Rheological and thermal behaviour of poly(N-isopropylacrylamide)/alginate smart polymeric networks

Interpenetrating polymeric networks based on sodium alginate and poly(N-isopropylacrylamide) (PNIPAAm) covalently crosslinked with N,N′-methylenebisacrylamide have been investigated using rheology, thermogravimetry, differential scanning calorimetry, X-ray diffraction measurements and scanning electron microscopy (SEM). An improved elastic response of the samples with a higher PNIPAAm content and increased amount of crosslinking agent was found. The temperature-responsive behaviour of the hydrogel samples was evidenced by viscoelastic measurements performed at various temperatures. It is shown that the properties of these gels can be tuned according to composition, amount of crosslinking agent and temperature changes. X-ray scattering analysis revealed that the hydrophobic groups are locally segregated even in the swollen state whilst cryo-SEM showed the highly heterogeneous nature of the gels.

Synthesis and phase behaviour of a homologous series of polymethacrylate-based side-chain liquid crystal polymers

The homologous series of side chain liquid crystal polymers, the poly[x-(4-methoxyazobenzene- 40-oxy)alkyl methacrylate]s, has been prepared in which the length of the flexible alkyl spacer has been varied from 3 to 11 methylene units. All the polymers exhibit liquid crystalline behaviour. The propyl and butyl members show exclusively nematic behaviour. The pentyl, hexyl, octyl and decyl members show a nematic and a smectic A phase while the heptyl, nonyl and undecyl homologues exhibit only a smectic A phase. The smectic A phase has been studied using X-ray diffraction and assigned as a smectic A1 phase in which the side chains are fully overlapped and the backbones are confined to lie between the smectic layers. For the nonyl member an incommensurate smectic phase is observed. The dependence of the transition temperatures on the length of the flexible spacer is understood in terms of the average shapes of the side chains.

Complexes of NiX2 (X=Cl− and NO3−) with a NNO donor Schiff base: anion dependent structural variations and spectroscopic behaviour

Two new nickel(11) complexes, [NiLL'(H2O)(2)Cl] (1) and [{NiLL'(H2O)](2)(mu-H)]NO3·H2O(2), have been synthesized using a tridentate Schiff base ligand, HL, 2-[(2-dimethylamino-ethylimino)-methyl]-phenol, along with Cl- or NO3(-) as an anionic co-ligand or counter anion (where L'H = salicylaldehyde). Both complexes have been characterized by X-ray crystallography. The structural analyses reveal that complex 1 is mononuclear whereas 2 is a hydrogen-bridged dinuclear complex. The Ni(II) ions possess a distorted octahedral geometry in both structures. Both complexes show negative solvatochromic behaviour with increasing donor number (DN) of the solvent. In more coordinating solvents, like DMSO or methanol, the colour of the solutions is green, whereas in less coordinating solvents, like dichloromethane (DCM) or acetonitrile, it is red.

The influence of vegetation, fire spread and fire behaviour on biomass burning and trace gas emissions: results from a process-based model

A process-based fire regime model (SPITFIRE) has been developed, coupled with ecosystem dynamics in the LPJ Dynamic Global Vegetation Model, and used to explore fire regimes and the current impact of fire on the terrestrial carbon cycle and associated emissions of trace atmospheric constituents. The model estimates an average release of 2.24 Pg C yr−1 as CO2 from biomass burning during the 1980s and 1990s. Comparison with observed active fire counts shows that the model reproduces where fire occurs and can mimic broad geographic patterns in the peak fire season, although the predicted peak is 1–2 months late in some regions. Modelled fire season length is generally overestimated by about one month, but shows a realistic pattern of differences among biomes. Comparisons with remotely sensed burnt-area products indicate that the model reproduces broad geographic patterns of annual fractional burnt area over most regions, including the boreal forest, although interannual variability in the boreal zone is underestimated.

