Imaging and thickness measurement of amorphous intergranular films using TEM

Fresnel fringe analysis is shown to be unreliable for grain boundaries in yttrium-doped alumina: the determined thicknesses do not agree well with those measured from high resolution transmission electron microscopy (HRTEM), the asymmetry between under- and overfocus is very large, and Fresnel fringes are sometimes shown at boundaries which contain no amorphous film. An alternative approach to the analysis of HRTEM images of grain boundary films is demonstrated: Fourier filtering is used to remove the lattice fringes from the image thereby significantly enhancing the visibility of the intergranular films. The apparent film thickness shows a discrepancy between measurements from the original HRTEM image and the filtered image. It was shown that fringe delocalisation and diffuseness of the amorphous/crystalline interfaces will lead to a significant underestimate of the thickness in unprocessed HRTEM images. In contrast to this, the average thickness can be much more accurately measured from the Fourier-filtered image, provided the boundary is oriented accurately edge-on.     

A comparison of the microstructure of silicon nitride-silicon carbide composites made with and without deoxidized starting material

Two different types of silicon carbide (SiC) matrix composites, with either 10 wt% or 20 wt% silicon nitride (Si₃N₄) reinforcement, were fabricated to investigate the effect of pretreatment on the resulting composite micro-structure. The first type of composite was prepared from as-received α-SiC and α-Si₃N₄ powders, while the second type was prepared from powder compacts that had been deoxidized to eliminate surface silica on the powder particles. The composites were hot isostatically pressed in tantalum cans at 2373 K for 1h under a pressure of 200 MPa. Density measurements showed that full theoretical density was achieved for the composites prepared from the as-received powders, while much lower densities were obtained for the composites prepared from the deoxidized green compacts. Almost all of the α-SiC transformed into β-SiC, and almost all the α-Si₃N₄ transformed into α-Si₃N₄ in the composites made from the as-received powders, while in the composites made from the deoxidized material the α-SiC remained untransformed and both α-Si₃N₄ and β-Si₃N₄ phases were present in significant quantities. High-resolution transmission electron microscopy and Fresnel fringe imaging were used to identify the grain boundary and interphase boundary structure. Most interfaces were found to be covered with ? 1 nm thick amorphous intergranular films in the composites prepared from as-received powders, whereas most interfaces were found to be free of such amorphous intergranular films in the composites prepared from the deoxidized material. Taken together, the presence of intergranular films at the interfaces and the results from density measurements are consistent with the densification and reverse α → β-SiC transformation taking place in the composites made from as-received powders by a liquid-phase sintering route. An incomplete liquid-phase sintering mechanism is also able to explain the microstructure observed in the composites made from the deoxidized material.     

Identification of intergranular phases in ceramic nanocomposites

Analytical FEG-TEM was used for nanostructural and nanochemical characterization of Al₂O₃–TiN (composite I) and Si₃N₄–TiN (composite II) ceramic composite systems. The presence of vitreous intergranular phases in pockets at multiple grain junctions and in thin films (≈ 0.8 nm thick) at grain boundaries was revealed by high resolution and Fresnel fringe imaging techniques. The existence of a Ti-rich thin intergranular film at alumina grain boundaries was revealed by EDS line-scanning across internal interfaces at the 1.5 nm lateral resolution level. Extracting interface specific information at subnanometre levels by means of quantitative spatial difference EELS allowed an identification of intergranular phases. Ti sub-oxide existed in thin films at Al₂O₃ and TiN grain boundaries, whereas a mixed Al–Ti–O–N glassy phase was observed in pockets at triple grain junctions in composite I. In composite II, residual siliceous oxide and oxynitride glass phases were identified in thin films at Si₃N₄ grain boundaries and multiple grain junctions, respectively. These observations indicated that the chemistry of the intergranular phase in thin grain boundary films is notably different from that in larger pockets at multiple grain junctions.     

Measurement of magnetic domain wall width using energy-filtered Fresnel images

Magnetic domain walls in Nd₂Fe₁₄B have been examined using a series of energy‐filtered Fresnel images in the field emission gun transmission electron microscope (FEGTEM). We describe the changes in the intensity distribution of the convergent wall image as a function of defocus, foil thickness and domain wall width. The effect of tilted domain walls and beam convergence on the fringe pattern is also discussed. A comparison of the experimental intensity profile with that from simulations allows the domain wall width to be determined. Measurement of very narrow walls is made possible only by using a relatively thick foil, which necessitates energy‐filtering to allow quantitative comparison with simulations. The magnetic domain wall width in Nd₂Fe₁₄B was found to be 3 ± 2 nm.     

