3-Orders-of-magnitude density control of single-walled carbon nanotube networks by maximizing catalyst activation and dosing carbon supply

Tailoring the density of random single-walled carbon nanotube (SWCNT) networks is of paramount importance for various applications, yet it remains a major challenge due to the insufficient catalyst activation in most growth processes. Here we report on a simple and effective method to maximise the number of active catalyst nanoparticles using catalytic chemical vapor deposition (CCVD). By modulating short pulses of acetylene into a methane-based CCVD growth process, the density of SWCNTs is dramatically increased by up to three orders of magnitude without increasing the catalyst density and degrading the nanotube quality. In the framework of a vapor-liquid-solid model, we attribute the enhanced growth to the high dissociation rate of acetylene at high temperatures at the nucleation stage, which can be effective in both supersaturating the larger catalyst nanoparticles and overcoming the nanotube nucleation energy barrier of the smaller catalyst nanoparticles. These results are highly relevant to numerous applications of random SWCNT networks in next-generation energy, sensing and biomedical devices. © 2011 The Royal Society of Chemistry.

Two orders of magnitude increase in metal piezoresistor sensitivity through nanoscale inhomogenization

Metal-based piezoresistive sensing devices could find a much wider applicability if their sensitivity to mechanical strain could be substantially improved. Here, we report a simple method to enhance the strain sensitivity of metal films by over two orders of magnitude and demonstrate it on specially designed microcantilevers. By locally inhomogenizing thin gold films using controlled electromigration, we have achieved a logarithmic divergence in the strain sensitivity with progressive microstructural modification. The enhancement in strain sensitivity could be explained using non-universal tunneling-percolation transport. We find that the Johnson noise limited signal-to-noise ratio is an order of magnitude better than silicon piezoresistors. This method creates a robust platform for engineering low resistance, high gauge factor metallic piezoresistors that may have profound impact on micro and nanoscale self-sensing technology. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4761817]

Compositional model repositories via dynamic constraint satisfaction with order-of-magnitude preferences

J. Keppens and Q. Shen. Compositional model repositories via dynamic constraint satisfaction with order-of-magnitude preferences. Journal of Artificial Intelligence Research, 21:499-550, 2004.

Compositional Model Repositories via Dynamic Constraint Satisfaction with Order-of-Magnitude Preferences

The predominant knowledge-based approach to automated model construction, compositional modelling, employs a set of models of particular functional components. Its inference mechanism takes a scenario describing the constituent interacting components of a system and translates it into a useful mathematical model. This paper presents a novel compositional modelling approach aimed at building model repositories. It furthers the field in two respects. Firstly, it expands the application domain of compositional modelling to systems that can not be easily described in terms of interacting functional components, such as ecological systems. Secondly, it enables the incorporation of user preferences into the model selection process. These features are achieved by casting the compositional modelling problem as an activity-based dynamic preference constraint satisfaction problem, where the dynamic constraints describe the restrictions imposed over the composition of partial models and the preferences correspond to those of the user of the automated modeller. In addition, the preference levels are represented through the use of symbolic values that differ in orders of magnitude.

Influence of Bi 3+ ions in enhancing the magnitude of positive temperature coefficients of resistance in n-BaTiO3 ceramics

Bi3+ ions substituting at Ba-sites in a limited concentration range with another donor dopant occupying the Ti-sites in polycrystalline BaTiO3 enhanced the positive temperature coefficient of resistance (PTCR) by over seven orders of magnitude. These ceramics did not require normal post sinter annealing or a change to an oxygen atmosphere during annealing. These ceramics had low porosities coupled with better stabilities to large applied electric fields and chemically reducing atmospheres. Bi3+ ions limited the grain growth to less than 8 mum in size, they enhanced the concentration of acceptor-type trap centres at the grain-boundary-layer regions and maintained complete tetragonality at low grain sizes in BaTiO3 ceramics.

