An investigation of the kinetics of CO2 uptake by a synthetic calcium based sorbent

This study examines the kinetics of carbonation by CO2 at temperatures of ca. 750 °C of a synthetic sorbent composed of 15 wt% mayenite (Ca12Al14O33) and CaO, designated HA-85-850, and draws comparisons with the carbonation of a calcined limestone. In-situ XRD has verified the inertness of mayenite, which neither interacts with the active CaO nor does it significantly alter the CaO carbonation–calcination equilibrium. An overlapping grain model was developed to predict the rate and extent of carbonation of HA-85-850 and limestone. In the model, the initial microstructure of the sorbent was defined by a discretised grain size distribution, assuming spherical grains. The initial input to the model – the size distribution of grains – was a fitted parameter, which was in good agreement with measurements made with mercury porosimetry and by the analysis of SEM images of sectioned particles. It was found that the randomly overlapping spherical grain assumption offered great simplicity to the model, despite its approximation to the actual porous structure within a particle. The model was able to predict the performance of the materials well and, particularly, was able to account for changes in rate and extent of reaction as the structure evolved after various numbers of cycles of calcination and carbonation.

An investigation of the kinetics of CO 2 uptake by a synthetic calcium based sorbent

This study examines the kinetics of carbonation by CO 2 at temperatures of ca. 750°C of a synthetic sorbent composed of 15wt% mayenite (Ca 12Al 14O 33) and CaO, designated HA-85-850, and draws comparisons with the carbonation of a calcined limestone. In-situ XRD has verified the inertness of mayenite, which neither interacts with the active CaO nor does it significantly alter the CaO carbonation-calcination equilibrium. An overlapping grain model was developed to predict the rate and extent of carbonation of HA-85-850 and limestone. In the model, the initial microstructure of the sorbent was defined by a discretised grain size distribution, assuming spherical grains. The initial input to the model - the size distribution of grains - was a fitted parameter, which was in good agreement with measurements made with mercury porosimetry and by the analysis of SEM images of sectioned particles. It was found that the randomly overlapping spherical grain assumption offered great simplicity to the model, despite its approximation to the actual porous structure within a particle. The model was able to predict the performance of the materials well and, particularly, was able to account for changes in rate and extent of reaction as the structure evolved after various numbers of cycles of calcination and carbonation. © 2011 Elsevier Ltd.

The morphology of decorated amyloid fibers is controlled by the conformation and position of the displayed protein.

Self-assembled structures capable of mediating electron transfer are an attractive scientific and technological goal. Therefore, systematic variants of SH3-Cytochrome b(562) fusion proteins were designed to make amyloid fibers displaying heme-b(562) electron transfer complexes. TEM and AFM data show that fiber morphology responds systematically to placement of b(562) within the fusion proteins. UV-vis spectroscopy shows that, for the fusion proteins under test, only half the fiber-borne b(562) binds heme with high affinity. Cofactor binding also improves the AFM imaging properties and changes the fiber morphology through changes in cytochrome conformation. Systematic observations and measurements of fiber geometry suggest that longitudinal registry of subfilaments within the fiber, mediated by the interaction and conformation of the displayed proteins and their interaction with surfaces, gives rise to the observed morphologies, including defects and kinks. Of most interest is the role of small molecule modulation of fiber structure and mechanical stability. A minimum complexity model is proposed to capture and explain the fiber morphology in the light of these results. Understanding the complex interplay between these factors will enable a fiber design that supports longitudinal electron transfer.

Fabrication and electromechanical characterization of near-field electrospun composite fibers.

We report the use of near-field electrospinning (NFES) as a route to fabricate composite electrodes. Electrodes made of composite fibers of multi-walled carbon nanotubes in polyethylene oxide (PEO) are formed via liquid deposition, with precise control over their configuration. The electromechanical properties of free-standing fibers and fibers deposited on elastic substrates are studied in detail. In particular, we examine the elastic deformation limit of the resulting free-standing fibers and find, similarly to bulk PEO composites, that the plastic deformation onset is below 2% of tensile strain. In comparison, the apparent deformation limit is much improved when the fibers are integrated onto a stretchable, elastic substrate. It is hoped that the NFES fabrication protocol presented here can provide a platform to direct-write polymeric electrodes, and to integrate both stiff and soft electrodes onto a variety of polymeric substrates.

Accelerated and real-time creep and creep-rupture results for aramid fibers

This article presents results from conventional creep tests (CCT) and two accelerated test methods (the stepped isothermal method (SIM) and the stepped isostress method (SSM)) to determine the creep and creep-rupture behavior of two different aramid fibers, Kevlar 49 and Technora. CCT are regarded as the true behavior of the yarn, but they are impractical for long-term use where failures are expected only after many years. All the tests were carried out on the same batches of yarns, and using the same clamping arrangements, so the tests should be directly comparable. For both materials, SIM testing gives good agreement with CCT and gave stress-rupture lifetimes that followed the same trend. However, there was significant variation for SSM testing, especially when testing Technora fibers. The results indicate that Kevlar has a creep strain capacity that is almost independent of stress, whereas Technora shows a creep strain capacity that depends on stress. Its creep strain capacity is approximately two to three times that of Kevlar 49. The accelerated test methods give indirect estimates for the activation energy and the activation volume of the fibers. The activation energy for Technora is about 20% higher than that for Kevlar, meaning that it is less sensitive to the effects of increasing temperature. The activation volume for both materials was similar, and in both cases, stress dependent. Copyright © 2012 Wiley Periodicals, Inc.

