deposition in the TiCL₄-CH₄-N₂-H₂ system by quasi-continuously changing process parameters (growth time, CH₄ mole fraction) at 1400 K and at 10.7 kPa. Taper polishing of the graded coating was carried out by a simple apparatus converting a depth dimension into a lateral dimension. Auger electron spectroscopy line scan was then performed on the taper polished surface. Composition profile of the graded coating was determined to be in agreement with the designed one using surface profilometer traces and AES signals from C_KLL transition at 272 eV. AES/taper polishing approach facilitates composition-depth analysis with a minimal degree of sputtering and a substantial reduction of data acquisition time. Taper polishing could also be combined with other chemical analysis techniques such as X-ray microdiffraction.     

Three-dimensional visualization of pore structure in hardened cement paste by the gallium intrusion technique

It is widely known that the pore structure of concrete strongly influences its physical properties. Therefore, we developed a technique for the visualization of the pore structure because of clearing it correctly. However, this visualization is limited to two-dimensional imaging for sections of the specimen. As a result, in this study, we developed a technique for reconstructing the acquired 2D images of the pore structure into 3D form by stacking them. By using this image, the relationship between water permeability and pore connectivity was clarified, and it was shown clearly that the pore connectivity strongly affects the water permeability.     

Visualizing spatial and temporal heterogeneity of single molecule rotational diffusion in a glassy polymer by defocused wide-field imaging

Defocused wide-field fluorescence microscopy was used to follow the 3D molecular rotational diffusion of a fluorescent probe molecule in a polymer thin film. The technique allows for visualizing the molecular reorientation both in-plane and out-of-plane. The local environmental change driven by heterogeneous dynamics of the polymer can be probed on a scale of 1 μm as demonstrated by parallel imaging of several molecules. A multi-component rotational diffusion decay is observed which might reflect both different relaxation regimes of the polymer as well as rapid changes of the local environment.     

Dislocation analysis of a complex sub-grain boundary in UO2 ceramic using accurate electron channelling contrast imaging in a scanning electron microscope

In this work, accurate electron channelling contrast imaging (A-ECCI) assisted by high resolution selected area channelling patterns (HR-SACP) was used to characterize the structure of a complex low sub-grain boundary in a creep deformed uranium dioxide (UO₂) ceramic. The dislocations were characterized using TEM-style g·b = 0 and g·b × u = 0 contrast criteria. Misorientations across the boundary were measured using HR-SACPs with 0.04° precision and high accuracy EBSD. The boundary was determined to be asymmetric and mixed in nature, composed of two distinct regions with different dislocation morphologies and a misorientation below 0.5°. The A-ECCI, HR-SACP, and HR-EBSD results are consistent, confirming A-ECCI as a powerful tool for characterizing even complex dislocations structures using scanning electron microscopy. This is particularly true for UO₂, since this material is very difficult to thin, which makes TEM examination of sub-boundaries over the scale of several micrometers difficult. Furthermore, in this study, the change in dislocations arrangement along the breath of the complex low angle sub-grain boundary is related to the misorientation across the boundary.     

The mechanism for the colour change of iron chromium black pigments in glazes through transmission electron microscopy techniques

Black iron-chromium (Fe-Cr) bearing oxide pigments are generally utilised as effective colourants in a wide variety of applications. However, in the case of their use within ZnO-containing glazes, they yield an undesirable brown colour instead of expected black colour. In order to understand the colour change in this system, we report the use of focused ion beam (FIB) sample preparation technique followed by the use of analytical transmission electron microscopy (TEM) characterisation techniques. According to the results, the formation of a reaction layer between the pigment and glaze was identified with an average composition of Zn_0.48Fe_0.79Cr_1.32O₄. Additionally, the valance of Fe was determined as 3+ in the pigment grain, whereas 2+ in the reaction layer and the glaze, respectively. Therefore, it was concluded that the colour change is occurring as result of the valence variation of Fe, the formation of Zn_0.48Fe_0.79Cr_1.32O₄ compound and the outward diffusion of Fe into the glaze.     

Understanding the protective role of a gradient titanium oxide ceramic layer on Ti6Al4V against corrosion via analyses of Mott-Schottky curve and electron work function (EWF)

Thermal oxidation (TO) process was employed to generate a gradient titanium oxide ceramic layer for improving corrosion performance and service safety of Ti6Al4V alloy. The semiconductor characteristic of the TO layer was evaluated in CO₂-saturated simulated oilfield brine. The generated TO layer with a thickness of about 20 μm was dense and continuous without cracks or spalling characteristics. The TO layer mainly comprised of an oxide ceramic layer (rutile TiO₂ ceramic phase, minor anatase one, and Al₂O₃) and an oxygen diffusion layer. The conducted electrochemical analysis suggested that the corrosion resistance of Ti6Al4V alloy was improved using TO surface strengthening process. It was demonstrated that the TO layer with semiconductor characteristics showed a transition from n-type (donor) to p-type (acceptor) with the increasing applied electric potential. The electron work function of the TO layer was higher than that of Ti6Al4V alloy with a naturally formed passive film. The improvement in corrosion properties was attributed to the excellent chemical stability and semiconductor properties of the metal oxide ceramic phases (TiO₂, Al₂O₃) in the TO layer.     

