Dipole time correlation functions of the Stockmayer fluid in the microcanonical and canonical ensembles

Computer simulations of Stockmayer fluids were performed to generate dipole time correlation functions (TCF) at three temperatures and three dipole moments in both the microcanonical and canonical ensembles. The effect of Nosé constant-temperature dynamics on time-dependent quantities is discussed, and empirical results are given to show that the choice of thermal inertia parameter influences the speed with which a system moves through its phase space. The time correlation functions from the simulations were analyzed in terms of current theories for dipolar systems. A functional form is proposed to cover both the longtime and short-time behavior of the time correlation functions of dipoles. The relationship between this functional form and the dielectric function of the Stockmayer system is also discussed.

Thermal control of high pressure die casting using computational fluid dynamics

The quality of high pressure die castings is a function of many interdependent parameters. It has been observed that many defects detected in the HPDC castings can be tracked back to poor die temperature distribution in the critical areas. It has therefore been recommended that the development of a technique to directly control the critical features - making them less sensitive to thermal related parameters - be very beneficial to the HPDC industry. From the information obtained from thermal image (processing), computational fluid dynamics has been applied to design the layout of internal cooling system and assign the flow conditions such as flow rate and pressure of the cooling water. it is observed that CFD prediction provides an excellent insight into the thermal balance of the high pressure die casting.

Particle dynamics and heat transfer at workpiece surface in heat treatment fluidised beds

The particle behaviour is studied by the analysis of particle images taken with a high speed CCD digital video camera. The comparison of particle dynamics is performed for the fluidised beds without part, with single part and with multi-parts. The results show that there are significant differences in particle behaviours both in different beds and at different locations at part surfaces. The total and radiative heat transfer coefficients at different surfaces of a metallic component in a high temperature fluidised bed are measured by a heat transfer probe developed in the present work. The principle of the heat transfer probe is to measure the change in temperature of the heated metallic piece with time and, then, to extract the heat flux and heat transfer coefficients. The structure of the probe is optimized with numerical simulation of energy conservation for measuring the heat transfer coefficient of 150~600 W/m2 K. The relationship between the particle dynamics and the heat transfer is analysed to form the basis for future more rational designs of fluidised beds as well as for improved quality control.

