Condensed phase isomerization through tunneling gateways

We observe that the orientational isomerization of CO on a NaCl(100) surface proceeds by thermally-activated tunneling between 19 and 24K. The rate constants of three isotopomers follow an Arrhenius temperature dependence, exhibiting activation energies below the reaction’s predicted barrier height and anomalously small prefactors. In addition, the rates depend strongly on isotope, but non-intuitively on mass. A quantum rate theory of condensed-phase tunneling qualitatively explains these observations. Vibrationally excited states, accidentally close in energy but localized on opposite sides of the isomerization barrier, provide tunneling gateways between the isomers in a process that can be many orders-of-magnitude faster than rates predicted by commonly used semi-classical models. This suggests heavy-atom condensed-phase tunneling may be more important than currently assumed.

The Electrical Conductivity of Some Hydrous and Anhydrous Molten Silicates as a Function of Temperature and Pressure

<p>This thesis is concerned with the measurement and interpretation of electrical conductivity in molten silicates. Physicochemical properties and structural models of silica and silicates are reviewed first, to give a general picture of their behaviour. Electrical conductivity was measured as a function of temperature, pressure and water composition. To make these measurements an internally heated pressure vessel, designed to operate at temperatures up to 1200 degrees C and pressures up to 5 kbars was constructed. Conductivity measurements were made on the following anhydrous and hydrous silicate melts: SiO2/Na2O 60/40, 65/35, 75/25, 78/22 mol%; SiO2/Na2O/CaO 72/24/4 mol%; Mt. Erebus lava; SiO2/Na2O 78/22 mol% + ~5 wt% H2O and Mt. Erebus lava + ~4 wt% H2O in the temperature range 850-1000 degrees C and the pressure range 0-1.3 kbar. Arrhenius temperature and pressure dependencies on conductivity were observed. The pressure coefficient of conductivity was zero for the anhydrous melts well above Tg but small and positive for the hydrous silicates. Water caused ~40% reduction in conductivity when added to a melt which was accounted for in terms of the mixed alkali effect. Conductivity isobars for the hydrous silicates passed through a maximum as a function of increasing temperature. The conductivity behaviour as a function of temperature and pressure is analogous to that observed in partially ionised liquids and is intrepretated in an identical way. The range of operation of a piezoelectric alpha-quartz crystal viscometer was extended to allow measurement of viscosity as a function of temperature.</p>

The Electrical Conductivity of Some Hydrous and Anhydrous Molten Silicates as a Function of Temperature and Pressure

<p>This thesis is concerned with the measurement and interpretation of electrical conductivity in molten silicates. Physicochemical properties and structural models of silica and silicates are reviewed first, to give a general picture of their behaviour. Electrical conductivity was measured as a function of temperature, pressure and water composition. To make these measurements an internally heated pressure vessel, designed to operate at temperatures up to 1200 degrees C and pressures up to 5 kbars was constructed. Conductivity measurements were made on the following anhydrous and hydrous silicate melts: SiO2/Na2O 60/40, 65/35, 75/25, 78/22 mol%; SiO2/Na2O/CaO 72/24/4 mol%; Mt. Erebus lava; SiO2/Na2O 78/22 mol% + ~5 wt% H2O and Mt. Erebus lava + ~4 wt% H2O in the temperature range 850-1000 degrees C and the pressure range 0-1.3 kbar. Arrhenius temperature and pressure dependencies on conductivity were observed. The pressure coefficient of conductivity was zero for the anhydrous melts well above Tg but small and positive for the hydrous silicates. Water caused ~40% reduction in conductivity when added to a melt which was accounted for in terms of the mixed alkali effect. Conductivity isobars for the hydrous silicates passed through a maximum as a function of increasing temperature. The conductivity behaviour as a function of temperature and pressure is analogous to that observed in partially ionised liquids and is intrepretated in an identical way. The range of operation of a piezoelectric alpha-quartz crystal viscometer was extended to allow measurement of viscosity as a function of temperature.</p>

The Electrical Conductivity of Some Hydrous and Anhydrous Molten Silicates as a Function of Temperature and Pressure

<p>This thesis is concerned with the measurement and interpretation of electrical conductivity in molten silicates. Physicochemical properties and structural models of silica and silicates are reviewed first, to give a general picture of their behaviour. Electrical conductivity was measured as a function of temperature, pressure and water composition. To make these measurements an internally heated pressure vessel, designed to operate at temperatures up to 1200 degrees C and pressures up to 5 kbars was constructed. Conductivity measurements were made on the following anhydrous and hydrous silicate melts: SiO2/Na2O 60/40, 65/35, 75/25, 78/22 mol%; SiO2/Na2O/CaO 72/24/4 mol%; Mt. Erebus lava; SiO2/Na2O 78/22 mol% + ~5 wt% H2O and Mt. Erebus lava + ~4 wt% H2O in the temperature range 850-1000 degrees C and the pressure range 0-1.3 kbar. Arrhenius temperature and pressure dependencies on conductivity were observed. The pressure coefficient of conductivity was zero for the anhydrous melts well above Tg but small and positive for the hydrous silicates. Water caused ~40% reduction in conductivity when added to a melt which was accounted for in terms of the mixed alkali effect. Conductivity isobars for the hydrous silicates passed through a maximum as a function of increasing temperature. The conductivity behaviour as a function of temperature and pressure is analogous to that observed in partially ionised liquids and is intrepretated in an identical way. The range of operation of a piezoelectric alpha-quartz crystal viscometer was extended to allow measurement of viscosity as a function of temperature.</p>