A DFT study of the structures, stabilities and redox behaviour of the major surfaces of magnetite Fe3O4

The renewed interest in magnetite (Fe3O4) as a major phase in different types of catalysts has led us to study the oxidation–reduction behaviour of its most prominent surfaces. We have employed computer modelling techniques based on the density functional theory to calculate the geometries and surface free energies of a number of surfaces at different compositions, including the stoichiometric plane, and those with a deficiency or excess of oxygen atoms. The most stable surfaces are the (001) and (111), leading to a cubic Fe3O4 crystal morphology with truncated corners under equilibrium conditions. The scanning tunnelling microscopy images of the different terminations of the (001) and (111) stoichiometric surfaces were calculated and compared with previous reports. Under reducing conditions, the creation of oxygen vacancies in the surface leads to the formation of reduced Fe species in the surface in the vicinity of the vacant oxygen. The (001) surface is slightly more prone to reduction than the (111), due to the higher stabilisation upon relaxation of the atoms around the oxygen vacancy, but molecular oxygen adsorbs preferentially at the (111) surface. In both oxidized surfaces, the oxygen atoms are located on bridge positions between two surface iron atoms, from which they attract electron density. The oxidised state is thermodynamically favourable with respect to the stoichiometric surfaces under ambient conditions, although not under the conditions when bulk Fe3O4 is thermodynamically stable with respect to Fe2O3. This finding is important in the interpretation of the catalytic properties of Fe3O4 due to the presence of oxidised species under experimental conditions.

The mediating effect of environmental and ethical behaviour on supply chain partnership decisions and management appreciation of supplier partnership risks

Green supply chain management and environmental and ethical behaviour (EEB), a major component of corporate responsibility (CR), are rapidly developing fields in research and practice. The influence and effect of EEB at the functional level, however, is under-researched. Similarly, the management of risk in the supply chain has become a practical concern for many firms. It is important that managers have a good understanding of the risks associated with supplier partnerships. This paper examines the effect of firms’ investment in EEB as part of corporate social responsibility in mediating the relationship between supply chain partnership (SCP) and management appreciation of the risk of partnering. We hypothesise that simply entering into a SCP does not facilitate an appreciation of the risk of partnering and may even hamper such awareness. However, such an appreciation of the risk is facilitated through CR’s environmental and stakeholder management ethos. The study contributes further by separating risk into distinct relational and performance components. The results of a firm-level survey confirm the mediation effect, highlighting the value to supply chain strategy and design of investing in EEB on three fronts: building internal awareness, monitoring and sharing best practice.

Commercial thickeners used by patients with dysphagia: rheological and structural behaviour in different food matrices

In order to achieve a safe swallowing in patients with dysphagia, liquids must be thickened. In this work, two commercial starch based thickeners dissolved in water, whole milk, apple juice and tomato juice were studied. The thickeners were Resource®, composed of modified maize starch and Nutilis®, composed of modified maize starch and gums. They were formulated at two different concentrations corresponding to nectar- and pudding-like consistencies. Influence of composition, concentration and food matrix on rheological properties and structure of the resulting pastes were analysed. Viscoelastic measurements and microscopic observations of the thickeners dissolved in water revealed structural differences due to the presence of gums. When the thickeners were dissolved in the other food matrices significant statistical interactions were found between the matrix and the thickener-type in both the viscoelastic and flow parameters. The most relevant differences were observed for the nectar-like consistency with Nutilis® thickener in milk and apple juice. These samples had lower zero viscosity values and higher loss tangent values, that corresponded to weaker structured systems. Light microscopy images showed that the matrix formed by swollen starch granules was interrupted by the presence of gums. The structure of the matrices in pudding-like formulations became more continuous irrespectively of the matrix employed, and also differences in viscoelasticity among samples diminished. Although differences were observed in zero shear viscosity values among samples, the viscosity of the beverages at 50 s−1 – commonly used as a reference for swallowing – was similar for all samples regardless of the matrix used.

