Segregation of Mg to the (0001) Surface of Doped Sapphire

Auger electron spectroscopy (AES) and low-energy electron diffraction (LEED) were used to study the segregation of Mg to the surface of a sapphire crystal doped with 40 ppm of Mg. In situ vacuum annealing and AES measurements at 900° to =1800°C failed to reveal Mg segregation on the (0001) plane above the detectability limit of the cylindrical mirror analyzer. However, when identical crystals were placed together to simulate a "closed system" and annealed in air, surface segregation of Me was detected above 1200°C. The variation of the equilibrium surface concentration of Mg with temperature in the range 1300° to =1500°C, gave an effective Langmuir heat Of segregation of Mg of =–146 kJ/mol. Evidence for the formation of a two-dimensional ordered structure on the sapphire surface was also obtained through LEED studies. The implications of these segregation results for our understanding of the sintering behavior of magnesia-doped alumina are discussed.     

Microstructure of natural graphite flakes revealed by oxidation: Limitations of XRD and Raman techniques for crystallinity estimates

The estimation of the active surface area (ASA) of various macrocrystalline graphitic materials is industrially valuable but the microstructures of these materials are still contestable. This in turn has led to difficulties in the unambiguous interpretation of crystallographic measurements with powder X-ray diffraction (pXRD) and Raman spectroscopy as well as their relationship to the ASA. To resolve this issue a systematic approach is required. As a starting point two widely accepted pXRD and Raman methodologies were utilized. Purified, oxidized, natural graphite flakes were extensively examined to elucidate the essential microstructural features. Based on this an illustrative model was formulated as grounds for interpreting the measured crystallite domain sizes. Only one of the crystallographic parameters could be linked to the observed microstructure. For macrocrystalline graphite both techniques are subject to instrumental limitations and should not be used. Due to the non-linearity of the correlations they are prone to measurement uncertainty and should not be used above acceptable limits. In addition, the current inability to distinguish between different defect types leads to ambiguous results. Despite being a single, interrelated crystal the composite nature of the flakes will make it difficult to relate even an ideal, accurate domain size measurement to the ASA.     

Electrochemical Formation of CdSe Monolayers on the Low Index Planes of Au

The electrochemical analog of atomic layer epitaxy (ALE) is being studied. ALE is a method for growing thin films of materials using a cycle of surface limited reactions. The surface limited reactions control the deposition by limiting the growth to an atomic layer at a time. In electrochemistry, a surface limited deposition is generally referred to as underpotential deposition (UPD), and UPD is used to form the atomic layers in electrochemical ALE (ECALE). The work presented here is an atomic level study of the deposition of the first few monolayers of CdSe via ECALE: by the alternated UPD of atomic layers of Se and Cd on the low index planes of Au. UPD of Se resulted in the formation of ordered structures on each of the low index planes of Au, as observed by low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). The subsequent UPD of Cd resulted in CdSe deposits which exhibited 1:1 stoichiometry, as determined by coulometry and Auger electron spectroscopy (AES). The following LEED patterns were observed for the CdSe monolayers: Au(111)(√7×√7)R19.1°, Au(111)(3×3), Au(110)(2×3), and the Au(100)(√2×2√2)R45°. Similar LEED patterns were observed on each surface for deposits formed using up to three ECALE cycles. In situ STM studies of Cd deposition on Se-covered Au(111) indicated the formation of a (3×3) structure, consistent with LEED results, and with previous TEM studies. The same LEED patterns were also observed for CdSe monolayers where Cd was deposited as the first atomic layer. AES indicated that the element deposited first remained on the bottom, and that deposited second remained on top.     

An empirical estimation of Scherrer parameters for the evaluation of true crystallite size in fibrous polymers

Optical diffraction profiles obtained from computer-drawn masks which simulate the effects of both size and distortion, have been used to evaluate Scherrer (K) parameters in terms of the ratio of true crystallite size to apparent crystallite size. These empirical parameters are in reasonable agreement with parameters established by comparing the results of X-ray and electron diffraction analyses with direct measurement on lattice-fringe images. Tables are given for K parameters to be used in the evaluation of true crystallite size from the integral breadth or half-width of diffraction profiles.     

Molten salt corrosion of graphite as a possible way to make carbon nanostructures

The structural and microstructural changes in graphite occurring by heating a mixture of synthetic polycrystalline graphite and lithium chloride to 1250 °C are studied by thermal analysis, X-ray diffraction, Raman scattering and microscopy. The average crystallite size of the graphite was found to increase significantly after the heat treatment. Although the oxidation of graphite was largely inhibited, different forms of corrosion attack on the graphite were observed. Consequently, these led to the formation of different microstructures comprising exfoliated carbon sheets and nanosheets, pitted particles and carbon nanorods. The possible mechanisms related to the microstructural changes are discussed. The effect of heating rate on the oxidation in air of graphite powder is also investigated.     

