Ni-silicide growth kinetics in Si and Si/SiO2 core/shell nanowires.

A systematic study of the kinetics of axial Ni silicidation of as-grown and oxidized Si nanowires (SiNWs) with different crystallographic orientations and core diameters ranging from ∼ 10 to 100 nm is presented. For temperatures between 300 and 440 °C the length of the total axial silicide intrusion varies with the square root of time, which provides clear evidence that the rate limiting step is diffusion of Ni through the growing silicide phase(s). A retardation of Ni-silicide formation for oxidized SiNWs is found, indicative of a stress induced lowering of the diffusion coefficients. Extrapolated growth constants indicate that the Ni flux through the silicided NW is dominated by surface diffusion, which is consistent with an inverse square root dependence of the silicide length on the NW diameter as observed for (111) orientated SiNWs. In situ TEM silicidation experiments show that NiSi(2) is the first forming phase for as-grown and oxidized SiNWs. The silicide-SiNW interface is thereby atomically abrupt and typically planar. Ni-rich silicide phases subsequently nucleate close to the Ni reservoir, which for as-grown SiNWs can lead to a complete channel break-off for prolonged silicidation due to significant volume expansion and morphological changes.

An investigation of the kinetics of CO2 uptake by a synthetic calcium based sorbent

This study examines the kinetics of carbonation by CO2 at temperatures of ca. 750 °C of a synthetic sorbent composed of 15 wt% mayenite (Ca12Al14O33) and CaO, designated HA-85-850, and draws comparisons with the carbonation of a calcined limestone. In-situ XRD has verified the inertness of mayenite, which neither interacts with the active CaO nor does it significantly alter the CaO carbonation–calcination equilibrium. An overlapping grain model was developed to predict the rate and extent of carbonation of HA-85-850 and limestone. In the model, the initial microstructure of the sorbent was defined by a discretised grain size distribution, assuming spherical grains. The initial input to the model – the size distribution of grains – was a fitted parameter, which was in good agreement with measurements made with mercury porosimetry and by the analysis of SEM images of sectioned particles. It was found that the randomly overlapping spherical grain assumption offered great simplicity to the model, despite its approximation to the actual porous structure within a particle. The model was able to predict the performance of the materials well and, particularly, was able to account for changes in rate and extent of reaction as the structure evolved after various numbers of cycles of calcination and carbonation.

An investigation of the kinetics of CO 2 uptake by a synthetic calcium based sorbent

This study examines the kinetics of carbonation by CO 2 at temperatures of ca. 750°C of a synthetic sorbent composed of 15wt% mayenite (Ca 12Al 14O 33) and CaO, designated HA-85-850, and draws comparisons with the carbonation of a calcined limestone. In-situ XRD has verified the inertness of mayenite, which neither interacts with the active CaO nor does it significantly alter the CaO carbonation-calcination equilibrium. An overlapping grain model was developed to predict the rate and extent of carbonation of HA-85-850 and limestone. In the model, the initial microstructure of the sorbent was defined by a discretised grain size distribution, assuming spherical grains. The initial input to the model - the size distribution of grains - was a fitted parameter, which was in good agreement with measurements made with mercury porosimetry and by the analysis of SEM images of sectioned particles. It was found that the randomly overlapping spherical grain assumption offered great simplicity to the model, despite its approximation to the actual porous structure within a particle. The model was able to predict the performance of the materials well and, particularly, was able to account for changes in rate and extent of reaction as the structure evolved after various numbers of cycles of calcination and carbonation. © 2011 Elsevier Ltd.

Measuring the kinetics of amyloid fibril elongation using quartz crystal microbalances.

Kinetic measurements of amyloid growth provide insight into the free energy landscape of this supramolecular process and are crucial in the search for potent inhibitors of the main disorders with which it is associated, including Alzheimer's and Parkinson's diseases and Type II diabetes. In recent years, a new class of surface-bound biosensor assays, e.g., those based on surface plasmon resonance (SPR) and the quartz crystal microbalance (QCM) have been established as extremely valuable tools for kinetic measurements of amyloid formation. Here we describe detailed protocols of how QCM techniques can be used to monitor the elongation of amyloid fibrils in real time and to study the influence of external factors on the kinetics of amyloid growth with unprecedented accuracy.

Catalyst composition and impurity-dependent kinetics of nanowire heteroepitaxy.

The mechanisms and kinetics of axial Ge-Si nanowire heteroepitaxial growth based on the tailoring of the Au catalyst composition via Ga alloying are studied by environmental transmission electron microscopy combined with systematic ex situ CVD calibrations. The morphology of the Ge-Si heterojunction, in particular, the extent of a local, asymmetric increase in nanowire diameter, is found to depend on the Ga composition of the catalyst, on the TMGa precursor exposure temperature, and on the presence of dopants. To rationalize the findings, a general nucleation-based model for nanowire heteroepitaxy is established which is anticipated to be relevant to a wide range of material systems and device-enabling heterostructures.

Growth kinetics and uniform scaling-up of graphene synthesis

Chemical vapor deposition on copper is the most widely used method to synthesize graphene at large scale. However, the clear understanding of the fundamental mechanisms that govern this synthesis is lacking. Using a vertical-flow, cold-wall reactor with short gas residence time we observe the early growths to study the kinetics of chemical vapor deposition of graphene on copper foils and demonstrate uniform synthesis at wafer scale. Our results indicate that the growth is limited by the catalytic dissociative dehydrogenation on the surface and copper sublimation hinders the graphene growth. We report an activation energy of 3.1 eV for ethylene-based graphene synthesis. © The Electrochemical Society.