Rozprawy doktorskie na temat „PEG HYDROGEL”

Type 1 diabetes affects one in every 400-600 children and adolescents in the US. Standard therapy with exogenous insulin is burdensome, associated with a significant risk of dangerous hypoglycemia, and only partially efficacious in preventing the long term complications of diabetes. Pancreatic islet transplantation has emerged as a promising therapy for type 1 diabetes. However, this cell-based therapy is significantly limited by inadequate islet supply (more than one donor pancreas is needed per recipient), instant blood-mediated inflammatory reaction, and loss of islet viability/function during isolation and following implantation. In particular, inadequate revascularization of transplanted islets results in reduced islet viability, function, and engraftment. Delivery of pro-vascularization factors has been shown to improve vascularization and islet function, but these strategies are hindered by insufficient and/or complex release pharmacokinetics and inadequate delivery matrices as well as technical and safety considerations. We hypothesized that controlled presentation of angiogenic cues within a bioartificial matrix could enhance the vascularization, viability, and function of transplanted islets. The primary objective of this dissertation was to enhance allogenic islet engraftment, survival and function by utilizing synthetic hydrogels as engineered delivery matrices. Polyethylene glycol (PEG)-maleimide hydrogels presenting cell adhesive motifs and vascular endothelial growth factor (VEGF) were designed to support islet activities and promote vascularization in vivo. We analyzed the material properties and cyto-compatibility of these engineered materials, islet engraftment in a transplantation model, and glycemic control in diabetic subjects. The rationale for this project is to establish novel biomaterial strategies for islet delivery that support islet viability and function via the induction of local vascularization.

Die Funktionalisierung von tetra-PEG Makromolekülen mit fotoreaktiven Gruppen und die anschließende Umsetzung zu Hydrogelen durch fotochemische Vernetzung werden beschrieben. Die Funktionalisierung der Makromoleküle wird mittels UV-Vis- und NMR-Spektroskopie nachgewiesen, während der Verlauf der Vernetzung über die dynamische Lichtstreuung und IR-Spektroskopie betrachtet wird. Die hergestellten Hydrogele werden hinsichtlich des Sol-Anteils und der Quelleigenschaften untersucht. Über den Umsatz wird die Konzentration der Netzketten theoretisch berechnet. Einen weiteren Schwerpunkt bildet die Charakterisierung der Hydrogele hinsichtlich der mechanischen Eigenschaften. Über den Speichermodul wird die Konzentration der Netzketten experimentell bestimmt. Mittels dynamischer Lichtstreuung werden die kooperativen Diffusionskoeffizienten und Maschenweiten der Hydrogele bestimmt.

Advancements in the biomedical field are driven by the design of novel materials with controlled physical and bio-interactive properties. To develop such materials, researchers rely on the use of highly efficient reactions for the assembly of advanced polymeric scaffolds that meet the demands of a functional biomaterial. In this thesis two main strategies for such materials have been explored; these include the use of off-stoichiometric thiol-ene networks and dendritic polymer scaffolds. In the first case, the highly efficient UV-induced thiol-ene coupling (TEC) reaction was used to create crosslinked polymeric networks with a predetermined and tunable excess of thiol or ene functionality. These materials rely on the use of readily available commercial monomers. By adopting standard molding techniques and simple TEC surface modifications, patterned surfaces with tunable hydrophobicity could be obtained. Moreover, these materials are shown to have great potential for rapid prototyping of microfluidic devices. In the second case, dendritic polymer scaffolds were evaluated for their ability to increase surface interactions and produce functional 3D networks. More specifically, a self-assembled dendritic monolayer approach was explored for producing highly functional dendronized surfaces with specific interactions towards pathogenic E. coli bacteria. Furthermore, a library of heterofunctional dendritic scaffolds, with a controllable and exact number of dual-purpose azide and ene functional groups, has been synthesized. These scaffolds were explored for the production of cell interactive hydrogels and primers for bone adhesive implants. Dendritic hydrogels decorated with a selection of bio-relevant moieties and with Young’s moduli in the same range as several body tissues could be produced by facile UV-induced TEC crosslinking. These gels showed low cytotoxic response and relatively rapid rates of degradation when cultured with normal human dermal fibroblast cells. When used as primers for bone adhesive patches, heterofunctional dendrimers with high azide-group content led to a significant increase in the adhesion between a UV-cured hydrophobic matrix and the wet bone surface (compared to patches without primers).

