Detrital layer thickness in 12 varved sediment cores in Lake Mondsee and related flood events AD1976-2005

A succession of 23 sub-millimetre to maximum 12-mm-thick, mostly flood-triggered detrital layers, deposited between 1976 and 2005, was analysed in 12 varved surface sediment cores from meso-scale peri-alpine Lake Mondsee applying microfacies and high-resolution micro X-ray fluorescence analyses. Detailed intrabasin comparison of these layers enabled identification of (i) different source areas of detrital sediments, (ii) flood-triggered sediment flux and local erosion events, and (iii) seasonal differences of suspended flood sediment distribution within the lake basin. Additional calibration of the detrital layer record with river discharge and precipitation data reveals different empirical thresholds for flood layer deposition for different parts of the basin. At proximal locations detrital layer deposition requires floods exceeding a daily discharge of 40 m**3/s, whereas at a location 2 km more distal an hourly discharge of 80 m**3/s and at least 2 days of discharge above 40 m**3/s are necessary. Furthermore, we observe a better correlation between layer thickness and flood amplitude in the depocentre than in distal and proximal areas of the basin. Although our results are partly site-specific, the applied dual calibration approach is suitable to precisely decipher flood layer formation processes and, thereby, improve the interpretation of long flood time series from lake sediments.

Permafrost cores and active layer pits on Herschel Island: link to shape files

Twelve permafrost cores and active layer pits were drilled/dug on Herschel Island in order to estimate the soil organic carbon and total nitrogen contents in the first 30, 100 and 200 cm of ground. The data are shapefile points with attribute table, which contains different core information.

An ether-functionalised cyclic sulfonium based ionic liquid as an electrolyte for electrochemical double layer capacitors

A novel cyclic sulfonium cation-based ionic liquid (IL) with an ether-group appendage and the bis{(trifluoromethyl)sulfonyl}imide anion was synthesised and developed for electrochemical double layer capacitor (EDLC) testing. The synthesis and chemical-physical characterisation of the ether-group containing IL is reported in parallel with a similarly sized alkyl-functionalised sulfonium IL. Results of the chemical-physical measurements demonstrate how important transport properties, i.e. viscosity and conductivity, can be promoted through the introduction of the ether-functionality without impeding thermal, chemical or electrochemical stability of the IL. Although the apparent transport properties are improved relative to the alkyl-functionalised analogue, the ether-functionalised sulfonium cation-based IL exhibits moderately high viscosity, and poorer conductivity, when compared to traditional EDLC electrolytes based on organic solvents (propylene carbonate and acetonitrile). Electrochemical testing of the ether-functionalised sulfonium IL was conducted using activated carbon composite electrodes to inspect the performance of the IL as a solvent-free electrolyte for EDLC application. Good cycling stability was achieved over the studied range and the performance was comparable to other solvent free,
IL-based EDLC systems. Nevertheless, limitations of the attainable performance are primarily the result of sluggish transport properties and a restricted operative voltage of the IL, thus highlighting key aspects of this field which require further attention.

Experimental Study on Key Generation for Physical Layer Security in Wireless Communications

This paper presents a thorough experimental study on key generation principles, i.e. temporal variation, channel reciprocity, and spatial decorrelation, via a testbed constructed by using wireless open-access research platform (WARP). It is the first comprehensive study through (i) carrying out a number of experiments in different multipath environments, including an anechoic chamber, a reverberation chamber and an indoor office environment, which represents little, rich, and moderate multipath, respectively; (ii) considering static, object moving, and mobile scenarios in these environments, which represents different levels of channel dynamicity; (iii) studying two most popular channel parameters, i.e., channel state information and received signal strength. Through results collected from over a hundred tests, this paper offers insights to the design of a secure and efficient key generation system. We show that multipath is essential and beneficial for key generation as it increases the channel randomness. We also find that the movement of users/objects can help introduce temporal variation/randomness and help users reach an agreement on the keys. This paper complements existing research by experiments constructed by a new hardware platform.

Physical Layer Security with Threshold-Based Multiuser Scheduling in Multi-antenna Wireless Networks

