Coupling of magnetic, strain and electric polarization fields in the structure of multiferroic material

The comprehensive study on the coupling of magnetism, electrical polarization and the crystalline lattice with the off-stoichiometric effects in self-doped multiferroic hexagonal h-LuMnxO3±δ (0.92≤x≤1.12) ceramic oxides was carried out for the PhD work. There is a complex coupling of the three ferroic degrees. The cancelation of the magnetic moments of ions in the antiferromagnetic order, electric polarization with specific vortex/antivortex topology and lattice properties have pushed researchers to find out ways to disclose the underlying physics and chemistry of magneto-electric and magneto-elastic couplings of h-RMnO3 multiferroic materials. In this research work, self-doping of Lu-sites or Mn-sites of h-LuMnxO3±δ ceramics prepared via solid state route was done to pave a way for deeper understanding of the antiferromagnetic transition, the weak ferromagnetism often reported in the same crystalline lattices and the ferroelectric properties coupled to the imposed lattice changes. Accordingly to the aim of the PhD thesis, the objectives set for the sintering study in the first chapter on experimental results were two. First, study of sintering off-stoichiometric samples within conditions reported in the bibliography and also extracted from the phase diagrams of the LuMnxO3±δ, with a multiple firings ending with a last high temperature step at 1300ºC for 24 hours. Second, explore longer annealing times of up to 240 hours at the fixed temperature of 1300 ºC in a search for improving the properties of the solid solution under study. All series of LuMnxO3±δ ceramics for each annealing time were characterized to tentatively build a framework enabling comparison of measured properties with results of others available in literature. XRD and Rietveld refinement of data give the evolution the lattice parameters as a function to x. Shrinkage of the lattice parameters with increasing x values was observed, the stability limit of the solid solution being determined by analysis of lattice parameters. The evolution of grain size and presence of secondary phases have been investigated by means of TEM, SEM, EDS and EBSD techniques. The dependencies of grain growth and regression of secondary phases on composition x and time were further characterized. Magnetic susceptibility of samples and magnetic irreversibility were extensively examined in the present work. The dependency of magnetic susceptibility, Neel ordering transition and important magnetic parameters are determined and compared to observation in other multiferroics in the following chapter of the thesis. As a tool of high sensitivity to detect minor traces of the secondary phase hausmannite, magnetic measurements are suggested for cross-checking of phase diagrams. Difficulty of previous studies on interpreting the magnetic anomaly below 43 K in h-RMnO3 oxides was discussed and assigned to the Mn3O4 phase, with supported of the electron microscopy. Magneto-electric coupling where AFM ordering is coupled to dielectric polarization is investigated as a function of x and of sintering condition via frequency and temperature dependent complex dielectric constant measurements in the final chapter of the thesis. Within the limits of solid solubility, the crystalline lattice of off-stoichiometric ceramics was shown to preserve the magneto-electric coupling at TN. It represents the first research work on magneto-electric coupling modified by vacancy doping to author’s knowledge. Studied lattices would reveal distortions at the atomic scale imposed by local changes of x dependent on sintering conditions which were widely inspected by using TEM/STEM methods, complemented with EDS and EELS spectroscopy all together to provide comprehensive information on cross coupling of distortions, inhomogeneity and electronic structure assembled and discussed in a specific chapter. Internal interfaces inside crystalline grains were examined. Qualitative explanations of the measured magnetic and ferroelectric properties were established in relation to observed nanoscale features of h-LuMnxO3±δ ceramics. Ferroelectric domains and topological defects are displayed both in TEM and AFM/PFM images, the later technique being used to look at size, distribution and switching of ferroelectric domains influenced by vacancy doping at the micron scale bridging to complementary TEM studies on the atomic structure of ferroelectric domains. In support to experimental study, DFT simulations using Wien2K code have been carried out in order to interpret the results of EELS spectra of O K-edge and to obtain information on the cation hybridization to oxygen ions. The L3,2 edges of Mn is used to access the oxidation state of the Mn ions inside crystalline grains. In addition, rehybridization driven ferroelectricity is also evaluated by comparing the partial density of states of the orbitals of all ions of the samples, also the polarization was calculated and correlated to the off-stoichiometric effect.

