Experimental investigation into the effect of stress on dissolution and growth of very soluble brittle salts in aqueous solution

Das Studium der Auflösungs- und Wachstumsprozesse an Feststoff-Flüssigkeits-Grenzflächen unter nicht-hydrostatischen Beanspruchungen ist wesentlich für das Verständnis von Defor-mationsprozessen, die in der Erde ablaufen. Unter diesen genannten Prozessen gehört die Drucklösung zu den wichtigsten duktilen Deformationsprozessen, von der Diagenese bishin zur niedrig- bis mittelgradigen metamorphen Bedingungen. Bisher ist allerdings wenig darüber bekannt, welche mechanischen, physikalischen oder chemischen Potentialenergie-Gradienten die Drucklösung steuern. I.a. wird angenommen, daß die Drucklösung durch Un-terschiede kristallplastischer Verformungsenergien oder aber durch Unterschiede der Normal-beanspruchung an Korngrenzen gesteuert wird. Unterschiede der elastischen Verformungs-energien werden dabei allerdings als zu gering erachtet, um einen signifikanten Beitrag zu leisten. Aus diesem Grund werden sie als mögliche treibende Kräfte für die Drucklösung vernachlässigt. Andererseits haben neue experimentelle und theoretische Untersuchungen gezeigt, daß die elastische Verformung in der Tat einen starken Einfluß auf Lösungs- und Wachstumsmechanismen von Kristallen in einer Lösung haben kann. Da die in der Erdkruste vorherrschenden Deformationsmechanismen überwiegend im elastischen Verformungsbereich der Gesteine ablaufen, ist es sehr wichtig, das Verständnis für die Effekte, die die elastische Verformung verursacht, zu erweitern, und ihre Rolle während der Deformation durch Drucklösung zu definieren. Die vorliegende Arbeit beschäftigt sich mit Experimenten, bei denen der Effekt der mechanisch kompressiven Beanspruchung auf Lösungs- und Wachstumsprozesse von Einzelkristallen unterschiedlicher, sehr gut löslicher, elastisch/spröder Salze untersucht wurde. Diese Salze wurden als Analoga gesteinsbildender Minerale wie Quarz und Calcit ausgewählt. Der Einfluß von Stress auf die Ausbildung der Oberflächenmikrostrukturen in einer untersättigten Lösung wurde an Kaliumalaun untersucht.Lösungsrillen (20 – 40 µm breit, 10 – 40 µm tief und 20 – 80 µm Abstand) entwickelten sich in den Bereichen, in denen die Beanspruchung im Kristall am größten war. Sie verschwanden wieder, sobald der Kristall entlastet wurde. Diese Rillen entwickelten sich parallel zu niedrig indizierten kristallographischen Richtungen und sub-perpendikular zu den Trajektorien, die der maximalen, lokalen kompressiven Beanspruchung entsprachen. Die Größe der Lösungsrillen hing von der lokalen Oberflächenbeanspruchung, der Oberflächenenergie und dem Untersättigungsgrad der wässrigen Lösung ab. Die mikrostrukturelle Entwicklung der Kristalloberflächen stimmte gut mit den theoretischen Vorhersagen überein, die auf den Modellen von Heidug & Leroy (1994) und Leroy & Heidug (1994) basieren. Der Einfluß der Beanspruchung auf die Auflösungsrate wurde an Natriumchlorat-Einzelkristallen untersucht. Dabei wurde herausgefunden, daß sich gestresste Kristalle schneller lösen als Kristalle, auf die keine Beanspruchung einwirkt. Der experimentell beobachtete Anstieg der Auflösungsrate der gestressten Kristalle war ein bis zwei Größenordnungen höher als theoretisch erwartet. Die Auflösungsrate stieg linear mit dem Stress an, und der Anstieg war um so größer, je stärker die Lösung untersättigt war. Außerdem wurde der Effekt der Bean-spruchung auf das Kristallwachstum an Kaliumalaun- und Kaliumdihydrogenphosphat-Ein-zelkristallen untersucht. Die Wachstumsrate der Flächen {100} und {110} von Kalium-alaun war bei Beanspruchung stark reduziert. Für all diese Ergebnisse spielte die Oberflächenrauhigkeit der Kristalle eine Schlüsselrolle, indem sie eine nicht-homogene Stressverteilung auf der Kristalloberfläche verursachte. Die Resultate zeigen, daß die elastische Verformung eine signifikante Rolle während der Drucklösung spielen kann, und eine signifikante Deformation in der oberen Kruste verursachen kann, bei Beanspruchungen, die geringer sind, als gemeinhin angenommen wird. Somit folgt, daß die elastische Bean-spruchung berücksichtigt werden muß, wenn mikrophysikalische Deformationsmodelle entwickelt werden sollen.

