Development of new biomaterials based on liquid crystalline phases of cellulose derivatives

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do Grau de Mestre em Engenharia Biomédica

Evaluation of mechanical soft-abrasive blasting and chemical cleaning methods on alkyd-paint graffiti made on carbonate stones

In the context of this dissertation several studies were developed resulting in submission and publication “Evaluation of mechanical soft-abrasive blasting and chemical cleaning methods on alkyd-paint graffiti made on calcareous stones” to Journal of Cultural Heritage. (http://dx.doi.org/10.101 /j.culher.2014.10.004)

Micro/nano-structured superhydrophobic surfaces in the biomedical field: part I: basic concepts and biomimetic approaches.

Inspired by natural structures, great attention has been devoted to the study and development of surfaces with extreme wettable properties. The meticulous study of natural systems revealed that the micro/nano-topography of the surface is critical to obtaining unique wettability features, including superhydrophobicity. However, the surface chemistry also has an important role in such surface characteristics. As the interaction of biomaterials with the biological milieu occurs at the surface of the materials, it is expected that synthetic substrates with extreme and controllable wettability ranging from superhydrophilic to superhydrophobic regimes could bring about the possibility of new investigations of cellâ material interactions on nonconventional surfaces and the development of alternative devices with biomedical utility. This first part of the review will describe in detail how proteins and cells interact with micro/nano-structured surfaces exhibiting extreme wettabilities.

Basic Surface Properties of Mononuclear Cells from Didelphis marsupialis

The electrostatic surface charge and surface tension of mononuclear cells/monocytes obtained from young and adult marsupials (Didelphis marsupialis) were investigated by using cationized ferritin and colloidal iron hydroxyde, whole cell electrophoresis, and measurements of contact angles. Anionic sites were found distributed throughout the entire investigated cell surfaces. The results revealed that the anionic character of the cells is given by electrostatic charges corresponding to -18.8 mV (cells from young animals) and -29.3 mV (cells from adult animals). The surface electrostatic charge decreased from 10 to 65.2% after treatment of the cells with each one of trypsin, neuraminidase and phospholipase C. The hydrophobic nature of the mononuclear cell surfaces studied by using the contact angle method revealed that both young and adult cells possess cell surfaces of high hidrofilicity since the angles formed with drops of saline water were 42.5°and 40.8°, respectively. Treatment of the cells with trypsin or neuraminidase rendered their surfaces more hydrophobic, suggesting that sialic acid-containing glycoproteins are responsible for most of the hydrophilicity observed in the mononuclear cell surfaces from D. marsupialis.

Equilibrium of drops on inclined hydrophilic surfaces

Why does not gravity make drops slip down the inclined surfaces, e.g., plant leaves? The current explanation is based on the existence of surface inhomogeneities, which cause a sustaining force that pins the contact line. Following this theory, the drop remains in equilibrium until a critical value of the sustaining force is reached. We propose an alternative analysis, from the point of view of energy balance, for the particular case in which the drop leaves a liquid film behind. The critical angle of the inclined surface at which the drop slips down is predicted. This result does not depend explicitly on surface inhomogeneities, but only on the drop size and surface tensions. There is good agreement with experiments for contact angles below 90° where the formation of the film is expected, whereas for greater contact angles great discrepancies arise

Characterization of the surface hydrophobicity of filamentous fungi.

A method for the quantitative analysis of the hydrophobicity of the mycelial mat of filamentous fungi based on contact angle measurements is presented. It was tested for a range of fungi belonging to the classes of basidiomycetes, ascomycetes and deuteromycetes. The measured contact angles of the mycelial mats ranged between hydrophilic (<30 degrees) for the deuteromycetes Fusarium oxysporum Fo47 GUS1 and Trichoderma harzianum P1[pZEGA1] and hydrophobic (>60 degrees) for the ascomycete Cladosporium sp. DSE48.1b and the basidiomycetes Paxillus involutus WSL 37.7, Hebeloma crustiliniforme WSL 6.2, Suillus bovinus WSL 48.1 and Laccaria bicolor WSL 73.1. For some fungi, variations in the hydrophobicity of the mycelium depending on the growth medium, the physiological state and the exposure to water were distinguished.