QC 20140116

This dissertation is focused on the controlled release of drugs from a biodegradable amphiphilic hydrogel based on hydrophobic poly(lactic acid), poly(glycolic acid) and hydrophilic poly(ethylene glycol) (PLGA-PEG-PLGA, ABA) and its modification with itaconic anhydride (ITA). The resulting ,-itaconyl(PLGA-PEG-PLGA) copolymer is referred to as ITA/PLGA-PEG-PLGA/ITA or ITA/ABA/ITA. Itaconic acid provides reactive double bonds and a functional carboxyl group at the ends of the PLGA-PEG-PLGA copolymer chain, thereby rendering the modified ITA/ABA/ITA copolymer less hydrophobic and offering the possibility of forming a carrier for hydrophilic drug substances. These functional copolymers are thermosensitive and change in the external environment (e.g. temperature) causes a sol-gel phase transition due to the formation of micellar structure. The bioactive substances can thus be mixed with a copolymer which is in a low viscous phase (sol phase) and subsequently the mixture can be injected into patient's body at the target site where it forms a gel at 37 °C. This hydrogel becomes a drug depot, which gradually releases the active substance. Prediction of the substance’s release profile from the hydrogel is an effective tool to determine the frequency of administration, potentially enhancing efficacy, and assessment of side effects associated with dosing. The analgesic paracetamol and the sulfonamide antibiotic sulfathiazole were used as model drugs, representing hydrophilic and hydrophobic substances, respectively. The active substances had a significant effect on the resulting hydrogel stiffness. Type of solvent, incubation medium and nanohydroxyapatite also influenced on the gel stiffness and subsequent stability of the hydrogel-drug system. Controlled release of drugs took place in simulated conditions of the human body. Verification of Korsmeyer-Peppas (KP) drug-release model is also discussed in this thesis. The KP model was found suitable for simulating the release of sulfathiazole from ABA and ITA/ABA/ITA hydrogels. On the contrary, the performance of KP model was not suitable for describing the release of paracetamol from the ABA hydrogels. Therefore, a new regression model suitable for both buffered simulated media and water has been proposed. The proposed model fitted better the release of both sulfathiazole and paracetamol from composite material prepared from ABA hydrogel and nanohydroxyapatite.

In pharmaceutical development cell cultures are used as in vitro models to evaluate the function of drug candidates. In such research it is vital to have models that resemble the in vivo environment to get reliable results. In 3D models with hydrogels ECM like scaffolds are supporting the cells in a more in vivo like environment than flat 2D cultures. In this project PEG-peptide based hydrogels with cell binding RGD incorporated on one PEG-peptide type has been evaluated for culturing of HepG2 cells. Structure and viscoelastic properties were evaluated with techniques like circular dichroism spectroscopy, dynamic light scattering and rheology. Sterilisation impact was also evaluated for PEG-peptides. For cell culturing, observations in light microscope and evaluation with Live/Dead assay and albumin assay were performed. A few companies were interviewed regarding 3D culturing and interest in mechanically tuneable hydrogels. The HepG2 cells grows and forms spherical clusters in the 3D environment with hydrogels, percentage of RGD seems to not impact cell adhesion, growth or albumin secretion. UV irradiation was the most suitable sterilisation method for gel components. The most rigid gel combination formed had storage modulus of around 230 Pa. Mechanically tuneable hydrogels is interesting for the industry. The PEG-peptide based gels are suitable tor growing cells but too soft to closely resemble the in vivo rigidity of hepatocytes.

Ce travail de recherche est consacré à l’ingénierie d’un nouveau nanobiohybride à base de nanorubans de titanates pour la médecine régénérative. Dans un premier temps, les nanorubans ont été synthétisés par traitement hydrothermal et leurs caractéristiques morphologiques, structurales et chimiques ont été définies. Une caractérisation fine par différentes techniques de microscopie électronique à transmission a notamment permis de déterminer leur épaisseur; dimension qui n’avait encore jamais été mesurée. Par la suite, les nanorubans de titanates ont été fonctionnalisés par différents PEG hétérobifonctionnels préalablement synthétisés au laboratoire. Ces polymères présentent à l’une de leurs extrémités des groupements fonctionnels spécifiques pouvant se coupler à de nombreuses molécules biologiques. Des peptides de type collagène contenant des sites de reconnaissance cellulaire ont alors été greffés sur ces extrémités. Le nanobiohybride ainsi formé devra permettre l'adhésion et la prolifération des cellules favorisant in fine la cicatrisation et la régénération tissulaire. Pour évaluer les propriétés biologiques du nouveau nanobiohybride, la cytoxicité et le pouvoir agrégeant des nanorubans de titanes ont été déterminés par des tests MTT, réalisés sur deux populations de cellules (cardiomyocytes et fibroblastes) et par des tests d’agrégation plaquettaire (sang humain). Enfin, dans le cas d’une utilisation pour favoriser le processus de cicatrisation, le nouveau nanobiohybride a été formulé sous forme d’un hydrogel d’alginate de sodium permettant une application directe sur les tissus lésés. Pour confirmer l’intérêt de cette formulation galénique, des premiers tests in vivo ont été réalisés
This research work is devoted to new nanohybrid engineering composed of titanate nanoribbons for regenerative medicine. Over a first phase, nanoribbons were synthesized by hydrothermal treatment and their morphological, structural and chemical features were defined. A fine characterization by means of different techniques of transmission electron microscopy mainly enabled to determine their thickness; dimension which had never been measured so far. Subsequently, titanate nanoribbons were functionalized by different home-made heterobifunctional PEG. