Formation of metastable liquid catalyst during subeutectic growth of germanium nanowires.

Lattice-resolved, video-rate environmental transmission electron microscopy shows the formation of a liquid Au-Ge layer on sub-30-nm Au catalyst crystals and the transition of this two-phase Au-Ge/Au coexistence to a completely liquid Au-Ge droplet during isothermal digermane exposure at temperatures far below the bulk Au-Ge eutectic temperature. Upon Ge crystal nucleation and subsequent Ge nanowire growth, the catalyst either recrystallizes or remains liquid, apparently stabilized by the Ge supersaturation. We argue that there is a large energy barrier to nucleate diamond-cubic Ge, but not to nucleate the Au-Ge liquid. As a result, the system follows the more kinetically accessible path, forming a liquid even at 240 degrees C, although there is no liquid along the most thermodynamically favorable path below 360 degrees C.

The oxidation of CH2O in the intermediate temperature range (943-995 K)

New atmospheric pressure flow reactor data on the oxidation of formaldehyde in the temperature range 943-995 K and over equivalence ratios from 0.013 to 36.7 are reported and discussed. A detailed mechanism assembled from previously published results produced acceptable agreement with the experimental data for the fuel-lean conditions, but failed to predict results for oxidative pyrolysis. Analysis or the very fuel-lean conditions, but failed to modelling results are principally sensitive to CH2O+HO2→HCO+H2O2 (6) and H2O2 +M→OH+OH+M (33). Whereas the specific rate of each reaction cannot be independently determined, it is found that the product k33.k6 is a well defined function of temperature: (3.4±3.0).1028 exp(-(26,800±400)/T). Inadequacies in the mechanism which may be responsible for the disagreement under fuel-rich conditions are discussed. © 1991 Combustion Institute.

The local and global stability of confined planar wakes at intermediate Reynolds number

At high Reynolds numbers, wake flows become more globally unstable when they are confined within a duct or between two flat plates. At Reynolds numbers around 100, however, global analyses suggest that such flows become more stable when confined, while local analyses suggest that they become more unstable. The aim of this paper is to resolve this apparent contradiction by examining a set of obstacle-free wakes. In this theoretical and numerical study, we combine global and local stability analyses of planar wake flows at $\mathit{Re}= 100$ to determine the effect of confinement. We find that confinement acts in three ways: it modifies the length of the recirculation zone if one exists, it brings the boundary layers closer to the shear layers, and it can make the flow more locally absolutely unstable. Depending on the flow parameters, these effects work with or against each other to destabilize or stabilize the flow. In wake flows at $\mathit{Re}= 100$ with free-slip boundaries, flows are most globally unstable when the outer flows are 50 % wider than the half-width of the inner flow because the first and third effects work together. In wake flows at $\mathit{Re}= 100$ with no-slip boundaries, confinement has little overall effect when the flows are weakly confined because the first two effects work against the third. Confinement has a strong stabilizing effect, however, when the flows are strongly confined because all three effects work together. By combining local and global analyses, we have been able to isolate these three effects and resolve the apparent contradictions in previous work.

Metastable crystalline AuGe catalysts formed during isothermal germanium nanowire growth

We observe the formation of metastable AuGe phases without quenching, during strictly isothermal nucleation and growth of Ge nanowires, using video-rate lattice-resolved environmental transmission electron microscopy. We explain the unexpected formation of these phases through a novel pathway involving changes in composition rather than temperature. The metastable catalyst has important implications for nanowire growth, and more broadly, the isothermal process provides both a new approach to growing and studying metastable phases, and a new perspective on their formation. © 2012 American Physical Society.

Complex chemistry DNS of n-heptane spray autoignition at high pressure and intermediate temperature conditions

Direct Numerical Simulations (DNS) of turbulent n-heptane sprays autoigniting at high pressure (P=24bar) and intermediate air temperature (Tair=1000K) have been performed to investigate the physical mechanisms present under conditions where low-temperature chemistry is expected to be important. The initial turbulence in the carrier gas, the global equivalence ratio in the spray region, and the initial droplet size distribution of the spray were varied. Results show that spray ignition exhibits a spotty nature, with several kernels developing independently in those regions where the mixture fraction is close to its most reactive value ξMR (as determined from homogeneous reactor calculations) and the scalar dissipation rate is low. Turbulence reduces the ignition delay time as it promotes mixing between air and the fuel vapor, eventually resulting in lower values of scalar dissipation. High values of the global equivalence ratio are responsible for a larger number of ignition kernels, due to the higher probability of finding regions where ξ=ξMR. Spray polydispersity results in the occurrence of ignition over a wider range of mixture fraction values. This is a consequence of the inhomogeneities in the mixing field that characterize these sprays, where poorly mixed rich spots are seen to alternate with leaner ones which are well-mixed. The DNS simulations presented in this work have also been used to assess the applicability of the Conditional Moment Closure (CMC) method to the simulation of spray combustion. CMC is found to be a valid method for capturing spray autoignition, although care should be taken in the modelling of the unclosed terms appearing in the CMC equations. © 2013 The Combustion Institute.

Modelling and design of stress-induced martensite formation in metastable β Ti alloys

The temperature dependence of the stress-induced martensite (SIM) formation in a Ti-10V-2Fe-3Al (Ti-1023) alloy under compressive loading has been studied. At low temperatures, the stress level at which martensite starts to form increases linearly with the deformation temperature, while the stress at which the deformation switches to regular plastic deformation is roughly temperature independent. A thermostatistical model for dislocation evolution is employed to describe deformation twinning in martensite. Combined effects of twinning induced plasticity and solid solution strengthening are considered in terms of temperature variations. The SIM effect disappears on deformation at temperatures beyond ~ 233 ° C, which is close to the predicted Ms temperature of 240°C. The thermostatistical model predicts a transition from twinned martensite to pure slip at 250°C. By providing a model to predict the martensite formation, and by describing deformation twinning, the present work provides a number of tools that may be employed to conceive new titanium alloys combining improved strength and ductility. © 2013 Elsevier B.V.