Photoclickable surfaces for profluorescent covalent polymer coatings

The nitrile imine-mediated tetrazole-ene cycloaddition reaction (NITEC) is introduced as a powerful and versatile conjugation tool to covalently ligate macromolecules onto variable (bio)surfaces. The NITEC approach is initiated by UV irradiation and proceeds rapidly at ambient temperature yielding a highly fluorescent linkage. Initially, the formation of block copolymers by the NITEC methodology is studied to evidence its efficacy as a macromolecular conjugation tool. The grafting of polymers onto inorganic (silicon) and bioorganic (cellulose) surfaces is subsequently carried out employing the optimized reaction conditions obtained from the macromolecular ligation experiments and evidenced by surface characterization techniques, including X-ray photoelectron spectroscopy and FT-IR microscopy. In addition, the patterned immobilization of variable polymer chains onto profluorescent cellulose is achieved through a simple masking process during the irradiation. Photoinduced nitrile imine-alkene 1,3-dipolar cycloaddition (NITEC) is employed to covalently bind well-defined polymers onto silicon oxide or cellulose. A diaryl tetrazole-functionalized molecule is grafted via silanization or amidification, respectively. Under UV light, a reactive nitrile imine rapidly forms and reacts with maleimide-functionalized polymers yielding a fluorescent linkage. Via a masking method, polymeric fluorescent patterns are achieved.

The effect of polymer coatings on physicochemical properties of spray-dried liposomes for nasal delivery of BSA

This work describes the development of spray dried polymer coated liposomes composed of soy phosphatidylcholine (SPC) and phospholipid dimyristoyl phosphatidylglycerol (DMPG) coated with alginate, chitosan or trimethyl chitosan (TMC), that are able to penetrate through the nasal mucosa and offer enhanced penetration over uncoated liposomes when delivered as a dry powder. All the liposome formulations, loaded with BSA as model antigen, were spray-dried to obtain powder size and liposome size in a suitable range for nasal delivery. Although coating resulted in some reduction in encapsulation efficiency, levels were still maintained between 60% and 69% and the structural integrity of the entrapped protein and its release characteristics were maintained. Coating with TMC gave the best product characteristics in terms of entrapment efficiency, glass transition (Tg) and mucoadhesive strength, while penetration of nasal mucosal tissue was very encouraging when these liposomes were administered as dispersions although improved results were observed for the dry powders