采用自适应可靠因子的联合双边散斑条纹滤波方法

在基于电子散斑干涉法的测量系统中,干涉条纹常常会存在大量噪声从而影响后续相位的提取。 为解决双边滤波无法 处理大噪声的问题,提出了一种融合加窗傅里叶滤波的联合双边滤波方法并用于处理存在高噪声的电子散斑干涉条纹。 在该 方法中,引入加窗傅里叶初步滤波后的图像作为联合双边滤波的导向图,并构建更可靠的自适应像素值相似度因子,从而提供 更可靠的引导信息和更好的滤波效果。 该方法被应用到高、中、低、可变密度 4 种不同密度的模拟条纹和实验采集到的大噪声 条纹上,并将其与原始双边滤波和加窗傅里叶滤波相对比。 实验结果表明:与其它滤波方法相比,该方法得到的条纹最光滑,结 构最完整。 对本文模拟的条纹滤波后峰值信噪比提高 1. 0 ~ 4. 2 dB,结构相似度和边缘保持指数最高,相位的均方误差最小。 所提出的方法调整更方便,对 330×330 大小的模拟条纹处理时间仅为 4 s 左右。     

Successful application of spatial difference technique to electron energy-loss spectroscopy studies of Mo/SrTiO3 interfaces

The electron energy‐loss near‐edge structure (ELNES) of Mo/SrTiO₃ interfaces has been studied using high spatial resolution electron energy‐loss spectroscopy (EELS) in a dedicated scanning transmission electron microscope. Thin films of Mo with a thickness of 50 nm were grown on (001)‐orientated SrTiO₃ surfaces by molecular beam epitaxy at 600 °C. High‐resolution transmission electron microscopy revealed that the interfaces were atomically abrupt with the (110)_Mo plane parallel to the substrate surface. Ti‐L_2,3 (～460 eV), O‐K (～530 eV), Sr‐L_2,3 (～1950 eV) and Mo‐L_2,3 (～2500 eV) absorption edges were acquired by using the Gatan Enfina parallel EELS system with a CCD detector. The interface‐specific components of the ELNES were extracted by employing the spatial difference method. The interfacial Ti‐L_2,3 edge shifted to lower energy values and the splitting due to crystal field became less pronounced compared to bulk SrTiO₃, which indicated that the Ti atoms at the interface were in a reduced oxidation state and that the symmetry of the TiO₆ octahedra was disturbed. No interfacial Sr‐L_2,3 edge was observed, which may demonstrate that Sr atoms do not participate in the interfacial bonding. An evident interface‐specific O‐K edge was found, which differs from that of the bulk in both position (0.8 ± 0.2 eV positive shift) and shape. In addition, a positive shift (0.9 ± 0.3 eV) occurred for the interfacial Mo‐L_2,3, revealing an oxidized state of Mo at the interface. Our results indicated that at the interface SrTiO₃ was terminated with TiO₂. The validity of the spatial difference technique is discussed and examined by introducing subchannel drift intentionally.     

Specimen preparation technique for high resolution transmission electron microscopy studies on model supported metal catalysts

A new technique is described which can be used for preparing transmission electron microscopy (TEM) specimens suitable for high resolution studies on supported metal catalysts. By conventional silicon processing techniques 200 × 200 μm² Si₃N₄ membranes on Si wafers are produced. These membranes are extremely flat and have a uniform thickness of 13 nm. They can be used as a support in various kinds of thin film deposition. A TiO₂ film, optimally structured with respect to the requirements for high resolution TEM work in TiO₂–metal cluster systems, is deposited on the Si₃N₄ layer. It consists of one monolayer of 10–25 nm TiO₂ crystallites. TiO₂ lattice images show that a line resolution down to 0.19 nm is possible. Examples of TiO₂–Pd and TiO₂–Rh are given using respectively photodeposition and impregnation reduction to produce l.5–4 nm metal clusters.     