Importance of poly(ethylene oxide)-modification and chloride anion for the electron transfer reaction of cytochrome c in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide

Horse heart cytochrome c (cyt c) was chemically modified with poly(ethylene oxide) (PEO) to dissolve it in room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([emim][TFSI]). The redox response of the modified cyt c, hereafter PEO-cyt c, was analyzed in [emim][TFSI]. PEO modification to the surface of cyt c, which exceeded 60% of the total mass of the PEO-cyt c, was an effective method to solubilize the cyt c. In spite of the high ion density and sufficient ionic conductivity of [emim][TFSI], no redox response of pure PEO-cyt c was detected. However, a reversible redox response of PEO-cyt c was observed after adding a simple electrolyte such as KCl to [emim][TFSI]. The redox response of PEO-cyt c was sensitive to the anion radius of the added salt, and the chloride anion was found to be the best anion species to produce a redox response of PEO-cyt c in [emim][TFSI]. However, above a certain salt concentration, the resulting increase in solution viscosity would suppress the redox reaction. The results strongly indicate that the chloride anions, because of their mobility in the polypeptide matrix, compensate the charge change of heme during the electron transfer reaction. Larger anions did not show such an effect due to sterical restrictions on the migration through the protein shell to the heme pocket of cyt c.     

Quantitative analysis of the microstructure of interfaces in steel reinforced concrete

This article reports the results of a backscattered electron imaging study of the microstructure of the steel– and aggregate–cement paste interfaces in concrete containing 9 mm ribbed reinforcing bars. The water to cement (w/c) ratio, hydration age, steel orientation, and surface finish were varied. For vertically cast bars, there was more calcium hydroxide (CH) and porosity and less unreacted cement at both the steel– and aggregate–cement paste interfaces when compared to the bulk cement paste. As the hydration age increased, the porosity near the interfaces decreased, and the CH increased with more CH close to the steel than to the aggregate. Horizontal bars had more porosity and less CH under them than above. An increase in the w/c ratio produced interfaces of higher porosity and lower levels of CH. Wire-brush cleaned bars had higher levels of CH at the steel–cement paste interface at 365 days when compared to uncleaned bars.     

Direct atomic scale analysis of the distribution of Cu valence states in Cu/γ-Al2O3 catalysts

In this paper, the microstructure of a 1 wt.% Cu/γ-Al₂O₃ catalyst that was reduced in a 4% hydrogen/argon atmosphere at temperatures of 523, 773 and 1073 K, is studied by Z-contrast imaging and electron energy-loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM). Results show that the copper species are well dispersed when the catalyst is reduced below 523 K. At 773 K, separated Cu(I) and Cu(0) species are found existing as ring-like and bulk-like particles. This appears to indicate that the copper has not been reduced to its metallic form due to the interaction between the copper oxide and the support. Large spherical particles having core-shell structures with Cu(I) in the shells and Cu(0) in the cores are generated when the catalyst is reduced at 1073 K. The formation of partially oxidized copper species upon reduction at 1073 K is attributed to the metallic copper interaction with the alumina support. This study also demonstrates that high-spatial resolution Z-contrast imaging and EELS performed simultaneously can provide unique information on the morphology and chemistry of metal species in supported metal catalysts.     

ATRP in the design of functional materials for biomedical applications

Atom Transfer Radical Polymerization (ATRP) is an effective technique for the design and preparation of multifunctional, nanostructured materials for a variety of applications in biology and medicine. ATRP enables precise control over macromolecular structure, order, and functionality, which are important considerations for emerging biomedical designs. This article reviews recent advances in the preparation of polymer-based nanomaterials using ATRP, including polymer bioconjugates, block copolymer-based drug delivery systems, cross-linked microgels/nanogels, diagnostic and imaging platforms, tissue engineering hydrogels, and degradable polymers. It is envisioned that precise engineering at the molecular level will translate to tailored macroscopic physical properties, thus enabling control of the key elements for realized biomedical applications.     

Realizing the enhancement of interfacial interaction in semicrystalline polymer/filler composites via interfacial crystallization

Polymer/filler composites have been widely used in various areas. One of the keys to achieve the high performance of these composites is good interfacial interaction between polymer matrix and filler. As a relatively new approach, the possibility to enhance polymer/filler interfacial interaction via crystallization of polymer on the surface of fillers, i.e., interfacial crystallization, is summarized and discussed in this paper. Interfacial crystallization has attracted tremendous interest in the past several decades, and some unique hybrid crystalline structures have been observed, including hybrid shish-kebab and hybrid shish-calabash structures in which the filler served as the shish and crystalline polymer as the kebab/calabash. Thus, the manipulation of the interfacial crystallization architecture offers a potential highly effective route to achieve strong polymer/filler interaction. This review is based on the latest development of interfacial crystallization in polymer/filler composites and will be organized as follows. The structural/morphological features of various interfacial crystallization fashions are described first. Subsequently, various influences on the final structure/morphology of hybrid crystallization and the nucleation and/or growth mechanisms of crystallization behaviors at polymer/filler interface are reviewed. Then recent studies on interfacial crystallization induced interfacial enhancement ascertained by different research methodologies are addressed, including a comparative analysis to highlight the positive role of interfacial crystallization on the resultant mechanical reinforcement. Finally, a conclusion, including future perspectives, is presented.