Functional polymer coatings — My-Patterning and My-Analysis

In dieser Arbeit werden Strukturen beschrieben, die mit Polymeren auf Oberflächen erzeugt wurden. Die Anwendungen reichen von PMMA und PNIPAM Polymerbürsten, über die Restrukturierung von Polystyrol durch Lösemittel bis zu 3D-Strukturen, die aus PAH/ PSS Polyelektrolytmultischichten bestehen. Im ersten Teil werden Polymethylmethacrylat (PMMA) Bürsten in der ionischen Flüssigkeit 1-Butyl-3-Methylimidazolium Hexafluorophospat ([Bmim][PF6]) durch kontrollierte radikalische Polymerisation (ATRP) hergestellt. Kinetische Untersuchungen zeigten ein lineares und dichtes Bürstenwachstum mit einer Wachstumsrate von 4600 g/mol pro nm. Die durchschnittliche Pfropfdichte betrug 0.36 µmol/m2. Als Anwendung wurden Mikrotropfen bestehend aus der ionischen Flüssigkeit, Dimethylformamid und dem ATRP-Katalysator benutzt, um in einer definierten Geometrie Polymerbürsten auf Silizium aufzubringen. Auf diese Weise lässt sich eine bis zu 13 nm dicke Beschichtung erzeugen. Dieses Konzept ist durch die Verdampfung des Monomers Methylmethacrylat (MMA) limitiert. Aus einem 1 µl großen Tropfen aus ionischer Flüssigkeit und MMA (1:1) verdampft MMA innerhalb von 100 s. Daher wurde das Monomer sequentiell zugegeben. Der zweite Teil konzentriert sich auf die Strukturierung von Oberflächen mit Hilfe einer neuen Methode: Tintendruck. Ein piezoelektrisch betriebenes „Drop-on-Demand“ Drucksystem wurde verwendet, um Polystyrol mit 0,4 nl Tropfen aus Toluol zu strukturieren. Die auf diese Art und Weise gebildeten Mikrokrater können Anwendung als Mikrolinsen finden. Die Brennweite der Mikrolinsen kann über die Anzahl an Tropfen, die für die Strukturierung verwendet werden, eingestellt werden. Theoretisch und experimentell wurde die Brennweite im Bereich von 4,5 mm bis 0,21 mm ermittelt. Der zweite Strukturierungsprozess nutzt die Polyelektrolyte Polyvinylamin-Hydrochlorid (PAH) und Polystyrolsulfonat (PSS), um 3D-Strukturen wie z.B. Linien, Schachbretter, Ringe, Stapel mit einer Schicht für Schicht Methode herzustellen. Die Schichtdicke für eine Doppelschicht (DS) liegt im Bereich von 0.6 bis 1.1 nm, wenn NaCl als Elektrolyt mit einer Konzentration von 0,5 mol/l eingesetzt wird. Die Breite der Strukturen beträgt im Mittel 230 µm. Der Prozess wurde erweitert, um Nanomechanische Cantilever Sensoren (NCS) zu beschichten. Auf einem Array bestehend aus acht Cantilevern wurden je zwei Cantilever mit fünf Doppelschichten PAH/ PSS und je zwei Cantilever mit zehn Doppelschichten PAH/ PSS schnell und reproduzierbar beschichtet. Die Massenänderung für die individuellen Cantilever war 0,55 ng für fünf Doppelschichten und 1,08 ng für zehn Doppelschichten. Der daraus resultierende Sensor wurde einer Umgebung mit definierter Luftfeuchtigkeit ausgesetzt. Die Cantilever verbiegen sich durch die Ausdehnung der Beschichtung, da Wasser in das Polymer diffundiert. Eine maximale Verbiegung von 442 nm bei 80% Luftfeuchtigkeit wurde für die mit zehn Doppelschichten beschichteten Cantilever gefunden. Dies entspricht einer Wasseraufnahme von 35%. Zusätzlich konnte aus den Verbiegungsdaten geschlossen werden, dass die Elastizität der Polyelektrolytmultischichten zunimmt, wenn das Polymer gequollen ist. Das thermische Verhalten in Wasser wurde im nächsten Teil an nanomechanischen Cantilever Sensoren, die mit Poly(N-isopropylacrylamid)bürsten (PNIPAM) und plasmapolymerisiertem N,N-Diethylacrylamid beschichtet waren, untersucht. Die Verbiegung des Cantilevers zeigte zwei Bereiche: Bei Temperaturen kleiner der niedrigsten kritischen Temperatur (LCST) ist die Verbiegung durch die Dehydration der Polymerschicht dominiert und bei Temperaturen größer der niedrigsten kritischen Temperatur (LCST) reagiert der Cantilever Sensor überwiegend auf Relaxationsprozesse innerhalb der kollabierten Polymerschicht. Es wurde gefunden, dass das Minimum in der differentiellen Verbiegung mit der niedrigsten kritischen Temperatur von 32°C und 44°C der ausgewählten Polymeren übereinstimmt. Im letzten Teil der Arbeit wurden µ-Reflektivitäts- und µ-GISAXS Experimente eingeführt als neue Methoden, um mikrostrukturierte Proben wie NCS oder PEM Linien mit Röntgenstreuung zu untersuchen. Die Dicke von jedem individuell mit PMMA Bürsten beschichtetem NCS ist im Bereich von 32,9 bis 35,2 nm, was mit Hilfe von µ-Reflektivitätsmessungen bestimmt wurde. Dieses Ergebnis kann mit abbildender Ellipsometrie als komplementäre Methode mit einer maximalen Abweichung von 7% bestätigt werden. Als zweites Beispiel wurde eine gedruckte Polyelektrolytmultischicht aus PAH/PSS untersucht. Die Herstellungsprozedur wurde so modifiziert, dass Goldnanopartikel in die Schichtstruktur eingebracht wurden. Durch Auswertung eines µ-GISAXS Experiments konnte der Einbau der Partikel identifiziert werden. Durch eine Anpassung mit einem Unified Fit Modell wurde herausgefunden, dass die Partikel nicht agglomeriert sind und von einer Polymermatrix umgeben sind.

