X-ray absorption fine structure (XAFS) spectra were collected on a series of ferrihydrite samples prepared over a range of precipitation and drying conditions. Analysis of the XAFS pre-edge structures shows clear evidence of the presence of lower coordination sites in the material. These sites, which are most likely tetrahedral, are believed to be at the surface and become coordination unsaturated (CUS) after dehydroxylation. With chemisorbed water molecules, the CUS sites become the crystal growth sites responsible for the phase transformation of ferrihydrite to hematite at low temperatures. On the other hand, when impurity anions such as SiO4−4 are present in the precipitation solution, the CUS sites may instead absorb the impurity anions, thereby blocking the crystal growth sites and inhibiting the formation of hematite.

Atomistic simulations of 2:1 clay minerals based on parameterized forcefields have been applied successfully to provide a detailed description of the interfacial structure and dynamics of basal planes and interlayers, but have made limited progress in exploring the edge surfaces of these ubiquitous layer-type aluminosilicates. In the present study, molecular dynamics simulations and energy-minimization calculations of the edge surfaces using the fully flexible CLAYFF forcefield are reported. Pyrophyllite provides an ideal prototype for the 2:1 clay-mineral edge surface because it possesses no structural charge, thus rendering the basal planes inert, while crystal-growth theory can be applied to identify two major candidates for the structure of the edge surfaces. Models based on these candidate structures reproduced bulk crystal bond distances accurately when compared to X-ray data and ab initio molecular simulations, and the predicted edge surface bond distances were in agreement with those determined via ab initio simulation. The calculated surface free energy and surface stress led to an accurate prediction of pyrophyllite nanoparticle morphology, while surface excess energies calculated for the edge surfaces were always negative. These results are consistent with the observed pyrophyllite nanoparticle morphology, with the concept of negative interfacial energies, and conditions that may give rise to them including a role in the stabilization of layer-type nanoparticulate minerals. Molecular dynamics simulations of hydrated nanoparticle edge surfaces indicated five reactive surface oxygen sites on the dominant candidate edge, in agreement with a recent model of proton titration data for 2:1 clay minerals. These promising results illustrate the potential for classical mechanical atomistic simulations that explore edge surface phenomena at much greater length- and times-scales than are currently possible with computationally expensive ab initio methods.

The atomic structure of dioctahedral 2:1 phyllosilicate edge surfaces was calculated using pseudopotential planewave density functional theory. Bulk structures of pyrophyllite and ferripyrophyllite were optimized using periodic boundary conditions, after which crystal chemical methods were used to obtain initial terminations for ideal (110)- and (010)-type edge surfaces. The edge surfaces were protonated using various schemes to neutralize the surface charge, and total minimized energies were compared to identify which schemes are the most energetically favorable. The calculations show that significant surface relaxation should occur on the (110)-type faces, as well as in response to different protonation schemes on both surface types. This result is consistent with atomic force microscopy observations of phyllosilicate dissolution behavior. Bond-valence methods incorporating bond lengths from calculated structures can be used to predict intrinsic acidity constants for surface functional groups on (110)- and (010)-type edge surfaces. However, the occurrence of surface relaxation poses problems for applying current bond-valence methods. An alternative method is proposed that considers bond relaxation, and accounts for the energetics of various protonation schemes on phyllosilicate edges.

Crystal truncation rod (CTR) X-ray diffraction is an invaluable tool for measuring mineral surface and adsorbate structures, and has been applied to several environmentally and geochemically important systems. Traditionally, the method has been restricted to single crystals with lateral dimensions >3 mm. Minerals that meet this size criterion represent a minute fraction of those that are relevant to interfacial geochemistry questions, however. Crystal screening, data collection, and CTR measurement methods have been developed for crystals of <0.3 mm in lateral size using the manganese oxide mineral chalcophanite (ZnMn3O7·3H2O) as a case study. This work demonstrates the feasibility of applying the CTR technique to previously inaccessible surfaces, opening up a large suite of candidate substrates for future study.

The characterization of freshly cleaved mica surfaces for surface structure and chemical composition was briefly reviewed and focused on surface crystal chemistry using X-ray photoelectron spectroscopy (XPS) and other surface-sensitive techniques. This paper considers micas, which are useful as a first approximation for the behavior of many clay surfaces. Emphasis was given to phyllosilicate XPS binding energies (“chemical shift”), which were described and used to obtain oxidation state, layer charge, and chemical bonding information from the chemical shifts of different peaks. The chemical shift of the Si2p binding-energy to lower values can result from a negative charge increase because of Si4+ replacement by Al3+ and/or Fe3+. The apparent interlayer coordination number reduction from twelve to eight at muscovite and tetraferri-phlogopite (001) surfaces was indicated by the XPS measured K2p binding-energy and is consistent with bond relaxation. Although chemical shifts are valuable to distinguish chemical bonding and oxidation state, chemical shifts usually cannot distinguish between different Al coordination environments where Al is in both tetrahedral and octahedral sites.

