Transport and relaxation properties of isotopomeric hydrogen–helium binary mixtures. II. HD,D2, T2–He mixtures

The comprehensive comparison between calculated bulk non-equilibrium properties of hydrogen–helium isotopomeric mixtures and experiment that has previously been carried out for H₂–helium mixtures [2004, Molec. Phys., submitted] has been extended to mixtures of HD, D₂ and T₂ with ³He and ⁴He. For HD–⁴He mixtures, comparison is also made, where possible, with previous calculations of Köhler and Schaefer [1983, Physica A, 120, 185]. The phenomena examined herein include low temperature interaction second virial coefficients, binary diffusion and thermal conductivity coefficients, rotational relaxation, transport property field effects and flow birefringence. Scattering calculations have been carried out for the HD–He PES of Schaefer and Köhler [1985, Physica A, 129, 469], and for both the Köhler–Schaefer and Tao [1994, J. chem. Phys., 100, 4947] potential surfaces for the D₂–He and T₂–He interactions. Comparisons between calculated and experimental results for HD, D₂, T₂–He mixtures confirm the conclusion, reached earlier from the H₂–He comparisons, that these potential surfaces are very close to the correct one for the hydrogen–helium interaction, and that the small differences between them cannot be distinguished readily by measurements of bulk gas phenomena unless the attendant experimental uncertainties are better than ±0.3%.     

Transport properties of H–N2 mixtures

Transport coefficients (shear viscosity, volume viscosity, thermal conductivity, and mass and thermal diffusion coefficients) of H–N₂ mixtures in the dilute-gas limit have been calculated from the intermolecular potential in the temperature range 300–2000K using the classical trajectory method. The intermediate results pertaining to H–N₂ binary interactions are reported, mainly in terms of cross-section ratios. Cross-sections evaluated with the Mason–Monchick approximation yield very good results for this system, the largest deviations, about 2.5%, being observed for the thermal diffusion coefficient. The accuracy here of this approximation can primarily be attributed to a light H atom and a weakly non-spherical potential resulting in a high rotational collision number. Furthermore, we investigate to which H–N₂ cross-sections and their ratios the values of the mixture transport coefficients are most sensitive. Our results indicate that, for some cross-section ratios, reliance on universal correlations at high temperatures, often used in flame codes, can induce sizeable errors in the thermal conductivity coefficient and especially in the thermal diffusion coefficients. We also observed that the volume viscosity is particularly sensitive to the value of the cross-section for internal energy relaxation in H–N₂ collisions.     

Shock wave dispersion of gas–particle mixtures

The decay of a discontinuity in a two-component homogeneous gas mixture and the dispersion of a gas–particle mixture with a two-component carrier medium are numerically simulated. The mathematical model of the dynamics of heterogeneous media takes into account the interphase force interaction and interphase heat exchange. Experimental results known from the literature are compared with numerical results describing the dispersion of a gas–particle mixture in a shock tube.     

Pulsating one-dimensional detonations in hydrogen–air mixtures

The propagation of one-dimensional detonations in hydrogen–air mixtures is investigated numerically by solving the one-dimensional Euler equations with detailed finite-rate chemistry. The numerical method is based on a second-order spatially accurate total-variation-diminishing scheme and a point implicit time marching algorithm. The hydrogen–air combustion is modelled with a 9-species, 19-step reaction mechanism. A multi-level, dynamically adaptive grid is utilized, in order to resolve the structure of the detonation. Parametric studies for an equivalence ratio range of 0.4–2.0, initial pressure range of 0.2–0.8 bar and different degrees of detonation overdrive demonstrate that the detonation is unstable for low degrees of overdrive, but the dynamics of wave propagation varies with fuel–air equivalence ratio and pressure. For equivalence ratios less than approximately 1.2 and for all pressures, the detonation exhibits a short-period oscillatory mode, characterized by high-frequency, low-amplitude waves. Richer mixtures exhibit a period-doubled bifurcation that depends on the initial pressure. Parametric studies over a degree of overdrive range of 1.0–1.2 for stoichiometric mixtures at 0.42 bar initial pressure indicate that stable detonation wave propagation is obtained at the high end of this range. For degrees of overdrive close to one, the detonation wave exhibits a low-frequency mode characterized by large fluctuations in the detonation wave speed. The McVey–Toong short-period wave-interaction theory is in qualitative agreement with the numerical simulations; however, the frequencies obtained from their theory are much higher, especially for near-stoichiometric mixtures at high pressure. Modification of this theory to account for the finite heat-release time significantly improves agreement with the numerically computed frequency over the entire equivalence ratio and pressure ranges.     

