Ammonia Decomposition on Ir(100): From Ultrahigh Vacuum to Elevated Pressures

Ammonia decomposition on Ir(100) has been studied over the pressure range from ultrahigh vacuum to 1.5 Torr and at temperatures ranging from 200 to 800 K. The kinetics of the ammonia decomposition reaction was monitored by total pressure change. The apparent activation energy obtained in this study (84 kJ/mol) is in excellent agreement with our previous studies using supported Ir catalysts (Ir/Al₂O₃ 82 kJ/mol). Partial pressure dependence studies of the reaction rate yielded a positive order (0.9±0.1) with respect to ammonia and negative order (–0.7 ±0.1) with respect to hydrogen. Temperature-programmed desorption data from clean and hydrogen co-adsorbed Ir(100) surfaces indicate that ammonia undergoes facile decomposition on both these surfaces. Recombinative desorption of N₂ is the rate-determining step with a desorption activation energy of 63 kJ/mol. Co-adsorption data also indicate that the observed negative order with respect to hydrogen pressure is due to enhancement of the reverse reaction (NH _x + H NH _x+1, x=0–2) in the presence of excess H atoms on the surface.     

HOW LIQUIDS SPREAD ON SOLIDS

A theory of the wetting of solids by liquids is put forward. The theory accounts for capillary pressure gradient, gravitational potential gradient, surface tension gradient, disjoining pressure gradient driving forces of flow in thick thin-films and of surface diffusion in thin thin-films. Disjoining pressure stems from the way intermolecular forces aggregate in submicroscopically thin films. For thick thin-films of slowly varying thickness the lubrication approximation to velocity distributions is appropriate. With this approximation the spontaneous, unsteady, two-dimensional spreading of liquid is shown to be governed by a nonlinear convective-diffusion equation for the evolution of the film thickness profile. The predictions of the theory agree with Marmur and Lelah's (1980, 1981) observations of water drops spreading on glass and with Bascom, Cottington and Singleterry's (1964) and Ludviksson and Lightfoot's (1971) observations of oils spreading on high energy surfaces. The theory is used to analyze Derjaguin and co-workers' (1944, 1957, 1970) blowing-off experiments designed to measure thin-film rheology. The theory is also used to buttress the proposition that much contact angle hysteresis is due simply to slow attainment of equilibrium.     

Pressure effects on shear deformation of borosilicate glasses

The shear behaviors of two multicomponent borosilicate glasses, Borofloat®33 (Boro33) and N-BK7® (N-BK7), under different pressures are investigated using molecular dynamics simulations. The addition of alkali ions lowers the yield stress and changes the pressure dependence of shear modulus. Shear-induced densification is observed in both glasses. It is found that the decreases of the oxygen-centered bond angle and the coordination number change of B are responsible for the density changes at low pressures, and the increase of 5-coordinated Si is the dominant mechanism for densification at high pressures. The average shear stresses experienced by Si and B decrease with pressure except that the flow stress of Si at the end of shear deformation in N-BK7. Moreover, the average shear stress of B is more sensitive to the applied pressures compared to Si, suggesting that B is able to relax mechanical stress more easily under pressurized-shear. By analyzing the nonaffine displacement of atoms, it is found that N-BK7 exhibits more localized plastic deformation compared to Boro33 at low pressures and the local rearrangements in both glasses become more homogeneous with increasing pressure. The mean squared nonaffine displacement curves show that alkali ions have the highest mobility induced by shear compared to the network formers and B is more mobile than Si for both glasses. We also observed that plastic deformation tends to take place around boron atoms for Boro33, whereas it occurs in the alkali-rich regions for N-BK7, indicating that these two glasses have different atomic-scale deformation mechanisms.     