Considering user attitude and behaviour in persuasive systems design: the 3D-RAB model

As in any technology systems, analysis and design issues are among the fundamental challenges in persuasive technology. Currently, the Persuasive Systems Development (PSD) framework is considered to be the most comprehensive framework for designing and evaluation of persuasive systems. However, the framework is limited in terms of providing detailed information which can lead to selection of appropriate techniques depending on the variable nature of users or use over time. In light of this, we propose a model which is intended for analysing and implementing behavioural change in persuasive technology called the 3D-RAB model. The 3D-RAB model represents the three dimensional relationships between attitude towards behaviour, attitude towards change or maintaining a change, and current behaviour, and distinguishes variable levels in a user’s cognitive state. As such it provides a framework which could be used to select appropriate techniques for persuasive technology.

Behaviour change in the UK climate debate : an assessment of responsibility, agency and political dimensions

This paper explores the politics around the role of agency in the UK climate change debate. Government interventions on the demand side of consumption have increasingly involved attempts to obtain greater traction with the values, attitudes and beliefs of citizens in relation to climate change and also in terms of influencing consumer behaviour at an individual level. With figures showing that approximately 40% of the UK’s carbon emissions are attributable to household and transport behaviour, policy initiatives have progressively focused on the facilitation of “sustainable behaviours”. Evidence suggests however, that mobilisation of pro-environmental attitudes in addressing the perceived “value-action gap” has so far had limited success. Research in this field suggests that there is a more significant and nuanced “gap” between context and behaviour; a relationship that perhaps provides a more adroit reflection of reasons why people do not necessarily react in the way that policy-makers anticipate. Tracing the development of the UK Government’s behaviour change agenda over the last decade, we posit that a core reason for the limitations of this programme relates to an excessively narrow focus on the individual. This has served to obscure some of the wider political and economic aspects of the debate in favour of a more simplified discussion. The second part of the paper reports findings from a series of focus groups exploring some of the wider political views that people hold around household energy habits, purchase and use of domestic appliances, and transport behaviour-and discusses these insights in relation to the literature on the agenda’s apparent limitations. The paper concludes by considering whether the aims of the Big Society approach (recently established by the UK’s Coalition Government) hold the potential to engage more directly with some of these issues or whether they merely constitute a “repackaging” of the individualism agenda.

The national dialogue on behaviour change in UK climate policy: some observations on responsibility, agency and political dimensions

This chapter explores the politics around the role of agency in the UK climate change debate. Government interventions on the demand side of consumption have increasingly involved attempts to obtain greater traction with the values, attitudes and beliefs of citizens in relation to climate change and also in terms of influencing consumer behaviour at an individual level. With figures showing that approximately 40% of the UK’s carbon emissions are attributable to household and transport behaviour, policy initiatives have progressively focused on the facilitation of “sustainable behaviours”. Evidence suggests however, that mobilisation of pro-environmental attitudes in addressing the perceived “value-action gap” has so far had limited success. Research in this field suggests that there is a more significant and nuanced “gap” between context and behaviour; a relationship that perhaps provides a more adroit reflection of reasons why people do not necessarily react in the way that policy-makers anticipate. Tracing the development of the UK Government’s behaviour change agenda over the last decade, we posit that a core reason for the limitations of this programme relates to an excessively narrow focus on the individual. This has served to obscure some of the wider political and economic aspects of the debate in favour of a more simplified discussion. The second part of the chapter reports findings from a series of focus groups exploring some of the wider political views that people hold around household energy habits, purchase and use of domestic appliances, and transport behaviour-and discusses these insights in relation to the literature on the agenda’s apparent limitations. The chapter concludes by considering whether the aims of the Big Society approach (recently established by the UK’s Coalition Government) hold the potential to engage more directly with some of these issues or whether they merely constitute a “repackaging” of the individualism agenda.

