Momentum transfer effects in the transport of adsorbate at a nano-patterned surface

Adsorbate molecules scattered in the repulsive field of a surface feature in the form of a semi-cylindrical stripe may be considered as a simple model for a nano-patterned surface. The extent of scattering was conveniently expressed as the tangential momentum accommodation coefficient. An analytical result was obtained using a simple local specular reflection hypothesis in contrast to the more complicated situation of an array of atoms discussed elsewhere, in which screening and secondary reflection may occur (Nicholson and Bhatia 2005). It was also demonstrated that a simple 2D representation leads to the same result for the tangential momentum accommodation coefficient.

Design of high quality doped CeO2 solid electrolytes with nanohetero structure

Doped ceria (CeO2) compounds are fluorite related oxides which show oxide ionic conductivity higher than yttria-stabilized zirconia in oxidizing atmosphere. As a consequence of this, a considerable interest has been shown in application of these materials for low (400-650 degrees C) temperature operation of solid oxide fuel cells (SOFCs). In this paper, our experimental data about the influence of microstructure at the atomic level on electrochemical properties were reviewed in order to develop high quality doped CeO2 electrolytes in fuel cell applications. Using this data in the present paper, our original idea for a design of nanodomain structure in doped CeO2 electrolytes was suggested. The nanosized powders and dense sintered bodies of M doped CeO2 (M:Sm,Gd,La,Y,Yb, and Dy) compounds were fabricated. Also nanostiructural features in these specimens were introduced for conclusion of relationship between electrolytic properties and domain structure in doped CeO2. It is essential that the electrolytic properties in doped CeO2 solid electrolytes reflect in changes of microstructure even down to the atomic scale. Accordingly, a combined approach of nanostructure fabrication, electrical measurement and structure characterization was required to develop superior quality doped CeO2 electrolytes in the fuel cells.

Investigation of spontaneous microemulsion formation in supercritical carbon dioxide using high-pressure NMR

NMR spectroscopy and relaxometry were used to investigate microemulsion formation in supercritical CO2. The droplets were stabilised by the salt of a perfluorinated polyether. Spontaneous microemulsion formation was observed over a period of 5 h in the absence of applied sheer. Time-resolved relaxation times of the surfactant tail showed a stepwise increase in mobility of the tail over this period. Conversely, the translational mobility of water confined within the droplet decreased over the same interval. This data is consistent with the gradual decrease in droplet size as time progressed. Indeed, NMR self-diffusion coefficients were used to show that droplets with a radius of approximately 5 nm were formed at equilibrium.

Modelling trickle irrigation: Comparison of analytical and numerical models for estimation of wetting front position with time

Irrigation practices that are profligate in their use of water have come under closer scrutiny by water managers and the public. Trickle irrigation has the propensity to increase water use efficiency but only if the system is designed to meet the soil and plant conditions. Recently we have provided a software tool, WetUp (http://www.clw.csiro.au/products/wetup/), to calculate the wetting patterns from trickle irrigation emitters. WetUp uses an analytical solution to calculate the wetted perimeter for both buried and surface emitters. This analytical solution has a number of assumptions, two of which are that the wetting front is defined by water content at which the hydraulic conductivity (K) is I mm day(-1) and that the flow occurs from a point source. Here we compare the wetting patterns calculated with a 2-dimensional numerical model, HYDRUS2D, for solving the water flow into typical soils with the analytical solution. The results show that the wetting patterns are similar, except when the soil properties result in the assumption of a point source no longer being a good description of the flow regime. Difficulties were also experienced with getting stable solutions with HYDRUS2D for soils with low hydraulic conductivities. (c) 2005 Elsevier Ltd. All rights reserved.

Simulation process of biodiesel production over heterogeneous catalysts

Biodiesel production is a very promising area due to the relevance that it is an environmental-friendly diesel fuel alternative to fossil fuel derived diesel fuels. Nowadays, most industrial applications of biodiesel production are performed by the transesterification of renewable biological sources based on homogeneous acid catalysts, which requires downstream neutralization and separation leading to a series of technical and environmental problems. However, heterogeneous catalyst can solve these issues, and be used as a better alternative for biodiesel production. Thus, a heuristic diffusion-reaction kinetic model has been established to simulate the transesterification of alkyl ester with methanol over a series of heterogeneous Cs-doped heteropolyacid catalysts. The novelty of this framework lies in detailed modeling of surface reacting kinetic phenomena and integrating that with particle-level transport phenomena all the way through to process design and optimisation, which has been done for biodiesel production process for the first time. This multi-disciplinary research combining chemistry, chemical engineering and process integration offers better insights into catalyst design and process intensification for the industrial application of Cs-doped heteropolyacid catalysts for biodiesel production. A case study of the transesterification of tributyrin with methanol has been demonstrated to establish the effectiveness of this methodology.

Simulation process of biodiesel production over heterogeneous catalysts

Biodiesel production is a very promising area due to the relevance that it is an environmental-friendly diesel fuel alternative to fossil fuel derived diesel fuels. Nowadays, most industrial applications of biodiesel production are performed by the transesterification of renewable biological sources based on homogeneous acid catalysts, which requires downstream neutralization and separation leading to a series of technical and environmental problems. However, heterogeneous catalyst can solve these issues, and be used as a better alternative for biodiesel production. Thus, a heuristic diffusion-reaction kinetic model has been established to simulate the transesterification of alkyl ester with methanol over a series of heterogeneous Cs-doped heteropolyacid catalysts. The novelty of this framework lies in detailed modeling of surface reacting kinetic phenomena and integrating that with particle-level transport phenomena all the way through to process design and optimisation, which has been done for biodiesel production process for the first time. This multi-disciplinary research combining chemistry, chemical engineering and process integration offers better insights into catalyst design and process intensification for the industrial application of Cs-doped heteropolyacid catalysts for biodiesel production. A case study of the transesterification of tributyrin with methanol has been demonstrated to establish the effectiveness of this methodology.

System-on-a-Chip (SOC) based environmental monitoring platform for the detection of hazardous materials

The purpose of this research is design considerations for environmental monitoring platforms for the detection of hazardous materials using System-on-a-Chip (SoC) design. Design considerations focus on improving key areas such as: (1) sampling methodology; (2) context awareness; and (3) sensor placement. These design considerations for environmental monitoring platforms using wireless sensor networks (WSN) is applied to the detection of methylmercury (MeHg) and environmental parameters affecting its formation (methylation) and deformation (demethylation). ^ The sampling methodology investigates a proof-of-concept for the monitoring of MeHg using three primary components: (1) chemical derivatization; (2) preconcentration using the purge-and-trap (P&T) method; and (3) sensing using Quartz Crystal Microbalance (QCM) sensors. This study focuses on the measurement of inorganic mercury (Hg) (e.g., Hg2+) and applies lessons learned to organic Hg (e.g., MeHg) detection. ^ Context awareness of a WSN and sampling strategies is enhanced by using spatial analysis techniques, namely geostatistical analysis (i.e., classical variography and ordinary point kriging), to help predict the phenomena of interest in unmonitored locations (i.e., locations without sensors). This aids in making more informed decisions on control of the WSN (e.g., communications strategy, power management, resource allocation, sampling rate and strategy, etc.). This methodology improves the precision of controllability by adding potentially significant information of unmonitored locations.^ There are two types of sensors that are investigated in this study for near-optimal placement in a WSN: (1) environmental (e.g., humidity, moisture, temperature, etc.) and (2) visual (e.g., camera) sensors. The near-optimal placement of environmental sensors is found utilizing a strategy which minimizes the variance of spatial analysis based on randomly chosen points representing the sensor locations. Spatial analysis is employed using geostatistical analysis and optimization occurs with Monte Carlo analysis. Visual sensor placement is accomplished for omnidirectional cameras operating in a WSN using an optimal placement metric (OPM) which is calculated for each grid point based on line-of-site (LOS) in a defined number of directions where known obstacles are taken into consideration. Optimal areas of camera placement are determined based on areas generating the largest OPMs. Statistical analysis is examined by using Monte Carlo analysis with varying number of obstacles and cameras in a defined space. ^

Reduced organic sulfur: Analysis and interaction with mercury in the aquatic environment