Gravity-driven slug motion in capillary tubes

The velocity of a liquid slug falling in a capillary tube is lower than predicted for Poiseuille flow due to presence of menisci, whose shapes are determined by the complex interplay of capillary, viscous, and gravitational forces. Due to the presence of menisci, a capillary pressure proportional to surface curvature acts on the slug and streamlines are bent close to the interface, resulting in enhanced viscous dissipation at the wedges. To determine the origin of drag-force increase relative to Poiseuille flow, we compute the force resultant acting on the slug by integrating Navier-Stokes equations over the liquid volume. Invoking relationships from differential geometry we demonstrate that the additional drag is due to viscous forces only and that no capillary drag of hydrodynamic origin exists (i.e., due to hydrodynamic deformation of the interface). Requiring that the force resultant is zero, we derive scaling laws for the steady velocity in the limit of small capillary numbers by estimating the leading order viscous dissipation in the different regions of the slug (i.e., the unperturbed Poiseuille-like bulk, the static menisci close to the tube axis and the dynamic regions close to the contact lines). Considering both partial and complete wetting, we find that the relationship between dimensionless velocity and weight is, in general, nonlinear. Whereas the relationship obtained for complete-wetting conditions is found in agreement with the experimental data of Bico and Quere [J. Bico and D. Quere, J. Colloid Interface Sci. 243, 262 (2001)], the scaling law under partial-wetting conditions is validated by numerical simulations performed with the Volume of Fluid method. The simulated steady velocities agree with the behavior predicted by the theoretical scaling laws in presence and in absence of static contact angle hysteresis. The numerical simulations suggest that wedge-flow dissipation alone cannot account for the entire additional drag and that the non-Poiseuille dissipation in the static menisci (not considered in previous studies) has to be considered for large contact angles.

Membrane emulsification in preparation of single site catalyst

In the theory part the membrane emulsification was studied. Emulsions are used in many industrial areas. Traditionally emulsions are prepared by using high shear in rotor-stator systems or in high pressure homogenizer systems. In membrane emulsification two immiscible liquids are mixed by pressuring one liquid through the membrane into the other liquid. With this technique energy could be saved, more homogeneous droplets could be formed and the amount of surfactant could be decreased. Ziegler-Natta and single-site catalysts are used in olefin polymerization processes. Nowadays, these catalysts are prepared according to traditional mixing emulsification. More homogeneous catalyst particles that have narrower particle size distribution might be prepared with membrane emulsification. The aim of the experimental part was to examine the possibility to prepare single site polypropylene catalyst using membrane emulsification technique. Different membrane materials and solidification techniques of the emulsion were examined. Also the toluene-PFC phase diagram was successfully measured during this thesis work. This phase diagram was used for process optimization. The polytetrafluoroethylene membranes had the largest contact angles with toluene and also the biggest difference between the contact angles measured with PFC and toluene. Despite of the contact angle measurement results no significant difference was noticed between particles prepared using PTFE membrane or metal sinter. The particle size distributions of catalyst prepared in these tests were quite wide. This would probably be fixed by using a membrane with a more homogeneous pore size distribution. It is also possible that the solidification rate has an effect on the particle sizes and particle morphology. When polymeric membranes are compared PTFE is probably still the best material for the process as it had the best chemical durability.

Physical characteristics of oily spraying liquids and droplets formed on coffee leaves and glass surfaces

The physical characteristics of a spray liquid are important in getting a good droplet formation and control efficiency over a particular target. As a function of these characteristics, it is possible to decipher which is the best adjuvant based on the respective concentration used during the spray. Therefore, ten spraying liquids were prepared, which varied in concentrations of pesticide lufenuron + profenofos, mineral oil, water and manganese sulfate. Pendant droplets formed from these mixtures were measured to examine their impact on surface tension. Droplets were applied to the surface of coffee leaves and the surface tension, contact angle formed and the leaf area wetted by the droplet, were measured. A smooth glass surface was taken as a comparative to the coffee leaves. The highest concentrations of oil resulted in lower surface tension, smaller contact angles of droplets on leaf surfaces and larger areas wetted by the droplets. Both surfaces showed hydrophilic behavior.