Hybrid inorganic-polymer coatings prepared via miniemulsion process

A synthetic route was designed for the incorporation of inorganic materials within water-based miniemulsions with a complex and adjustable polymer composition. This involved co-homogenization of two inverse miniemulsions constituting precursors of the desired inorganic salt dispersed within a polymerizable continuous phase, followed by transfer to a direct miniemulsion via addition to an o/w surfactant solution with subsequent homogenization and radical polymerization. To our knowledge, this is the first work done where a polymerizable continuous phase has been used in an inverse (mini)emulsion formation followed by transfer to a direct miniemulsion, followed by polymerization, so that the result is a water-based dispersion. The versatility of the process was demonstrated by the synthesis of different inorganic pigments, but also the use of unconventional mixture of vinylic monomers and epoxy resin as the polymerizable phase (unconventional as a miniemulsion continuous phase but typical combination for coating applications). Zinc phosphate, calcium carbonate and barium sulfate were all successfully incorporated in the polymer-epoxy matrix. The choice of the system was based on a typical functional coatings system, but is not limited to. This system can be extended to incorporate various inorganic and further materials as long as the starting materials are water-soluble or hydrophilic. rnThe hybrid zinc phosphate – polymer water-based miniemulsion prepared by the above route was then applied to steel panels using autodeposition process. This is considered the first autodeposition coatings process to be carried out from a miniemulsion system containing zinc phosphate particles. Those steel panels were then tested for corrosion protection using salt spray tests. Those corrosion tests showed that the hybrid particles can protect substrate from corrosion and even improve corrosion protection, compared to a control sample where corrosion protection was performed at a separate step. Last but not least, it is suggested that corrosion protection mechanism is related to zinc phosphate mobility across the coatings film, which was proven using electron microscopy techniques.

Influence of pretreatment on corrosion behaviour of duplex zinc/polymer coatings on steel substrates

An investigation has been undertaken to determine the major factors influencing the corrosion resistance of duplex-zinc coatings on steel substrates.Premature failure of these systems has been attributed to the presence of defects such as craters and pinholes in the polymer film and debonding of the polymer film from the zinc substrate.Defects found on commercially produced samples have been carefully characterised using metallographic and scanning electron microscopy techniques. The influence of zinc substrate surface roughness, polymer film thickness and degassing of conversion coatings films on the incidence of defects has been determined.Pretreatments of the chromate, chromate-phosphate, non chromate, and alkali-oxide types were applied and the conversion coatings produced characterised with respect to their nature and composition. The effect of degassing on the properties of the films was also investigated. Electrochemical investigations were carried out to determine the effect of the presence of the eta or zeta phase as the outermost layer of the galvanized coating.Flow characteristics of polyester on zinc electroplated hot-dip continuous and batch galvanized and zinc sprayed samples were investigated using hot-stage microscopy. The effects of different pretreatments and degassing after conversion coating formation on flow characteristics were determined.Duplex coatings were subjected to the acetic acid salt spray test. The effect on adhesion was determined using an indentation debonding test and the results compared with those obtained using cross-cut/peel and pull-off tests. The locus of failure was determined using scanning electron microscopy and X-ray photoelectron spectroscopy techniques.

Corrosion protection of aluminium alloy by cerium conversion and conducting polymer duplex coatings

The corrosion protection of AA6063 aluminium alloy by cerium conversion, polyaniline conducting polymer and by duplex coatings has been investigated. The electrochemical behaviour was evaluated in aerated 3.5 wt.% NaCl. All coatings tested shifted the corrosion and pitting potentials to more positive values, indicating protection against corrosion. The duplex coatings are significantly more effective than each coating alone: corrosion and pitting potentials were shifted by +183 and +417 mV(SCE), respectively, by duplex coatings in relation to the untreated aluminium alloy. Optical microscopy and scanning electron microscopy are in agreement with the electrochemical results, reinforcing the superior performance of duplex coatings. (C) 2012 Elsevier Ltd. All rights reserved.

Porous polyurethane coatings bonded onto surface-modified titanium substrates for the growth of an endothelial cell layer

Cardiovascular diseases refer to the class of diseases that involve the heart or blood vessels (arteries and veins). Examples of medical devices for treating the cardiovascular diseases include ventricular assist devices (VADs), artificial heart valves and stents. Metallic biomaterials such as titanium and its alloy are commonly used for ventricular assist devices. However, titanium and its alloy show unacceptable thrombosis, which represents a major obstacle to be overcome. Polyurethane (PU) polymer has better blood compatibility and has been used widely in cardiovascular devices. Thus one aim of the project was to coat a PU polymer onto a titanium substrate by increasing the surface roughness, and surface functionality. Since the endothelium of a blood vessel has the most ideal non-thrombogenic properties, it was the target of this research project to grow an endothelial cell layer as a biological coating based on the tissue engineering strategy. However, seeding endothelial cells on the smooth PU coating surfaces is problematic due to the quick loss of seeded cells which do not adhere to the PU surface. Thus it was another aim of the project to create a porous PU top layer on the dense PU pre-layer-coated titanium substrate. The method of preparing the porous PU layer was based on the solvent casting/particulate leaching (SCPL) modified with centrifugation. Without the step of centrifugation, the distribution of the salt particles was not uniform within the polymer solution, and the degree of interconnection between the salt particles was not well controlled. Using the centrifugal treatment, the pore distribution became uniform and the pore interconnectivity was improved even at a high polymer solution concentration (20%) as the maximal salt weight was added in the polymer solution. The titanium surfaces were modified by alkli and heat treatment, followed by functionlisation using hydrogen peroxide. A silane coupling agent was coated before the application of the dense PU pre-layer and the porous PU top layer. The ability of the porous top layer to grow and retain the endothelial cells was also assessed through cell culture techniques. The bonding strengths of the PU coatings to the modified titanium substrates were measured and related to the surface morphologies. The outcome of the project is that it has laid a foundation to achieve the strategy of endothelialisation for the blood compatibility of medical devices. This thesis is divided into seven chapters. Chapter 2 describes the current state of the art in the field of surface modification in cardiovascular devices such as ventricular assist devices (VADs). It also analyses the pros and cons of the existing coatings, particularly in the context of this research. The surface coatings for VADs have evolved from early organic/ inorganic (passive) coatings, to bioactive coatings (e.g. biomolecules), and to cell-based coatings. Based on the commercial applications and the potential of the coatings, the relevant review is focused on the following six types of coatings: (1) titanium nitride (TiN) coatings, (2) diamond-like carbon (DLC) coatings, (3) 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer coatings, (4) heparin coatings, (5) textured surfaces, and (6) endothelial cell lining. Chapter 3 reviews the polymer scaffolds and one relevant fabrication method. In tissue engineering, the function of a polymeric material is to provide a 3-dimensional architecture (scaffold) which is typically used to accommodate transplanted cells and to guide their growth and the regeneration of tissue. The success of these systems is dependent on the design of the tissue engineering scaffolds. Chapter 4 describes chemical surface treatments for titanium and titanium alloys to increase the bond strength to polymer by altering the substrate surface, for example, by increasing surface roughness or changing surface chemistry. The nature of the surface treatment prior to bonding is found to be a major factor controlling the bonding strength. By increasing surface roughness, an increase in surface area occurs, which allows the adhesive to flow in and around the irregularities on the surface to form a mechanical bond. Changing surface chemistry also results in the formation of a chemical bond. Chapter 5 shows that bond strengths between titanium and polyurethane could be significantly improved by surface treating the titanium prior to bonding. Alkaline heat treatment and H2O2 treatment were applied to change the surface roughness and the surface chemistry of titanium. Surface treatment increases the bond strength by altering the substrate surface in a number of ways, including increasing the surface roughness and changing the surface chemistry. Chapter 6 deals with the characterization of the polyurethane scaffolds, which were fabricated using an enhanced solvent casting/particulate (salt) leaching (SCPL) method developed for preparing three-dimensional porous scaffolds for cardiac tissue engineering. The enhanced method involves the combination of a conventional SCPL method and a step of centrifugation, with the centrifugation being employed to improve the pore uniformity and interconnectivity of the scaffolds. It is shown that the enhanced SCPL method and a collagen coating resulted in a spatially uniform distribution of cells throughout the collagen-coated PU scaffolds.In Chapter 7, the enhanced SCPL method is used to form porous features on the polyurethane-coated titanium substrate. The cavities anchored the endothelial cells to remain on the blood contacting surfaces. It is shown that the surface porosities created by the enhanced SCPL may be useful in forming a stable endothelial layer upon the blood contacting surface. Chapter 8 finally summarises the entire work performed on the fabrication and analysis of the polymer-Ti bonding, the enhanced SCPL method and the PU microporous surface on the metallic substrate. It then outlines the possibilities for future work and research in this area.