Supercritical carbon dioxide (scCO2) processing has been proven as a method for preparing polymer/montmorillonite (MMT) nanocomposites with improved platelet dispersion. The influence of scCO2 processing on the shape and size of the MMT tactoid/platelet, which is of great importance to the final platelet dispersion in the polymer matrix, is scarcely reported in the literature. In the present study, the pristine MMT was first surface modified with 3-glycidoxypropyltrimethoxysilane (the grafted MMT is labeled as GMMT), and then intercalated using three kinds of intercalating agents, myristyltrimethyl-ammonium bromide (MTAB), tetradecyltrihexylphosphonium chloride (TDTHP), and ethoxyltriphenyl-phosphonium chloride (ETPC), in water or scCO2, to study the effect of intercalating agent type and intercalation method on the morphology and thermal properties of GMMT, as a part of a program devoted to the synthesis of polymer/MMT nanocomposites. The structure of intercalated GMMT was characterized by thermogravimetric analysis, X-ray powder diffraction, and scanning electron microscopy (SEM). The optimum intercalation conditions in scCO2 were established by trying a range of reaction times and pressures. The structures of intercalated GMMT obtained under optimum scCO2 conditions and water were compared. The basal spacing of GMMT intercalated in scCO2 was almost the same as that in water, and both were obviously larger than that of GMMT. The GMMT exhibited a compact spherical morphology (examined using SEM), and the surface structures (including surface morphology, surface roughness, and surface compactness) of samples intercalated in water became ‘less compact’ and the degree of the ‘compactness’ of samples intercalated in scCO2 decreased further. Whether in water or scCO2, samples intercalated with TDTHP exhibited a larger basal spacing and the extent of disorder increased compared to that for samples intercalated with MTAB. The pristine MMT was also intercalated for comparison and silane grafting was proven to contribute to the increased basal spacing and ‘less compact’ surface structure.

This paper aims to explore the influence of solvent effects on the crystal habit of venlafaxine hydrochloride using the modified attachment energy (MAE) model by molecular dynamics (MD) simulation. Solvent effects were investigated based on the different morphologies of venlafaxine hydrochloride acquired by simulation and experimental technology from the solvents of isopropanol, dimethyl sulfoxide, and acetonitrile. Firstly, morphologically dominant crystal faces were obtained through the prediction of crystal habit in vacuum by the attachment energy (AE) model. Subsequently, the MAEs were calculated by the MD simulation to modify the crystal shapes in a real solvent environment, and the simulation results were in agreement with the experimental ones. Meanwhile, in order to have a better understanding of the solvent effects, the surface structure was introduced to analyze the solvent adsorption behaviors. The results show that the crystal habits of venlafaxine hydrochloride are affected by the combination of the AE and surface structures. Finally, the flowability of the obtained crystal powders from different solvents was investigated by measurement and analysis of the angle of repose and compressibility. The above results verify that the physical properties are closely related to the morphologies of the crystals.

To maintain functional tolerances of gear sets over their lifetime, especially in polymer-seel gear sets, the wear behaviour must be considered. The state of the art in wear modelling does not take the run-in behaviour of polymer-metal contacts into account. This results in oversizing of wear allowances in the stationary wear phase and undersizing in the run-in phase. Therefore, a modified wear model is presented in this paper. With this method the issues of over- and undersizing can be eliminated.

The method is then applied in a case study to show two things. Firstly, using the presented method the calculated necessary wear allowances were reduced by 30%. Secondly, the effect of surface structures on the wear behaviour was investigated. It is shown that the run-in process is not dependent on roughness in sliding direction, but on overall contact area. Thus, the state of the art, i.e. tolerating only the roughness in sliding direction, is insufficient. Considering the process-induced surface topology during design of gear sets can decrease run-in wear. Together with the optimised wear model, this allows wider manufacturing tolerances and thus lower costs during production.