Synthese von Azobenzolderivaten zur Darstellung photoschaltbarer, selbstorganisierter Monolagen

Im Vordergrund dieser Arbeit stehen die Synthesen des Azobenzol-4-trichlorsilans sowie des Bis(4-azobenzol)disulfids, ausgehend von einfachen und kommerziell erhältlichen Verbindungen. Moleküle, aus denen sich diese Verbindungen synthetisieren lassen, sind die Iodderivate des Azobenzols, welche über die Kondensation von Benzolaminen (Anilinen) und Nitrosobenzolen dargestellt wurden, aber auch über die altbewährte Azokupplung. Insgesamt wurden 19 neue Azobenzolderivate, das neue [(4-Aminophenyl)ethinyl]ferrocen und das neue Bis[4-(4'-bromazobenzol)]disulfid synthetisiert und charakterisiert. Außerdem wurden 13 neue Kristallstrukturen erzeugt. Mit den synthetisierten Molekülen wurden Substrat-Adsorbat-Systeme gebildet. Als Substrate wurden oberflächenoxidiertes Silizium und Gold gewählt. Die Präparation dieser sogennanten selbstorganisierten Monolagen (SAMs) bzw. der kovalent gebundenen Monolagen im Falle der Trichlorsilylderivate (CAMs) wurde eingehend studiert. Das Azobenzol wurde als photoschaltbare Einheit gewählt, da es bereits Kern zahlreicher Untersuchungen war und als solcher als guter und zuverlässiger Baustein für reversible photoschaltbare Systeme etabliert ist. Zur Charakterisierung Schichten und zur Untersuchung ihres photoresponsiven Verhaltens sowie sowie zur Untersuchung der Schichtbildung selbst wurden mehrere physikalische Messmethoden angewandt. Die Schichtbildung wurde mit SHG (optische Frequenzverdopplung) verfolgt, die fertigen Schichten wurden mit XPS (Röntgen-Photonen-Spektroskopie) und NEXAFS (Nahkanten-Röntgen-Absorptions-Feinstruktur) untersucht, um Orientierung und Ordnung der Moleküle in der Schicht zu ermitteln. Das Schaltverhalten wurde mit Ellipsometrie und durch Messungen des Wasserkontaktwinkels beobachtet. Durch Variation der Endgruppe des Azobenzols ist es möglich, die Oberflächeneigenschaften einstellen gezielt zu können, wie Hydrophobie, Hydrophilie, Komplexierungsverhalten oder elektrische Schaltbarkeit. Dies gelingt durch Gruppen wie N,N-Dimethylamino-, Methoxy-, Ethoxy-, Octyloxy-, Dodecyloxy-, Benzyloxy-, Methyl-, Trifluormethyl-, Pyridyl-, Phenylethinyl- und Ferrocenyl-Restgruppen, um nur eine Auswahl zu nennen. Einerseits wurde Silizium als Substrat gewählt, da es wegen seiner Verwendung in der Halbleiterindustrie ein nicht uninteressantes Substrat darstell und die Möglichkeiten der kovalenten Anbindung von Trichlorsilanen aber auch Trialkoxysilanen auch gut untersucht ist. Andererseits wurden auch Untersuchungen mit Gold als Substrat angestellt, bei dem Thiole und Disulfide die bevorzugten Ankergruppen bilden. Während sich auf Gold sogenannte SAMs bilden, verleiht die kovalente Siloxanbindung den CAMs auf Silizium eine besondere Stabilität.

Modification and Analysis of Group-13-Nitride Semiconductor Surfaces: Influence of Adsorbates on Device Characteristics and Processing

Im Rahmen dieser interdisziplinären Doktorarbeit wird eine (Al)GaN Halbleiteroberflächenmodifikation untersucht, mit dem Ziel eine verbesserte Grenzfläche zwischen dem Material und dem Dielektrikum zu erzeugen. Aufgrund von Oberflächenzuständen zeigen GaN basierte HEMT Strukturen üblicherweise große Einsatzspannungsverschiebungen. Bisher wurden zur Grenzflächenmodifikation besonders die Entfernung von Verunreinigungen wie Sauerstoff oder Kohlenstoff analysiert. Die nasschemischen Oberflächenbehandlungen werden vor der Abscheidung des Dielektrikums durchgeführt, wobei die Kontaminationen jedoch nicht vollständig entfernt werden können. In dieser Arbeit werden Modifikationen der Oberfläche in wässrigen Lösungen, in Gasen sowie in Plasma analysiert. Detaillierte Untersuchungen zeigen, dass die inerte (0001) c-Ebene der Oberfläche kaum reagiert, sondern hauptsächlich die weniger polaren r- und m- Ebenen. Dies kann deutlich beim Defektätzen sowie bei der thermischen Oxidation beobachtet werden. Einen weiteren Ansatz zur Oberflächenmodifikation stellen Plasmabehandlungen dar. Hierbei wird die Oberflächenterminierung durch eine nukleophile Substitution mit Lewis Basen, wie Fluorid, Chlorid oder Oxid verändert, wodurch sich die Elektronegativitätsdifferenz zwischen dem Metall und dem Anion im Vergleich zur Metall-Stickstoff Bindung erhöht. Dies führt gleichzeitig zu einer Erhöhung der Potentialdifferenz des Schottky Kontakts. Sauerstoff oder Fluor besitzen die nötige thermische Stabilität um während einer Silicium-nitridabscheidung an der (Al)GaN Oberfläche zu bleiben. Sauerstoffvariationen an der Oberfläche werden in NH3 bei 700°C, welches die nötigen Bedingungen für die Abscheidung darstellen, immer zu etwa 6-8% reduziert – solche Grenzflächen zeigen deswegen auch keine veränderten Ergebnisse in Einsatzspannungsuntersuchungen. Im Gegensatz dazu zeigt die fluorierte Oberfläche ein völlig neues elektrisches Verhalten: ein neuer dominanter Oberflächendonator mit einem schnellen Trapping und Detrapping Verhalten wird gefunden. Das Energieniveau dieses neuen, stabilen Donators liegt um ca. 0,5 eV tiefer in der Bandlücke als die ursprünglichen Energieniveaus der Oberflächenzustände. Physikalisch-chemische Oberflächen- und Grenzflächenuntersuchung mit XPS, AES oder SIMS erlauben keine eindeutige Schlussfolgerung, ob das Fluor nach der Si3N4 Abscheidung tatsächlich noch an der Grenzfläche vorhanden ist, oder einfach eine stabilere Oberflächenrekonstruktion induziert wurde, bei welcher es selbst nicht beteiligt ist. In beiden Fällen ist der neue Donator in einer Konzentration von 4x1013 at/cm-2 vorhanden. Diese Dichte entspricht einer Oberflächenkonzentration von etwa 1%, was genau an der Nachweisgrenze der spektroskopischen Methoden liegt. Jedoch werden die elektrischen Oberflächeneigenschaften durch die Oberflächenmodifikation deutlich verändert und ermöglichen eine potentiell weiter optimierbare Grenzfläche.

Termination of diamond surfaces with hydrogen, oxygen and fluorine using a small, simple plasma gun

We have formed and characterized polycrystalline diamond films with surfaces having hydrogen terminations, oxygen terminations, or fluorine terminations, using a small, simple and novel plasma gun to bombard the diamond surface, formed by plasma assisted CVD in a prior step, with ions of the wanted terminating species. The potential differences between surface regions with different terminations were measured by Kelvin Force Microscopy (KFM). The highest potential occurred for oxygen termination regions and the lowest for fluorine. The potential difference between regions with oxygen terminations and hydrogen terminations was about 80 mV, and between regions with hydrogen terminations and fluorine terminations about 150 mV. Regions with different terminations were identified and imaged using the secondary electron signal provided by scanning electron microscopy (SEM). since this signal presents contrast for surfaces with different electrical properties. The wettability of the surfaces with different terminations was evaluated, measuring contact angles. The sample with oxygen termination was the most hydrophilic, with a contact angle of 75 degrees. hydrogen-terminated regions with 83 degrees, and fluorine regions 93 degrees, the most hydrophobic sample. (C) 2010 Elsevier B.V. All rights reserved.