Novel polymer synthesis methodologies using combination of thermally and photochemically-induced nitroxide mediated polymerisation

The combination of thermally- and photochemically-induced polymerization using light sensitive alkoxyamines was investigated. The thermally driven polymerizations were performed via the cleavage of the alkoxyamine functionality, whereas the photochemically-induced polymerizations were carried out either by nitroxide mediated photo-polymerization (NMP2) or by a classical type II mechanism, depending on the structure of the light-sensitive alkoxyamine employed. Once the potential of the various structures as initiators of thermally- and photo-induced polymerizations was established, their use in combination for block copolymer syntheses was investigated. With each alkoxyamine investigated, block copolymers were successfully obtained and the system was applied to the post-modification of polymer coatings for application in patterning and photografting.

Biocompatibility Assessment of Biosorbable Polymer Coated Nitinol Alloys

Owing to an increased risk of aging population and a higher incidence of coronary artery disease (CAD), there is a need for more reliable and safer treatments. Numerous varieties of durable polymer-coated drug eluting stents (DES) are available in the market in order to mitigate in-stent restenosis. However, there are certain issues regarding their usage such as delayed arterial healing, thrombosis, inflammation, toxic corrosion by-products, mechanical stability and degradation. As a result, significant amount of research has to be devoted to the improvement of biodegradable polymer-coated implant materials in an effort to enhance their bioactive response. In this investigation, magneto-electropolished (MEP) and a novel biodegradable polymer coated ternary Nitinol alloys, NiTiTa and NiTiCr were prepared to study their bio and hemocompatibility properties. The initial interaction of a biomaterial with its surroundings is dependent on its surface characteristics such as, composition, corrosion resistance, work of adhesion and morphology. In-vitro corrosion tests such as potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) studies were conducted to determine the coating stability and longevity. In-vitro hemocompatibility studies and HUVEC cell growth was performed to determine their thrombogenic and biocompatibility properties. Critical delamination load of the polymer coated Nitinol alloys was determined using Nano-scratch analysis. Sulforhodamine B (SRB) assays were performed to elucidate the effect of metal ions leached from Nitinol alloys on the viability of HUVEC cells. Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), contact angle meter and X-ray diffraction (XRD) were used to characterize the surface of the alloys. MEP treated and polymer coated (PC) Nitinol alloys displayed a corrosion resistant polymer coating as compared to uncoated alloys. MEP and PC has resulted in reduced Ni and Cr ion leaching from NiTi5Cr and subsequently low cytotoxicity. Thrombogenicity tests revealed significantly less platelet adhesion and confluent endothelial cell growth on polymer coated and uncoated ternary MEP Nitinol alloys. Finally, this research addresses the bio and hemocompatibility of MEP + PC ternary Nitinol alloys that could be used to manufacture blood contacting devices such as stents and vascular implants which can lead to lower U.S. healthcare spending.

Characterisation of multi wall carbon nanotube–polymer composites for strain sensing applications

Carbon nanotubes (CNTs) have excellent electrical, mechanical and electromechanical properties. When CNTs are incorporated into polymers, electrically conductive composites with high electrical conductivity at very low CNT content (often below 1% wt CNT) result. Due to the change in electrical properties under mechanical load, carbon nanotube/polymer composites have attracted significant research interest especially due to their potential for application in in-situ monitoring of stress distribution and active control of strain sensing in composite structures or as strain sensors. To sucessfully develop novel devices for such applications, some of the major challenges that need to be overcome include; in-depth understanding of structure-electrical conductivity relationships, response of the composites under changing environmental conditions and piezoresistivity of different types of carbon nanotube/polymer sensing devices. In this thesis, direct current (DC) and alternating current (AC) conductivity of CNT-epoxy composites was investigated. Details of microstructure obtained by scanning electron microscopy were used to link observed electrical properties with structure using equivalent circuit modeling. The role of polymer coatings on macro and micro level electrical conductivity was investigated using atomic force microscopy. Thermal analysis and Raman spectroscopy were used to evaluate the heat flow and deformation of carbon nanotubes embedded in the epoxy, respectively, and related to temperature induced resistivity changes. A comparative assessment of piezoresistivity was conducted using randomly mixed carbon nanotube/epoxy composites, and new concept epoxy- and polyurethane-coated carbon nanotube films. The results indicate that equivalent circuit modelling is a reliable technique for estimating values of the resistance and capacitive components in linear, low aspect ratio-epoxy composites. Using this approach, the dominant role of tunneling resistance in determining the electrical conductivity was confirmed, a result further verified using conductive-atomic force microscopy analysis. Randomly mixed CNT-epoxy composites were found to be highly sensitive to mechanical strain and temperature variation compared to polymer-coated CNT films. In the vicinity of the glass transition temperature, the CNT-epoxy composites exhibited pronounced resistivity peaks. Thermal and Raman spectroscopy analyses indicated that this phenomenon can be attributed to physical aging of the epoxy matrix phase and structural rearrangement of the conductive network induced by matrix expansion. The resistivity of polymercoated CNT composites was mainly dominated by the intrinsic resistivity of CNTs and the CNT junctions, and their linear, weakly temperature sensitive response can be described by a modified Luttinger liquid model. Piezoresistivity of the polymer coated sensors was dominated by break up of the conducting carbon nanotube network and the consequent degradation of nanotube-nanotube contacts while that of the randomly mixed CNT-epoxy composites was determined by tunnelling resistance between neighbouring CNTs. This thesis has demonstrated that it is possible to use microstructure information to develop equivalent circuit models that are capable of representing the electrical conductivity of CNT/epoxy composites accurately. New designs of carbon nanotube based sensing devices, utilising carbon nanotube films as the key functional element, can be used to overcome the high temperature sensitivity of randomly mixed CNT/polymer composites without compromising on desired high strain sensitivity. This concept can be extended to develop large area intelligent CNT based coatings and targeted weak-point specific strain sensors for use in structural health monitoring.

Bacterial adherence and biofilm formation on medical implants : a review

Biofilms are a complex group of microbial cells that adhere to the exopolysaccharide matrix present on the surface of medical devices. Biofilm-associated infections in the medical devices pose a serious problem to the public health and adversely affect the function of the device. Medical implants used in oral and orthopedic surgery are fabricated using alloys such as stainless steel and titanium. The biological behavior, such as osseointegration and its antibacterial activity, essentially depends on both the chemical composition and the morphology of the surface of the device. Surface treatment of medical implants by various physical and chemical techniques are attempted in order to improve their surface properties so as to facilitate bio-integration and prevent bacterial adhesion. The potential source of infection of the surrounding tissue and antimicrobial strategies are from bacteria adherent to or in a biofilm on the implant which should prevent both biofilm formation and tissue colonization. This article provides an overview of bacterial biofilm formation and methods adopted for the inhibition of bacterial adhesion on medical implants

Surface Initiated Polymerization from Substrates of Low Initiator Density and Its Applications in Biosensors

Surface initiated polymerization (SIP) has become an attractive method for tailoring physical and chemical properties of surfaces for a broad range of applications. Most of those application relied on the merit of a high density coating. In this study we explored a long overlooked field of SIP. SIP from substrates of low initiator density. We combined ellipsometry with AFM to investigate the effect of initiatior density and polymerization time on the morphology of polymer coatings. In addition, we carefully adjusted the nanoscale separation of polymer chains to achieve a balance between nonfouling and immobilization capacities. We further tested the performance of those coating on various biosensors, such as quartz crystal microbalance, surface plasmon resonance, and protein microarrays. The optimized matrices enhanced the performance of those biosensors. This report shall encourage researches to explore new frontiers in SIP that go beyond polymer brushes.

