Desorption from concentrated polymer solutions in good and poor solvents

The objective of the study was to investigate the effects of the nature of solvent and polymer concentration on the mass-transfer coefficients in desorption of solvents and to develop a correlation to predict them. Desorption was experimentally studied in a Lewis cell with concentrated binary solutions of polymer in good and poor solvents. The range of parameters covered are polymer weight fraction between 0.25 and 0.6, Reynolds number between 3 and 100; Schmidt number between 1.4 X lo6 and 2.5 X lo8, and Sherwood number between 3.5 X lo2 and 1.2 X lo4. Desorption from moderately concentrated solutions (polymer weight fraction -0.25) is gas-phase controlled. Studies with more concentrated solutions showed that the effects of solvent and concentration were such that corrections due to concentration-dependent diffusivity and viscosity as well as high flux had to be applied to the mass-transfer coefficients before they could be correlated.

Critical phenomena in polymer solutions: Scaling of the free energy

The thermodynamics of monodisperse solutions of polymers in the neighborhood of the phase separation temperature is studied by means of Wilson’s recursion relation approach, starting from an effective ϕ4 Hamiltonian derived from a continuum model of a many‐chain system in poor solvents. Details of the chain statistics are contained in the coefficients of the field variables ϕ, so that the parameter space of the Hamiltonian includes the temperature, coupling constant, molecular weight, and excluded volume interaction. The recursion relations are solved under a series of simplifying assumptions, providing the scaling forms of the relevant parameters, which are then used to determine the scaling form of the free energy. The free energy, in turn, is used to calculate the other singular thermodynamic properties of the solution. These are characteristically power laws in the reduced temperature and molecular weight, with the temperature exponents being the same as those of the 3d Ising model. The molecular weight exponents are unique to polymer solutions, and the calculated values compare well with the available experimental data.

Solution properties of star and linear poly(N-isopropylacrylamide)

The LCST transitions of novel N-isopropylacrylamide ( NIPAM) star polymers, prepared using the four-armed RAFT agent pentaerythritoltetrakis(3-(S-benzyltrithiocarbonyl) propionate) (PTBTP) and their hydrolyzed linear arms were studied using H-1 NMR, PFG-NMR, and DLS. The aim was to determine the effect of polymer architecture and the presence of end groups derived from RAFT agents on the LCST. The LCST transitions of star PNIPAM were significantly depressed by the presence of the hydrophobic star core and possibly the benzyl end groups. The effect was molecular weight dependent and diminished once the number of repeating units per arm >= 70. The linear PNIPAM exhibited an LCST of 35 degrees C, regardless of molecular weight; the presence of both hydrophilic and hydrophobic end groups after hydrolysis from the star core was suggested to cancel effects on the LCST. A significant decrease in R-H was observed below the LCST for star and linear PNIPAM and was attributed to the formation of n-clusters. Application of a scaling law to the linear PNIPAM data indicated the cluster size n = 6. Tethering to the hydrophobic star core appeared to inhibit n-cluster formation in the lowest molecular weight stars; this may be due to enhanced stretching of the polymer chains, or the presence of larger numbers of n-clusters at temperatures below those measured.

The Study of Electroactive Block Copolymer Containing Aniline Pentamer Isolated from Different Solvents

For the films and powder of polymers containing conductive oligomer are usually obtained from solution, the choice of better solvents for the regular arrangement of oligomers is very important for the higher conductivity. Because of the poor solubility of the oligomers, it is difficult to study the arrangement directly in most common solvents, so, we synthesized a triblock copolymer, mPEG2k-aniline pentamer-mPEG2k, as the model to investigate the arrangement-solvent relationship. For the poor solubility of the AP block in common solvents, the copolymer self-assembled into spheric micelles in toluene and into lamellar crystals in water and THF. The crystallinity (X-c) and crystallization temperature (T-c) values of mPEG blocks in powders prepared from different solvents differed obviously, which may be the effect of different self-assembled structures. From the two-phase model of one-dimensional electron density correlation function of SAXS, the long period of copolymer prepared from THF was presumably equal to the long period of pure mPEG plus the chain length of AP, which demonstrates that the AP blocks arrange regularly in the noncrystalline regions.