Invertebrate larval dynamics in seasonally closed estuaries

Estuarine benthic assemblages are often numerically dominated by polychaetes. The limits of these populations are determined by larval, and probably to a lesser extent adult movement. A previous study (Newton 1996), indicated that planktonic polychaete larvae were very abundant over the summer months in the Hopkins River; however, the identification and source of these larvae was not known. Defining the extent of a population, and therefore the likelihood of that population recovering following a perturbation, is crucial for effective estuarine management. This study investigated both the likely source of the larvae, (i.e. estuarine or marine) and the extent of larval dispersal within and between estuaries by addressing the following questions: Which taxa produced the planktonic larvae? Are these taxa resident estuarine species? Are the larvae of different taxa evenly distributed within the estuary or do physicochemical parameters or other factors influence their abundance? Are the same larvae found in other estuaries along the coast? and Is there exchange of these larval taxa with the marine environment and other estuaries? Larvae were identified and described by culturing commonly occurring planktonic larvae until adult characteristics appeared. The spionids, Carazziella victoriensis and Prionospio Tatura, numerically dominated the plankton in the Hopkins and the spionid, Orthoprionospio cirriformia was recorded from the Hopkins, Curdies and Gellibrand estuaries. Two spionids, Carazziella sp. and Polydora sp. were identified from tidal waters. Mouth status and physicochemical conditions (salinity, temperature and dissolved oxygen) were monitored in each estuary. Whereas the Merri and Gellibrand estuaries were predominantly stratified over the sampling period, the Curdies was more often well mixed and the Hopkins varied from well mixed to stratified. The duration of mouth opening and hence the opportunity for larval exchange also varied in each estuary. The Merri River was closed for 13.5% of days over the study period, the Gellibrand River for 18.4%, the Hopkins River for 49% and the Curdies River for 71.0%. The distributions of larvae at spatial scales of metres, 100s of metres and kilometres were investigated within a single estuary. While the same larvae, C. victoriensis, P. Tatura and bivalve larvae, were found along the length of the Hopkins estuary the abundances varied at different spatial scales suggesting different processes were influencing the distribution of P. Tatura larvae, and C. victoriensis and bivalve larvae. The distribution of larvae between several estuaries was investigated by monitoring meroplankton at two sites at the mouth of each of the four estuaries approximately monthly (except for winter months). Different meroplanktonic assemblages were found to distinguish each estuary. Further, C. victoriensis and P. Tatura larvae were only recorded in the Hopkins but larvae of the spionid, Orthoprionopio cirriformia were detected in the Hopkins, Curdies and Gellibrand estuaries. The extent of larval exchange with other estuaries and the marine environment was determined by monitoring tidal waters. Settlement trays were also deployed to determine if larvae were moving into estuaries and settling but not recruiting. P. tatura larvae were not detected in the tidal waters of any estuary and while C. victoriensis and O. cirriformia were found in both flood and ebb tides there was no evidence of movement of theses taxa to other estuaries. Larvae of the spionids, Carazziella sp. and Polydora sp., were found in tidal waters of each estuary but were rarely detected in the plankton within the estuaries. Neither species was found as an adult in background cores from any estuary, nor with the exception of a few individuals in the Merri, were they detected in settlement trays in any estuary. I conclude that the source of the larvae of C. victoriensis, P. Tatura and O. cirriformia is estuarine and while C. victoriensis, and O. cirriformia move in and outh of the source estuary in tidal waters there was no evidence for movement to other estuaries. The spionids, Carazziella sp. and Polydora sp were considered to be marine and while they moved in and out of estuaries in tidal waters they did not usually settle in the estuaries. The results of this study are a crucial first step in the development of ecological models to better understand dispersal in seasonally closed estuaries that are typical of southern Australia. This study emphasises the unique physicochemical characteristics and biological assemblages within these estuaries and the need for estuarine management to reflect these differences.