In this paper, we consider a multiuser downlink wiretap network consisting of one base station (BS) equipped with AA antennas, NB single-antenna legitimate users, and NE single-antenna eavesdroppers over Nakagami-m fading channels. In particular, we introduce a joint secure transmission scheme that adopts transmit antenna selection (TAS) at the BS and explores threshold-based selection diversity (tSD) scheduling over legitimate users to achieve a good secrecy performance while maintaining low implementation complexity. More specifically, in an effort to quantify the secrecy performance of the considered system, two practical scenarios are investigated, i.e., Scenario I: the eavesdropper’s channel state information (CSI) is unavailable at the BS, and Scenario II: the eavesdropper’s CSI is available at the BS. For Scenario I, novel exact closed-form expressions of the secrecy outage probability are derived, which are valid for general networks with an arbitrary number of legitimate users, antenna configurations, number of eavesdroppers, and the switched threshold. For Scenario II, we take into account the ergodic secrecy rate as the principle performance metric, and derive novel closed-form expressions of the exact ergodic secrecy rate. Additionally, we also provide simple and asymptotic expressions for secrecy outage probability and ergodic secrecy rate under two distinct cases, i.e., Case I: the legitimate user is located close to the BS, and Case II: both the legitimate user and eavesdropper are located close to the BS. Our important findings reveal that the secrecy diversity order is AAmA and the slope of secrecy rate is one under Case I, while the secrecy diversity order and the slope of secrecy rate collapse to zero under Case II, where the secrecy performance floor occurs. Finally, when the switched threshold is carefully selected, the considered scheduling scheme outperforms other well known existing schemes in terms of the secrecy performance and complexity tradeoff

Binary Mixtures of 1-Butyl-1-Methylpyrrolidinium Bis{(trifluoromethyl)Sulfonyl}Imide and Aliphatic Nitrile Solvents As Electrolyte for Electrochemical Double Layer Capacitors (Invited).

Electrochemical double layer capacitors (EDLCs), also known as supercapacitors, are promising energy storage devices, especially when considering high power applications [1]. EDLCs can be charged and discharged within seconds [1], feature high power (10 kW·kg-1) and an excellent cycle life (>500,000 cycles). All these properties are a result of the energy storage process of EDLCs, which relies on storing energy by charge separation instead of chemical redox reactions, as utilized in battery systems. Upon charging, double layers are forming at the electrode/electrolyte interface consisting of the electrolyte’s ions and electric charges at the electrode surface.In state-of-the-art EDLC systems activated carbons (AC) are used as active materials and tetraethylammonium tetrafluoroborate ([Et4N][BF4]) dissolved in organic solvents like propylene carbonate (PC) or acetonitrile (ACN) are commonly used as the electrolyte [2]. These combinations of materials allow operative voltages up to 2.7 V - 2.8 V and an energy in the order of 5 Wh·kg-1[3]. The energy of EDLCs is dependent on the square of the operative voltage, thus increasing the usable operative voltage has a strong effect on the delivered energy of the device [1]. Due to their high electrochemical stability, ionic liquids (ILs) were thoroughly investigated as electrolytes for EDLCs, as well as, batteries, enabling high operating voltages as high as 3.2 V - 3.5 V for the former [2]. While their unique ionic structure allows the usage of neat ILs as electrolyte in EDLCs, ILs suffer from low conductivity and high viscosity increasing the intrinsic resistance and, as a result, a lower power output of the device. In order to overcome this issue, the usage of blends of ionic liquids and organic solvents has been considered a feasible strategy as they combine high usable voltages, while still retaining good transport properties at the same time.In our recent work the ionic liquid 1-butyl-1-methylpyrrolidinium bis{(trifluoromethyl)sulfonyl}imide ([Pyrr14][TFSI]) was combined with two nitrile-based organic solvents, namely butyronitrile (BTN) and adiponitrile (ADN), and the resulting blends were investing regarding their usage in electrochemical double layer capacitors [4,5]. Firstly, the physicochemical properties were investigated, showing good transport properties for both blends, which are similar to the state-of-the-art combination of [Et4N][BF4] in PC. Secondly, the electrochemical properties for EDLC application were studied in depth revealing a high electrochemical stability with a maximum operative voltage as high as 3.7 V. In full cells these high voltage organic solvent based electrolytes have a good performance in terms of capacitance and an acceptable equivalent series resistance at cut-off voltages of 3.2 and 3.5 V. However, long term stability tests by float testing revealed stability issues when using a maximum voltage of 3.5 V for prolonged time, whereas at 3.2 V no such issues are observed (Fig. 1).Considering the obtained results, the usage of ADN and BTN blends with [Pyrr14][TFSI] in EDLCs appears to be an interesting alternative to state-of-the-art organic solvent based electrolytes, allowing the usage of higher maximum operative voltages while having similar transport properties to 1 mol∙dm-3 [Et4N][BF4] in PC at the same time.

Application of WRF-Chem to Forecasting PM10 Concentration Over Poland

The meteorological and chemical transport model WRF-Chem was implemented to forecast PM10 concentrations over Poland. WRF-Chem version 3.5 was configured with three one-way nested domains using the GFS meteorological data and the TNO MACC II emissions. The 48 hour forecasts were run for each day of the winter and summer period of 2014 and there is only a small decrease in model performance for winter with respect to forecast lead time. The model in general captures the variability in observed PM10 concentrations for most of the stations. However, for some locations and specific episodes, the model performance is poor and the results cannot yet be used by official authorities. We argue that a higher resolution sector-based emission data will be helpful for this analysis in connection with a focus on planetary boundary layer processes in WRF-Chem and their impact on the initial distribution of emissions on both time and space.