Reduced organic sulfur (ROS) compounds are environmentally ubiquitous and play an important role in sulfur cycling as well as in biogeochemical cycles of toxic metals, in particular mercury. Development of effective methods for analysis of ROS in environmental samples and investigations on the interactions of ROS with mercury are critical for understanding the role of ROS in mercury cycling, yet both of which are poorly studied. Covalent affinity chromatography-based methods were attempted for analysis of ROS in environmental water samples. A method was developed for analysis of environmental thiols, by preconcentration using affinity covalent chromatographic column or solid phase extraction, followed by releasing of thiols from the thiopropyl sepharose gel using TCEP and analysis using HPLC-UV or HPLC-FL. Under the optimized conditions, the detection limits of the method using HPLC-FL detection were 0.45 and 0.36 nM for Cys and GSH, respectively. Our results suggest that covalent affinity methods are efficient for thiol enrichment and interference elimination, demonstrating their promising applications in developing a sensitive, reliable, and useful technique for thiol analysis in environmental water samples. The dissolution of mercury sulfide (HgS) in the presence of ROS and dissolved organic matter (DOM) was investigated, by quantifying the effects of ROS on HgS dissolution and determining the speciation of the mercury released from ROS-induced HgS dissolution. It was observed that the presence of small ROS (e.g., Cys and GSH) and large molecule DOM, in particular at high concentrations, could significantly enhance the dissolution of HgS. The dissolved Hg during HgS dissolution determined using the conventional 0.22 μm cutoff method could include colloidal Hg (e.g., HgS colloids) and truly dissolved Hg (e.g., Hg-ROS complexes). A centrifugal filtration method (with 3 kDa MWCO) was employed to characterize the speciation and reactivity of the Hg released during ROS-enhanced HgS dissolution. The presence of small ROS could produce a considerable fraction (about 40% of total mercury in the solution) of truly dissolved mercury (< 3 kDa), probably due to the formation of Hg-Cys or Hg-GSH complexes. The truly dissolved Hg formed during GSH- or Cys-enhanced HgS dissolution was directly reducible (100% for GSH and 40% for Cys) by stannous chloride, demonstrating its potential role in Hg transformation and bioaccumulation.

Photochemical dynamics of laser-irradiated semiconductor nanostructures

Thesis (Ph.D.)--University of Washington, 2016-08

Evaluation of isoprene degradation in the detailed tropospheric chemical mechanism, MCM v3, using environmental chamber data

The isoprene degradation mechanism included in version 3 of the Master Chemical Mechanism (MCM v3) has been evaluated and refined, using the Statewide Air Pollution Research Center (SAPRC) environmental chamber datasets on the photo-oxidation of isoprene and its degradation products, methacrolein (MACR) and methylvinyl ketone (MVK). Prior to this, the MCM v3 butane degradation chemistry was also evaluated using chamber data on the photo-oxidation of butane, and its degradation products, methylethyl ketone (MEK), acetaldehyde (CH3CHO) and formaldehyde (HCHO), in conjunction with an initial evaluation of the chamber-dependent auxiliary mechanisms for the series of relevant chambers. The MCM v3 mechanisms for both isoprene and butane generally performed well and were found to provide an acceptable reaction framework for describing the NOx-photo-oxidation experiments on the above systems, although a number of parameter modifications and refinements were identified which resulted in an improved performance. All these relate to the magnitude of sources of free radicals from organic chemical process, such as carbonyl photolysis rates and the yields of radicals from the reactions of O3 with unsaturated oxygenates, and specific recommendations are made for refinements. In addition to this, it was necessary to include a representation of the reactions of O(3P) with isoprene, MACR and MVK (which were not previously treated in MCM v3), and conclusions are drawn concerning the required extent of free radical formation from these reactions. Throughout the study, the performance of MCM v3 was also compared with that of the SAPRC-99 mechanism, which was developed and optimized in conjunction with the chamber datasets.

