Cobalt incorporation in calcite: Thermochemistry of (Ca,Co)CO3 solid solutions from density functional theory simulations

The incorporation of cobalt in mixed metal carbonates is a possible route to the immobilization of this toxic element in the environment. However, the thermodynamics of (Ca,Co)CO3 solid solutions are still unclear due to conflicting data from experiment and from the observation of natural ocurrences. We report here the results of a computer simulation study of the mixing of calcite (CaCO3) and spherocobaltite (CoCO3), using density functional theory calculations. Our simulations suggest that previously proposed thermodynamic models, based only on the range of observed compositions, significantly overestimate the solubility between the two solids and therefore underestimate the extension of the miscibility gap under ambient conditions. The enthalpy of mixing of the disordered solid solution is strongly positive and moderately asymmetric: calcium incorporation in spherocobaltite is more endothermic than cobalt incorporation in calcite. Ordering of the impurities in (0001) layers is energetically favourable with respect to the disordered solid solution at low temperatures and intermediate compositions, but the ordered phase is still unstable to demixing. We calculate the solvus and spinodal lines in the phase diagram using a sub-regular solution model, and conclude that many Ca1-xCoxCO3 mineral solid solutions (with observed compositions of up to x=0.027, and above x=0.93) are metastable with respect to phase separation. We also calculate solid/aqueous distribution coefficients to evaluate the effect of the strong non-ideality of mixing on the equilibrium with aqueous solution, showing that the thermodynamically-driven incorporation of cobalt in calcite (and of calcium in spherocobaltite) is always very low, regardless of the Co/Ca ratio of the aqueous environment.

Effective separation of Am(III) and Eu(III) from HNO3 Q1 Q2 solutions using CyMe4-BTPhen-functionalized silica-coated magnetic nanoparticles

It has been shown that CyMe4-BTPhen-functionalized silica-coated maghemite (c-Fe2O3) magnetic nanoparticles (MNPs) are capable of quantitative separation of Am(III) from Eu(III) from HNO3 solutions. These MNPs also show a small but significant selectivity for Am(III) over Cm(III) with a separation factor of around 2 in 4 M HNO3. The water molecule in the cavity of the BTPhen may also play an important part in the selectivity.

Effective separation of Am(III) and Eu(III) from HNO3 solutions using CyMe4-BTPhen-functionalized silica-coated magnetic nanoparticles

It has been shown that CyMe4-BTPhen-functionalized silica-coated maghemite (c-Fe2O3) magnetic nanoparticles (MNPs) are capable of quantitative separation of Am(III) from Eu(III) from HNO3 solutions. These MNPs also show a small but significant selectivity for Am(III) over Cm(III) with a separation factor of around 2 in 4 M HNO3. The water molecule in the cavity of the BTPhen may also play an important part in the selectivity.

Evaluation of water properties in HEA–HEMA hydrogels swollen in aqueous-PEG solutions using thermoanalytical techniques

Hydrogels are polymeric materials used in many pharmaceutical and biomedical applications due to their ability to form 3D hydrophilic polymeric networks, which can absorb large amounts of water. In the present work, polyethylene glycols (PEG) were introduced into the hydrogel liquid phase in order to improve the mechanical properties of hydrogels composed of 2-hydroxyethylacrylate and 2-hydroxyethylmethacrylate (HEA–HEMA) synthesized with different co-monomer compositions and equilibrated in water or in 20 % water–PEG 400 and 600 solutions. The thermoanalytical techniques [differential scanning calorimetry (DSC) and thermogravimetry (TG)] were used to evaluate the amount and properties of free and bound water in HEA–HEMA hydrogels. The internal structure and the mechanical properties of hydrogels were studied using scanning electron microscopy and friability assay. TG “loss-on-drying” experiments were applied to study the water-retention properties of hydrogels, whereas the combination of TG and DSC allowed estimating the total amount of freezable and non-freezing water in hydrogels. The results show that the addition of viscous co-solvent (PEG) to the liquid medium results in significant improvement of the mechanical properties of HEA–HEMA hydrogels and also slightly retards the water loss from the hydrogels. A redistribution of free and bound water in the hydrogels equilibrated in mixed solutions containing 20 vol% of PEGs takes place.

Pragmatic solutions for syntactic problems: Understanding some L2 syntactic errors in terms of discourse-pragmatic deficits

Contemporary research in generative second language (L2) acquisition has attempted to address observable target-deviant aspects of L2 grammars within a UG-continuity framework (e.g. Lardiere 2000; Schwartz 2003; Sprouse 2004; Prévost & White 1999, 2000). With the aforementioned in mind, the independence of pragmatic and syntactic development, independently observed elsewhere (e.g. Grodzinsky & Reinhart 1993; Lust et al. 1986; Pacheco & Flynn 2005; Serratrice, Sorace & Paoli 2004), becomes particularly interesting. In what follows, I examine the resetting of the Null-Subject Parameter (NSP) for English learners of L2 Spanish. I argue that insensitivity to associated discoursepragmatic constraints on the discursive distribution of overt/null subjects accounts for what appear to be particular errors as a result of syntactic deficits. It is demonstrated that despite target-deviant performance, the majority must have native-like syntactic competence given their knowledge of the Overt Pronoun Constraint (Montalbetti 1984), a principle associated with the Spanish-type setting of the NSP.

