Fractionated crystallization and fractionated melting of confined PEO microdomains in PB-b-PEO and PE-b-PEO diblock copolymers

The confined crystallization of poly(ethylene oxide) (PEO) in predominantly spherical microdomains formed by several diblock copolymers was studied and compared. Two polybutadiene-b-poly(ethylene oxide) diblock copolymers were prepared by sequential anionic polymerization (with approximately 90 and 80 wt % polybutadiene (PB)). These were compared to equivalent samples after catalytic hydrogenation that produced double crystalline polyethylene-b-poly(ethylene oxide) diblock copolymers. Both systems are segregated into microdomains as indicated by small-angle X-ray scattering (SAXS) experiments performed in the melt and at lower temperatures. However, the PB-b-PEO systems exhibited a higher degree of order in the melt. A predominantly spherical morphology of PEO in a PB or a PE matrix was observed by both SAXS and transmission electron microscopy, although a possibly mixed morphology (spheres and cylinders) was formed when the PEO composition was close to the cylinder-sphere domain transitional composition as indicated by SAXS. Differential scanning calorimetry experiments showed that a fractionated crystallization process for the PEO occurred in all samples, indicating that the PE cannot nucleate PEO in these diblock copolymers. A novel result was the observation of a subsequent fractionated melting that reflected the crystallization process. Sequential isothermal crystallization experiments allowed us to thermally separate at least three different crystallization and melting peaks for the PEO microdomains. The lowest melting point fraction was the most important in terms of quantity and corresponded to the crystallization of isolated PEO spheres (or cylinders) that were either superficially or homogeneously nucleated. This was confirmed by Avrami index values of approximately 1. The isothermal crystallization results indicate that the PE matrix restricts the crystallization of the covalently bonded PEO to a higher degree compared to PB.

SAXS observation of RCM1 under cyclical shear

A cylinder forming poly(styrene-b-butadiene-b-styrene) triblock copolymer melt is cyclically processed through a capillary at a high shear rate in the Cambridge Multipass Rheometer (MPR). In situ X-ray diffraction experiments enable observation of the effect of the shear on the block copolymer (BCP) nanophase orientation, both during and after processing. Temporal resolution of the X-ray exposures is increased, whilst retaining intensity, by exploiting the cyclical nature of the shear and the material's response to it; short exposures from many cycles, individually having few counts, are added together to produce well resolved X-ray patterns. Orientation of the cylinders reduces during processing, then increases during pauses between processing. The loss of orientation is attributed to the high shear rate deforming the melt faster than the structure can respond, whilst it is believed that melt relaxation, linked to the compressibility of the material, produces much lower shear rates after mechanical processing has ceased, which induces strong orientation of the nanostructure.

Ordering on multiple lengthscales in a series of side group liquid crystal block copolymers containing a cholesteryl-based mesogen

Hierarchical ordering in a side group liquid crystal block copolymer is investigated by differential scanning calorimetry, polarized optical microscopy, small-angle X-ray and neutron scattering (SAXS and SANS) and transmission electron microscopy (TEM). A series of block copolymers with a range of compositions was prepared by atom transfer radical polymerization, comprising a polystyrene block and a poly(methyl methacrylate) block bearing chiral cholesteryl mesogens. Smectic ordering is observed as well as microphase separation of the block copolymer. Lamellar structures were observed for far larger volume fractions than for coil-coil copolymers (up to a volume fraction of liquid crystal block, f(LC) = 0.8). A sample with f(LC) = 0.86 exhibited a hexagonal-packed cylinder morphology, as confirmed by SAXS and TEM. The matrix comprised the liquid crystal block, with the mesogens forming smectic layers. For the liquid crystal homopolymer and samples with high f(LC), a smectic-smectic phase transition was observed below the clearing point. At low temperature, the smectic phase comprises coexisting domains with monolayer S-A,S-1 coexisting with interdigitated S-A,S-d domains. At high temperature a SA,1 phase is observed. This is the only structure observed for samples with lower f(LC). These unprecedented results point to the influence of block copolymer microphase separation on the smectic ordering.