Investigating Marine Boundary Layer Aerosol Budgets and Variability

Thesis (Master's)--University of Washington, 2016-08

Adsorption Calorimetry for Energy Conversion Technologies: Applications in Organic Photovoltaics, Catalysis, and Atomic Layer Deposition

Thesis (Ph.D.)--University of Washington, 2016-07

Investigating routes toward atomic layer deposition of silicon carbide: Ab initio screening of potential silicon and carbon precursors

Silicon carbide (SiC) is a promising material for electronics due to its hardness, and ability to carry high currents and high operating temperature. SiC films are currently deposited using chemical vapor deposition (CVD) at high temperatures 1500–1600 °C. However, there is a need to deposit SiC-based films on the surface of high aspect ratio features at low temperatures. One of the most precise thin film deposition techniques on high-aspect-ratio surfaces that operates at low temperatures is atomic layer deposition (ALD). However, there are currently no known methods for ALD of SiC. Herein, the authors present a first-principles thermodynamic analysis so as to screen different precursor combinations for SiC thin films. The authors do this by calculating the Gibbs energy ΔGΔG of the reaction using density functional theory and including the effects of pressure and temperature. This theoretical model was validated for existing chemical reactions in CVD of SiC at 1000 °C. The precursors disilane (Si2H6), silane (SiH4), or monochlorosilane (SiH3Cl) with ethyne (C2H2), carbontetrachloride (CCl4), or trichloromethane (CHCl3) were predicted to be the most promising for ALD of SiC at 400 °C.

Kinetics and coverage dependent reaction mechanisms of the copper atomic layer deposition from copper dimethylamino-2-propoxide and diethylzinc

Atomic layer deposition (ALD) has been recognized as a promising method to deposit conformal and uniform thin film of copper for future electronic devices. However, many aspects of the reaction mechanism and the surface chemistry of copper ALD remain unclear. In this paper, we employ plane wave density functional theory (DFT) to study the transmetalation ALD reaction of copper dimethylamino-2-propoxide [Cu(dmap)2] and diethylzinc [Et2Zn] that was realized experimentally by Lee et al. [ Angew. Chem., Int. Ed. 2009, 48, 4536−4539]. We find that the Cu(dmap)2 molecule adsorbs and dissociates through the scission of one or two Cu–O bonds into surface-bound dmap and Cu(dmap) fragments during the copper pulse. As Et2Zn adsorbs on the surface covered with Cu(dmap) and dmap fragments, butane formation and desorption was found to be facilitated by the surrounding ligands, which leads to one reaction mechanism, while the migration of ethyl groups to the surface leads to another reaction mechanism. During both reaction mechanisms, ligand diffusion and reordering are generally endothermic processes, which may result in residual ligands blocking the surface sites at the end of the Et2Zn pulse, and in residual Zn being reduced and incorporated as an impurity. We also find that the nearby ligands play a cooperative role in lowering the activation energy for formation and desorption of byproducts, which explains the advantage of using organometallic precursors and reducing agents in Cu ALD. The ALD growth rate estimated for the mechanism is consistent with the experimental value of 0.2 Å/cycle. The proposed reaction mechanisms provide insight into ALD processes for copper and other transition metals.

An IP capable data link layer protocol for narrow band half-duplex packet data radio networks

The wide adaptation of Internet Protocol (IP) as de facto protocol for most communication networks has established a need for developing IP capable data link layer protocol solutions for Machine to machine (M2M) and Internet of Things (IoT) networks. However, the wireless networks used for M2M and IoT applications usually lack the resources commonly associated with modern wireless communication networks. The existing IP capable data link layer solutions for wireless IoT networks provide the necessary overhead minimising and frame optimising features, but are often built to be compatible only with IPv6 and specific radio platforms. The objective of this thesis is to design IPv4 compatible data link layer for Netcontrol Oy's narrow band half-duplex packet data radio system. Based on extensive literature research, system modelling and solution concept testing, this thesis proposes the usage of tunslip protocol as the basis for the system data link layer protocol development. In addition to the functionality of tunslip, this thesis discusses the additional network, routing, compression, security and collision avoidance changes required to be made to the radio platform in order for it to be IP compatible while still being able to maintain the point-to-multipoint and multi-hop network characteristics. The data link layer design consists of the radio application, dynamic Maximum Transmission Unit (MTU) optimisation daemon and the tunslip interface. The proposed design uses tunslip for creating an IP capable data link protocol interface. The radio application receives data from tunslip and compresses the packets and uses the IP addressing information for radio network addressing and routing before forwarding the message to radio network. The dynamic MTU size optimisation daemon controls the tunslip interface maximum MTU size according to the link quality assessment calculated from the radio network diagnostic data received from the radio application. For determining the usability of tunslip as the basis for data link layer protocol, testing of the tunslip interface is conducted with both IEEE 802.15.4 radios and packet data radios. The test cases measure the radio network usability for User Datagram Protocol (UDP) based applications without applying any header or content compression. The test results for the packet data radios reveal that the typical success rate for packet reception through a single-hop link is above 99% with a round-trip-delay of 0.315s for 63B packets.

Growth and application of planar III-V semiconductor nanowires grown with MOCVD

The semiconductor nanowire has been widely studied over the past decade and identified as a promising nanotechnology building block with application in photonics and electronics. The flexible bottom-up approach to nanowire growth allows for straightforward fabrication of complex 1D nanostructures with interesting optical, electrical, and mechanical properties. III-V nanowires in particular are useful because of their direct bandgap, high carrier mobility, and ability to form heterojunctions and have been used to make devices such as light-emitting diodes, lasers, and field-effect transistors. However, crystal defects are widely reported for III-V nanowires when grown in the common out-of-plane <111>B direction. Furthermore, commercialization of nanowires has been limited by the difficulty of assembling nanowires with predetermined position and alignment on a wafer-scale. In this thesis, planar III-V nanowires are introduced as a low-defect and integratable nanotechnology building block grown with metalorganic chemical vapor deposition. Planar GaAs nanowires grown with gold seed particles self-align along the <110> direction on the (001) GaAs substrate. Transmission electron microscopy reveals that planar GaAs nanowires are nearly free of crystal defects and grow laterally and epitaxially on the substrate surface. The nanowire morphology is shown to be primarily controlled through growth temperature and an ideal growth window of 470 +\- 10 °C is identified for planar GaAs nanowires. Extension of the planar growth mode to other materials is demonstrated through growth of planar InAs nanowires. Using a sacrificial layer, the transfer of planar GaAs nanowires onto silicon substrates with control over the alignment and position is presented. A metal-semiconductor field-effect transistor fabricated with a planar GaAs nanowire shows bulk-like low-field electron transport characteristics with high mobility. The aligned planar geometry and excellent material quality of planar III-V nanowires may lead to highly integrated III-V nanophotonics and nanoelectronics.

Mixed-layer salinity budget in the tropical Indian Ocean: seasonal cycle based only on observations

The mixed-layer salinity (MLS) budget in the tropical Indian Ocean is estimated from a combination of satellite products and in situ observations over the 2004-2012 period, to investigate the mechanisms controlling the seasonal MLS variability. In contrast with previous studies in the tropical Indian Ocean, our results reveal that the coverage, resolution, and quality of available observations are now sufficient to approach a closed monthly climatology seasonal salt budget. In the South-central Arabian Sea and South-western Tropical Indian Ocean (SCAS and STIO, respectively), where seasonal variability of the MLS is pronounced, the monthly MLS tendency terms are well captured by the diagnostic. In the SCAS region, in agreement with previous results, the seasonal cycle of the MLS is mainly due to meridional advection driven by the monsoon winds. In the STIO, contrasting previous results indicating the control of the meridional advection over the seasonal MLS budget, our results reveal the leading role of the freshwater flux due to precipitation.

Development of paper-based color test-strip for drug detection in aquatic environment: Application to oxytetracycline

The wide use of antibiotics in aquaculture has led to the emergence of resistant microbial species. It should be avoided/minimized by controlling the amount of drug employed in fish farming. For this purpose, the present work proposes test-strip papers aiming at the detection/semi-quantitative determination of organic drugs by visual comparison of color changes, in a similar analytical procedure to that of pH monitoring by universal pH paper. This is done by establishing suitable chemical changes upon cellulose, attributing the paper the ability to react with the organic drug and to produce a color change. Quantitative data is also enabled by taking a picture and applying a suitable mathematical treatment to the color coordinates given by the HSL system used by windows. As proof of concept, this approach was applied to oxytetracycline (OXY), one of the antibiotics frequently used in aquaculture. A bottom-up modification of paper was established, starting by the reaction of the glucose moieties on the paper with 3-triethoxysilylpropylamine (APTES). The so-formed amine layer allowed binding to a metal ion by coordination chemistry, while the metal ion reacted after with the drug to produce a colored compound. The most suitable metals to carry out such modification were selected by bulk studies, and the several stages of the paper modification were optimized to produce an intense color change against the concentration of the drug. The paper strips were applied to the analysis of spiked environmental water, allowing a quantitative determination for OXY concentrations as low as 30 ng/mL. In general, this work provided a simple, method to screen and discriminate tetracycline drugs, in aquaculture, being a promising tool for local, quick and cheap monitoring of drugs.