Configurational temperature control for atomic and molecular systems

A new configurational temperature thermostat suitable for molecules with holonomic constraints is derived. This thermostat has a simple set of motion equations, can generate the canonical ensemble in both position and momentum space, acts homogeneously through the spatial coordinates, and does not intrinsically violate the constraints. Our new configurational thermostat is closely related to the kinetic temperature Nosé-Hoover thermostat with feedback coupled to the position variables via a term proportional to the net molecular force. We validate the thermostat by comparing equilibrium static and dynamic quantities for a fluid of n-decane molecules under configurational and kinetic temperature control. Practical aspects concerning the implementation of the new thermostat in a molecular dynamics code and the potential applications are discussed

New parametrization method for dissipative particle dynamics

We introduce an improved method of parameterizing the Groot-Warren version of Dissipative Particle Dynamics (DPD) by exploiting a correspondence between DPD and Scatchard-Hildebrand regular solution theory. The new parameterization scheme widens the realm of applicability of DPD by first removing the restriction of equal repulsive interactions between like beads, and second, by relating all conservative interactions between beads directly to cohesive energy densities. We establish the correspondence by deriving an expression for the Helmoltz free energy of mixing obtaining a heat of mixing which is exactly the same form as that for a regular mixture (quadratic in the volume fraction) and an entropy of mixing which reduces to the ideal entropy of mixing for equal molar volumes. We equate the conservative interaction parameters in the DPD force law to the cohesive energy densities of the pure fluids providing an alternative method of calculating the self-interaction parameters as well as a route to the cross-interaction parameter. We validate the new parameterization by modelling the binary system: SnI4/SiCl4, which displays liquid-liquid coexistence below an upper critical solution temperature around 140°C. A series of DPD simulations were conducted at a set of temperatures ranging from 0°C to above the experimental upper critical solution temperature using conservative parameters based on extrapolated experimental data. These simulations can be regarded as being equivalent to a quench from a high temperature to a lower one at constant volume. Our simulations recover the expected phase behaviour ranging from solid-liquid coexistence to liquid-liquid co-existence and eventually leading to a homogeneous single phase system. The results yield a binodal curve in close agreement with one predicted using regular solution theory, but, significantly, in closer agreement with actual solubility measurements

High-density support matrices: Key to the deep borehole disposal of spent nuclear fuel

Deep (4–5 km) boreholes are emerging as a safe, secure, environmentally sound and potentially cost-effective option for disposal of high-level radioactive wastes, including plutonium. One reason this option has not been widely accepted for spent fuel is because stacking the containers in a borehole could create load stresses threatening their integrity with potential for releasing highly mobile radionuclides like 129I before the borehole is filled and sealed. This problem can be overcome by using novel high-density support matrices deployed as fine metal shot along with the containers. Temperature distributions in and around the disposal are modelled to show how decay heat from the fuel can melt the shot within weeks of disposal to give a dense liquid in which the containers are almost weightless. Finally, within a few decades, this liquid will cool and solidify, entombing the waste containers in a base metal sarcophagus sealed into the host rock

Lessons Learnt from the Development of Cementitious Grouts for Deep Borehole Disposal Applications

The performance of grouts made using oilwell cement is markedly different above 90°C than at lower temperatures, and the rapidity with which grouts thicken can cause failures in well cementing. One grouting application in which such temperatures are encountered is deep borehole disposal (DBD). DBD is a concept for disposing of high-level radioactive wastes where the temperature and pressure will be 90–140°C and 30–50 MPa, respectively. In developing DBD grouts, a number of issues have been identified that will be of interest to well-cementing organizations. (1) The type of retarder used to delay grout thickening above 90°C is of extreme importance, and should be selected based on local temperature, pressure, and geochemical environment. Addition level might vary considerably depending on the retarder used. (2) Temperature and pressure will shorten the time for grouts to thicken, particularly the former. Water content will also affect grout properties such as consistency, viscosity, and flow. (3) The retarder may not influence hardened grout composition, which suggests that only the time at which the cement hydration reactions occur is influenced

Effect of plutonium doping on radiation damage in zirconolite: A computer simulation study