Population dynamics of the infaunal bivalve, Soletellina alba

The population dynamics of the infaunal bivalve Soletellina alba was investigated at three sites situated within close proximity to the mouth of the Hopkins River estuary. The initial study design was planned to examine the importance of winter flooding to the persistence of this bivalve mollusc within the Hopkins estuary, since mass mortalities have been observed during previous years coincident with periods of winter flooding. Unfortunately, the climatic conditions experienced during this study were atypical compared to the long-term average, so detailed sampling was limited to two, unanticipated, non-flood years rather than two, highly anticipated, flood years. This hampered my ability to conduct complete tests of the importance of winter flooding. Patterns of river discharge and the frequency and duration of mouth opening and closing differed greatly from that expected. Unexpectedly, periods of mouth closure were not always associated with periods of minimal river discharge; low salinities were another unexpected result during an extended period of mouth closure during 1998. As expected, salinities varied considerably with increasing water depth when the estuary mouth was open. Mouth closure lead to salinities becoming more uniform between water depths but hypoxic and anoxic conditions became evident via stratification in the water column at 1 m below the Australian Height Datum (AHD). Other than trends associated with increased water depth, significant variation was not evident between measurements of salinity taken from three sites within close proximity of the estuary mouth (approximately 500 m), or during changes in tide. The most pertinent anomaly was the absence of winter flooding. The distribution and abundance of juvenile and adult S. alba was variable across all Dates, Sites and Channel elevations (i.e. water depths) sampled during this study. An experimental test comparing the recruitment of juveniles at different channel elevations and in sediments of varying particle size was conducted during an exceptionally successful period of recruitment during 1999. The results of these tests showed that recruitment was greatest at the shallowest channel elevation used, and there was little evidence that sediment particle size influenced recruitment. In contrast to 1999, recruitment during 1997 or 1998 was extremely poor. Growth rates were monitored using tagged individuals held in caged and uncaged plots, which revealed that growth was highly variable among individuals, but not between Sites. These tests also revealed that growth was negligible during the colder, winter months, and that the fastest growing individuals were capable of growing 0.2 mm/day. Mixed results were obtained for tests of potential cage artifacts and the influence of handling. Caging and differing amounts of handling did not appear to influence growth, but there was evidence that cages and handling influenced bivalve condition and number of mortalities. These direct tests appeared to be the most appropriate method for determining growth rates of this species, since attempts to analyse length-frequency data were made difficult by the apparent convergence of cohorts, and shell aging is difficult due to the thin, fragile nature of the shell. As expected, mass mortalities were observed during the flood of 1996, but not during the two non-flood years of 1997 and 1998. There were, however, some considerable declines in abundances at some channel elevations during the two non-flood years. However, these declines were attributable to the complete disappearance of individuals, rather than the sudden presence of numerous, recently dead individuals that typify observed declines during winter flooding. The complete disappearance of individuals suggest that S. alba may be capable of post-settlement emigration, or that they were consumed by an unknown predator. Salinity tolerance tests showed that bivalves exposed to low salinities (≤6 ppt), exhibited poorer condition and took longer to re-burrow into sediments than those exposed to greater salinities (≥14 ppt), while death of bivalves exposed to salinities ≤1 ppt occurred after 8 days of exposure. These tests provide evidence that low salinities are probably the principal cause of mass mortalities during winter flooding, although the interaction between salinity, temperature and turbidity also deserve consideration. The results of this study indicate that certain aspects of winter flooding, especially salinity, are responsible for the mass mortalities of S. alba rather than the result of a short-lived life history. I hypothesise that the survival of very young juveniles (between 0.5 and 1 mm shell length) and rapid growth rates are important features of the life history of S. alba that explain its successful persistence within the Hopkins River estuary. The rapid rates of growth suggest that it may be possible for juveniles that survive winter flooding to grow, reach sexual maturity, and reproduce before the onset of the next flood event. Unfortunately, the increased survivorship of juveniles during periods of winter flooding was not demonstrated by this study because of the absence of winter flooding and also relatively poor recruitment. It is highly likely that this species is capable of completing it entire life cycle within the estuary since the absence of other nearby populations, together with periods of mouth closure, are likely to greatly limit the potential contribution made by larvae entering from the surrounding marine environment. This study has added considerably to our knowledge of how infauna cope with life in the intermittently closing estuaries that typify semi-arid coastlines in the Southern Hemisphere.

Equilibration strategies in molecular dynamics simulation of polyethers

A comparison of the NVT and NVE ensemble simulations of tetraglyme showed that, in terms of energy, temperature and most of the structural features the results were very similar. However, major differences were observed in dynamic properties, ie in the mean square displacement and in the O--O distances. A fast equilibration method suitable for amorphous polymer systems is also detailed. This was accomplished by the reassignment of the velocity distribution to the particles, after the interruption of an NVE simulation.

Transport and phase dynamics of poly(vinyl pyrrolidone) doped plastically crystalline N-methyl-N-propylpyrrolidinium tetrafluoroborate

The plastic crystal phase forming N-methyl-N-propylpyrrolidinium tetrafluoroborate organic salt (P₁₃BF₄) was combined with 2, 5 and 10 wt.% poly(vinyl pyrrolidone) (PVP). The ternary 2 wt.% PVP/2 wt.% LiBF₄/P₁₃BF₄ was also investigated. Thermal analysis, conductivity, optical thermomicroscopy, and Nuclear Magnetic Resonance (¹¹B, ¹⁹F, ¹H, ⁷Li) were used to probe the fundamental transport processes. Both the onset of phase I and the final melting temperature were reduced with increasing additions of PVP. Conductivity in phase I was 2.6 × 10^{− 4} S cm^{− 1} 5.2 × 10^{− 4} S cm^{− 1} 1.1 × 10^{− 4} S cm^{− 1} and 3.9 × 10− 5 S cm− 1 for 0, 2, 5 and 10 wt.%PVP/P₁₃BF₄, respectively. Doping with 2 wt.% LiBF₄ increased the conductivity by up to an order of magnitude in phase II. Further additions of 2 wt.% PVP slightly reduced the conductivity, although it remained higher than for pure P₁₃BF₄.