Visual representations as 'artifacts of knowing'

How does the manipulation of visual representations play a role in the practices of generating, evolving and exchanging knowledge? The role of visual representation in mediating knowledge work is explored in a study of design work of an architectural practice, Edward Cullinan Architects. The intensity of interactions with visual representations in the everyday activities on design projects is immediately striking. Through a discussion of observed design episodes, two ways are articulated in which visual representations act as 'artefacts of knowing'. As communication media they are symbolic representations, rich in meaning, through which ideas are articulated, developed and exchanged. Furthermore, as tangible artefacts they constitute material entities with which to interact and thereby develop knowledge. The communicative and interactive properties of visual representations constitute them as central elements of knowledge work. The paper explores emblematic knowledge practices supported by visual representation and concludes by pinpointing avenues for further research.

Subcontract and supply enquiries in the tender process of contractors

In the tender process, contractors often rely on subcontract and supply enquiries to calculate their bid prices. However, this integral part of the bidding process is not empirically articulated in the literature. Over 30 published materials on the tendering process of contractors that talk about enquiries were reviewed and found to be based mainly on experiential knowledge rather than systematic evidence. The empirical research here helps to describe the process of enquiries precisely, improve it in practice, and have some basis to support it in theory. Using a live participant observation case study approach, the whole tender process was shadowed in the offices of two of the top 20 UK civil engineering construction firms. This helped to investigate 15 research questions on how contractors enquire and obtain prices from subcontractors and suppliers. Forty-three subcontract enquiries and 18 supply enquiries were made across two different projects with average value of 7m. An average of 15 subcontract packages and seven supply packages was involved. Thus, two or three subcontractors or suppliers were invited to bid in each package. All enquiries were formulated by the estimator, with occasional involvement of three other personnel. Most subcontract prices were received in an average of 14 working days; and supply prices took five days. The findings show 10 main activities involved in processing enquiries and their durations, as well as wasteful practices associated with enquiries. Contractors should limit their enquiry invitations to a maximum of three per package, and optimize the waiting time for quotations in order to improve cost efficiency.

Sustaining linguistic diversity within the global cultural economy: issues of language rights and linguistic possibilities

This paper draws on ethnographic case-study research conducted amongst a group of first and second generation immigrant children in six inner-city schools in London. It focuses on language attitudes and language choice in relation to cultural maintenance, on the one hand, and career aspirations on the other. It seeks to provide insight into some of the experiences and dilemmatic choices encountered and negotiations engaged in by transmigratory groups, how they define cultural capital, and the processes through which new meanings are shaped as part of the process of defining a space within the host society. Underlying this discussion is the assumption that alternative cultural spaces in which multiple identities and possibilities can be articulated already exist in the rich texture of everyday life amongst transmigratory groups. The argument that whilst the acquisition of 'world languages' is a key variable in accumulating cultural capital, the maintenance of linguistic diversity retains potent symbolic power in sustaining cohesive identities is a recurring theme.

Numerical study of 2D heat transfer in a scraped surface heat exchanger

A numerical study of fluid mechanics and heat transfer in a scraped surface heat exchanger with non-Newtonian power law fluids is undertaken. Numerical results are generated for 2D steady-state conditions using finite element methods. The effect of blade design and material properties, and especially the independent effects of shear thinning and heat thinning on the flow and heat transfer, are studied. The results show that the gaps at the root of the blades, where the blades are connected to the inner cylinder, remove the stagnation points, reduce the net force on the blades and shift the location of the central stagnation point. The shear thinning property of the fluid reduces the local viscous dissipation close to the singularity corners, i.e. near the tip of the blades, and as a result the local fluid temperature is regulated. The heat thinning effect is greatest for Newtonian fluids where the viscous dissipation and the local temperature are highest at the tip of the blades. Where comparison is possible, very good agreement is found between the numerical results and the available data. Aspects of scraped surface heat exchanger design are assessed in the light of the results. (C) 2003 Elsevier Ltd. All rights reserved.