Tribological and mechanical investigation of SiO2 and Si3N4 coatings on fused silica and borosilicate glass

Amorphous SiO₂ and Si₃N₄ plasma‐enhanced chemical vapour deposited (PECVD) coatings were deposited on two different substrate materials (fused silica and borosilicate glass), with three coating thicknesses (0.1, 0.5, and 1.0 μm). The mechanical properties (hardness and elastic modulus) were determined by depth‐sensing indentation, with loads from 700 mN down to 0.1 mN. Tribological behaviour was studied in instrumented oscillating sliding tests at room temperature with a ball‐on‐flat arrangement, in which the coated disc was tested against an alumina ball, at a load of 1 N. Interpretation of the measurement of hardness and modulus of the coatings has to take into consideration the influence of layer thickness and the effect of the substrate. Tensile film stress and crack generation were only observed for Si₃N₄ on fused silica above a threshold thickness. Friction and wear measurements show that the coating has an effect on friction, while wear is affected by the thin coatings only for a short running‐in phase. The morphology of the wear scars indicates that the coatings have good adhesion. Despite crack generation, delamination effects were not observed. Indentation patterns similarly showed excellent lateral homogeneity of the mechanical properties over the entire film surface, and indicated that load‐displacement curves may be used to characterise the system.     

Monochromatic image analysis of elastohydrodynamic lubrication film thickness by fringe intensity computation

Point contact film thickness in elastohydrodynamic lubrication (EHL) is analyzed by image processing method for the images from an optical interferometer with monochromatic incident light. Interference between the reflected lights both on half mirrorCr coating of glass disk and on super finished ball makes circular fringes depending on the contact conditions such as sliding velocity, applied load, viscosity-pressure characteristics and viscosity of lubricant under ambient pressure. In this situation the film thickness is regarded as the difference of optical paths between those reflected lights, which make dark and bright fringes with monochromatic incident light. The film thickness is computed by numbering the dark and bright fringe orders and the intensity (gray scale image) in each fringe regime is mapped to the corresponding film thickness. In this work, we developed a measuring technique for EHL film thickness by dividing the image patterns into two typical types under the condition of monochromatic incident light. During the image processing, the captured image is converted into digitally formatted data over the contact area without any loss of the image information of interferogram and it is also interpreted with consistency regardless of the observer’ s experimental experience. It is expected that the developed image processing method will provide a valuable basis to develop the image processing technique for color fringes, which is generally used for the measurement of relatively thin films in higher resolution.     

Particulate Matter Generation Properties from Sliding Parts Made of Various Carbonaceous Films

The purpose of this work is to reduce the particulate matter (PM) generation from sliding parts by applying carbonaceous films. We investigate particle generation properties of wear-resistant carbonaceous films in the form of a particle size distribution chart. Using a laser scattering type particle counter, we evaluated the particle generation properties of sliding parts coated with high crystallinity, N⁺-implanted high-crystallinity and low-crystallinity diamond films, diamond-like carbon films deposited by ion beam enhanced deposition using static and dynamic mixing methods, Si₃N₄ silicon nitride, and SUS340C stainless steel. The diamond films showed significantly lower particle generation, especially for large particles, than DLC, Si₃N₄, and SUS340C films owing to lower wear. Particle generation from N⁺-implanted diamond films was greater for small particles than for the other diamond films owing to the wear of the N⁺-implanted layer.     

Tribological Characterization of Several Silicon-Based Materials Under Ionic-Liquids Lubrication

The tribological behaviors of three silicon-based materials (low temperature silicon oxide (LTO), polysilicon (Poly Si) and silicon nitride (Si₃N₄) films) under ion liquids (ILs) lubrication have been investigated by varying the applied load and the sliding velocity. An atomic force microscope and a nanoindentor were used to characterize the deposited films, and the worn surfaces after frictional tests were analyzed by an optical microscope, a scanning electron microscope (SEM) with an energy dispersive spectrometer (EDS) and an X-ray photoelectron spectrometer (XPS). The results show the best lubricating properties of the IL lubricants are obtained at the intermediate load of 150 g for the three tribo-pairs. For the Si₃N₄/Si₃N₄ tribo-pair, the coefficients of friction (COFs) and the wear rates under ILs lubrication are larger than those under dry friction. The COF values decrease with sliding velocity, and the COFs of the Si₃N₄/Si₃N₄ tribo-pair are greater than the ones of the other two tribo-pairs (LTO/Si₃N₄ and Poly Si/Si₃N₄) at low velocities. The COF of 1-ethyl-3-methylimidazolium tetrafluoroborate is nearly 3 times larger than the other two IL lubricants (1-butyl-2,3-dimethylimidazolium tetrafluoroborate and N-butylpyridinium tetrafluoroborate) for the Si₃N₄/Si₃N₄ tribo-pair. The differences in COFs between the latter two lubricants for the three tribo-pairs are negligible. Different mechanisms of these results have been analyzed in the paper.     