Estudo da molhabilidade de ligas de adição à base de prata sobre insertos cerâmicos para aplicação em brocas perfuração de poços de petróleo

Metal-ceramic interfaces are present in tricone drill bits with hard ceramic inserts for oil well drilling operations. The combination of actions of cutting, crushing and breaking up of rocks results in the degradation of tricone drill bits by wear, total or partial rupture of the drill bit body or the ceramic inserts, thermal shock and corrosion. Also the improper pressfitting of the ceramic inserts on the bit body may cause its total detachment, and promote serious damages to the drill bit. The improvement on the production process of metal-ceramic interfaces can eliminate or minimize some of above-mentioned failures presented in tricone drill bits, optimizing their lifetime and so reducing drilling metric cost. Brazing is a widely established technique to join metal-ceramic materials, and may be an excellent alternative to the common mechanical press fitting process of hard ceramic inserts on the steel bit body for tricone drill bit. Wetting phenomena plays an essential role in the production of metal/ceramic interfaces when a liquid phase is present in the process. In this work, 72Silver-28Copper eutectic based brazing alloys were melted onto zirconia, silicon nitride and tungsten carbide/Co substrates under high vacuum. Contact angle evolution was measured and graphically plotted, and the interfaces produced were analysed by SEM-EDX. The AgCu eutectic alloy did not wet any ceramic substrates, showing high contact angles, and so without chemical interaction between the materials. Better results were found for the systemns containing 3%wt of titanium in the AgCu alloy. The presence os titanium as a solute in the alloy produces wettable cand termodinamically stable compounds, increasing the ceramics wetting beahviour

Mecanismos de desgaste de poliuretano em ensaios de microabrasão

Wear mechanisms and thermal history of two non-conforming sliding surfaces was investigated in laboratory. A micro-abrasion testing setup was used but the traditional rotative sphere method was substituted by a cylindrical surface of revolution which included seven sharp angles varying between 15o to 180o. The micro-abrasion tests lead to the investigation on the polyurethane response at different contact pressures. For these turned counterfaces with and without heat treatment. Normal load and sliding speeds were changed. The sliding distance was fixed at 5 km in each test. The room and contact temperatures were measured during the tests. The polyurethane was characterized using tensile testing, hardness Shore A measurement, Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC) and Thermomechanical Analyze (TMA). The Vickers micro-hardness of the steel was measured before and after the heat treatment and the metallographic characterization was also carried out. Worn surface of polyurethane was analysed using Scanning Electron Microscope (SEM) and EDS (Electron Diffraction Scanning) microanalyses. Single pass scratch testing in polyurethane using indenters with different contact angles was also carried out. The scar morphology of the wear, the wear mechanism and the thermal response were analyzed in order to correlate the conditions imposed by the pressure-velocity pair to the materials in contact. Eight different wear mechanisms were identified on the polyurethane surface. It was found correlation between the temperature variation and the wear scar morphology.

Tensão superficial dinâmica e ângulo de contato de soluções aquosas com surfatantes em superfícies artificiais e naturais

O trabalho objetivou avaliar o efeito de surfatantes em soluções aquosas sobre a tensão superficial dinâmica e ângulo de contato das gotas em diferentes superfícies: artificiais (lâmina de vidro e de óxido de alumínio) e naturais (superfícies adaxiais de folhas de Euphorbia heterophylla, Ipomoea grandifolia e Brachiaria plantaginea). Seis formulações de surfatantes (Antideriva®; Uno®; Pronto 3®; Li-700®; Supersil® e Silwet L-77®), respectivamente nas doses recomendadas do produto comercial (0,050; 0,025; 0,100; 0,250; 0,100 e 0,100 % v v-1) e o dobro delas, foram avaliadas em soluções aquosas. A tensão superficial dinâmica e o ângulo de contato formado sobre as superfícies naturais foram medidos por tensiômetro. Os ângulos de contato formados pelas gotas nas superfícies artificiais foram obtidos por análise de imagens capturadas por uma câmera digital. Os surfatantes influenciam nas propriedades físico-químicas de soluções aquosas. As soluções contendo os surfatantes Silwet L-77® e Supersil®; nas doses de 0,100 e 0,200% v v-1; proporcionaram maiores reduções na tensão superficial dinâmica e menores ângulos de contato das gotas sobre as superfícies artificiais e naturais. Os surfatantes organossiliconados em solução aquosa foram mais eficientes na redução da tensão superficial e proporcionaram maior molhamento de superfícies natural e artificial. em alvos naturais, essas propriedades obtidas com organossiliconados são dependentes das características de superfície das espécies vegetais.