Engineering bio-based polymers using alternative solvents and processes

The work presented in this thesis explores novel routes for the processing of bio-based polymers, developing a sustainable approach based on the use of alternative solvents such as supercritical carbon dioxide (scCO2), ionic liquids (ILs) and deep eutectic solvents (DES). The feasibility to produce polymeric foams via supercritical fluid (SCF) foaming, combined with these solvents was assessed, in order to replace conventional foaming techniques that use toxic and harmful solvents. A polymer processing methodology is presented, based on SCF foaming and using scCO2 as a foaming agent. The SCF foaming of different starch based polymeric blends was performed, namely starch/poly(lactic acid) (SPLA) and starch/poly(ε-caprolactone) (SPCL). The foaming process is based on the fact that CO2 molecules can dissolve in the polymer, changing their mechanical properties and after suitable depressurization, are able to create a foamed (porous) material. In these polymer blends, CO2 presents limited solubility and in order to enhance the foaming effect, two different imidazolium based ILs (IBILs) were combined with this process, by doping the blends with IL. The use of ILs proved useful and improved the foaming effect in these starch-based polymer blends. Infrared spectroscopy (FTIR-ATR) proved the existence of interactions between the polymer blend SPLA and ILs, which in turn diminish the forces that hold the polymeric structure. This is directly related with the ability of ILs to dissolve more CO2. This is also clear from the sorption experiments results, where the obtained apparent sorption coefficients in presence of IL are higher compared to the ones of the blend SPLA without IL. The doping of SPCL with ILs was also performed. The foaming of the blend was achieved and resulted in porous materials with conductivity values close to the ones of pure ILs. This can open doors to applications as self-supported conductive materials. A different type of solvents were also used in the previously presented processing method. If different applications of the bio-based polymers are envisaged, replacing ILs must be considered, especially due to the poor sustainability of some ILs and the fact that there is not a well-established toxicity profile. In this work natural DES – NADES – were the solvents of choice. They present some advantages relatively to ILs since they are easy to produce, cheaper, biodegradable and often biocompatible, mainly due to the fact that they are composed of primary metabolites such as sugars, carboxylic acids and amino-acids. NADES were prepared and their physicochemical properties were assessed, namely the thermal behavior, conductivity, density, viscosity and polarity. With this study, it became clear that these properties can vary with the composition of NADES, as well as with their initial water content. The use of NADES in the SCF foaming of SPCL, acting as foaming agent, was also performed and proved successful. The SPCL structure obtained after SCF foaming presented enhanced characteristics (such as porosity) when compared with the ones obtained using ILs as foaming enhancers. DES constituted by therapeutic compounds (THEDES) were also prepared. The combination of choline chloride-mandelic acid, and menthol-ibuprofen, resulted in THEDES with thermal behavior very distinct from the one of their components. The foaming of SPCL with THEDES was successful, and the impregnation of THEDES in SPCL matrices via SCF foaming was successful, and a controlled release system was obtained in the case of menthol-ibuprofen THEDES.

The extracurriculum in an input-poor environment

This paper reports on the experiences of an extracurricular program in English language learning (ELL) that was implemented in an institute of technology in the hinterland of the People's Republic of China (PRC). Following the guidelines set out in an impact study of the reform of curriculum change in Hong Kong (Adamson & Morris, 2000), this study takes account of the context of the particular socio-cultural and political environment in which the research program takes place. Three distinct phases emerged in the career of the extracurricular program - the establishment of the program; successful implementation; and the decline. The study identifies three key factors that shaped these phases: teacher motivation; student motivation and its various influences; and available resources (including collegial and administrative support). The findings suggest that of the key factors impacting on the ELL extracurriculum, student motivation was the most influential.