13 C NMR spin–lattice relaxation times as a probeof local polymer dynamics in plasticized polyethers

¹³C NMR spin–lattice relaxation times T₁ are used to investigate the effect of low molecular weight diluents, including N,N-dimethylformamide, N-methylformamide, propylene carbonate, γ-butyrolactone, triglyme and tetraglyme, on the local polymer segmental motion in polyether–urethane networks. In all cases, an increase in the local mobility is deduced from the increasing T₁ measurements consistent with a decreasing glass transition temperature. The extent of plasticization, however, is dependent on the nature of the small molecules. Those molecules which can either form strong polymer-diluent interactions (for example through dipolar interactions) or are themselves rigid, give the least enhancement of polymer mobility and the greatest deviation from the Fox equation for T_g. In the presence of alkali metal salts, N,N-dimethylformamide and propylene carbonate are shown to have opposite effects on the local polymer motion, as seen from the T₁ measurements. In both cases, addition of the plasticizers increases the ¹³C T₁ relaxation times for the plasticizer. However, propylene carbonate decreases the polymer ¹³C T₁ whilst N,N-dimethylformamide results in the expected increase in polymer ¹³C T₁.

Molecular dynamics simulations of highly concentrated salt solutions : structural and transport effects in polymer electrolytes

Structural, thermodynamic and transport properties have been calculated in concentrated non-aqueous NaI solutions using molecular dynamics simulations. Although the solvent has been represented by a simplistic Stockmayer fluid (spherical particles with point dipoles), the general trends observed are still a useful indication of the behavior of real non-aqueous electrolyte systems. Results indicate that in low dielectric media, significant ion pairing and clustering occurs. Contact ion pairs become more prominent at higher temperatures, independent of the dielectric strength of the solvent. Thermodynamic analysis shows that this temperature behavior is predominantly entropically driven. Calculation of ionic diffusivities and conductivities in the NaI/ether system confirms the clustered nature of the salt, with the conductivities significantly lower than those predicted from the Nernst-Einstein relation. In systems where the solvent-ion interactions increase relative to ion-ion interactions (lower charge or higher solvent dipole moment), less clustering is observed and the transport properties indicate independent motion of the ions, with higher calculated conductivities. The solvent in this system is the most mobile species, in comparison with the polymer electrolytes where the solvent is practically immobile.

Highly concentrated salt solutions : molecular dynamics simulations of structure and transport

Molecular dynamics (MD) simulations in NaI solutions, where the solvent has been represented by the Stockmayer fluid, were performed as a function of temperature, salt concentration, and solvent dipole strength. At higher temperatures contact ion pairs become more prevalent, regardless of solvent strength. An examination of the temperature dependence of the potential of mean force demonstrates the entropic nature of this effect. The transport properties calculated in the simulations are dependent on the balance between solvent dielectric constant and ion charge. In systems with a large solvent dipole moment, the ions appear to be independently mobile, and deviations from Nernst–Einstein behavior are small. In systems of smaller solvent dipole moment or greater ion charge, the ions form clusters, and large deviations from Nernst–Einstein behavior are observed.

Localized relaxational dynamics of succinonitrile

Succinonitrile (N≡C—CH₂—CH₂—C≡N) is a good ionic conductor, when doped with an ionic compound, at room temperature, where it is in its plastic crystalline phase (Long et al. Solid State Ionics 2003, 161, 105; Alarco et al. Nat. Mater. 2004, 3, 476). We report on the relaxational dynamics of the plastic phase near the two first-order phase transitions and on the effect of dissolving a salt in the plastic matrix by quasi-elastic neutron scattering. At 240 K, the three observed relaxations are localized and we can describe their dynamics (τ ≈ 1.7, 17, and 140 ps) to a certain extent from a model using a single molecule that was proposed by B_ée et al. allowing for all conformations in its unit cell (space group IM3M). The extent of the localized motion as observed is however larger than that predicted by the model and suggests that the isomerization of succinonitrile is correlated with a jump to the nearest neighbor site in the unit cell. The salt containing system is known to be a good ionic conductor, and our results show that the effect of the ions on the succinonitrile matrix is homogeneous. Because the isomerizations and rotations are governed by intermolecular interactions, the dissolved ions have an effect over an extended range. Due to the addition of the salt, the dynamics of one of the components (τ ≈ 17 ps) shows more diffusive character at 300 K. The calculated upper limit of the corresponding diffusion constant of succinonitrile in the electrolyte is a factor 30 higher than what is reported for the ions. Our results suggest that the succinonitrile diffusion is caused by nearest neighbor jumps that are localized on the observed length and time scales.

Investigation of proton dynamics and the proton transport pathway in choline dihydrogen phosphate using solid-state NMR

Choline dihydrogen phosphate has previously been shown to be a good ionic conductor as well as an excellent host for acid doping, leading to high proton conductivities required for e.g., electrochemical devices including proton membrane fuel cells and sensors. A combination of variable-temperature ¹H solid-state NMR and 2D NMR pulse sequences, including ³¹P and ¹³C CODEX and ¹H BaBa, show that the proton conduction mechanism primarily involves assisted transport via a restricted three-site motion of the phosphate unit around the P–O bond that is hydrogen bonded to the choline and exchange of protons between these anions. In other words, proton transport at ambient temperatures appears to occur most favorably along the crystallographic b axis, from phosphate dimer to dimer. At elevated temperatures exchange between the protons of the hydroxyl group on the choline cation and the hydrogen-bonded dihydrogen phosphate groups also contributes to the structural diffusion of the protons in this solid state conductor.

Changes in organic-matter dynamics and physicochemistry, associated with riparian vegetation loss and river regulation in floodplain wetlands of the Murray River, Australia

Extensive clearing of floodplain forests potentially reduces organic matter available to floodplain wetlands. Furthermore, on rivers regulated to provide irrigation water in summer, floodplain wetlands that were previously inundated in spring, now flood in summer/autumn. In the Murray–Darling Basin, Australia, this has changed the timing of organic matter entering the aquatic phase, since leaf fall peaks in summer. Field surveys and mesocosm experiments on floodplain wetlands on the River Murray revealed faster processing rates of leaves in summer/autumn than spring, and no difference between cleared and forested wetlands. Temperature and leaf carbon : nitrogen ratio could not explain these differences, and instead, changes to leaf chemistry associated with ‘terrestrial ageing’ between peak leaf fall in summer and inundation in spring is more likely. The results indicated that the reduction of input of organic matter through riparian tree clearing and changing the timing of inundation interact to alter organic-matter standing stocks and rates of decomposition in floodplain wetlands. Restoring both natural timing of high flows and riparian vegetation might be required for recovery of these wetlands.

Investigation of process dynamics and control of polystyrene batch reactor using hybrid model

The effects of operating conditions such as initiator and monomer concentration as well as reactor temperature of polymerization reactors are studied in this work. A recently developed hybrid model for polystyrene batch reactor is utilized in simulation study. The simulation results reveal the sensitivity of polymer properties and monomer conversion to variation of process operating conditions. In the second phase of this study, the optimization problem involving minimum time optimal temperature policy is considered for control study. An advanced neural network-based model predictive controller (NN-MPC) is designed and tested online. The experimental studies reveal that the developed controller is able to track the optimal setpoint with a minor oscillation and overshoot.