Electrical behavior of cerium dioxide films exposed to different gases atmospheres

Here we present an easy-reproducible microwave-assisted hydrothermal route for preparing pure nanocrystalline CeO₂ films. The produced materials were characterized using a wide range of techniques (X-ray diffraction, field emission gun scanning electron microscopy, Raman spectroscopy) to understand the synthesis dependent changes in crystallographic structure, and crystallite size. Raman and X-ray diffraction techniques revealed that the films were free of secondary phases and that they crystallize in the cubic structure. The observed hydrodynamic particle size larger than the crystallite size confirms the aggregation phenomenon. Gas sensing measurements have been carried out to rationalize the type and number of surface adsorbed groups and overall nanostructure. Electrical conductance variations, owing to gases adsorption onto semiconductor oxide films surfaces, were observed in this work. Chemiresistive CeO₂ film properties depend on the intergranular barrier heights and width.     

Consumption of graphite anodes in chlorine manufacture by brine electrolysis

The anodic behaviour of carbon and graphite electrodes in aqueous electrolytes is described and the important reactions leading to the consumption of graphite during chlorine manufacture by brine electrolysis are discussed in detail. The present state of knowledge concerning the effects of chlorine cell electrolysis conditions on graphite consumption is also reviewed. A new investigation of the influence of graphite manufacturing variables and properties on consumption is also described. The variables studied were coke particle size, degree of pitch impregnation and the final heat treatment at the graphitization stage. Properties considered included electrical resistivity, apparent density, average crystallite size and unpaired electron spin density. The resistance of the graphite to anodic oxidation was found to increase with increasing coke particle size, increasing pitch impregnation and increasing final heat treatment temperature (up to 3000°C). Unpaired electron spin density was the property found best to correlate with this resistance.     

Structural study of cokes using optical microscopy and X-ray diffraction

Cokes exhibiting a range of optical texture from isotropie to anisotropic domains > 60 μm diameter were examined by X-ray diffraction. The variation of an optical texture index (OTI) with crystallite height and interlayer spacing was studied. The OTI varies little with the X-ray parameters for cokes whose optical texture is larger than medium-grained (1.5–5.0 μm) mosaic anisotropy. For cokes of smaller optical texture there is a sharp decrease in crystallite height and an increase in interlayer spacing. These results are discussed in terms of fluid mesophase removing defects in cokes of optical texture of size of coarsegrained mosaics and larger. The cokes of smaller optical texture are formed from less fluid mesophase which does not coalesce. Defects therefore remain in this anisotropic carbon of the coke so reducing crystallographic order.     

X-ray diffraction patterns of graphite and turbostratic carbon

To identify the influence of microstructural variation on the X-ray diffraction intensities, X-ray diffraction patterns of hexagonal graphite (h-graphite) and turbostratic carbon (t-carbon) were simulated by using the general Debye equation. The numeric density of interatomic distance (NDID) is sensitive to the size and microstructure of a crystallite, so that it is used to characterize the structures of h-graphite and t-carbon. The dependence of the diffraction angles and full width at half maximums (FWHMs) of diffraction lines on the crystallite size and distortion factors is examined by computer simulation. The distortion factors for t-carbon, including rotation, translation, curvature, local positive fluctuation of interlayer spacing of graphene layers and fluctuation of atomic positions, have different influence on the NDIDs, hence on the X-ray diffraction patterns. The simulation results indicate that the diffraction angles and FWHMs of diffraction lines cannot be simply used to characterize the lattice parameters and crystallite sizes of t-carbon.     

Effect of high-temperature neutron irradiation on the crystallites of graphite materials

Changes in crystal lattice parameter, c-axis lattice strain and apparent crystallite height induced by neutron irradiation at 720–1350°C were investigated by means of X-ray diffraction for fourteen specimens which included five bands of nuclear graphite and two kinds of pyrolytic graphite. All irradiated materials show a marked increase in c-axis lattice strain, while changes in the lattice parameters are very small. The relation between lattice strain and layer spacing was analyzed for pre- and post-irradiated graphites, and it is inferred that, whereas the predominant constituent of strain in the unirradiated graphite is the statistical fluctuation in distribution of layer spacings, for the irradiated material it is the distortion of layer planes. On the basis of the relation between c-axis lattice strain and apparent crystallite height, the stacking height of graphite layer planes is estimated to be about 70 Å for pre-irradiated graphite.     

