New liquid-crystalline heteroalicyclic compounds

Abstract

A wide variety of new sulphur-containing heteroalicyclic liquid-crystalline compounds have been synthesized. Special attention has thus been focussed on the influence of the heteroatoms on the mesomorphic behaviour. 2-Cyclohexyl substituted 1,3-dithianes and 1,3-oxathianes have been found to be superior to those with 2-phenyl substituents. The clearing temperatures of the 2-phenyl-1,3-dithianes depend on the electron donating or electron accepting properties of the substituents attached to the phenyl group. The mesophase stability of the 2-cyclohexyl substituted (hetero)alicycles increases in the order: 1,3-dioxane < 1,3-oxathiane < cyclohexane < 1,3-dithiane. This order is partly reversed for the cyclohexane annulated compounds: 1-oxa-3-thiadecalin < 1,3-dioxadecalin < decalin < 1,3-dithiadecalin. Selected values of the birefrigence and some melting enthalpies have been measured.     

Experimental and numerical investigation of one and two phase natural convection in storage tanks

Experiments were performed to investigate heating up processes of fluids in storage tanks under the influence of an external heat source. As a consequence of an external fire, the heat-up of the inventory may lead to the evaporation of the liquid and to release of significant quantities of dangerous gases into the environment. Several tests were performed both with heating from the bottom and with heating from the side walls. In recent tests in addition to thermocouples, the tank was equipped with needle probes for measuring of the local void fraction. The paper presents experimental and numerical investigations of single and two phase heating up processes of tanks with side wall heating. The measurement of the temperature and of the void fraction makes interesting phenomena evident, which could be explained by an own 2D model. The gained experimental results may be used for the validation of boiling models in 3D CFD codes. Received on 17 January 2000     

Reversing the Brazil-nut effect: competition between percolation and condensation

We report on experiments on vertically shaken binary granular mixtures, which separate into their components due to the external excitation. This well-known phenomenon, where large particles rise to the top of the mixture, is called the Brazil-nut effect. Recent theoretical findings predict also a reverse Brazil-nut effect, where large particles sink to the bottom of the container. We choose spherical beads of various diameters and materials in order to observe the transition from Brazil-nut effect to its reverse form. The direction of demixing depends sensitively on the external excitation, so that it is possible to switch between both effects for a given mass density ratio.     

Three-dimensional flow pattern visualization and bubble size distributions in stationary and transient upward flashing flow

For the first time, an experimental three-dimensional reconstruction and visualization of stationary and transient flashing flow in a vertical pipe (47 mm diameter) is presented. The measurements have been performed by means of wire-mesh sensors. This type of sensor delivers two-dimensional void-fraction distributions in the pipe cross-section where it is mounted with a maximum sampling rate of 10,000 frames per second. A sampling rate of 1200 frames per second has been used in this work. Steam bubbles have been identified from the wire-mesh data and their complete three-dimensional reconstruction has been performed by taking into account the steam bubble velocity. For the estimation of the bubble velocity, two wire-mesh sensors positioned at a small axial distance from each other have been used. The velocity has been determined by cross-correlation of the two wire-mesh signals, by direct identification of the traveling time of the steam bubbles between the two sensors and by means of a drift-flux model. A comparison between the three methods of bubbles velocity measurement is reported. Stationary and time-dependent bubble size distributions have been derived. The stationary radial void-fraction profiles have been decomposed according to bubble size classes and compared with the results obtained with an equilibrium model.     

Dynamic film thickness between bubbles and wall in a narrow channel

The present paper describes a novel technique to characterize the behavior of the liquid film between gas bubbles and the wall in a narrow channel. The method is based on the electrical conductance. Two liquid film sensors are installed on both opposite walls in a narrow rectangular channel. The liquid film thickness underneath the gas bubbles is recorded by the first sensor, while the void fraction information is obtained by measuring the conductance between the pair of opposite sensors. Both measurements are taken on a large two-dimensional domain and with a high speed. This makes it possible to obtain the two-dimensional distribution of the dynamic liquid film between the bubbles and the wall. In this study, this method was applied to an air–water flow ranging from bubbly to churn regimes in the narrow channel with a gap width of 1.5 mm.     