Development of computer application for determination of chemical diffusion properties in biological tissues

The main objective of this work was to develop an application capable of determining the diffusion times and diffusion coefficients of optical clearing agents and water inside a known type of muscle. Different types of chemical agents can also be used with the method implemented, such as medications or metabolic products. Since the diffusion times can be calculated, it is possible to describe the dehydration mechanism that occurs in the muscle. The calculation of the diffusion time of an optical clearing agent allows to characterize the refractive index matching mechanism of optical clearing. By using both the diffusion times and diffusion of water and clearing agents not only the optical clearing mechanisms are characterized, but also information about optical clearing effect duration and magnitude is obtained. Such information is crucial to plan a clinical intervention in cooperation with optical clearing. The experimental method and equations implemented in the developed application are described in throughout this document, demonstrating its effectiveness. The application was developed in MATLAB code, but the method was personalized so it better fits the application needs. This process significantly improved the processing efficiency, reduced the time to obtain he results, multiple validations prevents common errors and some extra functionalities were added such as saving application progress or export information in different formats. Tests were made using glucose measurements in muscle. Some of the data, for testing purposes, was also intentionally changed in order to obtain different simulations and results from the application. The entire project was validated by comparing the calculated results with the ones found in literature, which are also described in this document.

A graph-based hyper heuristic for timetabling problems

This paper presents an investigation of a simple generic hyper-heuristic approach upon a set of widely used constructive heuristics (graph coloring heuristics) in timetabling. Within the hyperheuristic framework, a Tabu Search approach is employed to search for permutations of graph heuristics which are used for constructing timetables in exam and course timetabling problems. This underpins a multi-stage hyper-heuristic where the Tabu Search employs permutations upon a different number of graph heuristics in two stages. We study this graph-based hyper-heuristic approach within the context of exploring fundamental issues concerning the search space of the hyper-heuristic (the heuristic space) and the solution space. Such issues have not been addressed in other hyper-heuristic research. These approaches are tested on both exam and course benchmark timetabling problems and are compared with the fine-tuned bespoke state-of-the-art approaches. The results are within the range of the best results reported in the literature. The approach described here represents a significantly more generally applicable approach than the current state of the art in the literature. Future work will extend this hyper-heuristic framework by employing methodologies which are applicable on a wider range of timetabling and scheduling problems.

King of the Renaissance: Art and Politics at the Neapolitan Court of Ferrante I, 1458-1494

In the second half of the fifteenth century, King Ferrante I of Naples (r. 1458-1494) dominated the political and cultural life of the Mediterranean world. His court was home to artists, writers, musicians, and ambassadors from England to Egypt and everywhere in between. Yet, despite its historical importance, Ferrante’s court has been neglected in the scholarship. This dissertation provides a long-overdue analysis of Ferrante’s artistic patronage and attempts to explicate the king’s specific role in the process of art production at the Neapolitan court, as well as the experiences of artists employed therein. By situating Ferrante and the material culture of his court within the broader discourse of Early Modern art history for the first time, my project broadens our understanding of the function of art in Early Modern Europe. I demonstrate that, contrary to traditional assumptions, King Ferrante was a sophisticated patron of the visual arts whose political circumstances and shifting alliances were the most influential factors contributing to his artistic patronage. Unlike his father, Alfonso the Magnanimous, whose court was dominated by artists and courtiers from Spain, France, and elsewhere, Ferrante differentiated himself as a truly Neapolitan king. Yet Ferrante’s court was by no means provincial. His residence, the Castel Nuovo in Naples, became the physical embodiment of his commercial and political network, revealing the accretion of local and foreign visual vocabularies that characterizes Neapolitan visual culture.

Las novelas de la nebulosa y lo ominoso

[es] El concepto freudiano de Das Unheimliche, «lo ominoso», también conocido en español como «lo siniestro», es un fenómeno complejo del inconsciente de la psique humana. Comprende el inquietante momento de inseguridad al ver la inesperada metamorfosis de lo familiar y conocido en otra cosa. Este fenómeno no solo se evidencia en la vida real, sino también con mucha frecuencia en el arte y la literatura. Un escritor cuya creación ofrece un excelente ejemplo para estudiar la presencia de las teorías freudianas, en especial la de lo ominoso en la literatura, es el autor vanguardista español Ramón Gómez de la Serna. El escritor usó a menudo la técnica de impresión de lo siniestro en las novelas de la nebulosa: El incongruente (1922), El novelista (1923), ¡Rebeca! (1936) y El hombre perdido (1947). [en] The Freudian concept of the uncanny is a phenomenon as complex as interesting of the unconscious of the human psyche which comprises the disturbing moment of insecurity of seeing the unexpected metamorphosis of the familiar and known to the unknown. This phenomenon is evident not only in real life, but very often in art and literature. A writer whose creation provides an excellent example for the presence of Freud’s theories, especially the uncanny in the literature, is the avant-garde Spanish author Ramón Gómez de la Serna. The writer often used the impression of uncanny; a trend that stands in the novels of the nebula, which are rich in uncanny themes: El incongruente (1922), El novelista (1923), ¡Rebeca! (1936) and El hombre perdido (1947).

A graph-based hyper heuristic for timetabling problems

This paper presents an investigation of a simple generic hyper-heuristic approach upon a set of widely used constructive heuristics (graph coloring heuristics) in timetabling. Within the hyperheuristic framework, a Tabu Search approach is employed to search for permutations of graph heuristics which are used for constructing timetables in exam and course timetabling problems. This underpins a multi-stage hyper-heuristic where the Tabu Search employs permutations upon a different number of graph heuristics in two stages. We study this graph-based hyper-heuristic approach within the context of exploring fundamental issues concerning the search space of the hyper-heuristic (the heuristic space) and the solution space. Such issues have not been addressed in other hyper-heuristic research. These approaches are tested on both exam and course benchmark timetabling problems and are compared with the fine-tuned bespoke state-of-the-art approaches. The results are within the range of the best results reported in the literature. The approach described here represents a significantly more generally applicable approach than the current state of the art in the literature. Future work will extend this hyper-heuristic framework by employing methodologies which are applicable on a wider range of timetabling and scheduling problems.

Up-Link/Down-Link capacity Unbalance analysis in UMTS using a GIS based Planning Tool and MATLAB simulation

Capacity analysis using simulation is not a new thing in literature. Most of the development process of UMTS standardization have used simulation tools; however, we thing that the use of GIS planning tools and matrix manipulation capacity of MATLAB can show us different scenarios and make a more realistic analysis. Some work is been doing in COST 273 in order to have more realistic scenarios for UMTS planning. Our work initially was centered in uplink analysis, but we are now working in downlink analysis, specifically in two areas: capacity in number of users for RT and NRT services, and Node B power. In this work we will show results for up-link capacity and some results for downlink capacity and BS power consumption.

Sparse Signal Representation in Digital and Biological Systems

Theories of sparse signal representation, wherein a signal is decomposed as the sum of a small number of constituent elements, play increasing roles in both mathematical signal processing and neuroscience. This happens despite the differences between signal models in the two domains. After reviewing preliminary material on sparse signal models, I use work on compressed sensing for the electron tomography of biological structures as a target for exploring the efficacy of sparse signal reconstruction in a challenging application domain. My research in this area addresses a topic of keen interest to the biological microscopy community, and has resulted in the development of tomographic reconstruction software which is competitive with the state of the art in its field. Moving from the linear signal domain into the nonlinear dynamics of neural encoding, I explain the sparse coding hypothesis in neuroscience and its relationship with olfaction in locusts. I implement a numerical ODE model of the activity of neural populations responsible for sparse odor coding in locusts as part of a project involving offset spiking in the Kenyon cells. I also explain the validation procedures we have devised to help assess the model's similarity to the biology. The thesis concludes with the development of a new, simplified model of locust olfactory network activity, which seeks with some success to explain statistical properties of the sparse coding processes carried out in the network.

