Shell Model Study of Local and Global Energy Barriers in KDP

We perform a study of the energetics of KH2PO4 (KDP) by using a shell model (SM) which was constructed by adjusting the interaction parameters to ab initio calculations, and was fitted to reproduce phonons, polarization-inversion energies and structural properties. We calculate the energy profiles by performing global displacements and local distortions following the ferroelectric (FE) mode pattern in clusters of different sizes embedded in a paraelectric (PE) phase matrix. These properties are expected to be relevant to the PE-FE phase transition. The obtained SM results are compared to corresponding ab initio (AI) data. The global instabilities are found in good agreement for both KDP and DKDP. We also find qualitative good agreement in the KDP structure and even quantitative agreement in the expanded DKDP structure for the local distortions. The SM results reproduce well different trends like increasing instabilities as the cluster sizes grows, as the heavier atoms are included, and as the volume is increased, in accordance with the corresponding data from AI calculations.

Catalysing the Irish Energy Transition: Capacities and Challenges

The transition to a “low carbon, climate resilient and environmentally sustainable economy by the end of the 
year 2050” has been conceptualised as the “national transition objective” in the Irish Climate Action and Low Carbon Development Bill, passed in late 2015. This has raised a myriad of questions over how this can be operationalised and resourced and whether it can maintain political momentum. This paper assesses the utility of framings informed by the transitions (MLP) and technological innovation systems perspectives in contributing to transformative societal processes, by examining their application in an Irish case study on policy and technology. Through a qualitative exploration of the broader societal and policy context of the energy sector and a more detailed examination of the innovation systems of selected niche technologies (bioenergy and electric vehicles), the Irish case study sought to identify potential catalysts for a sustainability transition in the energy sector in Ireland: where these exist, how these are being built or enabled, and barriers to change. Following a discussion on the theoretical approaches used, a description will be given of how these were applied in the conducting of the research on transition in Ireland case study and the key findings which emerged. A critical reflection will then be made on the utility of these perspectives (as applied) to contribute to broader processes of societal transformation in Ireland.

Benchmarking Energy Transitions: An Irish Case Study

The challenges of a low carbon energy transition have now been recognized by most nation states, each of whom have responded with differing visions, strategies and programmes, with variable veracity and effectiveness. Given the complexity of each country’s energy system (and sub-systems such as mobility, food etc), the differing sources and wealth of indigenous energy resources, the variable legacy of the fossil fuel regime and differing capacity to respond to global shifts in energy markets, it is clear that each country will respond to this challenge in very different ways.
This poses difficulties for understanding the extent to which a transition may be taking hold in any territory as simple indicators such as GHG emission data or increases in renewable energy ignore the complex contexts in which transitions take place. Drawing on the results of a study, funded by the Irish Environmental Protection Agency (Characterizing and Catalyzing Transitions) and using the wider theoretical framework of socio-technological transitions, this paper will explore the challenges, virtues and constraints of attempting to ‘benchmark’ the Republic of Ireland’s transition. This will lead to wider observations on the normative nature of benchmarking and a critical review of how we conceptualize the very idea of transition.

Mapping Ireland’s Energy Pathways: Characterizing and Catalyzing Transition

In 2015 Ireland has arguably begun to make its first bold steps in confronting the challenges of energy transition, with the objective of a “low carbon, climate resilient and environmentally sustainable economy by the end of the
year 2050” expressed in the 2015 Climate Action and Low Carbon Development Bill and the 2015 Energy Bill acknowledging that energy transformation relied on a new breed of ‘energy citizens’. These represent the first formal articulation of Ireland’s ambition to engage in a radical, long-term and far-reaching transition process, and raises a myriad of questions over how this can be operationalised, resourced and whether it can maintain political momentum. A range of perspectives on these issues is provided in the growing body of literature on transition theories (Rotmans et al 2001, Markard et al 2012) and the inter-disciplinary EPA-funded CC Transitions project, based at Queen’s University Belfast, represents an attempt to translate this into the context of Ireland’s institutions and technological profile. By relating this to international research on sustainability transitions, which conceptualises transitions as multi-level, multi-phase and multi-actor processes, this paper will explore the opportunities of alternative pathways that could take Ireland towards a more progressing, inclusive and effective low carbon future. Drawing on a number of case studies it will highlight some of the capacities for transition required in Irish society: where these exist, how they are being built or enabled, and the barriers to wider social change.