The STRATIFY tool and clinical judgment were poor predictors of falling in an acute hospital setting

Objective: To compare the effectiveness of the STRATIFY falls tool with nurses’ clinical judgments in predicting patient falls. Study Design and Setting: A prospective cohort study was conducted among the inpatients of an acute tertiary hospital. Participants were patients over 65 years of age admitted to any hospital unit. Sensitivity, specificity, and positive predictive value (PPV) and negative predictive values (NPV) of the instrument and nurses’ clinical judgments in predicting falls were calculated. Results: Seven hundred and eighty-eight patients were screened and followed up during the study period. The fall prevalence was 9.2%. Of the 335 patients classified as being ‘‘at risk’’ for falling using the STRATIFY tool, 59 (17.6%) did sustain a fall (sensitivity50.82, specificity50.61, PPV50.18, NPV50.97). Nurses judged that 501 patients were at risk of falling and, of these, 60 (12.0%) fell (sensitivity50.84, specificity50.38, PPV50.12, NPV50.96). The STRATIFY tool correctly identified significantly more patients as either fallers or nonfallers than the nurses (P50.027). Conclusion: Considering the poor specificity and high rates of false-positive results for both the STRATIFY tool and nurses’ clinical judgments, we conclude that neither of these approaches are useful for screening of falls in acute hospital settings.

Poor functional health literacy : the silent disability for older people

In this information age, people are confronted by verbal, visual and written information. This is especially important in the health field, where information is needed to follow directions, understand prescriptions and undertake preventive behaviours. If provided in written form, much of this information may be inaccessible to people who cannot adequately read. Although poor literacy skills affect all groups in the population, older adults with fewer years of education seem to be particularly disadvantaged by an increasing reliance on written communication of health information. With older age comes a higher risk of illness and disability and a greater potential need to access the health system. As a result, poor literacy skills of older individuals may directly impact their health status. This paper explores the link between functional literacy and health, particularly for the older population, provides strategies to practitioners for the management of this problem, and suggests research initiatives in this area.

Project diagnostics : assessing the condition of projects and identifying poor health combing forces

In many cases, construction projects do not achieve the objectives that the project participants set for them. If participants could better understand how their project is performing overall, at various stages of its delivery, then the opportunities to achieve project success would almost certainly be greater. This paper documents a method of assessing the status of a project, at a point in its design or construction phase, or after completion. The status is assessed in terms of up to seven (7) key success factors. Any evidence of less than adequate performance in these performance areas is scrutinised to seek out the root causes of why this situation is happening. Using these identified root causes of under performance, general suggestions can then be made as to how to return the project to good health. A software package that assists in assessing the status of the project has been developed. The package is currently being calibrated before commercial release.

Developing a quick and practical screen to improve the identification of poor hydration in geriatric and rehabilitative care

Dehydration has been associated with increased morbidity and mortality. Dehydration risk increases with advancing age, and will progressively become an issue as the aging population increases. Worldwide, those aged 60 years and over are the fastest growing segment of the population. The study aimed to develop a clinically practical means to identify dehydration amongst older people in the clinical care setting. Older people aged 60 years or over admitted to the Geriatric and Rehabilitation Unit (GARU) of two tertiary teaching hospitals were eligible for participation in the study. Ninety potential screening questions and 38 clinical parameters were initially tested on a single sample (n=33) with the most promising 11 parameters selected to undergo further testing in an independent group (n=86). Of the almost 130 variables explored, tongue dryness was most strongly associated with poor hydration status, demonstrating 64% sensitivity and 62% specificity within the study participants. The result was not confounded by age, gender or body mass index. With minimal training, inter-rater repeatability was over 90%. This study identified tongue dryness as a potentially practical tool to identify dehydration risk amongst older people in the clinical care setting. Further studies to validate the potential screen in larger and varied populations of older people are required

POOR ICARUS CHARMIAN : Review of The Life and Myth of Charmian Clift by Nadia Wheatley (2001) online