Predicting the thermal inactivation of bacteria in a solid matrix: simulation studies on the relative effects of microbial thermal resistance parameters and process conditions

A combined mathematical model for predicting heat penetration and microbial inactivation in a solid body heated by conduction was tested experimentally by inoculating agar cylinders with Salmonella typhimurium or Enterococcus faecium and heating in a water bath. Regions of growth where bacteria had survived after heating were measured by image analysis and compared with model predictions. Visualisation of the regions of growth was improved by incorporating chromogenic metabolic indicators into the agar. Preliminary tests established that the model performed satisfactorily with both test organisms and with cylinders of different diameter. The model was then used in simulation studies in which the parameters D, z, inoculum size, cylinder diameter and heating temperature were systematically varied. These simulations showed that the biological variables D, z and inoculum size had a relatively small effect on the time needed to eliminate bacteria at the cylinder axis in comparison with the physical variables heating temperature and cylinder diameter, which had a much greater relative effect. (c) 2005 Elsevier B.V All rights reserved.

Modelling oil absorption during post-frying cooling - I: model development

Several studies have highlighted the importance of the cooling period in oil absorption in deep-fat fried products. Specifically, it has been established that the largest proportion of oil which ends up into the food, is sucked into the porous crust region after the fried product is removed from the oil bath, stressing the importance of this time interval. The main objective of this paper was to develop a predictive mechanistic model that can be used to understand the principles behind post-frying cooling oil absorption kinetics, which can also help identifying the key parameters that affect the final oil intake by the fried product. The model was developed for two different geometries, an infinite slab and an infinite cylinder, and was divided into two main sub-models, one describing the immersion frying period itself and the other describing the post-frying cooling period. The immersion frying period was described by a transient moving-front model that considered the movement of the crust/core interface, whereas post-frying cooling oil absorption was considered to be a pressure driven flow mediated by capillary forces. A key element in the model was the hypothesis that oil suction would only begin once a positive pressure driving force had developed. The mechanistic model was based on measurable physical and thermal properties, and process parameters with no need of empirical data fitting, and can be used to study oil absorption in any deep-fat fried product that satisfies the assumptions made.

Modelling oil absorption during post-frying cooling - II: solution of the mathematical model, model testing and simulations

The mathematical models that describe the immersion-frying period and the post-frying cooling period of an infinite slab or an infinite cylinder were solved and tested. Results were successfully compared with those found in the literature or obtained experimentally, and were discussed in terms of the hypotheses and simplifications made. The models were used as the basis of a sensitivity analysis. Simulations showed that a decrease in slab thickness and core heat capacity resulted in faster crust development. On the other hand, an increase in oil temperature and boiling heat transfer coefficient between the oil and the surface of the food accelerated crust formation. The model for oil absorption during cooling was analysed using the tested post-frying cooling equation to determine the moment in which a positive pressure driving force, allowing oil suction within the pore, originated. It was found that as crust layer thickness, pore radius and ambient temperature decreased so did the time needed to start the absorption. On the other hand, as the effective convective heat transfer coefficient between the air and the surface of the slab increased the required cooling time decreased. In addition, it was found that the time needed to allow oil absorption during cooling was extremely sensitive to pore radius, indicating the importance of an accurate pore size determination in future studies.