Magnitude and Extent of Contaminated Sediment and Toxicity in Chesapeake Bay

INTRODUCTION: This report summarizes the results of NOAA's sediment toxicity, chemistry, and benthic community studies in the Chesapeake Bay estuary. As part of the National Status and Trends (NS&T) Program, NOAA has conducted studies to determine the spatial extent and severity of chemical contamination and associated adverse biological effects in coastal bays and estuaries of the United States since 1991. Sediment contamination in U.S. coastal areas is a major environmental issue because of its potential toxic effects on biological resources and often, indirectly, on human health. Thus, characterizing and delineating areas of sediment contamination and toxicity and demonstrating their effect(s) on benthic living resources are viewed as important goals of coastal resource management. Benthic community studies have a history of use in regional estuarine monitoring programs and have been shown to be an effective indicator for describing the extent and magnitude of pollution impacts in estuarine ecosystems, as well as for assessing the effectiveness of management actions. Chesapeake Bay is the largest estuarine system in the United States. Including tidal tributaries, the Bay has approximately 18,694 km of shoreline (more than the entire US West Coast). The watershed is over 165,000 km2 (64,000 miles2), and includes portions of six states (Delaware, Maryland, New York, Pennsylvania, Virginia, and West Virginia) and the District of Columbia. The population of the watershed exceeds 15 million people. There are 150 rivers and streams in the Chesapeake drainage basin. Within the watershed, five major rivers - the Susquehanna, Potomac, Rappahannock, York and James - provide almost 90% of the freshwater to the Bay. The Bay receives an equal volume of water from the Atlantic Ocean. In the upper Bay and tributaries, sediments are fine-grained silts and clays. Sediments in the middle Bay are mostly made of silts and clays derived from shoreline erosion. In the lower Bay, by contrast, the sediments are sandy. These particles come from shore erosion and inputs from the Atlantic Ocean. The introduction of European-style agriculture and large scale clearing of the watershed produced massive shifts in sediment dynamics of the Bay watershed. As early as the mid 1700s, some navigable rivers were filled in by sediment and sedimentation caused several colonial seaports to become landlocked. Toxic contaminants enter the Bay via atmospheric deposition, dissolved and particulate runoff from the watershed or direct discharge. While contaminants enter the Bay from several sources, sediments accumulate many toxic contaminants and thus reveal the status of input for these constituents. In the watershed, loading estimates indicate that the major sources of contaminants are point sources, stormwater runoff, atmospheric deposition, and spills. Point sources and urban runoff in the Bay proper contribute large quantities of contaminants. Pesticide inputs to the Bay have not been quantified. Baltimore Harbor and the Elizabeth River remain among the most contaminated areas in the Unites States. In the mainstem, deep sediment core analyses indicate that sediment accumulation rates are 2-10 times higher in the northern Bay than in the middle and lower Bay, and that sedimentation rates are 2-10 times higher than before European settlement throughout the Bay (NOAA 1998). The core samples show a decline in selected PAH compounds over the past several decades, but absolute concentrations are still 1 to 2 orders of magnitude above 'pristine' conditions. Core data also indicate that concentrations of PAHs, PCBs and, organochlorine pesticides do not demonstrate consistent trends over 25 years, but remain 10 times lower than sediments in the tributaries. In contrast, tri-butyl-tin (TBT) concentrations in the deep cores have declined significantly since it=s use was severely restricted. (PDF contains 241 pages)

Multi-frequency operation of a mems vibration energy harvester by accessing five orders of parametric resonance

The mechanical amplification effect of parametric resonance has the potential to outperform direct resonance by over an order of magnitude in terms of power output. However, the excitation must first overcome the damping-dependent initiation threshold amplitude prior to accessing this more profitable region. In addition to activating the principal (1st order) parametric resonance at twice the natural frequency ω0, higher orders of parametric resonance may be accessed when the excitation frequency is in the vicinity of 2ω0/n for integer n. Together with the passive design approaches previously developed to reduce the initiation threshold to access the principal parametric resonance, vacuum packaging (< 10 torr) is employed to further reduce the threshold and unveil the higher orders. A vacuum packaged MEMS electrostatic harvester (0.278 mm3) exhibited 4 and 5 parametric resonance peaks at room pressure and vacuum respectively when scanned up to 10 g. At 5.1 ms-2, a peak power output of 20.8 nW and 166 nW is recorded for direct and principal parametric resonance respectively at atmospheric pressure; while a peak power output of 60.9 nW and 324 nW is observed for the respective resonant peaks in vacuum. Additionally, unlike direct resonance, the operational frequency bandwidth of parametric resonance broadens with lower damping. © Published under licence by IOP Publishing Ltd.