Characterisation and fluidisation of synthetic pit latrine sludge

Half of the world’s urban population will live in informal settlements or “slums” by 2030. Affordable urban sanitation presents a unique set of challenges as the lack of space and resources to construct new latrines makes the de-sludging of existing pits necessary and is something that is currently done manually with significant associated health risks. Therefore various mechanised technologies have been developed to facilitate pit emptying, with the majority using a vacuum system to remove material from the top of the pit. However, this results in the gradual accumulation of unpumpable sludge in the pit, which eventually fills the latrine and forces it to be abandoned. This study has developed a method for fluidising unpumpable pit latrine sludge, based on laboratory experiments using a harmless synthetic sludge. Such a sludge consisting of clay and compost was developed to replicate the physical characteristics of pit latrine sludges characterised in Botswana during the 1980s. Undrained shear strength and density are identified as the critical parameters in controlling pumpability and a method of sludge characterisation based on these parameters is reported. In a series of fluidisation tests using a one fifth scale pit emptying device the reduction in sludge shear strength was found to be caused by i) dilution, which increases water content, and ii) remoulding, which involves mechanical agitation to break down the structure of the material. The tests demonstrated that even the strongest of sludges could be rendered “pumpable” by sufficient dilution. Additionally, air injection alone produced a three-fold decrease in strength of consolidated samples as a result of remoulding at constant water content. The implications for sludge treatment and disposal are discussed, and the classification of sludges according to the equipment required to remove them from the latrine is proposed. Possible field tests to estimate sludge density and shear strength are suggested. The feasibility of using low cost vacuum cleaners to replace expensive vane pumps is demonstrated. This offers great potential for the development of affordable pit emptying technologies that can remove significantly stronger sludges than current devices through fluidising the wastes at the bottom of the pit before emptying

Creep and strength retention of aramid fibers

Creep tests at ambient conditions have been carried out on Kevlar 49 and Technora yarns covering a wide stress spectrum (10-70% average breaking load) for a long period of time (up to a year). The results confirm that Kevlar 49 and Technora yarns show a nonlinear behavior at stresses below 40% of the breaking load and a linear behavior at stresses above 40%. The strength retention following creep for Kevlar 49 and Technora has also been examined. The results show a significant difference in the behavior of the two materials. Kevlar 49 appears to lose strength almost linearly with time, while Technora seems to lose strength much more rapidly. These results would have significant implications for design. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012 Copyright © 2012 Wiley Periodicals, Inc.

Characterisation and fluidisation of synthetic pit latrine sludge

Half of the world's urban population will live in informal settlements or ‘slums’ by 2030. Affordable urban sanitation presents a unique set of challenges as the lack of space and resources to construct new latrines makes the de-sludging of existing pits necessary and is something that is currently done manually with significant associated health risks. Various mechanised technologies have therefore been developed to facilitate pit emptying, with the majority using a vacuum system to remove material from the top of the pit. However, this results in the gradual accumulation of unpumpable sludge at the bottom of the pit, which eventually fills the latrine and forces it to be abandoned. This study has developed a method for fluidising unpumpable pit latrine sludge, based on laboratory experiments using a harmless synthetic sludge. The implications for sludge treatment and disposal are discussed, and the classification of sludges according to the equipment required to remove them from the latrine is proposed. Finally, further work is suggested, including the ongoing development of a device to physically characterise latrine sludge in-situ within the pit.

Fibers with integrated mechanochemical switches: minimalistic design principles derived from fibronectin.

Inspired by molecular mechanisms that cells exploit to sense mechanical forces and convert them into biochemical signals, chemists dream of designing mechanochemical switches integrated into materials. Using the adhesion protein fibronectin, whose multiple repeats essentially display distinct molecular recognition motifs, we derived a computational model to explain how minimalistic designs of repeats translate into the mechanical characteristics of their fibrillar assemblies. The hierarchy of repeat-unfolding within fibrils is controlled not only by their relative mechanical stabilities, as found for single molecules, but also by the strength of cryptic interactions between adjacent molecules that become activated by stretching. The force-induced exposure of cryptic sites furthermore regulates the nonlinearity of stress-strain curves, the strain at which such fibers break, and the refolding kinetics and fraction of misfolded repeats. Gaining such computational insights at the mesoscale is important because translating protein-based concepts into novel polymer designs has proven difficult.