Bose–Fermi mixtures in a three-dimensional optical lattice

Using the dynamical mean-field theory and the Gutzwiller method, we study the Mott transition in Bose–Fermi mixtures confined in a three-dimensional optical lattice and analyze the effect of fermions on the coherence of bosons. We conclude that increasing fermion composition reduces bosonic coherence in the presence of strong Bose–Fermi interactions and under the condition of the integer filling factors for composite fermions, which consist of one fermion and one or more bosonic holes. Various phases of the mixtures have been demonstrated including phase separation of two species, coexisting regions of superfluid bosons and fermionic liquids, and Mott regions in the phase space spanned by the chemical potentials of the bosons and the fermions.     

‘Guest–host’ effect in liquid crystal mixtures

The most important goal of our research is to show the influence of the ‘guest’ (bent-core mesogen, 1,3-phenyldicarboxylatebis{4-[(4-octylbenzoyl)sulphanyl]phenyl} [IFOS8], banana-shaped liquid crystal [BLC]) on the ‘host’ (calamitic liquid crystal [CLC], (S)-(+)-1-methylheptyloxybiphenyl-(4-n-octylphenyl)thiobenzoate [MHOBS8]), on the stability and the destabilization of the antiferroelectric B2 and the ferroelectric smectic C* (SmC*) phases, and change of the temperature ranges of other phases in the binary liquid crystal mixtures. This work is focused on polymorphism of three new binary liquid crystal mixtures, exhibiting a ‘guest–host’ (guest liquid crystal–host liquid crystal [GH-LC]) effect. MHOBS8 has, among others, a ferroelectric SmC* phase, and IFOS8 assumes the B2 phase with antiferroelectric properties. The observed properties of the mixtures, such as variation of the phase transition temperatures, spontaneous polarization, tilt angle and switching time, are characteristic of a ‘guest–host’ mixture. The influence of BLC on the character of the interactions within the CLC host is discussed, with particular attention paid to electro-optical properties of the GH-LC mixtures.     

Propagation of detonation in fuel–air mixtures in flat channels

The wide scatter of the values of the measured detonation cell size in fuel + air mixtures restricts the applicability of this parameter in the estimation of the geometric limits of detonation propagation, including in rectangular channels whose height is much larger than their width. The critical channel height for the propagation of detonation has been experimentally determined for hydrogen + air, propane + air, and ethylene + air mixtures. In order to reveal the specific features of the propagation and decay of detonation in a narrow channel, numerical simulation has been carried out for a hydrogen + air mixture with account taken of the cellular structure of the detonation wave.     

Thermodynamic properties of gold–water nanolayer mixtures using molecular dynamics

The physical behavior of a fluid in contact with solid layers is still not fully understood. The present work focuses on the study and understanding of thermodynamic and structural properties of gold–water nanolayer mixtures using molecular dynamics simulations. Two different systems are considered, where approximately 1,700 water molecules are confined between gold nanolayers with separations of 7.4 and 6.2 nm, respectively. Novelties of the present work are in the use of accurate force fields for modeling the inter- and intra-molecular interactions of the components, and providing comprehensive thermodynamic properties of the mixtures. The results are validated by examination of the pure fluid and pure solid properties. Results indicate that the thermodynamics of the system does not behave as an ideal mixture. The structure of the pure fluid is also analyzed and compared against the structure of the confined fluid in the mixture. Anisotropicity is observed in the fluid structure close to the surface of the nanolayer. Higher ordering and higher flux are detected in the fluid molecules close to the fluid–solid interface. Unusual thermodynamic behavior, anisotropicity, liquid layering, and higher interfacial fluid flux could be just some of the factors leading to the enhanced energy transport observed in mixtures involving at least one nanoscale component, such as nanofluids.     