Online Review

Darjeeling, a feature-rich VM for the resource poor

The programming and retasking of sensor nodes could benefit greatly from the use of a virtual machine (VM) since byte code is compact, can be loaded on demand, and interpreted on a heterogeneous set of devices. The challenge is to ensure good programming tools and a small footprint for the virtual machine to meet the memory constraints of typical WSN platforms. To this end we propose Darjeeling, a virtual machine modelled after the Java VM and capable of executing a substantial subset of the Java language, but designed specifically to run on 8- and 16-bit microcontrollers with 2 - 10 KB of RAM. The Darjeeling VM uses a 16- rather than a 32-bit architecture, which is more efficient on the targeted platforms. Darjeeling features a novel memory organisation with strict separation of reference from non-reference types which eliminates the need for run-time type inspection in the underlying compacting garbage collector. Darjeeling uses a linked stack model that provides light-weight threads, and supports synchronisation. The VM has been implemented on three different platforms and was evaluated with micro benchmarks and a real-world application. The latter includes a pure Java implementation of the collection tree routing protocol conveniently programmed as a set of cooperating threads, and a reimplementation of an existing environmental monitoring application. The results show that Darjeeling is a viable solution for deploying large-scale heterogeneous sensor networks. Copyright 2009 ACM.

Why do poor people perceive poor neighbourhoods? : the role of objective neighbourhood features and psychosocial factors

Compared to people with a high socioeconomic status, those with a lower socioeconomic status are more likely to perceive their neighbourhood as unattractive and unsafe, which is associated with their lower levels of physical activity. Agreement between objective and perceived environmental factors is often found to be moderate or low, so it is questionable to what extent ‘creating supportive neighbourhoods’ would change neighbourhood perceptions. This study among residents (N=814) of fourteen neighbourhoods in the city of Eindhoven (the Netherlands), investigated to what extent socioeconomic differences in perceived neighbourhood safety and perceived neighbourhood attractiveness can be explained by five domains of objective neighbourhood features (i.e. design, traffic safety, social safety, aesthetics, and destinations), and to what extent other factors may play a role. Unfavourable neighbourhood perceptions of low socioeconomic groups partly reflected their actual less aesthetic and less safe neighbourhoods, and partly their perceptions of low social neighbourhood cohesion and adverse psychosocial circumstances.

Towards improved speech recognition for resource poor languages

In recent times, the improved levels of accuracy obtained by Automatic Speech Recognition (ASR) technology has made it viable for use in a number of commercial products. Unfortunately, these types of applications are limited to only a few of the world’s languages, primarily because ASR development is reliant on the availability of large amounts of language specific resources. This motivates the need for techniques which reduce this language-specific, resource dependency. Ideally, these approaches should generalise across languages, thereby providing scope for rapid creation of ASR capabilities for resource poor languages. Cross Lingual ASR emerges as a means for addressing this need. Underpinning this approach is the observation that sound production is largely influenced by the physiological construction of the vocal tract, and accordingly, is human, and not language specific. As a result, a common inventory of sounds exists across languages; a property which is exploitable, as sounds from a resource poor, target language can be recognised using models trained on resource rich, source languages. One of the initial impediments to the commercial uptake of ASR technology was its fragility in more challenging environments, such as conversational telephone speech. Subsequent improvements in these environments has gained consumer confidence. Pragmatically, if cross lingual techniques are to considered a viable alternative when resources are limited, they need to perform under the same types of conditions. Accordingly, this thesis evaluates cross lingual techniques using two speech environments; clean read speech and conversational telephone speech. Languages used in evaluations are German, Mandarin, Japanese and Spanish. Results highlight that previously proposed approaches provide respectable results for simpler environments such as read speech, but degrade significantly when in the more taxing conversational environment. Two separate approaches for addressing this degradation are proposed. The first is based on deriving better target language lexical representation, in terms of the source language model set. The second, and ultimately more successful approach, focuses on improving the classification accuracy of context-dependent (CD) models, by catering for the adverse influence of languages specific phonotactic properties. Whilst the primary research goal in this thesis is directed towards improving cross lingual techniques, the catalyst for investigating its use was based on expressed interest from several organisations for an Indonesian ASR capability. In Indonesia alone, there are over 200 million speakers of some Malay variant, provides further impetus and commercial justification for speech related research on this language. Unfortunately, at the beginning of the candidature, limited research had been conducted on the Indonesian language in the field of speech science, and virtually no resources existed. This thesis details the investigative and development work dedicated towards obtaining an ASR system with a 10000 word recognition vocabulary for the Indonesian language.