We present the results of extensive Molecular Dynamics (MD) simulations of alpha-recoil radiation damage in a range of crystalline zirconolites, CaZrTi2O7. Our studied systems include pure zirconolite, which we use as a reference material and the first ever simulations of damage in Pu-doped zirconolite, where plutonium is doped onto both of the M1 sites in the material, i.e. (Ca0.7Pu0.3)ZrTi2O7 and Ca(Zr0.7Pu0.3)(Ti1.7Fe0.3)O7. Our goal was to determine the extent of local damage caused by a plutonium primary knock on atom (PKA) interacting with the crystal lattice. Recoil energies of up to 34.7 keV have been simulated. The damage is characterised using a number of analysis tools including: site specific radial distribution functions; defect statistics; and the asphericity parameter at various times during the annealing process. Our results show that there is much information to be gained by the use of novel techniques for radiation damage analysis. Also, we show inclusion of actinides in radiation damage simulations can significantly increase the extent of damage observed and should be considered carefully when describing radiation damage behaviour in future

Inorganic anions as retarders for deep borehole disposal grouts

Deep borehole disposal (DBD) provides an alternative to comparatively shallow mined repository concepts for many high-level radioactive wastes. Filling the annular space around the waste containers with cement grout will support them during placement and seal against ingress of groundwater. The elevated temperature and pressure (∼120°C and 50 MPa) will cause acceleration of grout thickening and setting, so retardation is required. The DBD Research Group at The University of Sheffield has developed grouts based on class G oil well cement that use organic retarders, but their presence may increase the solubility of any radionuclides released from the waste packages. New DBD grout formulations using sodium phosphate and sodium borate as inorganic retarders are reported in this paper. To place the wet grout, the onset of thickening needs to be delayed for at least 4 h. Sodium borate was found to provide this retardation at 90°C (0·75% addition) and nearly retarded sufficiently at 120°C (1% addition). Sodium phosphate did not provide sufficient retardation at either temperature. Neither compounds influenced the phases formed, but may suppress the crystallisation of calcium silicate hydrates. This work demonstrates that the performance of these inorganic materials in this application is inferior to that of organic retarders

Inorganic anions as retarders for deep borehole disposal grouts

Deep borehole disposal (DBD) provides an alternative to comparatively shallow mined repository concepts for many high-level radioactive wastes. Filling the annular space around the waste containers with cement grout will support them during placement and seal against ingress of groundwater. The elevated temperature and pressure (∼120°C and 50 MPa) will cause acceleration of grout thickening and setting, so retardation is required. The DBD Research Group at The University of Sheffield has developed grouts based on class G oil well cement that use organic retarders, but their presence may increase the solubility of any radionuclides released from the waste packages. New DBD grout formulations using sodium phosphate and sodium borate as inorganic retarders are reported in this paper. To place the wet grout, the onset of thickening needs to be delayed for at least 4 h. Sodium borate was found to provide this retardation at 90°C (0·75% addition) and nearly retarded sufficiently at 120°C (1% addition). Sodium phosphate did not provide sufficient retardation at either temperature. Neither compounds influenced the phases formed, but may suppress the crystallisation of calcium silicate hydrates. This work demonstrates that the performance of these inorganic materials in this application is inferior to that of organic retarders

Pressure dependence of the instability of multiwalled carbon nanotubes conveying fluids

10.1007/s00419-007-0184-3Archive of Applied Mechanics788637-648AAME

A long-term habitat fragmentation experiment leads to morphological change in a species of carabid beetle

1. Habitat fragmentation and transformation are key drivers of species declines in landscapes. Most of the current understanding of species’ responses to environmental change originates from studies of populations and communities. However, phenotypic variation offers another key aspect of species responses and could provide additional insights into the functional drivers of population change. 2. The goal of this study was to address this gap by exploring the morphological changes of a species of carabid beetle (Notonomus resplendens)with a known population response to theWogWog Habitat Fragmentation Experiment in Australia. We measured morphological traits associated with body size, head width, and dispersal ability. We quantified patterns of morphological variation over time and between native Eucalyptus forest fragments and the surrounding pine plantation matrix and the continuous intact native Eucalyptus forest controls. 3. We found sexually dimorphic morphological changes in response to the experimental treatments. Males increased in size, had larger legs and had smaller interocular widths in the matrix in both the short and long terms. Conversely, females became comparatively smaller and had increased interocular widths in the same treatments. Effects in the fragments were similar to those in the matrix, but exhibited more uncertainty. 4. Our results demonstrate that species can show morphological change in response to environmental change over very short time periods. We demonstrate that using both population and morphological data allows stronger inferences about the mechanisms behind species responses to environmental change.Funding to collect samples between 2009 and 2013 was provided by NSF DEB 0841892 to KFD. KFD was also supported by NSF DEB 1350872. MJE was funded by an Australian National University PhD Scholarshi