Demixing of amphiphile–polymer mixtures investigated using density functional theory

We construct a functional for amphiphile–polymer mixtures and investigate the demixing transition by using a proposed version of density functional theory. It is found that increase of the amphiphilic size ratio and polymer length can effectively promote phase separation of the systems. Phase diagrams are plotted to clarify these influences. The results provide an effective way of controlling the stability of the fluid–fluid phase equilibrium of the mixtures.     

High-power module based on inert gas–halogen mixtures for UV irradiation

We have developed a module based on exciplex barrier-discharge lamps for irradiation by high-power narrow-band ultraviolet radiation. The module uses air cooling and is intended for irradiation of substrates such as those used in microelectronics. The module provides close to uniform irradiation on a flat surface with power density up to 35 and 25 mW/cm² as a result of emission in B–X bands of the molecules XeBr^* (282 nm) and XeCl^* (308 nm) respectively.     

Heat of explosion and acceleration ability of explosive–inorganic oxidizer mixtures

Experimental results have shown that the use of inorganic oxidizers (ammonium nitrate, ammonium perchlorate, and ammonium dinitramide) as additives does not lead to a considerable increase in the heat of explosion and acceleration ability of HMX. Ammonium perchlorate does not have an effect on the acceleration ability; however, it leads to an increase in the heat of explosion of triaminotrinitrobenzene. Calculations have shown that the acceleration ability of explosives with a low oxygen ratio can be increased through the formation of nanostructured composites with inorganic oxidizers. Calculations suggest that the addition of the studied oxidizers to CL-20 leads to a decrease in the acceleration ability of this promising explosive.     

Binary pusher–puller mixtures of active microswimmers and their collective behaviour

ABSTRACT

Microswimmers are active particles of microscopic size that self-propel by setting the surrounding fluid into motion. According to the kind of far-field fluid flow that they induce, they are classified into pushers and pullers. Many studies have explored similarities and differences between suspensions of either pushers or pullers, but the behaviour of mixtures of the two is still to be investigated. Here, we rely on a minimal discrete microswimmer model, particle-resolved, including hydrodynamic interactions, to examine the orientational ordering in such binary pusher–puller mixtures. In agreement with existing literature, we find that our monodisperse suspensions of pushers do not show alignment, whereas those of solely pullers spontaneously develop ordered collective motion. By continuously varying the composition of the binary mixtures, starting from pure puller systems, we find that ordered collective motion is largely maintained up to pusher–puller composition ratios of about 1:2. Surprisingly, pushers when surrounded by a majority of pullers are more tightly aligned than indicated by the average overall orientational order in the system. Our study outlines how orientational order can be tuned in active microswimmer suspensions to a requested degree by doping with other species.     

Ultradilute self-bound quantum droplets in Bose–Bose mixtures at finite temperature

We theoretically investigate the finite-temperature structure and collective excitations of a self-bound ultradilute Bose droplet in a flat space realized in a binary Bose mixture with attractive inter-species interactions on the verge of meanfield collapse. As the droplet formation relies critically on the repulsive force provided by Lee–Huang–Yang quantum fluctuations, which can be easily compensated by thermal fluctuations, we find a significant temperature effect in the density distribution and collective excitation spectrum of the Bose droplet. A finite-temperature phase diagram as a function of the number of particles is determined. We show that the critical number of particles at the droplet-to-gas transition increases dramatically with increasing temperature. Towards the bulk threshold temperature for thermally destabilizing an infinitely large droplet, we find that the excitation-forbidden, self-evaporation region in the excitation spectrum, predicted earlier by Petrov using a zero-temperature theory, shrinks and eventually disappears. All the collective excitations, including both surface modes and compressional bulk modes, become softened at the droplet-to-gas transition. The predicted temperature effects of a self-bound Bose droplet in this work could be difficult to measure experimentally due to the lack of efficient thermometry at low temperatures. However, these effects may already present in the current cold-atom experiments.     