Cathodoluminescence (CL) provides a sensitive analytical probe of the near-surface region of insulating materials, and some new examples of the strengths of the technique are presented using recent data from the University of Sussex. Analysis of float glass shows that by spectral and lifetime resolved data it is possible to separate the emission bands from excitonic, intrinsic imperfections, and impurities in various valence states, as a function of their depth beneath the surface. Correlation of the CL data with those from Mössbauer, ion beam and other analyses then provides the basis for models of the defect sites. CL from a second glass, ZBLAN, reveals the presence of microcrystallites and growth defects, and the work underpins confidence in the high purity gas levitation method of ZBLAN production. New results on CL of wavelength shifts with crystal field of Mn in carbonates are presented, and of Nd emission from Nd:YAG. The effects are directly linked to surface damage and dislocations caused by sample preparation steps of cutting and polishing. Methods to minimise the damage, by furnace or pulsed laser annealing, and chemical routes, are mentioned. Such surface preparation damage has a profound effect on all CL monitoring, whether for fundamental studies or mineralogical applications. Finally, a route to eliminate such problems is demonstrated, with consequent improvements in luminescence, transmission and laser performance of surface waveguides. The implications of improved surface quality range widely from mineralogical CL imaging through improved photonic materials and epitaxial growth to elimination of surface damage, and additional information.

This article is an edited transcript based on the MRS Medal Award presentation given by Jacob N. Israelachvili on December 1, 2004, at the Materials Research Society Fall Meeting in Boston. An expanded article on this topic will be published in the August 2005 issue of the Journal of Materials Research. Recent experimental results have shown how surface texture, surface energy, and the bulk properties of materials can affect their adhesion and friction and, in turn, determine some of the fundamental differences between modes of failure of materials. Theoretical modeling and computer simulations, among other methods, provide examples and comparisons of surfaces that are rough or smooth, hard or soft (for example, viscoelastic), adhesive or non-adhesive, and dry (unlubricated) or lubricated. Such studies clarify the molecular and atomic basis of many well-established adhesion and tribological laws and empirical observations, revealing insights and relationships between nanoscale (molecular) and macroscale processes. Also of critical importance are the effects that occur at the sub-nanoscale, that is, in the sub-angstrom or picoscale regime. It is demonstrated and argued that the ultrafine picoscale details of a surface lattice, or its roughness, can be the most important factor in determining its friction (and mode II fracture), whereas such effects are quantitatively less important for adhesion and mode I fracture processes.

High-resolution transmission (HRTEM) and high-resolution scanning electron microscopy as well as atomic force microscopy (AFM), X-ray diffraction, and electron diffraction were used for studying the zeolites MFI, MEL, and the MFI/MEL intergrowth system. All three zeolites consisted of individual particles having a size in the range of approximately 0.5 μm to 5 μm. The particle habits varied from rather cubelike to almost spherelike with many intermediate habits. Typically, the particles of these three zeolites were assembled by many individual blocks that differed in the dimension from about 25 nm to 140 nm as well as in the shape from very frequently almost rectangular (for MFI, MEL, and MFI/MEL) to sometimes roundish or irregular habits (mainly for MFI/MEL). An estimate shows that some 104 up to more than 106 densely packed blocks typically may assemble each individual zeolite particle or, related to the corresponding unit cell dimension, about 108 up to 1010 unit cells. The fine surface structure of zeolite particles was terracelike with steps between adjacent terraces typically in the range of 20 nm to 60 nm; the minimum step measured was approximately 4 nm. A detailed study of the surface topography was performed by AFM, detecting organic molecules at the block intersections. The presence of topological defects was observed by HRTEM and electron diffraction.

About 1 monolayer of palladium was deposited onto a silicon (111) 7 × 7 surface at a temperature of about 550 K inside an ultrahigh vacuum transmission electron microscope, resulting in formation of Pd2Si nanoislands and a 1 × 1 surface layer. Pd clusters created from an excess of Pd atoms on the 1 × 1 surface layer were directly observed by in situ plan view high-resolution transmission electron microscopy. When an objective aperture was introduced so that electron diffractions less than 0.20 nm were filtered out, the lattice structure of the 1 × 1 surface with 0.33 nm spacing and the Pd clusters with a trimer shape were visualized. It was found that image contrast of the 1 × 1 lattice on the specific height terraces disappeared, and thereby an atomic structure of the Pd clusters was clearly observed. The appearance and disappearance of the 1 × 1 lattice was explained by the effect of the kinematical diffraction. It was identified that a Pd cluster was composed of three Pd atoms without a centered Si atom, which is consistent with the model proposed previously. The feature of the Pd clusters stuck at the surface step was also described.

Extended defect reduction at the surface of GaN grown by lateral epitaxial overgrowth (LEO) on large-area GaN/Al2O3 wafers by low pressure MOCVD is demonstrated by atomic force microscopy. The overgrown GaN has a rectangular cross section with smooth (0001) and {110} facets. The density of mixed character threading dislocations at the surface of the LEO GaN is reduced by at least 3-4 orders of magnitude from that of bulk GaN. Dislocation-free GaN surfaces exhibit an anisotropic step structure that is attributed to the orientation dependence of the dangling bond density at the step edges.