The Day After Tomorrow: Transition Management, Spatial Planning & the Low Carbon Economy

Many of the societal challenges that current spatial planning practice claims to be addressing (climate change, peak oil, obesity, aging society etc) encompass issues and timescales that lie beyond the traditional scope planning policy (Campbell 2006). The example of achieving a low carbon economy typifies this in that it demands a process of society-wide transition, involving steering a wide range of factors (markets, infrastructure, governance, individual behaviour etc). Such a process offers a challenge to traditional approaches to planning as they cannot be guided by a fixed blueprint, given the timescales involved (up to 50 years) and an enhanced level of uncertainty, social resistance, lack of control over implementation and a danger of ‘policy lock in’ (Kemp et al 2007). One approach to responding to these challenges is the concept of transition management which has emerged from studies of science, technology and innovation (Geels 2002, Markard et al 2012). Although not without criticism, this perspective attempts to uncertainty and complexity encompassing long term visions that integrates multi-level, multi-actor and multi-domain perspectives (Rotmans et al 2001).
 
Given its origins, research on transition management has tended to neglect spatial contexts (Coenen et al 2012) and, related to this, it’s relationship with spatial planning is poorly understood. Using the example of the low carbon transition, this paper will review the relationships between the concepts, methodologies and goals of transition management and spatial planning to explore whether a closer integration of the two fields offers benefits to achieving the long term challenges facing society.
 

Development of sustainable, innovative and energy-efficient concrete, based on the integration of all-waste materials: SUS-CON panels for building applications

The building sector requires the worldwide production of 4 billion tonnes of cement annually, consuming more than 40% of global energy and accounting for about 8% of the total CO2 emissions. The SUS-CON project aimed at integrating waste materials in the production cycle of concrete, for both ready-mixed and pre-cast applications, resulting in an innovative light-weight, ecocompatible and cost-effective construction material, made by all-waste materials and characterized by enhanced thermal insulation performance and low embodied energy and CO2. Alkali activated “cementless” binders, which have recently emerged as eco-friendly construction materials, were used in conjunction with lightweight recycled aggregates to produce sustainable concrete for a range of applications. This paper presents some results from the development of a concrete made with a geopolymeric binder (alkali activated fly ash) and aggregate from recycled mixed plastic. Mix optimisation was achieved through an extensive investigation on production parameters for binder and aggregate. The mix recipe was developed for achieving the required fresh and hardened properties. The optimised mix gave compressive strength of about 7 MPa, flexural strength of about 1.3 MPa and a thermal conductivity of 0.34 W/mK. Fresh and hardened properties were deemed suitable for the industrial production of precast products. Precast panels were designed and produced for the construction of demonstration buildings. Mock-ups of about 2.5 x 2.5 x 2.5 m were built at a demo park in Spain both with SUS-CON and Portland cement concrete, monitoring internal and external temperatures. Field results indicate that the SUS-CON mock-ups have better insulation. During the warmest period of the day, the measured temperature in the SUS-CON mock-ups was lower.

Numerical assessment of potential impacts of hydraulically fractured Bowland Shale on overlying aquifers

Natural gas extracted from hydraulically fractured shale formations potentially has a big impact on the global energy landscape. However, there are concerns of potential environmental impacts of hydraulic fracturing of the shale formations, particularly those related to water quality. To evaluate the potential impact of hydraulically fractured shale on overlying aquifers, we conduct realizations of numerical modeling simulations to assess fluid flow and chloride transport from a synthetic Bowland Shale over a period of 11,000 years. The synthetic fractured shale was represented by a three-dimensional discrete fracture model that was developed by using the data from a Bowland Shale gas exploration in Lancashire, UK. Chloride mass exchange between fractures and the rock matrix was fully accounted for in the model. The assessment was carried out to investigate fluid and chloride mass fluxes before, during, and after hydraulic fracturing of the Bowland Shale. Impacts of the upward fracture height and aperture, as well as hydraulic conductivity of the multilayered bedrock system, are also included this assessment. This modeling revealed that the hydraulically fractured Bowland Shale is unlikely to pose a risk to its overlying groundwater quality when the induced fracture aperture is ≤200 µm. With the fracture aperture ≥1000 µm, the upward chloride flux becomes very sensitive to the upward fracture height growth and hydraulic conductivity of the multilayered bedrock system. In the extremely unlikely event of the upward fracture growth directly connecting the shale formation to the overlying Sherwood Sandstone aquifer with the fracture aperture ≥1000 µm, the upward chloride mass flux could potentially pose risks to the overlying aquifer in 100 years. The model study also revealed that the upward mass flux is significantly intercepted by the horizontal mass flux within a high permeable layer between the Bowland Shale and its overlying aquifers, reducing further upward flux toward the overlying aquifers.

Unidirectional suppression of hydrogen oxidation on oxidized platinum clusters

Solar-driven water splitting to produce hydrogen may be an ideal solution for global energy and environment issues. Among the various photocatalytic systems, platinum has been widely used to co-catalyse the reduction of protons in water for hydrogen evolution. However, the undesirable hydrogen oxidation reaction can also be readily catalysed by metallic platinum, which limits the solar energy conversion efficiency in artificial photosynthesis. Here we report that the unidirectional suppression of hydrogen oxidation in photocatalytic water splitting can be fulfilled by controlling the valence state of platinum; this platinum-based cocatalyst in a higher oxidation state can act as an efficient hydrogen evolution site while suppressing the undesirable hydrogen back-oxidation. The findings in this work may pave the way for developing other high-efficientcy platinum-based catalysts for photocatalysis, photoelectrochemistry, fuel cells and water-gas shift reactions.