Changes in catches and biological characteristics of Nile tilapia (Oreochromis niloticus Linnaeus) in Lake Wamala (Uganda) under changing climatic conditions

There have been changes in catches and biological characteristics of the Nile Tilapia, Oreochromis niloticus (Linnaeus) in Lake Wamala (Uganda) since its introduction and establishment, but the factors which have contributed to these changes are not adequately understood. This study examined changes in catches and biological characteristics of Nile tilapia in relation to changes in temperature, rainfall and lake depth to provide an understanding of the role of changing climatic conditions. There was an increase in minimum, maximum and average temperature since 1980, but only minimum (0.021ºCyr-1) and average (0.018ºCyr-1) showed a significant trend (p < 0.05). Rainfall increased by 8.25 mmyr-1 since 1950 and accounted for 79.5% of the water input into the lake while evaporation accounted for 86.2% of the water loss from the lake. The lake depth was above 4 m during the years rainfall was above normal average of 1180 mm, except during the period 2011-2014. The contribution of Nile tilapia to total catch and CPUE changed with rainfall and lake depth up to 2000, after which they decreased despite increase in rainfall. There was a strong positive correlation between lake depth and average total length of Nile tilapia (r = 0.991, p < 0.001) and length at 50% maturity (r = 0.726, p < 0.001). The length-weight allometry between high and low lake depths was significantly different [t (6) = 3.225, p < 0.05], with Nile tilapia being heavier (for a given length) at high lake depth than at low lake depth. Fecundity of Nile tilapia was higher and egg diameter lower than what is reported in literature. Nile tilapia shifted from algal dominated diet during the wet season to include more insects during the dry season. The study showed that the catches and biological characteristics of Nile tilapia change with climate and hydrological factors and these need to be considered in management of the fisheries of Lake Wamala.

Evaluation and FMEA of Fabrication Techniques for Metallic Grating Couplers on Polymer Substrates with Low Glass Transition Temperatures

The main task is to analyze the state of the art of grating couplers production and low-cost polymer substrates. Then to provide a recommendation of a new or adapted process for the production of metallic gratings on polymer sheets, based on a Failure Mode and Effect Analysis (FMEA). In order to achieve that, this thesis is divided into four chapters. After the first introductory chapter, the second section provides details about the state-of-the-art in optical technology platforms with focus on polymers and their main features for the aimed application, such as flexibility, low cost and roll to roll compatibility. It defines then the diffraction gratings and their specifications and closes with the explanation of adhesion mechanisms of inorganic materials on polymer substrates. The third chapter discusses processing of grating couplers. It introduces the basic fabrication methods and details a selection of current fabrication schemes found in literature with an assessment of their potential use for the desired application. The last chapter is a FMEA analysis of the retained fabrication process, called Flip and Fuse, in order to check its capability to realize the grating structure.