Characterization of the effects of 3-MeV proton irradiation on fine-grained isotropic nuclear graphite

The irradiation-induced damage on the fine-grained isotropic nuclear graphite, IG-110, was investigated by 3-MeV proton irradiation at room temperature. The irradiation effects were characterized using scanning electron microscopy, transmission electron microscopy (TEM), Raman spectroscopy, X-ray diffraction (XRD), and nano-indentation. The surface morphology showed a fragmented shape after irradiation, indicating that the surface microstructure of the graphite was damaged by proton bombardment. The TEM images revealed clear and convincing evidence for the increase in defect clusters (probably interstitial clusters), basal plane bending, and basal plane dislocations, which might be the main reason for property changes. Raman studies indicated a rapid increase in the interstitial and vacancy defects, and decrease of in-plane “crystallite size”. The XRD results indicated a slight increase in the interlayer spacing and decrease in crystallite size. The enhancement in the hardness and modulus can be attributed to the pinning of basal plane dislocations by lattice defects produced by proton irradiation.     

The determination of the elastic properties of an anisotropic polycrystalline graphite using neutron diffraction and ultrasonic measurements

The elastic properties of an extruded graphite (GR-280) used in nuclear industry have been examined. The lattice preferred orientation was determined by time-of-flight neutron diffraction that revealed weak texture with a texture index of less than 1.2. The bulk elastic properties of polycrystalline graphite with such a texture have been calculated using various averaging methods and compared with the properties obtained from the measurements of the longitudinal sound velocities, performed using special equipment at different hydrostatic pressures up to 150 MPa. The static elastic modulus of the GR-280 graphite as well as the diffraction elastic modulus was measured in situ by high resolution neutron diffraction by observing the shift of the (0 0 2) Bragg reflection under uniaxial loads up to 20 MPa. The static elastic moduli of two pyrolytic graphites have also been measured for comparison. It was shown that the anisotropy of the elastic properties of reactor graphite GR-280 is due to the crystallographic texture formed during the extrusion process, but the internal pores and microcracks are not closed even at a pressure of 150 MPa and they greatly influence the exact values of the bulk elastic moduli of graphite.     

Graphite-to-diamond transformation induced by ultrasound cavitation

Diamond microcrystals have been synthesized using ultrasonic cavitation of a suspension of hexagonal graphite in various organic liquid media, at an average bulk temperature of the liquid up to 120°C and at atmospheric pressure. The yield of diamond is up to 10% by mass. The diamonds were characterized by scanning electron microscopy, X-ray diffraction and laser Raman spectroscopy. Analysis of the crystallite size distribution showed that the diamonds were nearly mono-dispersed, having a size 6 or 9μm ± 0.5μm, with cubic, crystalline morphology.     

Atomic-Level Characterization of Cubic Silicon Carbide Surfaces—A Review

Scanning tunneling microscopy (STM) images of the cubic β-SiC (100) and β-SiC (111) surfaces are taken after annealing to 1200°C to eliminate the surface oxide. Low-energy electron diffraction (LEED) patterns of the β-SiC (111) surface show a 6 √ 3 × 6 √ 3 geometry, while STM images show a 6 × 6 geometry. Contrast reversal is observed as tunneling voltage bias is reversed. Spectroscopic I/V measurements indicate the presence of a graphite layer on the top surface. A model of the surface is proposed where an incommensurate graphite monolayer is grown over a (1 × 1) Si-terminated β-SiC (111) surface. This model helps to explain the discrepancy between the 6 √ 3 × 6 √ 3 LEED pattern and the 6 × 6 geometry observed in STM images. Charge transfer between certain carbon atoms and silicon atoms gives rise to the 6 × 6 geometry and the contrast reversal.     

Structural study of cellophane

Fine structural aspects of cellophane have been investigated using X-ray and electron diffraction techniques as well as a kinetic study of the dissolution of cellophane in 0.5 M cupriethylene diamine solution. The X-ray diffraction pattern for cellophane shows a typical cellulose II structure while the electron diffraction pattern highlights a typical cellulose I structure with very weak reflection for a cellulose II type lattice. The kinetics study of cellophane dissolution in cupriethylene diamine confirms the presence of these polymorphic forms of cellulose in cellophane. The paper also reports studies of the X-ray and electron diffraction patterns of cellophane in relation to crystallite size and degradation under electron beam. It is shown that the observed anomaly between the X-ray and electron diffraction patterns of cellophane is a consequence of (i) the larger minimum crystallite size requirement for producing diffraction patterns with X-rays than with the electron beam (ii) the much faster degradation of cellulose II crystallites than that of cellulose I crystallites under the electron beam and (iii) the reduction in the crystallite size of cellulose II in cellophane from that in wood pulp alkali cellulose during the process of regeneration.     