Conformational analysis—CXVII : Methyl ethyl disulfide. Molecular mechanics and molecular orbital calculations

The conformation of methyl ethyl disulfide was investigated by molecular mechanics calculations using a recently developed force field for sulfur-containing alkanes. The results indicate that in the gas phase the molecule exists predominantly in two conformations, both with the CSSC dihedral angle gauche (84°), and the SSCC dihedral angle either gauche (72°) or trans (179°), and the methyl protons staggered. Ab initio molecular orbital calculations using an STO-3G basis set were employed to corroborate that these two conformations are of roughly equal stability, and that the next most stable conformation (by 0.6 kcal/mole) has the SSCC dihedral angle gauche (295°) with the terminal methyls proximal. In contrast to earlier CNDO/2 (spd) predictions, the SSCC cis conformer is the least stable, and no sizable attractive S?HC nonbonded interactions are discerned. Reasons for this are traced to a failure of the CNDO/2 method, which is especially serious when d orbitals are included in the basis set (spd) and the rigid rotor approximation is used. The present results are found to be consistent with recent electron diffraction, IR, Raman spectroscopic and X-ray diffraction data. The conformation of diethyl disulfide was also investigated by molecular mechanics calculations, and again gauche and trans SSCC arrangements are predicted to be preferred.     

Multiple lot-sizing decisions in a two-stage production with an interrupted geometric yield and non-rigid demand

In a production system with random yield, it may be more cost effective to release lots multiple times towards fulfilling a customer order. Such a decision, called the multiple lot-sizing problem, has been investigated in various contexts. This paper proposes an efficient algorithm for solving a new multiple lot-sizing problem defined in the context of a two-stage production system with non-rigid demand when its process yields are governed by interrupted geometric distributions. We formulate this problem as a dynamic program (DP) and develop lemmas to solve it. However, solving such a DP may be computationally extensive, particularly for large-scale cases with a high yield. Therefore, this study proposes an efficient algorithm for resolving computational issues. This algorithm is designed to reduce the DP network into a much simpler algorithm by combining a group of DP branches into a single one. Extensive experiments were carried out. Results indicate that the proposed reduction algorithm is quite helpful for practitioners dealing with large-scale cases characterized by high-yield.     

Time and spatially resolved measurements of interfacial waves in vertical annular flow

Film thickness measurements have been performed in a vertical air/water annular flow in a pipe of 0.05 m diameter. A sensor has been built which allows to measure the film thickness evolution in time at 320 positions, such that the interface of the vertical annular flow can be reconstructed. The large-scale structures moving on the interface are described statistically, with a special attention to the disturbance waves. Probability density functions and mean statistics are given for the height, length, velocity, frequency and spatial distribution of the disturbance waves. In particular, it is shown that the disturbance waves are three-dimensional structures with large height fluctuations in the circumferential and axial direction, giving a meandering path between the maximum height around the circumference. It is also shown that the disturbance waves can flow with a slight inclination with respect to the axial direction. Finally, the disturbance waves are shown to be located randomly in space, within a Gamma distribution whose order only depends on the liquid superficial velocity. Due to the nature of the Gamma distribution, it could indicate that the spatial distribution of the disturbance waves results from a cascade of coalescence processes between the original disturbance waves on the film.     

Development of co-current air–water flow in a vertical pipe

Measurements of the cross-sectional distribution of the gas fraction and bubble size distributions were conducted in a vertical pipe with an inner diameter of 51.2 mm and a length of about 3 m for air/water bubbly and slug flow regimes. The use of a wire-mesh sensor obtained a high resolution of the gas fraction data in space as well as in time. From this data, time averaged values for the two-dimensional gas fraction profiles were decomposed into a large number of bubble size classes. This allowed the extraction of the radial gas fraction profiles for a given range of bubble sizes as well as data for local bubble size distributions. The structure of the flow can be characterized by such data. The measurements were performed for up to 10 different inlet lengths and for about 100 combinations of gas and liquid volume flow rates. The data is very useful for the development and validation of meso-scale models to account for the forces acting on a bubble in a shear liquid flow and models for bubble coalescence and break-up. Such models are necessary for the validation of CFD codes for the simulation of bubbly flows.     

The characteristics of gas/liquid flow in large risers at high pressures

Although most of the work reported on two-phase flows are limited to small pipe diameters, two-phase flow in large risers are increasingly being encountered in the petroleum and nuclear industries. In the present work, a wire mesh sensor was employed to obtain void fraction and bubble size distribution data and visualizations of steam/water flow in a large vertical pipe (194 mm in diameter) at 46 bar. For comparison purposes, measurements were made at similar phase velocities and physical properties to a dataset for nitrogen/naphtha flow in a similar-sized riser. There exist significant differences between both sets of data. Churn-turbulent flow is observed in the present work instead of slug flow, and this differs from the intermittent and semi-annular flow patterns reported for nitrogen/naphtha data. The mean void fraction of the nitrogen/naphtha data is higher than that of the present steam/water data due to the differences in purity in the liquid phases. Furthermore, core peak distributions are observed for the present work in contrast to the flatter profiles deduced for the nitrogen/naphtha using a power law relationship.