Numerical Simulation of Deflagration to Detonation Transition in a Straight Duct: Effects of Energy Release and Detonation Stability

Numerical simulation based on the Euler equation and one-step reaction model is carried out to investigate the process of deflagration to detonation transition (DDT) occurring in a straight duct. The numerical method used includes a high resolution fifth-order weighted essentially non-oscillatory (WENO) scheme for spatial discretization, coupled with a third order total variation diminishing Runge-Kutta time stepping method. In particular, effect of energy release on the DDT process is studied. The model parameters used are the heat release at $q=50, 30, 25, 20, 15, 10$ and $5$, the specific heat ratio at $1.2$, and the activation temperature at $Ti=15$, respectively. For all the cases, the initial energy in the spark is about the same compared to the detonation energy at the Chapman-Jouguet (CJ) state. It is found from the simulation that the DDT occurrence strongly depends on the magnitude of the energy release. The run-up distance of DDT occurrence decreases with the increase of the energy release for $q$=50~20, and increases with the increase of the energy release for $q$=20~5. This phenomenon is found to be in agreement with the analysis of mathematical stability theory. It is suggested that the factors to strengthen the DDT would make the detonation more stable, and vice versa. Finally, it is concluded from the simulations that the interaction of the shock wave and the flame front is the main reason for leading to DDT.     

Influence of dispersive long-range interactions on properties of vapour–liquid equilibria and interfaces of binary Lennard-Jones mixtures

The influence of dispersive long-range interactions on properties of vapour–liquid equilibria and interfaces of six binary Lennard-Jones (LJ) mixtures was studied by molecular dynamics (MD) simulations and density gradient theory (DGT). The mixtures were investigated at a constant temperature T, at which the low-boiling component, which is the same in all mixtures, is subcritical. Two different high-boiling components were considered: one is subcritical, the other is supercritical at T. Furthermore, the unlike dispersive interaction was varied such that mixtures with three different types of phase behaviour were obtained: ideal, low-boiling azeotrope, and high-boiling azeotrope. In a first series of simulations, the full LJ potential was used to describe these mixtures. To assess the influence of the long-range interactions, these results were compared with simulations carried out with the LJ truncated and shifted (LJTS) potential applying the corresponding states principle. The dispersive long-range interactions have a significant influence on the surface tension and the interfacial thickness of the studied mixtures, whereas the relative adsorption and the enrichment are hardly affected. Furthermore, the influence of the long-range interactions on Henry's law constants and the phase envelopes of the vapour–liquid equilibrium was investigated. The long-range interactions have practically no influence on the composition dependency of the investigated mixture properties.     

Influence of chemical kinetics on spontaneous waves and detonation initiation in highly reactive and low reactive mixtures

Understanding the mechanisms of explosions is important for minimising devastating hazards. Due to the complexity of real chemistry, a single-step reaction mechanism is usually used for theoretical and numerical studies. The purpose of this study is to look more deeply into the influence of chemistry on detonation initiated by a spontaneous wave. The results of high-resolution simulations performed for one-step models are compared with simulations for detailed chemical models for highly reactive and low reactive mixtures. The calculated induction times for H₂/air and for CH₄/air are validated against experimental measurements for a wide range of temperatures and pressures. It is found that the requirements in terms of temperature and size of the hot spots, which can produce a spontaneous wave capable to initiate detonation, are quantitatively and qualitatively different for one-step models compared to detailed chemical models. The time and locations when the exothermic reaction affects the coupling between the pressure wave and spontaneous wave are considerably different for a one-step and detailed models. The temperature gradients capable to produce detonation and the corresponding size of hot spots are much shallower and, correspondingly, larger than those predicted using one-step models. The impact of the detailed chemical model is particularly pronounced for the methane-air mixture. In this case, not only the hot spot size is much greater than that predicted by a one-step model, but even at the elevated pressure, the initiation of detonation by a temperature gradient is possible only if the temperature outside the gradient is rather high, so that can ignite a thermal explosion. The obtained results suggest that the one-step models do not reproduce correctly the transient and ignition processes, so that interpretation of the simulations performed using a one-step model for understanding mechanisms of flame acceleration, DDT and the origin of explosions must be considered with great caution.     