Atomic-scale mechanisms of densification in cold-compressed borosilicate glasses

Knowledge of the underlying structural response during deformation processes is essential for understanding the macroscopic mechanical response of glass. Here we present results from cold compression-decompression molecular dynamics (MD) simulations of two multicomponent borosilicate glasses, Borofloat^®33 (Boro33) and N-BK7^® (N-BK7). Our results suggest that the densification of these two borosilicate glasses involves different types of structural changes. The fraction of permanent densification can be correlated to the change in intermediate-range structure. By performing Voronoi analysis, we quantify the contributions to densification from different cation types in these two multicomponent borosilicate glasses, finding that 3-coordinated cations facilitate the densification process. Higher-coordinated cations are relatively stable and can even show a slight expansion in their Voronoi volume.     

Privacy Preserving Geo-Linkage in the Big Urban Data Era

Big data technologies and a range of Government open data initiatives provide the basis for discovering new insights into cities; how they are planned, how they managed and the day-to-day challenges they face in health, transport and changing population profiles. The Australian Urban Research Infrastructure Network (AURIN – www.aurin.org.au) project is one example of such a big data initiative that is currently running across Australia. AURIN provides a single gateway providing online (live) programmatic access to over 2000 data sets from over 70 major and typically definitive data-driven organizations across federal and State government, across industry and across academia. However whilst open (public) data is useful to bring data-driven intelligence to cities, more often than not, it is the data that is not-publicly accessible that is essential to understand city challenges and needs. Such sensitive (unit-level) data has unique requirements on access and usage to meet the privacy and confidentiality demands of the associated organizations. In this paper we highlight a novel geo-privacy supporting solution implemented as part of the AURIN project that provides seamless and secure access to individual (unit-level) data from the Department of Health in Victoria. We illustrate this solution across a range of typical city challenges in localized contexts around Melbourne. We show how unit level data can be combined with other data in a privacy-protecting manner. Unlike other secure data access and usage solutions that have been developed/deployed, the AURIN solution allows any researcher to access and use the data in a manner that meets all of the associated privacy and confidentiality concerns, without obliging them to obtain ethical approval or any other hurdles that are normally put in place on access to and use of sensitive data. This provides a paradigm shift in secure access to sensitive data with geospatial content.     

Verification of Knowledge Assets in Electronic Repositories: Expert- and Community-Governance

Two mechanisms that verify knowledge contributions in electronic repositories are expert-governance and community-governance. Our goal is to examine repository users' perceptions of the conditions under which these mechanisms verify knowledge contributions. Qualitative data show that perceived credibility of experts, perceived ownership of content, and experts' (meticulous) execution of governance functions are salient for expert-governance, and the perceived involvement of community members, and community members' (continuous and collective) execution of governance functions are important for community-governance.     

Use of a dark object concept and support vector machines to automate forest cover change analysis

An automated method was developed for mapping forest cover change using satellite remote sensing data sets. This multi-temporal classification method consists of a training data automation (TDA) procedure and uses the advanced support vector machines (SVM) algorithm. The TDA procedure automatically generates training data using input satellite images and existing land cover products. The derived high quality training data allow the SVM to produce reliable forest cover change products. This approach was tested in 19 study areas selected from major forest biomes across the globe. In each area a forest cover change map was produced using a pair of Landsat images acquired around 1990 and 2000. High resolution IKONOS images and independently developed reference data sets were available for evaluating the derived change products in 7 of those areas. The overall accuracy values were over 90% for 5 areas, and were 89.4% and 89.6% for the remaining two areas. The user's and producer's accuracies of the forest loss class were over 80% for all 7 study areas, demonstrating that this method is especially effective for mapping major disturbances with low commission errors. IKONOS images were also available in the remaining 12 study areas but they were either located in non-forest areas or in forest areas that did not experience forest cover change between 1990 and 2000. For those areas the IKONOS images were used to assist visual interpretation of the Landsat images in assessing the derived change products. This visual assessment revealed that for most of those areas the derived change products likely were as reliable as those in the 7 areas where accuracy assessment was conducted. The results also suggest that images acquired during leaf-off seasons should not be used in forest cover change analysis in areas where deciduous forests exist. Being highly automatic and with demonstrated capability to produce reliable change products, the TDA-SVM method should be especially useful for quantifying forest cover change over large areas.