High-performance ceramic membranes with a separation layer of metal oxide nanofibers

In conventional fabrication of ceramic separation membranes, the particulate sols are applied onto porous supports. Major structural deficiencies under this approach are pin-holes and cracks, and the dramatic losses of flux when pore sizes are reduced to enhance selectivity. We have overcome these structural deficiencies by constructing hierarchically structured separation layer on a porous substrate using lager titanate nanofibers and smaller boehmite nanofibers. This yields a radical change in membrane texture. The resulting membranes effectively filter out species larger than 60 nm at flow rates orders of magnitude greater than conventional membranes. This reveals a new direction in membrane fabrication.

High-flux ceramic membranes with a nanomesh of metal oxide nanofibers

Traditional ceramic separation membranes, which are fabricated by applying colloidal suspensions of metal hydroxides to porous supports, tend to suffer from pinholes and cracks that seriously affect their quality. Other intrinsic problems for these membranes include dramatic losses of flux when the pore sizes are reduced to enhance selectivity and dead-end pores that make no contribution to filtration. In this work, we propose a new strategy for addressing these problems by constructing a hierarchically structured separation layer on a porous substrate using large titanate nanofibers and smaller boehmite nanofibers. The nanofibers are able to divide large voids into smaller ones without forming dead-end pores and with the minimum reduction of the total void volume. The separation layer of nanofibers has a porosity of over 70% of its volume, whereas the separation layer in conventional ceramic membranes has a porosity below 36% and inevitably includes dead-end pores that make no contribution to the flux. This radical change in membrane texture greatly enhances membrane performance. The resulting membranes were able to filter out 95.3% of 60-nm particles from a 0.01 wt % latex while maintaining a relatively high flux of between 800 and 1000 L/m2·h, under a low driving pressure (20 kPa). Such flow rates are orders of magnitude greater than those of conventional membranes with equal selectivity. Moreover, the flux was stable at approximately 800 L/m2·h with a selectivity of more than 95%, even after six repeated runs of filtration and calcination. Use of different supports, either porous glass or porous alumina, had no substantial effect on the performance of the membranes; thus, it is possible to construct the membranes from a variety of supports without compromising functionality. The Darcy equation satisfactorily describes the correlation between the filtration flux and the structural parameters of the new membranes. The assembly of nanofiber meshes to combine high flux with excellent selectivity is an exciting new direction in membrane fabrication.

Radiological aspects of petroleum exploration and production in the sultanate of Oman

This thesis is a study of naturally occurring radioactive materials (NORM) activity concentration, gamma dose rate and radon (222Rn) exhalation from the waste streams of large-scale onshore petroleum operations. Types of activities covered included; sludge recovery from separation tanks, sludge farming, NORM storage, scaling in oil tubulars, scaling in gas production and sedimentation in produced water evaporation ponds. Field work was conducted in the arid desert terrain of an operational oil exploration and production region in the Sultanate of Oman. The main radionuclides found were 226Ra and 210Pb (238U - series), 228Ra and 228Th (232Th - series), and 227Ac (235U - series), along with 40K. All activity concentrations were higher than the ambient soil level and varied over several orders of magnitude. The range of gamma dose rates at a 1 m height above ground for the farm treated sludge had a range of 0.06 0.43 µSv h 1, and an average close to the ambient soil mean of 0.086 ± 0.014 µSv h 1, whereas the untreated sludge gamma dose rates had a range of 0.07 1.78 µSv h 1, and a mean of 0.456 ± 0.303 µSv h 1. The geometric mean of ambient soil 222Rn exhalation rate for area surrounding the sludge was mBq m 2 s 1. Radon exhalation rates reported in oil waste products were all higher than the ambient soil value and varied over three orders of magnitude. This study resulted in some unique findings including: (i) detection of radiotoxic 227Ac in the oil scales and sludge, (ii) need of a new empirical relation between petroleum sludge activity concentrations and gamma dose rates, and (iii) assessment of exhalation of 222Rn from oil sludge. Additionally the study investigated a method to determine oil scale and sludge age by the use of inherent behaviour of radionuclides as 228Ra:226Ra and 228Th:228Ra activity ratios.