Perspectives on the specification of Building Integrated Photovoltaic (BIPV) technology in construction projects

Innovative, low carbon technologies are already available for use in the construction of buildings, but the impact of their specification on construction projects is unclear. This exploratory research identifies issues which arise following the specification of BIPV in non-residential construction projects. Rather than treating the inclusion of a new technology as a technical problem, the research explores the issue from a socio-technical perspective to understand the accommodations which the project team makes and their effect on the building and the technology. The paper is part of a larger research project which uses a Social Construction of Technology Approach (SCOT) to explore the accommodations made to working practices and design when Building Integrated PhotoVoltaic (BIPV) technology is introduced. The approach explores how the requirements of the technology from different groups of actors (Relevant Social Groups or RSG's) give rise to problems and create solutions. As such it rejects the notion of a rational linear view of innovation diffusion; instead it suggests that the variety and composition of the Relevant Social Groups set the agenda for problem solving and solutions as the project progresses. The research explores the experiences of three people who have extensive histories of involvement with BIPV in construction, looks at how SCOT can inform our understanding of the issues involved and identifies themes and issues in the specification of BIPV on construction projects. A key finding concerns the alignment of inflection points at which interviewees have found themselves changing from one RSG to another as new problems and solutions are identified. The points at which they change RSG often occurred at points which mirror conventional construction categories (in terms of project specification, tender, design and construction).

Spirit of corporate social responsibility transforming from corporatism to socialized capitalism

This paper offers a critique of current corporate social responsibility (CSR) practices in context of global trends. The legitimate modelling of CSR has yet to engage firm and political decision making with wider Society stakeholders. There is urgent need to transform towards socialized capitalism in which separate CSR board may focus on social and environmental concerns and offer more collaborative solutions to global/local CSR issues. This is underpinned with a need for returning to original moral purpose of CSR that has become eroded by narrower short term rational justifications.

Institutional investors: arbitrageurs or rational trend chasers?

This paper studies the relationship between institutional investor holdings and stock misvaluation in the U.S. between 1980 and 2010. I find that institutional investors overweigh overvalued and underweigh undervalued stocks in their portfolio, taking the market portfolio as a benchmark. Cross-sectionally, institutional investors hold more overvalued stocks than undervalued stocks. The time-series studies also show that institutional ownership of overvalued portfolios increases as the portfolios' degree of overvaluation. As an investment strategy, institutional investors' ride of stock misvaluation is neither driven by the fund flows from individual investors into institutions, nor industry-specific. Consistent with the agency problem explanation, investment companies and independent investment advisors have a higher tendency to ride stock misvaluation than other institutions. There is weak evidence that institutional investors make positive profit by riding stock misvaluation. My findings challenge the models that view individual investors as noise traders and disregard the role of institutional investors in stock market misvaluation.

Thermal and visual performance of real and theoretical thermochromic glazing solutions for office buildings

Thermochromic windows are able to modulate their transmittance in both the visible and the near-infrared field as a function of their temperature. As a consequence, they allow to control the solar gains in summer, thus reducing the energy needs for space cooling. However, they may also yield a reduction in the daylight availability, which results in the energy consumption for indoor artificial lighting being increased. This paper investigates, by means of dynamic simulations, the application of thermochromic windows to an existing office building in terms of energy savings on an annual basis, while also focusing on the effects in terms of daylighting and thermal comfort. In particular, due attention is paid to daylight availability, described through illuminance maps and by the calculation of the daylight factor, which in several countries is subject thresholds. The study considers both a commercially available thermochromic pane and a series of theoretical thermochromic glazing. The expected performance is compared to static clear and reflective insulating glass units. The simulations are repeated in different climatic conditions, showing that the overall energy savings compared to clear glazing can range from around 5% for cold climates to around 20% in warm climates, while not compromising daylight availability. Moreover the role played by the transition temperature of the pane is examined, pointing out an optimal transition temperatures that is irrespective of the climatic conditions.

Internal nanoparticle structure of temperature-responsive self-assembled PNIPAM-b-PEG-b-PNIPAM triblock copolymers in aqueous solutions: NMR, SANS and light scattering studies

In this study we report detailed information on the internal structure of PNIPAM-b-PEG-b-PNIPAM nanoparticles formed from self-assembly in aqueous solutions upon increase in temperature. NMR spectroscopy, light scattering and small-angle neutron scattering (SANS) were used to monitor different stages of nanoparticle formation as a function of temperature, providing insight into the fundamental processes involved. The presence of PEG in a copolymer structure significantly affects the formation of nanoparticles, making their transition to occur over a broader temperature range. The crucial parameter that controls the transition is the ratio of PEG/PNIPAM. For pure PNIPAM, the transition is sharp; the higher the PEG/PNIPAM ratio results in a broader transition. This behavior is explained by different mechanisms of PNIPAM block incorporation during nanoparticle formation at different PEG/PNIPAM ratios. Contrast variation experiments using SANS show that the structure of nanoparticles above cloud point temperatures for PNIPAM-b-PEG-b-PNIPAM copolymers is drastically different from the structure of PNIPAM mesoglobules. In contrast with pure PNIPAM mesoglobules, where solid-like particles and chain network with a mesh size of 1-3 nm are present; nanoparticles formed from PNIPAM-b-PEG-b-PNIPAM copolymers have non-uniform structure with “frozen” areas interconnected by single chains in Gaussian conformation. SANS data with deuterated “invisible” PEG blocks imply that PEG is uniformly distributed inside of a nanoparticle. It is kinetically flexible PEG blocks which affect the nanoparticle formation by prevention of PNIPAM microphase separation.