Thin mercury film electrodes in dynamic speciation studies of metals

No presente trabalho, foi avaliado o desempenho e a aplicabilidade do eléctrodo de filme fino de mercúrio, em estudos de especiação dinâmica de metais vestigiais. Para tal, foram utilizadas duas técnicas electroanalíticas de redissolução: a clássica Voltametria de Redissolução Anódica (ASV) e a recentemente desenvolvida, Cronopotenciometria de Redissolução com varrimento do potencial de deposição (SSCP). As propriedades de troca-iónica e de transporte de massa de películas mistas preparadas a partir de dois polímeros com características distintas, o Nafion (NA) e o 4-Poliestireno sulfonato de sódio (PSS), foram avaliadas, antes da sua aplicação no âmbito da especiação de metais. Estas películas de NA-PSS demonstraram uma elevada sensibilidade, reprodutibilidade, estabilidade mecânica, bem como, propriedades de anti-bloqueio adequadas na modificação química do eléctrodo de filme fino de mercúrio (TMFE) e, na sua aplicação na determinação de catiões metálicos vestigiais em amostras complexas, por ASV. Para além disso, o desempenho de membranas do polielectrólito PSS em estudos de voltametria de troca-iónica (IEV) foi estudado. O objectivo desta investigação foi reunir as condições ideais na preparação de películas de PSS estáveis e com uma densidade de carga negativa elevada, de modo a aumentar a acumulação electrostática de catiões metálicos no filme polimérico e por conseguinte, conseguir incrementos no sinal voltamétrico. O desempenho e aplicabilidade do TMFE em estudos de especiação de metais vestigiais foram extendidos à SSCP como técnica analítica. Dada a elevada sensibilidade e resolução evidenciada pelo TMFE, este revelou ser uma alternativa adequada aos eléctrodos de mercúrio convencionais, podendo ser utilizado durante um dia de trabalho, sem degradação aparente do sinal analítico de SCP. As curvas de SSCP obtidas experimentalmente utilizando o TMFE estavam em concordância com aquelas previstas pela teoria. Para além disso, a constante de estabilidade (K) calculada a partir do desvio do potencial de meia-onda, para dois sistemas metal-complexo lábeis, aproxima-se não só do valor teórico, como também daquele obtido utilizando o eléctrodo de mercúrio de gota suspensa (HMDE). Adicionalmente, o critério experimental de labilidade inerente a esta técnica foi validado e o grau de labilidade para um dado sistema metal-complexo foi determinado, utilizando o filme fino de mercúrio depositado sob um eléctrodo rotativo (TMF-RDE). Este eléctrodo é muito útil na determinação de parâmetros cinéticos, como é o caso da constante de velocidade de associação (ka), uma vez que as condições hidrodinâmicas, durante a etapa de deposição, se encontram bem definidas.

Desenvolvimento e caracterização de nanocompósito de resina epóxi com nanopartículas de sílica para revestimento de dutos para transporte de petróleo

The use of polymer based coatings is a promising approach to reduce the corrosion problem in carbon steel pipes used for the transport of oil and gas in the oil industry. However, conventional polymer coatings offer limited properties, which often cannot meet design requirements for this type of application, particularly in regard to use temperature and wear resistance. Polymer nanocomposites are known to exhibit superior properties and, therefore, offer great potential for this type of application. Nevertheless, the degree of enhancement of a particular property is greatly dependent upon the matrix/nanoparticle material system used, the matrix/nanoparticle interfacial bonding and also the state of dispersion of the nanoparticle in the polymer matrix. The objective of the present research is to develop and characterize polymer based nanocomposites to be used as coatings in metallic pipelines for the transportation of oil and natural gas. Epoxy/SiO2 nanocomposites with nanoparticle contents of 2, 4, and 8 wt % were processed using a high-energy mill. Modifications of the SiO2 nanoparticles‟ surfaces with two different silane agents were carried out and their effect on the material properties were investigated. The state of dispersion of the materials processed was studied using Scanning and Transmission Electron Microscopy (SEM and TEM) micrographs. Thermogravimetric analysis (TG) were also conducted to determine the thermal stability of the nanocomposites. In addition, the processed nanocomposites were characterized by dynamic mechanical analysis (DMA) to investigate the effect of nanoparticles content and silane treatment on the viscoelastic properties and on the glass transition temperature. Finally, wear tests of the pin-on-disc type were carried out to determine the effects of the nanoparticles and the silane treatments studied. According to the results, the addition of SiO2 nanoparticles treated with silane increased the thermal stability, the storage modulus and Tg of the epoxy resin and decreased wear rate. This confirms that the interaction between the nanoparticles and the polymer chains plays a critical role on the properties of the nanocomposites

