Density functional and Monte Carlo studies of sulfur. II. Equilibrium polymerization of the liquid phase

The equilibrium polymerization of sulfur is investigated by Monte Carlo simulations. The potential energy model is based on density functional results for the cohesive energy, structural, and vibrational properties as well as reactivity of sulfur rings and chains [Part I, J. Chem. Phys. 118, 9257 (2003)]. Liquid samples of 2048 atoms are simulated at temperatures 450less than or equal toTless than or equal to850 K and P=0 starting from monodisperse S-8 molecular compositions. Thermally activated bond breaking processes lead to an equilibrium population of unsaturated atoms that can change the local pattern of covalent bonds and allow the system to approach equilibrium. The concentration of unsaturated atoms and the kinetics of bond interchanges is determined by the energy DeltaE(b) required to break a covalent bond. Equilibrium with respect to the bond distribution is achieved for 15less than or equal toDeltaE(b)less than or equal to21 kcal/mol over a wide temperature range (Tgreater than or equal to450 K), within which polymerization occurs readily, with entropy from the bond distribution overcompensating the increase in enthalpy. There is a maximum in the polymerized fraction at temperature T-max that depends on DeltaE(b). This fraction decreases at higher temperature because broken bonds and short chains proliferate and, for Tless than or equal toT(max), because entropy is less important than enthalpy. The molecular size distribution is described well by a Zimm-Schulz function, plus an isolated peak for S-8. Large molecules are almost exclusively open chains. Rings tend to have fewer than 24 atoms, and only S-8 is present in significant concentrations at all T. The T dependence of the density and the dependence of polymerization fraction and degree on DeltaE(b) give estimates of the polymerization temperature T-f=450+/-20 K. (C) 2003 American Institute of Physics.

Mechanical behaviour of unsaturated kaolin (with isotropic and anisotropic stress history). Part 1: wetting and compression behaviour

Over the last 40 years considerable progress has been made in understanding the complex behaviour of unsaturated soils. Research using constitutive modelling has extended the critical state framework and the concept of yielding in saturated soils to encompass unsaturated soils experiencing suction. However, validation testing of the framework for unsaturated soils has shown disagreement with the basic propositions. The main reason for this disparity is the anisotropic properties of the soil specimens tested as a result of preparation using one-dimensional compaction. The paper describes the detailed testing carried out to justify this statement. As part of the work presented, samples of unsaturated kaolin were prepared using isotropic compression. The suctions in these samples were reduced to predefined values by wetting under low isotropic loading. The pore size distributions, the pressure–volume relationships and yielding under subsequent isotropic loading are compared with tests on samples prepared by statically compressing kaolin into a one-dimensional compaction mould. The anisotropically compressed samples had initial water contents and specific volumes similar to those of the isotropically prepared samples and were also tested under reducing suctions; they exhibited distinctly different behaviour when tested under similar conditions. The results obtained from the isotropically prepared and tested samples have shown, probably for the first time, the existence of a unique normal compression surface that is not dependent on the initial conditions of the samples. The shape of the loading–collapse (LC) yield locus is shown to be different from the generally accepted form.

Mechanical behaviour of unsaturated kaolin (with isotropic and anisotropic stress history). Part 2: performance under shear loading

Validation of a framework for unsaturated soil behaviour has frequently resulted in disagreement with basic propositions. A primary reason for this disparity is considered to be attributable to the anisotropic properties of the soil specimens tested as a result of preparation using one-dimensional compaction. As part of the work presented, comparison is made between tests on samples of unsaturated kaolin prepared at identical specific volumes and specific water volumes using isotropic compression and one-dimensional compression. The suctions in the samples were reduced to predefined values by wetting under low isotropic loading in a triaxial cell. The samples were then taken through various stress paths to failure, defined as the critical state strength, while the suctions were held constant. Stress path tests were also performed on samples without reducing the suction to predefined values. In the latter, constant water mass tests, the suctions were allowed to vary and were measured using a psychrometer. The results of the tests at critical state are compared with the propositions of Wheeler and Sivakumar. The shear strengths of samples with isotropic previous history are shown to be significantly greater than those of samples with one-dimensional stress history when plotted against the mean net stress. The normal compression lines, critical state lines and yield characteristics are also shown to be significantly influenced by the previous stress history and are shown to be different for isotropically and one-dimensionally prepared samples.

Saturated-unsaturated flow through leaky dams

This research investigated seepage flow through leaky dams using the well known finite-element method. Different areas, locations, and hydraulic conductivities of leaks were examined. An area of leak, equal to 4.4% of the core area, increased the seepage flow through the dam to be about 9.5 times the seepage flow through tight (nonleaky) core. This happened for a dam having a downstream horizontal drainage filter. When the drainage filter did not exist, the increase of flow because of the same area of leak was about seven times the flow through a tight core. When the leak existed at the centerline of the core in the out-of-plane direction, its impact was slightly greater than when it existed at the edge of the core. Moreover, as the location of the leak moved up vertically, its impact was observed to be less. It was also observed that when the leak existed in curtain wall driven into underneath the dam, its impact was not significant compared with the case when it existed in the core.