An investigation of the clinical utility of preoperative cardiopulmonary exercise testing in patients undergoing major pancreatic surgery

Pancreaticoduodenectomy with or without adjuvant chemotherapy remains the only modality of possible cure in patients with cancer involving the head of the pancreas and the periampullary region. While mortality rates after pancreaticoduodenectomy have improved considerably over the course of the last century, morbidity remains high. Patient selection is of paramount importance in ensuring that major surgery is offered to individuals who will most benefit from a pancreaticoduodenectomy. Moreover, identifying preoperative risk factors provides potential targets for prehabilitation and optimisation of the patient's physiology before undertaking surgery. In addition to this, early identification of patients who are likely to develop postoperative complications allows for better allocation of critical care resources and more aggressive management high risk patients. Cardiopulmonary exercise testing is becoming an increasingly popular tool in the preoperative risk assessment of the surgical patient. However, very little work has been done to investigate the role of cardiopulmonary exercise testing in predicting complications after pancreaticoduodenectomy. The impact of jaundice, systemic inflammation and other preoperative clinicopathological characteristics on cardiopulmonary exercise physiology has not been studied in detail before in this cohort of patients. The overall aim of the thesis was to examine the relationships between preoperative clinico-pathological characteristics including cardiopulmonary exercise physiology, obstructive jaundice, body composition and systemic inflammation and complications and the post-surgical systemic inflammatory response in patients undergoing pancreaticoduodenectomy. Chapter 1 reviews the existing literature on preoperative cardiopulmonary exercise testing, the impact of obstructive jaundice, perioperative systemic inflammation and the importance of body composition in determining outcomes in patients undergoing major surgery with particular reference to pancreatic surgery. Chapter 2 reports on the role of cardiopulmonary exercise testing in predicting postoperative complications after pancreaticoduodenectomy. The results demonstrate that patients with V˙O2AT less than 10 ml/kg/min are more likely to develop a postoperative pancreatic fistula, stay longer in hospital and less likely to receive adjuvant therapy. These results emphasise the importance of aerobic fitness to recover from the operative stress of major surgery without significant morbidity. Cardiopulmonary exercise testing may prove useful in selecting patients for intensive prehabilitation programmes as well as for other optimisation measures to prepare them for major surgery. Chapter 3 evaluates the relationship between cardiopulmonary exercise physiology and other clinicopathological characteristics of the patient. A detailed analysis of cardiopulmonary exercise test parameters in jaundiced versus non-jaundiced patients demonstrates that obstructive jaundice does not impair cardiopulmonary exercise physiology. This further supports emerging evidence in contemporary literature that jaundiced patients can proceed directly to surgery without preoperative biliary drainage. The results of this study also show an interesting inverse relationship between body mass index and anaerobic threshold which is analysed in more detail in Chapter 4. Chapter 4 examines the relationship between preoperative cardiopulmonary exercise physiology and body composition in depth. All parameters measured at cardiopulmonary exercise test are compared against body composition and body mass index. The results of this chapter report that the current method of reporting V˙O2, both at peak exercise and anaerobic threshold, is biased against obese subjects and advises caution in the interpretation of cardiopulmonary exercise test results in patients with a high BMI. This is particularly important as current evidence in literature suggests that postoperative outcomes in obese subjects are comparable to non-obese subjects while cardiopulmonary exercise test results are also abnormally low in this very same cohort of patients. Chapter 5 analyses the relationship between preoperative clinico-pathological characteristics including systemic inflammation and the magnitude of the postoperative systemic inflammatory response. Obstructive jaundice appears to have an immunosuppressive effect while elevated preoperative CRP and hypoalbuminemia appear to have opposite effects with hypoalbuminemia resulting in a lower response while elevated CRP in the absence of hypoalbuminemia resulted in a greater postoperative systemic inflammatory response. Chapter 6 evaluates the role of the early postoperative systemic inflammatory response in predicting complications after pancreaticoduodenectomy and aims to establish clinically relevant thresholds for C-Reactive Protein for the prediction of complications. The results of this chapter demonstrate that CRP levels as early as the second postoperative day are associated with complications. While post-operative CRP was useful in the prediction of infective complications, this was the case only in patients who did not develop a post-operative pancreatic fistula. The predictive ability of inflammatory markers for infectious complications was blunted in patients with a pancreatic fistula. Chapter 7 summarises the findings of this thesis, their place in current literature and future directions. The results of this thesis add to the current knowledge regarding the complex pathophysiological abnormalities in patients undergoing pancreaticoduodenectomy, with specific emphasis on the interaction between cardiopulmonary exercise physiology, obstructive jaundice, systemic inflammation and postoperative outcomes. The work presented in this thesis lays the foundations for further studies aimed at improving outcomes after pancreaticoduodenectomy through the development of individualised, goal-directed therapies that are initiated well before this morbid yet necessary operation is performed.