Sustainable binders for concrete: a structured approach from waste screening to binder composition development

Worldwide, the building sector requires the production of 4 billion tonnes of cement annually, consuming more than 40% of global energy. Alkali activated “cementless” binders have recently emerged as a novel eco-friendly construction material with a promising potential to replace ordinary Portland cement. These binders consist of a class of inorganic polymer formed mainly by the reaction between an alkaline solution and an aluminosilicate source. Precursor materials for this reaction can be found in secondary material streams from different industrial sectors, from energy to agro-alimentary. However, the suitability of these materials in developing the polymerisation reaction must be assessed through a detailed chemical and physical characterisation, ensuring the availability of required chemical species in the appropriate quantity and physical state. Furthermore, the binder composition needs to be defined in terms of proper alkali activation dosages, water content in the mix, and curing conditions. The mix design must satisfy mechanical requirements and compliance to desired engineering properties (workability, setting time) for ensuring the suitability of the binder in replacing Portland cement in concrete applications. This paper offers a structured approach for the development of secondary material-based binders, from their identification to mix design and production procedure development. Essential features of precursor material can be determined through chemical and physical characterisation methods and advanced microscope techniques. Important mixing parameters and binder properties requirements are examined and some examples of developed binders are reported.

Review and analysis of solar thermal facades

Harnessing solar energy to provide for the thermal needs of buildings is one of the most promising solutions to the global energy issue. Exploiting the additional surface area provided by the building’s façade can significantly increase the solar energy output. Developing a range of integrated and adaptable products that do not significantly affect the building’s aesthetics is vital to enabling the building integrated solar thermal market to expand and prosper. This work reviews and evaluates solar thermal facades in terms of the standard collector type, which they are based on, and their component make-up. Daily efficiency models are presented, based on a combination of the Hottel Whillier Bliss model and finite element simulation. Novel and market available solar thermal systems are also reviewed and evaluated using standard evaluation methods, based on experimentally determined parameters ISO 9806. Solar thermal collectors integrated directly into the facade benefit from the additional wall insulation at the back; displaying higher efficiencies then an identical collector offset from the facade. Unglazed solar thermal facades with high capacitance absorbers (e.g. concrete) experience a shift in peak maximum energy yield and display a lower sensitivity to ambient conditions than the traditional metallic based unglazed collectors. Glazed solar thermal facades, used for high temperature applications (domestic hot water), result in overheating of the building’s interior which can be reduced significantly through the inclusion of high quality wall insulation. For low temperature applications (preheating systems), the cheaper unglazed systems offer the most economic solution. The inclusion of brighter colour for the glazing and darker colour for the absorber shows the lowest efficiency reductions (<4%). Novel solar thermal façade solutions include solar collectors integrated into balcony rails, shading devices, louvers, windows or gutters.

Free energy and molecular dynamics calculations for the cubic-tetragonal phase transition in zirconia

The high-temperature cubic-tetragonal phase transition of pure stoichiometric zirconia is studied by molecular dynamics (MD) simulations and within the framework of the Landau theory of phase transformations. The interatomic forces are calculated using an empirical, self-consistent, orthogonal tight-binding model, which includes atomic polarizabilities up to the quadrupolar level. A first set of standard MD calculations shows that, on increasing temperature, one particular vibrational frequency softens. The temperature evolution of the free-energy surfaces around the phase transition is then studied with a second set of calculations. These combine the thermodynamic integration technique with constrained MD simulations. The results seem to support the thesis of a second-order phase transition but with unusual, very anharmonic behavior above the transition temperature.

The near-edge structure in energy-loss spectroscopy: many-electron and magnetic effects in transition metal nitrides and carbides

We investigate the ability of the local density approximation (LDA) in density functional theory to predict the near-edge structure in electron energy-loss spectroscopy in the dipole approximation. We include screening of the core hole within the LDA using Slater's transition state theory. We find that anion K-edge threshold energies are systematically overestimated by 4.22 +/- 0.44 eV in twelve transition metal carbides and nitrides in the rock-salt (B1) structure. When we apply this 'universal' many-electron correction to energy-loss spectra calculated within the transition state approximation to LDA, we find quantitative agreement with experiment to within one or two eV for TiC, TiN and VN. We compare our calculations to a simpler approach using a projected Mulliken density which honours the dipole selection rule, in place of the dipole matrix element itself. We find remarkably close agreement between these two approaches. Finally, we show an anomaly in the near-edge structure in CrN to be due to magnetic structure. In particular, we find that the N K edge in fact probes the magnetic moments and alignments of ther sublattice.