Determinants of biosecurity behaviour of British cattle and sheep farmers: a behavioural economics analysis

The paper analyses the impact of a priori determinants of biosecurity behaviour of farmers in Great Britain. We use a dataset collected through a stratified telephone survey of 900 cattle and sheep farmers in Great Britain (400 in England and a further 250 in Wales and Scotland respectively) which took place between 25 March 2010 and 18 June 2010. The survey was stratified by farm type, farm size and region. To test the influence of a priori determinants on biosecurity behaviour we used a behavioural economics method, structural equation modelling (SEM) with observed and latent variables. SEM is a statistical technique for testing and estimating causal relationships amongst variables, some of which may be latent using a combination of statistical data and qualitative causal assumptions. Thirteen latent variables were identified and extracted, expressing the behaviour and the underlying determining factors. The variables were: experience, economic factors, organic certification of farm, membership in a cattle/sheep health scheme, perceived usefulness of biosecurity information sources, knowledge about biosecurity measures, perceived importance of specific biosecurity strategies, perceived effect (on farm business in the past five years) of welfare/health regulation, perceived effect of severe outbreaks of animal diseases, attitudes towards livestock biosecurity, attitudes towards animal welfare, influence on decision to apply biosecurity measures and biosecurity behaviour. The SEM model applied on the Great Britain sample has an adequate fit according to the measures of absolute, incremental and parsimonious fit. The results suggest that farmers’ perceived importance of specific biosecurity strategies, organic certification of farm, knowledge about biosecurity measures, attitudes towards animal welfare, perceived usefulness of biosecurity information sources, perceived effect on business during the past five years of severe outbreaks of animal diseases, membership in a cattle/sheep health scheme, attitudes towards livestock biosecurity, influence on decision to apply biosecurity measures, experience and economic factors are significantly influencing behaviour (overall explaining 64% of the variance in behaviour).

Annual textural banding in Holocene estuarine silts, Severn Estuary Levels (SW Britain): patterns, cause and implications

A high-resolution textural study has been made of laminated and banded estuarine silts exposed intertidally at representative localities and horizons in the Holocene deposits of the Severn Estuary Levels. The laminae, on a submillimetre to millimetre scale, are sharp-based, graded couplets formed of a lower silty part overlain by a finer-textured clayey element. The centimetre- to decimetre-scale banding is formed of laminae in alternating, gradually intergrading sets of relatively coarse and relative fine-grained examples. At outcrop in the field, the banding is recognizable because the coarse sets prove to be recessive to varying degrees under the influence of weathering and current action. Independent evidence at two localities points toward an annual origin for the banding; at a third it arose during part of what appears to have been a relatively short period. Quantified physical arguments suggest that the textural banding is a response of suspended fine sediment to marked seasonal changes in sea temperature and windiness. The banded silts occur in four distinct stratigraphical contexts and record high deposition rates (order 0.01-0.1 m/yr). Because physical factors determine their textures, the silts potentially afford insights in all contexts into aspects of changing Holocene climatic conditions. In one context, the thickness of the bands points to high (order 0.01-0.1 m/yr) but comparatively short-lived (order 10s-100s yrs) rates of relative water-level rise. In the others, however, the banding has no implications for sea-level behaviour, and simply records gross environmental disequilibrium, for example, the recovery of mudflats/marshes after an erosional episode. Similarly, because on account of their rapid accumulation the banded silts preserve animal and human tracks and trackways especially well, they provide an archive of animal and human behaviour in the area during the Holocene.

Evaluating the risk of non-point source pollution from biosolids: integrated modelling of nutrient losses at field and catchment scales

A semi-distributed model, INCA, has been developed to determine the fate and distribution of nutrients in terrestrial and aquatic systems. The model simulates nitrogen and phosphorus processes in soils, groundwaters and river systems and can be applied in a semi-distributed manner at a range of scales. In this study, the model has been applied at field to sub-catchment to whole catchment scale to evaluate the behaviour of biosolid-derived losses of P in agricultural systems. It is shown that process-based models such as INCA, applied at a wide range of scales, reproduce field and catchment behaviour satisfactorily. The INCA model can also be used to generate generic information for risk assessment. By adjusting three key variables: biosolid application rates, the hydrological connectivity of the catchment and the initial P-status of the soils within the model, a matrix of P loss rates can be generated to evaluate the behaviour of the model and, hence, of the catchment system. The results, which indicate the sensitivity of the catchment to flow paths, to application rates and to initial soil conditions, have been incorporated into a Nutrient Export Risk Matrix (NERM).