Electronic structure of point defects in controlled self-doping of the TiO2 (110) surface: Combined photoemission spectroscopy and density functional theory study

Point defects in metal oxides such as TiO2 are key to their applications in numerous technologies. The investigation of thermally induced nonstoichiometry in TiO2 is complicated by the difficulties in preparing and determining a desired degree of nonstoichiometry. We study controlled self-doping of TiO2 by adsorption of 1/8 and 1/16 monolayer Ti at the (110) surface using a combination of experimental and computational approaches to unravel the details of the adsorption process and the oxidation state of Ti. Upon adsorption of Ti, x-ray and ultraviolet photoemission spectroscopy (XPS and UPS) show formation of reduced Ti. Comparison of pure density functional theory (DFT) with experiment shows that pure DFT provides an inconsistent description of the electronic structure. To surmount this difficulty, we apply DFT corrected for on-site Coulomb interaction (DFT+U) to describe reduced Ti ions. The optimal value of U is 3 eV, determined from comparison of the computed Ti 3d electronic density of states with the UPS data. DFT+U and UPS show the appearance of a Ti 3d adsorbate-induced state at 1.3 eV above the valence band and 1.0 eV below the conduction band. The computations show that the adsorbed Ti atom is oxidized to Ti2+ and a fivefold coordinated surface Ti atom is reduced to Ti3+, while the remaining electron is distributed among other surface Ti atoms. The UPS data are best fitted with reduced Ti2+ and Ti3+ ions. These results demonstrate that the complexity of doped metal oxides is best understood with a combination of experiment and appropriate computations.

A glacier inventory for the Buordakh Massif, Cherskiy Range, northeast Siberia, and evidence for recent glacier recession

The Buordakh Massif, in the Cherskiy Range of northeast Siberia, contains mountains over 3000 in and, despite its and climate, numerous glaciers. This paper presents a glacier inventory for the region and documents some 80 glaciers, which range in size from 0.1 to 10.4 km(2) (total glacierized area is ca. 70 km(2)). The inventory is based on mapping derived from Landsat 7 ETM+ satellite imagery from August 2001, augmented with data from field investigations obtained at that time. The glaciers in this region are of the 'firn-less,' cold, continental type, and their mass balance relies heavily on the formation of superimposed ice. The most recent glacier maximum extents have also been delineated, and these are believed to date from the Little Ice Age (ca. A.D. 1550-1850). Glacier areal extent has reduced by some 14.8 km(2) (ca. 17%) since this most. recent maximum. Of the 80 glaciers catalogued, 49 have undergone a measurable retreat from their most recent maximum extent.

Resilience planning, economic change and the politics of post-recession development in London and Hong Kong

For much of the 1990s and 2000s, the emphasis of urban policy in many global cities was on managing and mitigating the social and environmental effects of rapid economic growth. The credit crunch of 2008 and the subsequent recession have undermined some of the core assumptions on which such policies were based. It is in this context that the concept of resilience planning has taken on a new significance. Drawing on contemporary research in London and Hong Kong, the paper shows how resilience and recovery planning has become a key area of political debate. It examines what is meant by conservative and radical interpretations of resilience and how conservative views have come to dominate ‘recovery’ thinking, with élite groups unwilling to accept the limits to the neo-liberal orthodoxies that helped to precipitate the economic crisis. The paper explores the implications of such thinking for the politics of urban development.

Dynamics of interacting edge defects in copolymer lamellae

It is known that terraces at the air-polymer interface of lamella forming diblock copolymers do not make discontinuous jumps in height. Despite the underlying discretized structure, the height profiles are smoothly varying. The width of a transition region of a terrace edge in isolation is typically several hundreds of nanometres, resulting from a balance between surface tension, chain stretching penalties, and the enthalpy of mixing. What is less well known in these systems is what happens when two transition regions interact with one another. In this study, we investigate the dynamics of the interactions between copolymer lamellar edges. We find that the data can be well described by a model that assumes a repulsion between adjacent edges. While the model is simplistic, and does not include molecular level details, its agreement with the data suggest that some of the the underlying assumptions provide insight into the complex interplay between defects.

Critical success factors in urban brownfield regeneration: an analysis of ‘hardcore’ sites in Manchester and Osaka during the economic recession (2009–10)

Hardcore, or long-term derelict and vacant brownfield sites which are often contaminated, form a significant proportion of brownfield land in many cities, not only in the UK but also in other countries. The recent economic recession has placed the economic viability of such sites in jeopardy. This paper compares the approaches for bringing back hardcore brownfield sites into use in England and Japan by focusing on ten case studies in Manchester and Osaka, using an `agency'-based frame- work. The findings are set in the context of (i) national brownfield and related policy agendas; (ii) recent trends in land and property markets in both England and Japan; and (iii) city-level comparisons of brownfields in Manchester and Osaka. The research, which was conducted during 2009 ^ 10, suggests that hardcore brownfield sites have been badly affected by the recent recession in both Manchester and Osaka. Despite this, not only is there evidence that hardcore sites have been successfully regenerated in both cities, but also that the critical success factors (CSFs) operating in bringing sites back into use share a large degree of commonality. These CSFs include the presence of strong potential markets, seeing the recession as an opportunity, long-term vision, strong branding, strong partnerships, integrated development, and getting infrastructure into place. Finally, the paper outlines the policy implications of the research.

Placing defects at the heart of high quality new homes: a learning perspective

The UK new-build housing sector is facing dual pressures to expand supply, whilst delivering against tougher planning and Building Regulation requirements; predominantly in the areas of sustainability. The sector is currently responding by significantly scaling up production and incorporating new technical solutions into new homes. This trajectory of up-scaling and technical innovation has been of research interest; but this research has primarily focus on the ‘upstream’ implications for house builders’ business models and standardised design templates. There has been little attention, though, to the potential ‘downstream’ implications of the ramping up of supply and the introduction of new technologies for build quality and defects. This paper contributes to our understanding of the ‘downstream’ implications through a synthesis of the current UK defect literature with respect to new-build housing. It is found that the prevailing emphasis in the literature is limited to the responsibility, pathology and statistical analysis of defects (and failures). The literature does not extend to how house builders individually and collectively, in practice, collect and learn from defects information. The paper concludes by describing an ongoing collaborative research programme with the National House Building Council (NHBC) to: (a) understand house builders’ localised defects analysis procedures, and their current knowledge feedback loops to inform risk management strategies; and, (b) building on this understanding, design and test action research interventions to develop new data capture, learning processes and systems to reduce targeted defects.

Investigating the impact of defects on key stakeholders in the UK new housing sector

The UK house building sector is facing dual pressures to expand supply, along with delivering against tougher Building Regulations’ requirements, predominantly in the areas of sustainability. A review of current literature has highlighted that the pressures the UK house building industry is currently under may be having a negative impact on build quality, causing an increase in defects. A review and synthesis of the current defect literature with respect to new-build housing and the wider construction sector has found that the prevailing emphasis is limited to the classification, causes, pathology and statistical analysis of defects. There is thus a need to better understand the overall impact of individual defects on key stakeholders within the new-build housing defect detection and remediation process. As part of ongoing research to develop and verify a defect impact assessment rating system, this paper seeks to contribute to our understanding of the impact of individual defects from a key stakeholder perspective by undertaking the literature review and synthesis phase. The literature review identifies the three distinct, but interrelated, dominant impact factors: cost, disruption, and health and safety. By pulling the strands of defect literature together the theoretical lens and key stakeholder sampling strategy is formed as the basis for the subsequent impact weighting development phase.