Electrochemical, textural and microstructural effects of mechanical grinding on graphitized petroleum coke for lithium and sodium batteries

A graphitized coke material obtained from petroleum residua was mechanically ground at different milling times between 0 and 100 h. Electrochemical reactions with both lithium and sodium are significantly altered as a function of grinding time. Short-time ball milling of graphite (1 and 5 h) induces a limited decrease in particle size and an increase in microstrain content. Simultaneously, alkali metal intercalation and electrolyte decomposition are hindered, and thus the irreversible and reversible capacities decrease. For longer milling time (up to 100 h), average crystallite size decreases and particles adopt a lamellar shape. Simultaneously, the irreversible capacity increases and correlates with an increase of the resistance, as obtained by impedance spectroscopy. Ex-situ XRD shows that extensively ground graphite samples need a higher discharge specific capacity to reach the formation of n-stages as compared to non-ground graphite, this being indicative of lithium incorporation in energetically different sites to the interlayer space. Sodium storage capacity increases with prolonged grinding time. This effect is shown here for the first time for graphitized cokes.     

IR study of reaction of 2‐butene adsorbed on deuterated ZSM‐5 and mordenite

The dehydrogenation of ethylbenzene to styrene was studied over single-crystalline iron oxide model catalyst films grown epitaxially onto Pt(111) substrates. The role of the iron oxide stoichiometry and of atomic surface defects for the catalytic activity was investigated by preparing single-phased Fe₃O₄(111) and α-Fe₂O₃(0001) films with defined surface structures and varying concentrations of atomic surface defects. The structure and composition of the iron oxide films were controlled by low-energy electron diffraction (LEED) and Auger electron spectroscopy (AES), the surface defect concentrations were determined from the diffuse background intensities in the LEED patterns. These ultrahigh vacuum experiments were combined with batch reactor experiments performed in water–ethylbenzene mixtures with a total gas pressure of 0.6 mbar. No styrene formation is observed on the Fe₃O₄ films. The α-Fe₂O₃ films are catalytically active, and the styrene formation rate increases with increasing surface defect concentration on these films. This reveals atomic surface defects as active sites for the ethylbenzene dehydrogenation over unpromoted α-Fe₂O₃. After 30 min reaction time, the films were deactivated by hydrocarbon surface deposits. The deactivation process was monitored by imaging the surface deposits with a photoelectron emission microscope (PEEM). It starts at extended defects and exhibits a pattern formation after further growth. This indicates that the deactivation is a site-selective process. Post-reaction LEED and AES analysis reveals partly reduced Fe₂O₃ films, which shows that a reduction process takes place during the reaction which also deactivates the Fe₂O₃ films.     

Crystallite Size Measurements on Thoria Gel

As part of a detailed study of the sintering behavior of thoria gel, the crystallite size distribution in the gel was measured by electron microscopy. The distribution is in quantitative agreement with BET surface area and X-ray crystallite size measurement, and X-ray diffraction line profiles calculated using the measured size distribution agree with experiment. The relative accuracies of the integral and half-maximum intensity breadth techniques, and the relation between the size distribution and the crystallite size measured by each technique are discussed. Some implications of this work to the sintering study are mentioned.     

Synthesis of BaTiO3 by applying the sample controlled reaction temperature (SCRT) method to the thermal decomposition of barium titanyl oxalate

BaTiO₃ samples with a tailored microstructure, specific surface areas ranging from 6.5 to 18.5 m²/g, were obtained from the thermal decomposition of barium titanyl oxalate (BTO) by using a sample controlled reaction temperature (SCRT) method. These samples are constituted by nanosized crystallites with cubic structure. The use of reducing atmosphere promotes the size diminution of the coherently diffraction domains. The crystallite size and the strain of powdered BaTiO₃ samples were measured in several crystallographic directions by using the Warren-Averbach multiple order method. The results have shown that crystallite size is isotropic, whereas the strain has a marked anisotropic character.     

激光石墨化过程中激光功率和牵伸力对聚丙烯腈基碳纤维化学结构和微观结构的影响

采用自制的高温激光石墨化平台对聚丙烯腈（PAN）基碳纤维进行石墨化处理,分别在不同激光功率和不同牵伸力条件下制备了多种碳纤维实验样品,利用拉曼光谱和XRD射线衍射研究了不同条件下碳纤维样品的化学结构和微观结构。结果表明：在牵伸力不变时,随着激光功率的增大,碳纤维石墨化程度提高,当激光功率增大到一定值时,单方面继续提高激光功率对于提高碳纤维石墨化程度的影响将变小;在激光功率一定时,随着牵伸力的增大,石墨微晶尺寸L_c、L_a均逐渐增大,而d₀₀₂和取向角逐渐减小,在激光石墨化过程中,施加一定的牵伸力可以促使碳纤维中的石墨微晶沿纤维轴方向择优取向,改善微晶尺寸、减少石墨微晶层间距、提高微晶堆砌层数。