Uncertainties in projecting climate-change impacts in marine ecosystems

Projections of the impacts of climate change on marine ecosystems are a key prerequisite for the planning of adaptation strategies, yet they are inevitably associated with uncertainty. Identifying, quantifying, and communicating this uncertainty is key to both evaluating the risk associated with a projection and building confidence in its robustness. We review how uncertainties in such projections are handled in marine science. We employ an approach developed in climate modelling by breaking uncertainty down into (i) structural (model) uncertainty, (ii) initialization and internal variability uncertainty, (iii) parametric uncertainty, and (iv) scenario uncertainty. For each uncertainty type, we then examine the current state-of-the-art in assessing and quantifying its relative importance. We consider whether the marine scientific community has addressed these types of uncertainty sufficiently and highlight the opportunities and challenges associated with doing a better job. We find that even within a relatively small field such as marine science, there are substantial differences between subdisciplines in the degree of attention given to each type of uncertainty. We find that initialization uncertainty is rarely treated explicitly and reducing this type of uncertainty may deliver gains on the seasonal-to-decadal time-scale. We conclude that all parts of marine science could benefit from a greater exchange of ideas, particularly concerning such a universal problem such as the treatment of uncertainty. Finally, marine science should strive to reach the point where scenario uncertainty is the dominant uncertainty in our projections.

Pytanie o pamięć. Relacje autobiograficzne więźniów obozów koncentracyjnych

This book consists of two main parts. The first part offers a basic methodological introduction, presenting a concise but multifaceted overview of current problems of collective memory. The second part contains a set of interviews with former prisoners of concentration camps carried out by the authors. The research was conducted by Paweł Greń and Łukasz Posłuszny and focuses on issues of collective and cultural memory illustrated by individual life experiences of concentration camps prisoners. The field of oral history serves as the framework of analysis and narrative inquiry as its research tool. Interviews and additional research materials were collected by the authors and are not available in previous publications, making this work a precious supplement to the current scholarly body of knowledge and achievements in the discipline of memory studies. According to the authors, current historical and literary publications provide an incomplete picture of the WWII and its aftermaths for survivors, because descriptions of the war and imprisonment in the camp play still a dominate role in narratives. The importance of these issues in autobiographies is unquestionable and highly needed to create a common identity among generation of prisoners, though authors often wanted to perceive the fate of individuals in a broader perspective – including the periods before and after the war. Hence, interviews stressed personal experiences and their understanding over time by former prisoners. The interviews covered many topics on life before, during and after the camp – among them daily and neutral routines, but also difficult matters. The latter were connected on the one hand with traumatic events or harsh memories and emotions, and on the other hand with less extensively highlighted threads of prisoners’ lives - such as issues of the body and sexuality – and their dependence on particular representation or narrative. The authors are convinced that the book serves not only as a record of past remembered by eyewitnesses, but it also depicts their accounts in wider contexts and discourses, which expose specific dimensions of told and written stories. In the book Questions for Memory one examine the approach proposed by young scholars. Interviews were conducted from 2009-2011, seventy years after the end of the second world war, and this initiative was the result of questions and doubts of the authors from the existing literature. They also wanted to use the unique opportunity to meet with eyewitnesses and record their stories, because when they pass away we will irretrievably lose the possibility to listen to them and to pose sensitive questions. The majority of the interviewees were prisoners of KL Auschwitz-Birkenau, and their experiences differed greatly from each other based on social background and specific experience in the camps as well as their post-camp and postwar life. Aside from persons whose stories are already well known and open, readers will hear the stories of those who spoke only reluctantly and very rarely, or who had remained silent until the present author’s research. Qualitative differences between interviews occurred on the level of established relationship and atmosphere of trust, which varied according to circumstances and individual character and personality. For P. Greń and Ł. Posłuszny, each interviewed person is equally and highly valued due to the collected material and the personal experience of the meetings. Among the ten interviews placed in the book, seven of them are the stories told by women. Their testimonies exemplify realities of everyday prisoners’ existence and gravitate towards mirroring specifically feminine perspectives of imprisonment. For women, crucial problems stemmed from experiences of body that intertwine with suffering, feeling of shame and humiliation. Early discussions on holocaust literature and issues of representation that shaped the Polish narrative and collective memory imposed imperatives of silence on certain topics. A solution for reconciling heroic and inhuman deeds in stories with completely human physiology was impossible and improper for many years. There were also questions about life after, ways of dealing with a trauma or reflections on the present time. During conversations the authors attempted to come closer to something distant and incomprehensible for their generation and for people who did not experience the camps. Despite the fact that there have been seventy years of dealing with these events in literature, art, drama, film, memoirs and scientific works, the past still breeds more questions than answers. The book Questions for Memory serves as an example of this phenomenon.