The measurement of thermal conductivities using the photothermal deflection method for thin films with varying thickness

This study considers non-contact methods that obviate the causes of measurement error, such as thermal contact resistance and the unnecessary destruction of samples. Among the methods, the photothermal deflection method has been adopted and developed to measure the thermal conductivities of thin-film materials. To apply the developed method for thin films, bi-layered materials are manufactured by depositing the film on Corning 7740 glass plates. The study also investigates the optimal modulation frequency, as related to the thermal diffusion length of the sample, for measuring thermal conductivities of thin films.. Aluminum, TiO₂, and Si₃N₄ films with micro/nanometer thickness were selected as the objects for measurement; the thermal conductivities of these films were experimentally measured. Samples of thickness ranging from 1 μm to 200 nm were prepared to measure the variations in thermal conductivities with thickness. It was observed that the thermal conductivity in submicroscale films decreased as the thickness was reduced.     

Nano Si3N4 composites with improved tribological properties

Nano Si₃N₄ composites with tailored microstructure were developed using fine ß‐Si₃N₄ powders. Their wear behaviour was investigated. Whereas pure Si₃N₄ composites showed improved wear behaviour under dry rolling conditions with slip, TiN‐reinforced nano Si₃N₄ composites generate a self‐lubricating behaviour under dry sliding conditions. After chemical treatment with hydrogen sulphide, the friction coefficient and wear rate was found to be significantly decreased under dry sliding conditions. Additionally, the new composites possess higher fracture toughness than the pure nano Si₃N₄ materials. Copyright © 2009 John Wiley & Sons, Ltd.     

Interfacial reactions and silicate formation in highly dispersed Lu2O3– SiO2 system

Solid state interface reactions in highly dispersed Lu₂O₃– SiO₂ binary oxide system were studied at 600–1100 °C with X‐ray powder diffraction (XRD), high‐resolution transmission electron microscopy (HRTEM) and Fourier Transform Infrared spectroscopy (FTIR). The results show that at 600–900 °C an amorphous, nanometer thick Lu‐O‐Si layer covering SiO₂ particles exists in the system. At higher temperatures the breakage of the layer into amorphous islands occurs and crystalline silicates with various structures are formed. In particular, Lu₄[Si₃O₁₀][SiO₄] silicate, analogue of B‐type Dy – Tm disilicates, forms at 1000 °C.     

Lubrication at 750°C in a vacuum by a transfer film from self‐lubricating composites for roll/slide contact of Si3N4

Roll/slide friction tests were carried out at a temperature of 750°C in a vacuum. Disc specimens were made of Si₃N₄ with or without a sputtered MoS₂ film. A pin specimen was rubbed against one disc to supply a lubricating transfer film. With a pin made of an MoS₂‐based composite, the friction coefficient was around 0.3 and almost no wear of the discs was observed after 24 h of operation at a load of 50 N, a rotating speed of 0.5 m/s, and a slip ratio of 10%. Transferred patchy MoS₂ films were observed on the friction track. With a pin made of Ni‐based composite containing BN and graphite, the friction coefficient increased from 0.2 to 0.7 over a test time of about 8 h and severe disc wear was found. In an additional test using Si₃N₄ discs with a sputtered MoS₂ film without a pin, the friction coefficient was about 0.3, and no wear of the discs was found after 24 h of operation. The appearance of the friction track was similar to that in the test using the MoS₂‐based composite pin. It seems that the sputtered MoS₂ film wore, but wear particles reattached on the friction path to develop an effective lubricating film. These results demonstrate the effectiveness of transfer film lubrication for long‐term operation in a high‐temperature vacuum, and the superior ability of MoS₂ to develop an effective transfer film.     