N-Vinylamidderivate zur Synthese neuartiger Kern-Schale-Partikel und Hydrogele

N-Vinylamidderivate sind eine toxikologische unbedenkliche Monomerklasse. Mit diesen Monomeren wurden verschiedene technische Anwendungsgebiete im Bereich der Kern-Schale-Partikel und der fließfähigen und vernetzten Hydrogele untersucht. Kern-Schale-Partikel Für die Synthese von Kern-Schale-Partikeln wurden die N-Vinylamidderivate als Schalenpolymere auf kommerziellen Poly(styrol-stat.-butadien)-Kernpartikeln aufpolymerisiert. Mit Hilfe verschiedener Untersuchungsmethoden (DLS, SEM, FFF, Ultrazentrifuge) wurde die Kern-Schale-Strukturbildung und die Effizienz der Pfropfungsreaktion untersucht und eine erfolgreiche Synthese der Kern-Schale-Partikel belegt. Durch die gezielte Modifizierung des Schalenpolymers wurde ein kationisches, organisches Mikropartikelsystem entwickelt, charakterisiert und auf die Eignung als „Duales Flockungsmittel“ untersucht. Diese Versuche belegten die Eignung der modifizierten Kern-Schale-Partikel als „Duales Flockungsmittel“ und bieten eine Alternative zu kommerziell verwendeten Retentionsmitteln. Außerdem wurden die filmbildenden Eigenschaften der Poly(N﷓vinylformamid)-Kern-Schale-Dispersionen untersucht. Nach der Verfilmung der Dispersionen wurden transparente und harte Filme erhalten. Die Auswirkungen auf die mechanischen Eigenschaften der Filme wurden durch die Variation verschiedener Parameter eingehend studiert. Auf der Basis dieser Partikel wurden selbstvernetzende Dispersionssysteme entwickelt. Das P﷓(VFA)-Schalenpolymer wurde teilweise hydrolysiert und die generierten freien Aminogruppen des Poly(N-vinylamins) durch eine Michael-Addition mit einem divinylfunktionalisierten Acrylat (Tetraethylenglykoldiacrylat) vernetzt. Untersuchungen zur mechanischen Beständigkeit der Filme zeigten bei geringen Vernetzungsgraden eine deutliche Optimierung der maximalen Zugbelastungen. Die Untersuchungen belegten, dass die Verwendung des selbstvernetzenden Dispersionssystems als Dispersion für eine Polymerbeschichtung möglich ist. Hydrogele Die Synthese von fließfähigen und quervernetzten Hydrogelen erfolgte auf der Basis verschiedener N﷓Vinylamide. Mit Hilfe geeigneter Vernetzer wurden feste Hydrogelplatten synthetisiert und für die Auftrennung von DNA-Sequenzen mit Hilfe der Gelelektrophorese verwendet. Scharfe und gute Auftrennung der verschiedenen „DNA-Ladder Standards“ wurden durch die Variation des Vernetzeranteils, der Polymerzusammensetzung, der angelegten Spannung und der Verweilzeit in der Gelelektrophoresekammer mit P﷓(MNVA)-Hydrogelplatten erreicht. Fließfähige und quervernetzte Elektrolytgele auf Poly-(N-vinylamid)-Basis wurden in wartungsfreien pH﷓Elektroden eingesetzt. Die Eignung dieser Hydrogele wurden in Bezug auf die Anwendung eingehend charakterisiert. Elektroden befüllt mit Poly(N-vinylamid)-Gelen wurden in Dauerbelastungsexperimenten, direkt mit kommerziellen pH﷓Elektroden verglichen. Es konnte gezeigt werden, dass die fließfähigen und quervernetzten Poly-(N-vinylamid)-Elektrolytgele in ihren Messeigenschaften gleichwertige bzw. bessere Potentialstabilitäten aufweisen als kommerzielle Referenzelektroden. Die Hydrogele auf Basis von Poly(N-vinylamidderivaten) boten für die beiden getesteten Anwendungen eine toxikologisch unbedenkliche Alternative zu Poly(acrylamid)-Gelen. In dieser Arbeit konnten die durchgeführten Untersuchungen belegen, dass N﷓Vinylamide eine attraktive Monomerklasse ist, die erfolgreich in vielen technischen Anwendungen einsetzbar ist.