Numerical investigations of linear least squares methods for derivative estimation

The results of a numerical investigation into the errors for least squares estimates of function gradients are presented. The underlying algorithm is obtained by constructing a least squares problem using a truncated Taylor expansion. An error bound associated with this method contains in its numerator terms related to the Taylor series remainder, while its denominator contains the smallest singular value of the least squares matrix. Perhaps for this reason the error bounds are often found to be pessimistic by several orders of magnitude. The circumstance under which these poor estimates arise is elucidated and an empirical correction of the theoretical error bounds is conjectured and investigated numerically. This is followed by an indication of how the conjecture is supported by a rigorous argument.

The spermostatic and microbicidal actions of quinones and malemides : towards a dual-purpose contraceptive agent

There is an urgent need to develop safe, effective, dual-purpose contraceptive agents that combine the prevention of pregnancy with protection against sexually transmitted diseases. Here we report the identification of a group of compounds that on contact with human spermatozoa induce a state of “spermostasis,” characterized by the extremely rapid inhibition of sperm movement without compromising cell viability. These spermostatic agents were more active and significantly less toxic than the reagent in current clinical use, nonoxynol 9, giving therapeutic indices (ratio of spermostatic to cytotoxic activity) that were orders of magnitude greater than this traditional spermicide. Although certain compounds could trigger reactive oxygen species generation by spermatozoa, this activity was not correlated with spermostasis. Rather, the latter was associated with alkylation of two major sperm tail proteins that were identified as A Kinase-Anchoring Proteins (AKAP3 and AKAP4) by mass spectrometry. As a consequence of disrupted AKAP function, the abilities of cAMP to drive protein kinase A-dependent activities in the sperm tail, such as the activation of SRC and the consequent stimulation of tyrosine phosphorylation, were suppressed. Furthermore, analysis of microbicidal activity using Chlamydia muridarum revealed powerful inhibitory effects at the same low micromolar doses that suppressed sperm movement. In this case, the microbicidal action was associated with alkylation of Major Outer Membrane Protein (MOMP), a major chlamydial membrane protein. Taken together, these results have identified for the first time a novel set of cellular targets and chemical principles capable of providing simultaneous defense against both fertility and the spread of sexually transmitted disease.

Kinetics of electron recombination of dye-senitized solar cells based on TiO2 nanorod arrays sensitized with different dyes

The performance and electron recombination kinetics of dye-sensitized solar cells based on TiO2 films consisting of one-dimensional nanorod arrays (NR-DSSCs) which are sensitized with dye N719, C218 and D205 respectively have been studied. It has been found that the best efficiency is obtained with the dye C218 based NR-DSSCs, benefiting from a 40% higher short-circuit photocurrent density. However, the open circuit photovoltage of the N719 based cell is 40 mV higher than that of the organic dye C218 and D205 based devices. Investigation of the electron recombination kinetics of the NR-DSSCs has revealed that the effective electron lifetime, τn, of the N719 based NR-DSSC is the lowest whereas the τn of the C218 based NR-DSSC is the highest among the three dyes. The higher Voc with the N719 based NR-DSSC is originated from the more negative energy level of the conduction band of the TiO2 film. In addition, in comparison to the DSSCs with conventional nanocrystalline particles based TiO2 films, the NR-DSSCs have shown over two orders of magnitude higher τn when employing N719 as the sensitizer. Nevertheless, the τn of the DSSCs with the C218 based nanorod arrays is only ten-fold higher than the that of the nanoparticles based devices. The remarkable characteristic of the dye C218 in suppressing the electron recombination of DSSCs is discussed.

Practical improvements to simultaneous computation of multi-view geometry and radial lens distortion

This paper discusses practical issues related to the use of the division model for lens distortion in multi-view geometry computation. A data normalisation strategy is presented, which has been absent from previous discussions on the topic. The convergence properties of the Rectangular Quadric Eigenvalue Problem solution for computing division model distortion are examined. It is shown that the existing method can require more than 1000 iterations when dealing with severe distortion. A method is presented for accelerating convergence to less than 10 iterations for any amount of distortion. The new method is shown to produce equivalent or better results than the existing method with up to two orders of magnitude reduction in iterations. Through detailed simulation it is found that the number of data points used to compute geometry and lens distortion has a strong influence on convergence speed and solution accuracy. It is recommended that more than the minimal number of data points be used when computing geometry using a robust estimator such as RANSAC. Adding two to four extra samples improves the convergence rate and accuracy sufficiently to compensate for the increased number of samples required by the RANSAC process.