Lubrication of Si3N4 and Al2O3 in water with and without addition of silane coupling agents in the range of 0.05–0.10 mol/l

To improve water lubrication of ceramics at a lower sliding velocity, the effect of the addition of silane coupling agents was investigated. Si₃N₄ and Al₂O₃ were slid against themselves in water with and without the addition of silane coupling agents in amounts ranging from 0.05 to 0.10 mol/l. Silane coupling agents containing one or more amino groups were effective in reducing the friction of Si₃N₄ and Al₂O₃ in water. Si₃N₄ also showed significant wear reduction but not Al₂O₃. However, the addition of a silane coupling agent containing an epoxy group increased both friction and wear of Si₃N₄. Improved lubricative characteristics of Si₃N₄ in water and in silane coupling agent solutions were obtained when Si₃N₄ contained smaller amounts of sintering additives. The adsorption behaviour of a silane coupling agent on ceramics was examined using both Fourier transform infrared spectroscopy and thin layer chromatography to clarify the interaction between the silane coupling agent and the ceramics. The role of polysiloxane film formation on ceramics is discussed to demonstrate the lubrication properties of ceramics.     

Soft X-ray contact microscopy with nanosecond exposure times

High resolution (better than 20 nm) contact micrographs have been produced with exposure times of about a nanosecond. The illuminating source was a short-lived carbon plasma produced by focusing a single short (～1 ns) 100 J pulse from the Vulcan laser at the Rutherford Appleton Laboratory (RAL) to a 300 μm spot on a graphite target. This plasma emits strongly in the soft X-ray region, particularly at the CVI (3.37 nm) and CV (4.03 nm) lines. The specimens were behind a 100 nm thick Si₃N₄ window, at atmospheric pressure in an environmental cell. The images of diatoms recorded on X-ray resist showed features down to the limit of resolution of the SEM used to view the developed resist, which was about 20 nm.     

CUTTING PERFORMANCE AND WEAR MECHANISM OF Si3N4-BASED NANOCOMPOSITE CERAMIC CUTTING TOOL IN MACHINING OF CAST IRON

A type of Si₃N₄-based nanocomposites ceramic cutting tool material was prepared by the addition of nano-scale Si₃N_4W whisker and nano-scale TiN particle. Cutting performance of the Si₃N₄/Si₃N_4W/TiN nanocomposite ceramic tool in machining of cast iron was investigated in comparison with a commercial sialon ceramic tool, and the tool wear mechanism was studied. The two types of cutting tools have similar cutting performance at relatively low cutting parameters, while Si₃N₄/Si₃N_4W/TiN nanocomposite tool exhibits a better wear resistance than sialon tool at the relatively high cutting parameters. The wear of sialon ceramic cutting tool is dominated by the plastic deformation, abrasive action, microcracking, pullout of grains and chemical action at the higher cutting parameters. The higher mechanical properties, and the refined matrix grains, intragranular TiN grains and dislocation in the microstructure improve the resistances to plastic deformation, microcracking, and pullout of grains for Si₃N₄/Si₃N_4W/TiN nanocomposite ceramic cutting tool. The wear of Si₃N₄/Si₃N_4W/TiN nanocomposite ceramic cutting tool is dominated by the abrasive and chemical actions at the higher cutting parameters.     

High resolution studies of glass-crystal interfaces

High resolution electron microscopy has been used to image intergranular glassy phases in sintered and hot-pressed nitrogen ceramics, and the Si-SiO₂ interfaces important in MOS devices. The thin intergranular glassy phases were found at most grain boundaries in all liquid-phase sintered or hot-pressed ceramics examined. Silicon carbide sintered by a solid state diffusion process, however, contained no such phases. Si-SiO₂ interfaces have been examined in cross-section at about 0?3 nm resolution. The images show that the transition from the Si crystal to the amorphous oxide was abrupt, but that there were 0?3-0?5 nm high hills on the Si surface, separated by 2–4 nm, and long-range undulations of 0?6-0?8 nm height and 20–50 nm periodicity. Ultra-thin (3 nm) oxides were also examined and were found to be uniform in thinkness, indicating that the roughness at the Si-SiO₂ interfaces is initially caused by irregularities on the original, unoxidized Si surface.     

Architecture of superthick diamond-like carbon films with excellent high temperature wear resistance

A plasma-enhanced chemical vapor deposition system was used to deposit super thick diamond-like carbon (DLC)-based films ((Si_x-DLC/Si_y-DLC)_n). The aim of this work is to investigate the properties of super thick films to verify that increasing the thickness of DLC films offers the possibility of improving their properties at high temperatures. The investigation revealed that superthick (Si_x-DLC/Si_y-DLC)_n film exhibited excellent tribological property up to 500 °C. One reason is that a thin layer that consists of nanocrystals SiC is formed on the top of wear track. Another is that the stress mostly concentrates near the top surface.