The Electrical Conductivity of Some Hydrous and Anhydrous Molten Silicates as a Function of Temperature and Pressure

<p>This thesis is concerned with the measurement and interpretation of electrical conductivity in molten silicates. Physicochemical properties and structural models of silica and silicates are reviewed first, to give a general picture of their behaviour. Electrical conductivity was measured as a function of temperature, pressure and water composition. To make these measurements an internally heated pressure vessel, designed to operate at temperatures up to 1200 degrees C and pressures up to 5 kbars was constructed. Conductivity measurements were made on the following anhydrous and hydrous silicate melts: SiO2/Na2O 60/40, 65/35, 75/25, 78/22 mol%; SiO2/Na2O/CaO 72/24/4 mol%; Mt. Erebus lava; SiO2/Na2O 78/22 mol% + ~5 wt% H2O and Mt. Erebus lava + ~4 wt% H2O in the temperature range 850-1000 degrees C and the pressure range 0-1.3 kbar. Arrhenius temperature and pressure dependencies on conductivity were observed. The pressure coefficient of conductivity was zero for the anhydrous melts well above Tg but small and positive for the hydrous silicates. Water caused ~40% reduction in conductivity when added to a melt which was accounted for in terms of the mixed alkali effect. Conductivity isobars for the hydrous silicates passed through a maximum as a function of increasing temperature. The conductivity behaviour as a function of temperature and pressure is analogous to that observed in partially ionised liquids and is intrepretated in an identical way. The range of operation of a piezoelectric alpha-quartz crystal viscometer was extended to allow measurement of viscosity as a function of temperature.</p>

A Fatigue Crack Growth Model for Type 304 Austenitic Stainless Steels In a Pressurized Water Reactor Environment

The American Society of Mechanical Engineers (ASME) Boiler and Pressure Vessel Code, Section XI utilizes reference fatigue crack growth rate (FCGR) curves for flaw evaluations. Code Case N-809 describes a reference curve currently used in flaw evaluations of austenitic stainless steels exposed to a pressurized water reactor (PWR) environment in accordance with ASME, Section XI. Recently, an extensive database of Type 304, Type 304L, and Type 304/304L dual-certified stainless steels and the corresponding weld metal in PWR environments was assessed and an updated FCGR model generated. This database includes previously unreported FCGR data in 100°C PWR environments at an R-ratio of 0.7 and a rise time of either 51 sec or 510 sec. The results of this lower temperature testing are reported here and do not support the non-Arrhenius temperature relation in Code Case N-809, which predicts an increase in FCGRs with decreasing temperature below a temperature of 150°C. The updated model more accurately describes the FCGR behavior in the near-threshold, low ΔK regime. Additionally, the updated model eliminates the non-Arrhenius temperature dependence of the Code Case N-809 reference curves for temperatures below 150°C and replaces it with a single Arrhenius temperature dependence between 100°C and 338°C. Similar to the Code Case N-809 reference curve, this model does not describe the severely retarded FCGR behavior that has been observed to occur for austenitic stainless steel under certain conditions, nor does it attempt to predict the conditions under which severe retardation is likely to occur.

Structure, density and viscosity of water

We analyzed the possibilities of the use of the cluster model of water to assess its viscosity. The Nemethy-Scheraga model was used in our study. In a simplified version, this model implies the presence of water cluster that are linked by hydrogen bonds as well as individual molecules (monomolecules) interacting only by van der Waals forces. The paper gives an estimation of average cluster size. Based on the experimental temperature dependences of viscosity and density, the content of monomolecules in water was approximately determined. In the first case, the ratio of the viscosity of water to monomolecules was estimated from the inverse Arrhenius temperature dependence of viscosity by considering experimental activation energy ~18.6 kJ mol–1 (0÷300C) and energy of dispersion interactions ~7.4 kJ mol–1. Then, the volumetric content of monomolecules was estimated by using the inverse Betchelor's formula, which relates the viscosity of the suspension (clusters) and dispersion medium (monomolecules) to their ratio. On the other hand, a similar estimation was performed based on the density of water, clusters that were considered similar to ice floes, and the estimated density of monomolecules. Both estimates showed that the volumetric content of water not bound into clusters does not exceed 9%. It was concluded that the structure of water most likely corresponds to the clathrate model, according to which some of the H2O molecules move into the middle of ice-like clusters, and vacancies are stabilized by H3O+–OH– pairs.

Unentangled Vitrimer Melts: Interplay between Chain Relaxation and Cross-link Exchange Controls Linear Rheology

<div>Using this theoretical approach, we explore the influence of molecular structure and temperature on vitrimer linear viscoelasticity. We observe that vitrimers with uniform and random cross-link distributions exhibit larger viscosities and relaxation times than gradient and blocky types. Polydimethylsiloxane vitrimer (which has a flexible backbone) shows an Arrhenius temperature dependence for viscosity, while polystyrene vitrimers (which has rigid backbones) are only Arrhenius at high temperatures. During stress relaxation, the short time dynamics represent monomer friction, while the long time dynamics encompass a combination of network strand relaxation and cross-link exchange. Because of the different temperature dependences of the processes, time-temperature superposition fails. We also show that the effective rheological activation energy can be estimated a priori using only the cross-link exchange activation energy and the backbone Williams-Landel-Ferry parameters.</div><div><br></div><div>(Submitted to Macromolecules)</div>

A structural study and its relation to dynamics heterogeneity in a polymer glass former

The relationship between structure and dynamical behavior (super-Arrhenius temperature dependence of relaxation time accompanied by heterogeneous dynamics) in glassy materials remains an open issue in the physics of condensed matter....