Formation mechanisms of secondary organic aerosols in relation to laser printer emissions

Due to their large surface area, complex chemical composition and high alveolar deposition rate, ultrafine particles (UFPs) (< 0.1 ìm) pose a significant risk to human health and their toxicological effects have been acknowledged by the World Health Organisation. Since people spend most of their time indoors, there is a growing concern about the UFPs present in some indoor environments. Recent studies have shown that office machines, in particular laser printers, are a significant indoor source of UFPs. The majority of printer-generated UFPs are organic carbon and it is unlikely that these particles are emitted directly from the printer or its supplies (such as paper and toner powder). Thus, it was hypothesised that these UFPs are secondary organic aerosols (SOA). Considering the widespread use of printers and human exposure to these particles, understanding the processes involved in particle formation is of critical importance. However, few studies have investigated the nature (e.g. volatility, hygroscopicity, composition, size distribution and mixing state) and formation mechanisms of these particles. In order to address this gap in scientific knowledge, a comprehensive study including state-of-art instrumental methods was conducted to characterise the real-time emissions from modern commercial laser printers, including particles, volatile organic compounds (VOCs) and ozone (O3). The morphology, elemental composition, volatility and hygroscopicity of generated particles were also examined. The large set of experimental results was analysed and interpreted to provide insight into: (1) Emissions profiles of laser printers: The results showed that UFPs dominated the number concentrations of generated particles, with a quasi unimodal size distribution observed for all tests. These particles were volatile, non-hygroscopic and mixed both externally and internally. Particle microanalysis indicated that semi-volatile organic compounds occupied the dominant fraction of these particles, with only trace quantities of particles containing Ca and Fe. Furthermore, almost all laser printers tested in this study emitted measurable concentrations of VOCs and O3. A positive correlation between submicron particles and O3 concentrations, as well as a contrasting negative correlation between submicron particles and total VOC concentrations were observed during printing for all tests. These results proved that UFPs generated from laser printers are mainly SOAs. (2) Sources and precursors of generated particles: In order to identify the possible particle sources, particle formation potentials of both the printer components (e.g. fuser roller and lubricant oil) and supplies (e.g. paper and toner powder) were investigated using furnace tests. The VOCs emitted during the experiments were sampled and identified to provide information about particle precursors. The results suggested that all of the tested materials had the potential to generate particles upon heating. Nine unsaturated VOCs were identified from the emissions produced by paper and toner, which may contribute to the formation of UFPs through oxidation reactions with ozone. (3) Factors influencing the particle emission: The factors influencing particle emissions were also investigated by comparing two popular laser printers, one showing particle emissions three orders of magnitude higher than the other. The effects of toner coverage, printing history, type of paper and toner, and working temperature of the fuser roller on particle number emissions were examined. The results showed that the temperature of the fuser roller was a key factor driving the emission of particles. Based on the results for 30 different types of laser printers, a systematic positive correlation was observed between temperature and particle number emissions for printers that used the same heating technology and had a similar structure and fuser material. It was also found that temperature fluctuations were associated with intense bursts of particles and therefore, they may have impact on the particle emissions. Furthermore, the results indicated that the type of paper and toner powder contributed to particle emissions, while no apparent relationship was observed between toner coverage and levels of submicron particles. (4) Mechanisms of SOA formation, growth and ageing: The overall hypothesis that UFPs are formed by reactions with the VOCs and O3 emitted from laser printers was examined. The results proved this hypothesis and suggested that O3 may also play a role in particle ageing. In addition, knowledge about the mixing state of generated particles was utilised to explore the detailed processes of particle formation for different printing scenarios, including warm-up, normal printing, and printing without toner. The results indicated that polymerisation may have occurred on the surface of the generated particles to produce thermoplastic polymers, which may account for the expandable characteristics of some particles. Furthermore, toner and other particle residues on the idling belt from previous print jobs were a very clear contributing factor in the formation of laser printer-emitted particles. In summary, this study not only improves scientific understanding of the nature of printer-generated particles, but also provides significant insight into the formation and ageing mechanisms of SOAs in the indoor environment. The outcomes will also be beneficial to governments, industry and individuals.