Investigating automated chemical evolution of oil-in-water droplets

One of the main unresolved questions in science is how non-living matter became alive in a process known as abiognesis, which aims to explain how from a primordial soup scenario containing simple molecules, by following a ``bottom up'' approach, complex biomolecules emerged forming the first living system, known as a protocell. A protocell is defined by the interplay of three sub-systems which are considered requirements for life: information molecules, metabolism, and compartmentalization. This thesis investigates the role of compartmentalization during the emergence of life, and how simple membrane aggregates could evolve into entities that were able to develop ``life-like'' behaviours, and in particular how such evolution could happen without the presence of information molecules. Our ultimate objective is to create an autonomous evolvable system, and in order tp do so we will try to engineer life following a ``top-down'' approach, where an initial platform capable of evolving chemistry will be constructed, but the chemistry being dependent on the robotic adjunct, and how then this platform can be de-constructed in iterative operations until it is fully disconnected from the evolvable system, the system then being inherently autonomous. The first project of this thesis describes how the initial platform was designed and built. The platform was based on the model of a standard liquid handling robot, with the main difference with respect to other similar robots being that we used a 3D-printer in order to prototype the robot and build its main equipment, like a liquid dispensing system, tool movement mechanism, and washing procedures. The robot was able to mix different components and create populations of droplets in a Petri dish filled with aqueous phase. The Petri dish was then observed by a camera, which analysed the behaviours described by the droplets and fed this information back to the robot. Using this loop, the robot was then able to implement an evolutionary algorithm, where populations of droplets were evolved towards defined life-like behaviours. The second project of this thesis aimed to remove as many mechanical parts as possible from the robot while keeping the evolvable chemistry intact. In order to do so, we encapsulated the functionalities of the previous liquid handling robot into a single monolithic 3D-printed device. This device was able to mix different components, generate populations of droplets in an aqueous phase, and was also equipped with a camera in order to analyse the experiments. Moreover, because the full fabrication process of the devices happened in a 3D-printer, we were also able to alter its experimental arena by adding different obstacles where to evolve the droplets, enabling us to study how environmental changes can shape evolution. By doing so, we were able to embody evolutionary characteristics into our device, removing constraints from the physical platform, and taking one step forward to a possible autonomous evolvable system.

Scalar turbulent behavior in the roughness sublayer of an Amazonian forest.

An important current problem in micrometeorology is the characterization of turbulence in the roughness sublayer (RSL), where most of the measurements above tall forests are made. There, scalar turbulent fluctuations display significant departures from the predictions of Monin?Obukhov similarity theory (MOST). In this work, we analyze turbulence data of virtual temperature, carbon dioxide, and water vapor in the RSL above an Amazonian forest (with a canopy height of 40 m), measured at 39.4 and 81.6 m above the ground under unstable conditions. We found that dimensionless statistics related to the rate of dissipation of turbulence kinetic energy (TKE) and the scalar variance display significant departures from MOST as expected, whereas the vertical velocity variance follows MOST much more closely. Much better agreement between the dimensionless statistics with the Obukhov similarity variable, however, was found for the subset of measurements made at a low zenith angle Z, in the range 0°  <  |Z|  <  20°. We conjecture that this improvement is due to the relationship between sunlight incidence and the ?activation?deactivation? of scalar sinks and sources vertically distributed in the forest. Finally, we evaluated the relaxation coefficient of relaxed eddy accumulation: it is also affected by zenith angle, with considerable improvement in the range 0°  <  |Z|  <  20°, and its values fall within the range reported in the literature for the unstable surface layer. In general, our results indicate the possibility of better stability-derived flux estimates for low zenith angle ranges.

Brucite Microbialites in Living Coral Skeletons: Indicators of Extreme Microenvironments in Shallow-Marine Settings

Brucite [Mg(OH)2] microbialites occur in vacated interseptal spaces of living scleractinian coral colonies (Acropora, Pocillopora, Porites) from subtidal and intertidal settings in the Great Barrier Reef, Australia, and subtidal Montastraea from the Florida Keys, United States. Brucite encrusts microbial filaments of endobionts (i.e., fungi, green algae, cyanobacteria) growing under organic biofilms; the brucite distribution is patchy both within interseptal spaces and within coralla. Although brucite is undersaturated in seawater, its precipitation was apparently induced in the corals by lowered pCO2 and increased pH within microenvironments protected by microbial biofilms. The occurrence of brucite in shallow-marine settings highlights the importance of microenvironments in the formation and early diagenesis of marine carbonates. Significantly, the brucite precipitates discovered in microenvironments in these corals show that early diagenetic products do not necessarily reflect ambient seawater chemistry. Errors in environmental interpretation may arise where unidentified precipitates occur in microenvironments in skeletal carbonates that are subsequently utilized as geochemical seawater proxies.

Cobalt-doped cadmium selenide colloidal nanowires

Co2+-doped CdSe colloidal nanowires with tunable size and dopant concentration have been prepared by a solution–liquid–solid (SLS) approach for the first time. These doped nanowires exhibit anomalous photoluminescence temperature dependence in comparison with undoped nanowires.