Nuclear hyperfine coupling interactions in the rotational spectra of the linear and bent isomers of HF-N2O

The rotational spectra of six isotopomers of the linear and bent isomers of HF-N₂O have been collected in the 7-18 GHz region with a Fourier transform microwave spectrometer. The nuclear hyperfine structure in the spectra produced by HF spin-spin coupling interaction and nuclear quadrupole coupling interactions due to the D nucleus of DF and the nuclei of N₂O have been resolved and analyzed. In the linear isomer, H in HF is bonded to the terminal N in N₂O. The NF bond lengths are 2.9808(2) Å for the HF-containing isotopomers and 2.9732(2) Å for the DF-containing isotopomers. The zero point angles are 23.1° for HF and 31-34° for N₂O. The hyperfine constants suggest that the HF bond is lengthened by 0.0105 Å upon complexation and that the electric field gradients of the two nitrogen nuclei in N₂O are perturbed differently in the complex. In the bent isomer, the hydrogen bond is formed between HF and O in N₂O. The intermolecular distances are 3.4942(2) Å for the HF-containing isotopomers and 3.4436(2) Å for the DF-containing isotopomers, with HF and N₂O forming angles of 34° and 46°, respectively, with the intermolecular axis. The nuclear quadrupole coupling constants of the two nitrogen nuclei do not indicate electric field gradient perturbation in this isomer.     

The structure of and interactions in binary acetonitrile + water mixtures

Binary liquid mixtures of acetonitrile (AN) and water (W) are widely used as reaction media in such fields of chemistry as physical organic chemistry, reverse phase liquid chromatography, and electrochemistry, among others. Much information on the structure of these systems and the interactions in them has accumulated since the author's often quoted comprehensive 1990 paper, so that a review is merited. Macroscopic physical properties, results from diffraction and spectroscopic studies, theoretical considerations and computer simulations, and results from the use of solute probes all bear on the structure (and less so on the dynamics) of the mixtures. These are discussed in terms of the microheterogeneity that occurs in them at intermediate contents (that leads eventually to liquid‐liquid phase separation). Copyright © 2012 John Wiley & Sons, Ltd.     

Many particle magnetic dipole-dipole and hydrodynamic interactions in magnetizable stent assisted magnetic drug targeting

The implant assisted magnetic targeted drug delivery system of Avilés, Ebner and Ritter is considered both experimentally (in vitro) and theoretically. The results of a 2D mathematical model are compared with 3D experimental results for a magnetizable wire stent. In this experiment a ferromagnetic, coiled wire stent is implanted to aid collection of particles which consist of single domain magnetic nanoparticles (radius ). In order to model the agglomeration of particles known to occur in this system, the magnetic dipole-dipole and hydrodynamic interactions for multiple particles are included. Simulations based on this mathematical model were performed using open source C++ code. Different initial positions are considered and the system performance is assessed in terms of collection efficiency. The results of this model show closer agreement with the measured in vitro experimental results and with the literature. The implications in nanotechnology and nanomedicine are based on the prediction of the particle efficiency, in conjunction with the magnetizable stent, for targeted drug delivery.     

One-dimensional optical bright screening photovoltaic photorefractive solitons, soliton pairs and incoherent interaction between them in BaTiO3 crystal

By the use of theory of optical solitons, nonlinear equations governed by screening photorefractive photovoltaic solitons are introduced. By means of numerical methods, intensity profile, refractive index change of the media and also stability under propagation are investigated. Self-bending of solitons under first-order diffusion is also studied. Besides, incoherent coupled bright-bright soliton pairs and incoherent interaction are studied.     

Numerical studies on autoignition and detonation development from a hot spot in hydrogen/air mixtures

Detonation development inside spark ignition engines can result in the so called super-knock with extremely high pressure oscillation above 200?atm. In this study, numerical simulations of autoignitive reaction front propagation in hydrogen/air mixtures are conducted and the detonation development regime is investigated. A hot spot with linear temperature distribution is used to induce autoignitive reaction front propagation. With the change of temperature gradient or hot spot size, three typical autoignition reaction front modes are identified: supersonic reaction front; detonation development and subsonic reaction front. The effects of initial pressure, initial temperature, fuel type and equivalence ratio on detonation development regime are examined. It is found that the detonation development regime strongly depends on mixture composition (fuel and equivalence ratio) and thermal conditions (initial pressure and temperature). Therefore, to achieve the quantitative prediction of super-knock in engines, we need use the detonation development regime for specific fuel at specific initial temperature, initial pressure, and equivalence ratio.     

One-dimensional optical dark screening photovoltaic-photorefractive solitons, soliton pairs and incoherent interaction between them in BaTiO3 crystal

We studied the theory of the optical solitons and introduced the nonlinear equations governed by the screening photovoltaic-photorefractive dark solitons. By the use of the numerical methods, the intensity profile, refractive index change of the media and also stability under propagation are investigated. Also, we investigated incoherent coupled dark-dark soliton pairs and incoherent interaction between them.     