Hydrogen bond lifetimes in supercritical methanol–water mixtures via MD simulation

Dynamical features of hydrogen bonds in methanol–water mixtures have been analysed in terms of lifetime in the wide range of conditions, including supercritical states, using a molecular dynamics simulation with flexible potential models. Hydrogen bond characteristics in methanol–water mixtures were investigated by considering the combination of molecular species and donor–acceptor of hydrogen-bonded molecules. The hydrogen bond lifetimes mainly depend on temperature, and those in supercritical condition were about 1/10th of that at ambient condition. Focusing on the composition dependence of the hydrogen bond lifetime, the unique behaviour of that resulting from hydration structure was observed. Moreover, the molecular combination, which showed the largest hydrogen bond lifetime, was different for ambient and high temperature and high pressure conditions. The relationship between hydrogen bond lifetime and molar volume was also calculated to discuss the hydrogen bond lifetime in terms of the collision frequency of molecules and the intermolecular distance.     

Characteristics of the impact explosion initiation of HMX–energetic additive mixtures

Experimental data on the dependence of the conditions of explosion initiation in HMX-energetic additive mixtures by mechanical impact on the caloricity and content of the additive are presented. Introduction of various additives, such as boron, carborane, and some others, into HMX is shown to cause an increase in the sensitivity of the mixture. The increase in the sensitivity was explained by an additional heat release due to the chemical interaction between the oxygen-containing products of HMX decomposition and the energetic additive at impact-induced hotspots.     

Thermal diffusion in binary mixtures containing molecular gases. III. The temperature dependence of αT

A recent expression for the thermal diffusion factor α_T for binary atom-molecule mixtures, which includes a full range of inelastic collisional contributions [McCourt, F. R. W., 2003, Molec. Phys., 101, 2181] has been utilized to calculate its temperature dependence for equimolar N₂-He, Ne, Ar mixtures and for an equimolar CO₂-Ar mixture. Accurate classical trajectory values for the effective cross-sections entering into the expression for α_T, obtained for the most reliable potential energy surfaces available, have been employed in the calculations. Good agreement has been attained with experiment for all four binary mixtures, including the decrease of α_T with increase in temperature observed for CO₂-Ar mixtures, heretofore considered to be anomalous.     

Electronic absorption spectra of ascorbic acid in water and water–dialkylsulfoxide mixtures

Gaussian analysis (LinkFit program) was used to deconvolute overlapping absorption bands due to neutral and anionic forms of ascorbic acid (AA). It has been shown that the neutral form of AA predominates in aqueous solutions of AA containing dialkylsulfoxides (DASO) because a hydrogen-bonded complex forms between DASO and AA molecules.     

Absorption spectra of benzene-isooctane mixtures in the wavelength range 1620–1820 nm

Experimental absorption spectra of benzene, isooctane, and their mixtures are obtained in the wavelength range λ = 1620–1820 nm in which the first overtones of vibrational frequencies of CH, CH₂, and CH₃ hydrocarbon groups are located. Positions of fundamental absorption bands of benzene are refined. Absorption spectra of benzene-isooctane mixtures are shown to intersect in a narrow area near λ ≈ 1695 nm. The main maximum of benzene absorption at λ = 1671.5 ± 0.5 nm, where the influence of isooctane absorption is practically absent, is proposed for determining the content of benzene in benzene-isooctane mixtures. A linear calibration curve for λ = 1671.5 nm that encompasses the full range of benzene concentrations (0–100%) is presented. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 631–634, September–October, 2008.