High pressure induced water uptake characteristics of Thai glutinous rice

Glutinous rice (or sticky rice) has to be soaked in water over an extended period of time before cooking. Soaking provides some of the water needed for starch gelatinisation to occur during cooking. The extent of water uptake during soaking is known to be influenced by temperature. This paper explores the use of very high pressures up to 600 MPa to accelerate water uptake kinetics during soaking. Changes occurring in length, diameter and moisture content were determined as a function of soaking time, pressure and temperature. The results show that length and diameter are positively correlated with all three parameters. However, the expansion ratios are not very high: the maximum length expansion ratio observed was 1.2, while the maximum diameter expansion ratio was 1. 1. Given these low values, it was possible to model water uptake kinetics by using the well-known Fickian model applied to a finite cylinder, assuming uniform average dimensions and effective diffusion coefficient. The results showed that the overall rates of water uptake and the equilibrium moisture content increased with pressure and temperature. The effective diffusion coefficient, on the other hand, did not follow the same trend. Temperature influenced the effective diffusion coefficient below 300 MPa, but had a marginal effect at higher pressures. Moreover, the effective diffusion coefficient increased with temperature between 20 and 50 degrees C, but dropped at higher temperatures. This drop can be attributed to the gelatinisation of starch, which restricts the transport of water. Regardless, it is possible to increase the quantity of water absorbed by rice and the rate at which it is absorbed, by using high pressures and temperatures. (c) 2004 Elsevier Ltd. All rights reserved.

An ontological modelling of user requirements for personalised information provision

The knowledge economy offers opportunity to a broad and diverse community of information systems users to efficiently gain information and know-how for improving qualifications and enhancing productivity in the work place. Such demand will continue and users will frequently require optimised and personalised information content. The advancement of information technology and the wide dissemination of information endorse individual users when constructing new knowledge from their experience in the real-world context. However, a design of personalised information provision is challenging because users’ requirements and information provision specifications are complex in their representation. The existing methods are not able to effectively support this analysis process. This paper presents a mechanism which can holistically facilitate customisation of information provision based on individual users’ goals, level of knowledge and cognitive styles preferences. An ontology model with embedded norms represents the domain knowledge of information provision in a specific context where users’ needs can be articulated and represented in a user profile. These formal requirements can then be transformed onto information provision specifications which are used to discover suitable information content from repositories and pedagogically organise the selected content to meet the users’ needs. The method is provided with adaptability which enables an appropriate response to changes in users’ requirements during the process of acquiring knowledge and skills.

An isentropic flow algorithm with body fitted meshes

An efficient algorithm based on flux difference splitting is presented for the solution of the three-dimensional equations of isentropic flow in a generalised coordinate system, and with a general convex gas law. The scheme is based on solving linearised Riemann problems approximately and in more than one dimension incorporates operator splitting. The algorithm requires only one function evaluation of the gas law in each computational cell. The scheme has good shock capturing properties and the advantage of using body-fitted meshes. Numerical results are shown for Mach 3 flow of air past a circular cylinder. Furthermore, the algorithm also applies to shallow water flows by employing the familiar gas dynamics analogy.

On a class of non-self-adjoint periodic eigenproblems with boundary and interior singularities

We prove that all the eigenvalues of a certain highly non-self-adjoint Sturm–Liouville differential operator are real. The results presented are motivated by and extend those recently found by various authors (Benilov et al. (2003) [3], Davies (2007) [7] and Weir (2008) [18]) on the stability of a model describing small oscillations of a thin layer of fluid inside a rotating cylinder.

Evaluation of agri-environmental and forestry schemes with multiple objectives

The evaluation of EU policy in the area of rural land use management often encounters problems of multiple and poorly articulated objectives. Agri-environmental policy has a range of aims, including natural resource protection, biodiversity conservation and the protection and enhancement of landscape quality. Forestry policy, in addition to production and environmental objectives, increasingly has social aims, including enhancement of human health and wellbeing, lifelong learning, and the cultural and amenity value of the landscape. Many of these aims are intangible, making them hard to define and quantify. This article describes two approaches for dealing with such situations, both of which rely on substantial participation by stakeholders. The first is the Agri-Environment Footprint Index, a form of multi-criteria participatory approach. The other, applied here to forestry, has been the development of ‘multi-purpose’ approaches to evaluation, which respond to the diverse needs of stakeholders through the use of mixed methods and a broad suite of indicators, selected through a participatory process. Each makes use of case studies and involves stakeholders in the evaluation process, thereby enhancing their commitment to the programmes and increasing their sustainability. Both also demonstrate more ‘holistic’ approaches to evaluation than the formal methods prescribed in the EU Common Monitoring and Evaluation Framework.