Numerical study on the curling and warping of hardened rigid pavement slabs

In-service hardened concrete pavement suffers from environmental loadings caused by curling and warping of the slab. Traditionally, these loadings are computed on the basis of treating the slab as an elastic material, and of evaluating separately the curling and warping components. This dissertation simulates temperature distribution and moisture distribution through the slabs by use of a developed numerical model that couples the heat transfer and moisture transport. The computation of environmental loadings treats the slab as an elastic-viscous material, which considers the relaxation behavior and Pickett effect of the concrete. The heat transfer model considers the impacts of solar radiation, wind speed, air temperature, pavement slab albedo, etc. on the pavement temperature distribution. This dissertation assesses the difference between documented models that aim to predict pavement temperature, highlighting their pros and cons. The moisture transport model is unique for the documented models; it mimics the wetting and drying events occurring at the slab surface. These events are estimated by a proposed statistical algorithm, which is verified by field rainfall data. Analysis of the predicted results examines on the roles of the local air RH (relative humidity), wind speed, rainy pattern in the moisture distribution through the slab. The findings reveal that seasonal air RH plays a decisive role on the slab‘s moisture distribution; but wind speed and its daily variation, daily RH variation, and seasonal rainfall pattern plays only a secondary role. This dissertation sheds light on the computation of environmental loadings that in-service pavement slabs suffer from. Analysis of the computed stresses centers on the stress relaxation near the surface, stress evolution after the curing ends, and the impact of construction season on the stress‘s magnitude. An unexpected finding is that the total environmental loadings at the cyclically-stable state divert from the thermal stresses. At such a state, the total stress at the daytime is roughly equal to the thermal stress; whereas the total stress during the nighttime is far greater than the thermal stress. An explanation for this phenomenon is that during the night hours, the decline of the slab‘s near-surface temperature leads to a drop of the near-surface RH. This RH drop results in contraction therein and develops additional tensile stresses. The dissertation thus argues that estimating the environmental loadings by solely computing the thermally-induced stresses may reach delusive results. It recommends that the total environmental loadings of in-service slabs should be estimated by a sophisticated model coupling both moisture component and temperature component.

Lake surface temperatures in a changing climate: a global sensitivity analysis

We estimate the effects of climatic changes, as predicted by six climate models, on lake surface temperatures on a global scale, using the lake surface equilibrium temperature as a proxy. We evaluate interactions between different forcing variables, the sensitivity of lake surface temperatures to these variables, as well as differences between climate zones. Lake surface equilibrium temperatures are predicted to increase by 70 to 85 % of the increase in air temperatures. On average, air temperature is the main driver for changes in lake surface temperatures, and its effect is reduced by ~10 % by changes in other meteorological variables. However, the contribution of these other variables to the variance is ~40 % of that of air temperature, and their effects can be important at specific locations. The warming increases the importance of longwave radiation and evaporation for the lake surface heat balance compared to shortwave radiation and convective heat fluxes. We discuss the consequences of our findings for the design and evaluation of different types of studies on climate change effects on lakes.

(Table 1) Oxygen isotope composition and comparison between ages and sea surface temperature from sediment core KH-79-3_L-3

The Japan Sea experienced bottom water anoxia at the last glacial maximum (LGM) since it is surrounded by four shallow straits, the sill depths of which are close to, or shallower than, the drop in sea level (~120 m) that occurred then. A distinctive negative d18O excursion of planktonic foraminifera also took place during the LGM. This excursion has been interpreted from foraminiferal data as recording a drop in the paleosalinity of surface waters on the assumption of a constant low sea surface temperatures between 34 and 11 ka. We present here a profile of alkenone-based sea surface temperatures (alkenone-SSTs) over the past 36 kyr. Our results suggest that SSTs during the LGM were much higher than those previously assumed. After considering the factors that might affect estimation of alkenone-SSTs and comparisons of core-top alkenone-SSTs values with values for modern seawater we conclude that the higher alkenone-SSTs during the LGM are reliable and reasonable. These warm SSTs were probably caused by radiative equilibrium associated with the development of stable water stratification in the Japan Sea during the LGM.

