Graphite intercalation compounds under pressure

Motivated by recent experimental work, we use first-principles density functional theory methods to conduct an extensive search for low enthalpy structures of C$_6$Ca under pressure. As well as a range of buckled structures, which are energetically competitive over an intermediate range of pressures, we show that the high pressure system ($\gtrsim 18$ GPa) is unstable towards the formation of a novel class of layered structures, with the most stable compound involving carbon sheets containing five- and eight-membered rings. As well as discussing the energetics of the different classes of low enthalpy structures, we comment on the electronic structure of the high pressure compound and its implications for superconductivity.

A detailed chemistry multi-cycle simulation of a gasoline fueled HCCI engine operated with NVO

A previously developed Stochastic Reactor Model (SRM) is used to simulate combustion in a four cylinder in-line four-stroke naturally aspirated direct injection Spark Ignition (SI) engine modified to run in Homogeneous Charge Compression Ignition (HCCI) mode with a Negative Valve Overlap (NVO). A portion of the fuel is injected during NVO to increase the cylinder temperature and enable HCCI combustion at a compression ratio of 12:1. The model is coupled with GT-Power, a one-dimensional engine simulation tool used for the open valve portion of the engine cycle. The SRM is used to model in-cylinder mixing, heat transfer and chemistry during the NVO and main combustion. Direct injection is simulated during NVO in order to predict heat release and internal Exhaust Gas Recycle (EGR) composition and mass. The NOx emissions and simulated pressure profiles match experimental data well, including the cyclic fluctuations. The model predicts combustion characteristics at different fuel split ratios and injection timings. The effect of fuel reforming on ignition timing is investigated along with the causes of cycle to cycle variations and unstable operation. A detailed flux analysis during NVO unearths interesting results regarding the effect of NOx on ignition timing compared with its effect during the main combustion. © 2009 SAE International.

Forcing of self-excited round jet diffusion flames

In this experimental and numerical study, two types of round jet are examined under acoustic forcing. The first is a non-reacting low density jet (density ratio 0.14). The second is a buoyant jet diffusion flame at a Reynolds number of 1100 (density ratio of unburnt fluids 0.5). Both jets have regions of strong absolute instability at their base and this causes them to exhibit strong self-excited bulging oscillations at welldefined natural frequencies. This study particularly focuses on the heat release of the jet diffusion flame, which oscillates at the same natural frequency as the bulging mode, due to the absolutely unstable shear layer just outside the flame. The jets are forced at several amplitudes around their natural frequencies. In the non-reacting jet, the frequency of the bulging oscillation locks into the forcing frequency relatively easily. In the jet diffusion flame, however, very large forcing amplitudes are required to make the heat release lock into the forcing frequency. Even at these high forcing amplitudes, the natural mode takes over again from the forced mode in the downstream region of the flow, where the perturbation is beginning to saturate non-linearly and where the heat release is high. This raises the possibility that, in a flame with large regions of absolute instability, the strong natural mode could saturate before the forced mode, weakening the coupling between heat release and incident pressure perturbations, hence weakening the feedback loop that causes combustion instability. © 2009 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Experimental investigation of a control method for SI-HCCI-SI transition in a multi-cylinder gasoline engine

In HCCI engines, the Air/Fuel Ratio (AFR) and Residual Gas Fraction (RGF) are difficult to control during the SI-HCCI-SI transition, and this may result in incomplete combustion and/or high pressure raise rates. As a result, there may be undesirably high engine load fluctuations. The objectives of this work are to further understand this process and develop control methods to minimize these load fluctuations. This paper presents data on instantaneous AFR and RGF measurements, both taken by novel experimental techniques. The data provides an insight into the cyclic AFR and RGF fluctuations during the switch. These results suggest that the relatively slow change in the intake Manifold Air Pressure (MAP) and actuation time of the Variable Valve Timing (VVT) are the main causes of undesired AFR and RGF fluctuations, and hence an unacceptable Net IMEP (NIMEP) fluctuation. We also found large cylinder-to-cylinder AFR variations during the transition. Therefore, besides throttle opening control and VVT shifting, cyclic and individual cylinder fuel injection control is necessary to achieve a smooth transition. The control method was developed and implemented in a test engine, and the result was a considerably reduced NIMEP fluctuation during the mode switch. The instantaneous AFR and RGF measurements could furthermore be adopted to develop more sophisticated control methods for SI-HCCI-SI transitions. © 2010 SAE International.

Methane chemistry involved in a low-pressure electron cyclotron wave resonant plasma discharg

A low-pressure methane plasma generated by electron cyclotron wave resonance was characterized in terms of electron temperature, plasma density and composition. Methane plasmas were commonly used in the deposition of hydrogenated amorphous carbon thin films. Little variation in the plasma chemistry was observed by mass spectrometry measurements of the gas phase with increasing electron temperature. The results show that direct electron-impact reactions exert greater influence on the plasma chemistry than secondary ion-neutral reactions.

Nitrogen incorporation into tetrahedral hydrogenated amorphous carbon

Structural changes induced by the incorporation of nitrogen into ta-C : H films have been studied by Electron Energy Loss Spectroscopy, X-Ray Photoelectron Spectroscopy, Fourier Transformed Infrared Spectroscopy and Ultraviolet-Visible Spectroscopy. ta-C:H films have been synthesised using a low pressure Electron Cyclotron Wave Resonance (ECWR) source which provides a plasma beam with a high degree of ionisation and dissociation. Nitrogen was incorporated by adding N2 to the C2H2 plasma used for the deposition of ta-C : H films. The N/C atomic ratio in the films rises rapidly until the N2/C2H2 gas ratio reaches three, and then increases more gradually, while the deposition rate decreases steeply. Chemical sputtering of the forming films and the formation of molecular nitrogen within the films limit the maximum nitrogen content to about N/C = 0.6. For low nitrogen content the films retain their diamond-like properties, however as N/C atomic ratio increases, a polymeric-like material is formed, with >C=N- structures and terminating C=N and NH groups that decrease the connectivity of the network.

A constitutive description of the inelastic response of ceramics

The objective of the article is to present a unified model for the dynamic mechanical response of ceramics under compressive stress states. The model incorporates three principal deformation mechanisms: (i) lattice plasticity due to dislocation glide or twinning; (ii) microcrack extension; and (iii) granular flow of densely packed comminuted particles. In addition to analytical descriptions of each mechanism, prescriptions are provided for their implementation into a finite element code as well as schemes for mechanism transitions. The utility of the code in addressing issues pertaining to deep penetration is demonstrated through a series of calculations of dynamic cavity expansion in an infinite medium. The results reveal two limiting behavioral regimes, dictated largely by the ratio of the cavity pressure p to the material yield strength σY. At low values of p/σY, cavity expansion occurs by lattice plasticity and hence its rate diminishes with increasing σY. In contrast, at high values, expansion occurs by microcracking followed by granular plasticity and is therefore independent of σY. In the intermediate regime, the cavity expansion rate is governed by the interplay between microcracking and lattice plasticity. That is, when lattice plasticity is activated ahead of the expanding cavity, the stress triaxiality decreases (toward more negative values) which, in turn, reduces the propensity for microcracking and the rate of granular flow. The implications for penetration resistance to high-velocity projectiles are discussed. Finally, the constitutive model is used to simulate the quasi-static and dynamic indentation response of a typical engineering ceramic (alumina) and the results compared to experimental measurements. Some of the pertinent observations are shown to be captured by the present model whereas others require alternative approaches (such as those based on fracture mechanics) for complete characterization. © 2011 The American Ceramic Society.