Water behavior in the neighborhood of hydrophilic and hydrophobic membranes: Lessons from molecular dynamics simulations

The study of properties of water in the vicinity of surfaces poses a fascinating challenge. In this article we studied the behavior of water molecules in the neighborhood of membranes. We addressed the question of how these water molecules are influenced by the membranes’ hydrophilicity. Three systems were studied through molecular dynamics simulations: water in the presence of a hydrophilic membrane (PL), water in the presence of a hydrophobic (PB) one and water in the absence of membranes (BULK). Additionally, in order to study the dependence of the effect of the membrane on the behavior of neighboring water molecules with temperature, each system was simulated at three different temperatures (K): 250, 300 and 350. For each condition, kinetic and structural features were studied. The first feature involved the calculation of diffusion coefficients and activation energy. The second feature was evaluated through the study of water density and hydrogen bond distribution. From the present study we concluded that: (1) density studies underestimate the influence of both hydrophilic and hydrophobic membranes on the neighboring water molecules; (2) the hydrophilic and hydrophobic membranes disturb the hydrogen bond network within distances ranging from 1 to 8 nm, depending on the nature of the membrane and the temperature conditions; (3) the presence of a hydrophobic surface results in an enhancement of the natural hydrogen bond network present in liquid water, to a greater extent than what even an ordered Ih ice structure is able to achieve (i.e. PL membrane); (4) the structural enhancement due to the presence of a hydrophobic surface involves roughly 18 to 24 water hydration layers, for ambient and above temperature conditions.     

Molecular dynamics study on water self-diffusion in aqueous mixtures of methanol,ethylene glycol and glycerol: investigations from the point of view of hydrogen bonding

Molecular dynamics simulations have been performed to investigate the aqueous binary mixtures of alcohols, including methanol, ethylene glycol (EG) and glycerol of molalities ranging from 1 to 5 m at the temperatures of 273, 288 and 298 K, respectively. The primary purpose of this paper is to investigate the mechanism of water self-diffusion in water-alcohol mixtures from the point of view of hydrogen bonding. The effects of temperature and concentration on water self-diffusion coefficient are evaluated quantitatively in this work. Temperature and concentration to some extent affect the hydrogen bonding statistics and dynamics of the binary mixtures. It is shown that the self-diffusion coefficient of water molecules decreases as the concentration increases or the temperature decreases. Moreover, calculations of mean square displacements of water molecules initially with different number n of H-bonds indicate that the water self-diffusion coefficient decreases as n increases. We also studied the aggregation of alcohol molecules by the hydrophobic alkyl groups. The largest cluster size of the alkyl groups clearly increases as the concentration increases, implying the emergence of a closely connected network of water and alcohols. The clusters of water and alcohol that interacted could block the movement of water molecules in binary mixtures. These findings provide insight into the mechanisms of water self-diffusion in aqueous binary mixtures of methanol, EG and glycerol.     

Intermolecular interactions,ion solvation,and association in mixtures of 1‐n‐butyl‐3‐methylimidazolium hexafluorophosphate and γ‐butyrolactone: insights from Raman spectroscopy

By means of Raman spectroscopy coupled with density functional theory (DFT) calculations and perturbation correlation moving window two‐dimensional correlation spectroscopy intermolecular interactions were assessed in mixtures of ionic liquid (IL) 1‐n‐butyl‐3‐methylimidazolium hexafluorophosphate (BmimPF₆) with polar aprotic solvent γ‐butyrolactone (γ‐BL) over the entire range of compositions. The symmetrical P―F stretching vibration of the IL anion was found to be insensitive to the changes in mixture concentration in contrast to the CO stretching vibration of the γ‐BL and the imidazolium ring C―H stretching vibrations of the IL cation. Each of these vibrational profiles was decomposed in various spectral contributions, and their number was rationalized by the results of quantum‐chemical calculations and/or previous controversial published data. Progressive redshift of the ring C―H stretching wavenumbers was referred to pronounced solvation of the cation at the imidazolium ring site accompanied with H‐bond formation. This was especially pronounced at IL mole fraction less than 0.18. Complicated variations in the intensities of the individual contributions of the CO profile were treated as a manifestation of the changing with concentration pattern of the intermolecular interactions. The self‐association of γ‐BL molecules and distinct cation solvation as dominant intermolecular interactions at low IL content are replaced with weaker cation solvation and ion association at high concentrations of IL. Possible representative molecular structures were proposed on the basis of DFT calculations. Copyright © 2015 John Wiley & Sons, Ltd.