Solid-liquid interactions in microscale structures and devices

Liquid-solid interactions become important as dimensions approach mciro/nano-scale. This dissertation focuses on liquid-solid interactions in two distinct applications: capillary driven self-assembly of thin foils into 3D structures, and droplet wetting of hydrophobic micropatterned surfaces. The phenomenon of self-assembly of complex structures is common in biological systems. Examples include self-assembly of proteins into macromolecular structures and self-assembly of lipid bilayer membranes. The principles governing this phenomenon have been applied to induce self-assembly of millimeter scale Si thin films into spherical and other 3D structures, which are then integrated into light-trapping photovoltaic (PV) devices. Motivated by this application, we present a generalized analytical study of the self-folding of thin plates into deterministic 3D shapes, through fluid-solid interactions, to be used as PV devices. This study consists of developing a model using beam theory, which incorporates the two competing components — a capillary force that promotes folding and the bending rigidity of the foil that resists folding into a 3D structure. Through an equivalence argument of thin foils of different geometry, an effective folding parameter, which uniquely characterizes the driving force for folding, has been identified. A criterion for spontaneous folding of an arbitrarily shaped 2D foil, based on the effective folding parameter, is thus established. Measurements from experiments using different materials and predictions from the model match well, validating the assumptions used in the analysis. As an alternative to the mechanics model approach, the minimization of the total free energy is employed to investigate the interactions between a fluid droplet and a flexible thin film. A 2D energy functional is proposed, comprising the surface energy of the fluid, bending energy of the thin film and gravitational energy of the fluid. Through simulations with Surface Evolver, the shapes of the droplet and the thin film at equilibrium are obtained. A critical thin film length necessary for complete enclosure of the fluid droplet, and hence successful self-assembly into a PV device, is determined and compared with the experimental results and mechanics model predictions. The results from the modeling and energy approaches and the experiments are all consistent. Superhydrophobic surfaces, which have unique properties including self-cleaning and water repelling are desired in many applications. One excellent example in nature is the lotus leaf. To fabricate these surfaces, well designed micro/nano- surface structures are often employed. In this research, we fabricate superhydrophobic micropatterned Polydimethylsiloxane (PDMS) surfaces composed of micropillars of various sizes and arrangements by means of soft lithography. Both anisotropic surfaces, consisting of parallel grooves and cylindrical pillars in rectangular lattices, and isotropic surfaces, consisting of cylindrical pillars in square and hexagonal lattices, are considered. A novel technique is proposed to image the contact line (CL) of the droplet on the hydrophobic surface. This technique provides a new approach to distinguish between partial and complete wetting. The contact area between droplet and microtextured surface is then measured for a droplet in the Cassie state, which is a state of partial wetting. The results show that although the droplet is in the Cassie state, the contact area does not necessarily follow Cassie model predictions. Moreover, the CL is not circular, and is affected by the micropatterns, in both isotropic and anisotropic cases. Thus, it is suggested that along with the contact angle — the typical parameter reported in literature quantifying wetting, the size and shape of the contact area should also be presented. This technique is employed to investigate the evolution of the CL on a hydrophobic micropatterned surface in the cases of: a single droplet impacting the micropatterned surface, two droplets coalescing on micropillars, and a receding droplet resting on the micropatterned surface. Another parameter which quantifies hydrophobicity is the contact angle hysteresis (CAH), which indicates the resistance of the surface to the sliding of a droplet with a given volume. The conventional methods of using advancing and receding angles or tilting stage to measure the resistance of the micropatterned surface are indirect, without mentioning the inaccuracy due to the discrete and stepwise motion of the CL on micropillars. A micronewton force sensor is utilized to directly measure the resisting force by dragging a droplet on a microtextured surface. Together with the proposed imaging technique, the evolution of the CL during sliding is also explored. It is found that, at the onset of sliding, the CL behaves as a linear elastic solid with a constant stiffness. Afterwards, the force first increases and then decreases and reaches a steady state, accompanied with periodic oscillations due to regular pinning and depinning of the CL. Both the maximum and steady state forces are primarily dependent on area fractions of the micropatterned surfaces in our experiment. The resisting force is found to be proportional to the number of pillars which pin the CL at the trailing edge, validating the assumption that the resistance mainly arises from the CL pinning at the trailing edge. In each pinning-and-depinning cycle during the steady state, the CL also shows linear elastic behavior but with a lower stiffness. The force variation and energy dissipation involved can also be determined. This novel method of measuring the resistance of the micropatterned surface elucidates the dependence on CL pinning and provides more insight into the mechanisms of CAH.