Sea surface temperature and age analysis from sediment core KT94-15_PC-9, XP98-PC-4 and XP98-PC-2

The Japan Sea experienced bottom water anoxia at the last glacial maximum (LGM) since it is surrounded by four shallow straits, the sill depths of which are close to, or shallower than, the drop in sea level (~120 m) that occurred then. A distinctive negative d18O excursion of planktonic foraminifera also took place during the LGM. This excursion has been interpreted from foraminiferal data as recording a drop in the paleosalinity of surface waters on the assumption of a constant low sea surface temperatures between 34 and 11 ka. We present here a profile of alkenone-based sea surface temperatures (alkenone-SSTs) over the past 36 kyr. Our results suggest that SSTs during the LGM were much higher than those previously assumed. After considering the factors that might affect estimation of alkenone-SSTs and comparisons of core-top alkenone-SSTs values with values for modern seawater we conclude that the higher alkenone-SSTs during the LGM are reliable and reasonable. These warm SSTs were probably caused by radiative equilibrium associated with the development of stable water stratification in the Japan Sea during the LGM.

Validación local de la temperatura superficial del mar del sensor MODIS en aguas someras del Mediterráneo occidental

La temperatura superficial del mar (SST) estimada a partir de los productos 11 μm diurnos y nocturnos y 4 μm nocturnos del sensor MODIS (Moderate Resolution Imaging Spectroradiometer) a bordo de la plataforma Aqua, han sido comparados con datos medidos in situ a tres profundidades diferentes (15, 50 y 100 cm) en una zona costera del Mediterráneo Occidental. Esta comparación ha permitido analizar la incertidumbre que existe en la estimación de este parámetro en aguas someras y próximas a la costa mediante imágenes de satélite de baja resolución espacial. Los resultados obtenidos demuestran que el producto diurno SST_11 μm, obtiene los estadísticos RMSE (error cuadrático medio) y r2 (coeficiente de correlación de Pearson) más ajustados con valores de 1°C y 0,96, respectivamente, para la profundidad 50 cm.

Mechanisms of drying of particulate slurries

The literature on the evaporation of pure liquid drops and the drying of drops of solutions and slurries has been reviewed with particular reference to spray drying. A 0.1-0.2 mm glass filament-thermocouple was constructed and used to study simultaneously, heat and mass transfer from a single suspended drop placed in a humidity and temperature controlled, 28 mm OD vertical wind tunnel. Heat conduction through the filament was minimised eg at 100¦C it accounted for only 9.3% of the total heat transferred to a drop. Evaporation of single water drops was also studied in a 101 mm OD vertical wind tunnel. The Nusselt number was found to be a function of the Reynolds, Prandtl and Transfer number over an air temperature range of 17¦C to 107¦C. The proposed correlation is: Nu = 2+(-12.96B+0.76)Re¦-5Pr0-33 Experimental drying studies were carried out on single suspended 1 to 2.5 mm diameter drops of aqueous sodium sulphate decahydrate, sodium chloride, potassium sulphate, copper sulphate and sodium acetate solutions and slurries at temperatures of 20¦C to 124¦C. Dried crusts were examined by Scanning Electron Microscopy. The drying history of any material depended upon the nature of the crust formed. Sodium acetate formed a non-rigid skin prior to the formation of a rigid crust. A modified receding evaporation interface model was proposed for the drying of solutions and slurries. This covered both the constant rate period prior to crust formation and the subsequent falling rate period. The model was solved numerically for the variation in core temperature, drop weight and crust thickness. Good agreement was obtained between model predictions and experimental results for materials forming rigid crusts i.e. sodium sulphate decahydrate, sodium chloride, potassium sulphate and copper sulphate. However, the drying histories of drops of 10-20% weight initial concentration sodium acetate were unpredictable since formation of a non-rigid skin deviated from the model assumption of a rigid outer surface. At higher initial concentrations (40% weight) where a rigid crust was formed for sodium acetate, good agreement was obtained between experimental results and model predictions. Single suspended drop studies are concluded to provide a valuable insight into the drying mechanisms of specific solutions and slurries.

Measurement of residual stress by load and depth sensing indentation with spherical indenters

A new experimental technique is presented for making measurements of biaxial residual stress using load and depth sensing indentation (nanoindentation). The technique is based on spherical indentation, which, in certain deformation regimes, can be much more sensitive to residual stress than indentation with sharp pyramidal indenters like the Berkovich. Two different methods of analysis were developed: one requiring an independent measure of the material's yield strength and the other a reference specimen in the unstressed state or other known reference condition. Experiments conducted on aluminum alloys to which controlled biaxial bending stresses were applied showed that the methods are capable of measuring the residual stress to within 10-20% of the specimen yield stress. Because the methods do not require imaging of the hardness impressions, they are potentially useful for making localized measurements of residual stress, as in thin films or small volumes, or for characterization of point-to-point spatial variations of the surface stress.

Performance analysis of polymer optical fibre based Fabry-Perot sensor formed by two uniform Bragg gratings

The stress sensitivity of polymer optical fibre (POF) based Fabry-Perot sensors formed by two uniform Bragg gratings with finite dimensions is investigated. POF has received high interest in recent years due to its different material properties compared to its silica counterpart. Biocompatibility, a higher failure strain and the highly elastic nature of POF are some of the main advantages. The much lower Young’s modulus of polymer materials compared to silica offers enhanced stress sensitivity to POF based sensors which renders them great candidates for acoustic wave receivers and any kind of force detection. The main drawback in POF technology is perhaps the high fibre loss. In a lossless fibre the sensitivity of an interferometer is proportional to its cavity length. However, the presence of the attenuation along the optical path can significantly reduce the finesse of the Fabry-Perot interferometer and it can negatively affect its sensitivity at some point. The reflectivity of the two gratings used to form the interferometer can be also reduced as the fibre loss increases. In this work, a numerical model is developed to study the performance of POF based Fabry-Perot sensors formed by two uniform Bragg gratings with finite dimensions. Various optical and physical properties are considered such as grating physical length, grating effective length which indicates the point where the light is effectively reflected, refractive index modulation of the grating, cavity length of the interferometer, attenuation and operating wavelength. Using this model, we are able to identify the regimes in which the PMMA based sensor offer enhanced stress sensitivity compared to silica based one.

Development of calix[4]arene-functionalized microcantilever array sensing system for the rapid, sensitive and simultaneous detection of metal ions in aqueous solutions

The work described in this thesis was conducted with the aim of: 1) investigating the binding capabilities of calix[4]arene-functionalized microcantilevers towards specific metal ions and 2) developing a new16-microcantilever array sensing system for the rapid, and simultaneous detection of metal ions in fresh water. Part I of this thesis reports on the use of three new bimodal calix[4]arenes (methoxy, ethoxy and crown) as potential host/guest sensing layers for detecting selected ions in dilute aqueous solutions using single microcantilever experimental system. In this work it was shown that modifying the upper rim of the calix[4]arenes with a thioacetate end group allow calix[4]arenes to self-assemble on Au(111) forming complete highly ordered monolayers. It was also found that incubating the microcantilevers coated with 5 nm of Inconel and 40 nm of Au for 1 h in a 1.0 M solution of calix[4]arene produced the highest sensitivity. Methoxy-functionalized microcantilevers showed a definite preference for Ca²⁺ ions over other cationic guests and were able to detect trace concentration as low as 10⁻¹² M in aqueous solutions. Microcantilevers modified with ethoxy calix[4]arene displayed their highest sensitivity towards Sr²⁺ and to a lesser extent Ca²⁺ ions. Crown calix[4]arene-modified microcantilevers were however found to bind selectively towards Cs⁺ ions. In addition, the counter anion was also found to contribute to the deflection. For example methoxy calix[4]arene-modified microcantilever was found to be more sensitive to CaCl₂ over other water-soluble calcium salts such as Ca(NO₃)₂ , CaBr₂ and CaI₂. These findings suggest that the response of calix[4]arene-modified microcantilevers should be attributed to the target ionic species as a whole instead of only considering the specific cation and/or anion. Part II presents the development of a 16-microcantilever sensor setup. The implementation of this system involved the creation of data analysis software that incorporates data from the motorized actuator and a two-axis photosensitive detector to obtain the deflection signal originating from each individual microcantilever in the array. The system was shown to be capable of simultaneous measurements of multiple microcantilevers with different coatings. A functionalization unit was also developed that allows four microcantilevers in the array to be coated with an individual sensing layer one at the time. Because of the variability of the spring constants of different cantilevers within the array, results presented were quoted in units of surface stress unit in order to compare values between the microcantilevers in the array.

Modelagem molecular voltada para a construção de um nanobiossensor para detecção do herbicida Imazaquin

In this study, our goal was develop and describe a molecular model of the enzyme-inhibiting interaction which can be used for an optimized projection of a Microscope Force Atomic nanobiosensor to detect pesticides molecules, used in agriculture, to evaluate its accordance with limit levels stipulated in valid legislation for its use. The studied herbicide (imazaquin) is a typical member of imidazolinone family and is an inhibitor of the enzymatic activity of Acetohydroxiacid Synthase (AHAS) enzyme that is responsible for the first step of pathway for the synthesis of side-chains in amino acids. The analysis of this enzyme property in the presence of its cofactors was made to obtain structural information and charge distribution of the molecular surface to evaluate its capacity of became immobilized on the Microscopy Atomic Force tip. The computational simulation of the system, using Molecular Dynamics, was possible with the force-field parameters for the cofactor and the herbicides obtained by the online tool SwissParam and it was implemented in force-field CHARMM27, used by software GROMACS; then appropriated simulations were made to validate the new parameters. The molecular orientation of the AHAS was defined based on electrostatic map and the availability of the herbicide in the active site. Steered Molecular Dynamics (SMD) Simulations, followed by quantum mechanics calculations for more representative frames, according to the sequential QM/MM methodology, in a specific direction of extraction of the herbicide from the active site. Therefore, external harmonic forces were applied with similar force constants of AFM cantilever for to simulate herbicide detection experiments by the proposed nanobiosensor. Force value of 1391 pN and binding energy of -14048.52 kJ mol-1 were calculated.

Highly NO2 sensitive caesium doped graphene oxide conductometric sensors

Here we report on the synthesis of caesium doped graphene oxide (GO-Cs) and its application to the development of a novel NO2 gas sensor. The GO, synthesized by oxidation of graphite through chemical treatment, was doped with Cs by thermal solid-state reaction. The samples, dispersed in DI water by sonication, have been drop-casted on standard interdigitated Pt electrodes. The response of both pristine and Cs doped GO to NO2 at room temperature is studied by varying the gas concentration. The developed GO-Cs sensor shows a higher response to NO2 than the pristine GO based sensor due to the oxygen functional groups. The detection limit measured with GO-Cs sensor is ≈90 ppb.

Size effect on the lattice parameter of KCl during mechanical milling

The size effect on the lattice parameter of ionic KCl nanocrystals was studied systematically during mechanical milling of Pure KCl powder under vacuum. The results suggest anomalous lattice expansion, with the lattice parameter increasing from 6.278 angstrom at d = 6 mu m to 6.30307 angstrom at d = 85 mn. The defects generated during ball milling of KCl and surface stress are deemed to be responsible for this lattice parameter expansion. (C) 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Towards the Use of Radar Winds in Numerical Weather Prediction

Numerical weather prediction (NWP) models provide the basis for weather forecasting by simulating the evolution of the atmospheric state. A good forecast requires that the initial state of the atmosphere is known accurately, and that the NWP model is a realistic representation of the atmosphere. Data assimilation methods are used to produce initial conditions for NWP models. The NWP model background field, typically a short-range forecast, is updated with observations in a statistically optimal way. The objective in this thesis has been to develope methods in order to allow data assimilation of Doppler radar radial wind observations. The work has been carried out in the High Resolution Limited Area Model (HIRLAM) 3-dimensional variational data assimilation framework. Observation modelling is a key element in exploiting indirect observations of the model variables. In the radar radial wind observation modelling, the vertical model wind profile is interpolated to the observation location, and the projection of the model wind vector on the radar pulse path is calculated. The vertical broadening of the radar pulse volume, and the bending of the radar pulse path due to atmospheric conditions are taken into account. Radar radial wind observations are modelled within observation errors which consist of instrumental, modelling, and representativeness errors. Systematic and random modelling errors can be minimized by accurate observation modelling. The impact of the random part of the instrumental and representativeness errors can be decreased by calculating spatial averages from the raw observations. Model experiments indicate that the spatial averaging clearly improves the fit of the radial wind observations to the model in terms of observation minus model background (OmB) standard deviation. Monitoring the quality of the observations is an important aspect, especially when a new observation type is introduced into a data assimilation system. Calculating the bias for radial wind observations in a conventional way can result in zero even in case there are systematic differences in the wind speed and/or direction. A bias estimation method designed for this observation type is introduced in the thesis. Doppler radar radial wind observation modelling, together with the bias estimation method, enables the exploitation of the radial wind observations also for NWP model validation. The one-month model experiments performed with the HIRLAM model versions differing only in a surface stress parameterization detail indicate that the use of radar wind observations in NWP model validation is very beneficial.

Kinetic approach to dislocation bending in low-mobility films

A kinetic model has been developed for dislocation bending at the growth surface in compressively stressed low-mobility films such as III-V nitrides. It is based on a reduction in the number of atoms at the growth surface. Stress and nonstress sources of driving force for such a reduction are discussed. A comparison between the derived equations and experimentally measured stress evolution data yields good agreement between the predicted and observed angles through which dislocations bend.