Degradation of compounds present in cork boiling water by gamma radiation

Cork boiling water is an aqueous and complex dark liquor with high concentration of phenolic compounds such as phenolic acids and tannins [1, 2], which are considered biorecalcitrants [2]. Ionizing radiation has been widely studied as an alternative technology for the degradation of organic contaminants without the addition of any other (e.g.: Fenton technologies). The aim of this work was to identify the compounds present in cork boiling water and further evaluate the resulting stable degradation products after gamma irradiation. The irradiation experiments of standard solutions were carried out at room temperature using a Co-60 experimental equipment. The applied absorbed doses were 20 and 50 kGy at a dose rate of 1.5 kGy/h, determined by routine dosimeters [3]. The identification of radiolytic products was carried out by HPLC-DAD-ESI/MS. The phenolic compounds were identified by comparing their retention times and UV–vis and mass spectra with those obtained from standard compounds, when available, as well as by comparing the obtained information with available data reported in the literature. Concerning the obtained results and the literature review, the main cork wastewater components are: quinic, gallic, protocatechuic, vanillic, syringic and ellagic acids. Based on this, we used protocatechuic, vanillic and syringic acids as model compounds to study their degradation by gamma radiation in order to identify the corresponding radiolytic products. Standard aqueous solutions were irradiated and the derivatives of each model compound are represented in figure 1. The obtained results seem to demonstrate that the derivatives of the parent compounds could also be phenolic acids, since it was observed the loss of 44 u (CO2) from the [M-H]- ions. Gallic and protocatechuic acids are identified as derivatives of vanillic and syringic acids, and gallic acid as a protocatechuic acid derivative. Compound 5 ([M-H]- at m/z 169) was tentatively identified as 2,4,6-trihydroxybenzoic acid, since its fragmentation pattern (m/z 151, 125 and 107) is similar to that previously reported in literature [4]. The structure of compound 7 was proposed based on the molecular ion and its fragmentation and compound 6 remains unknown.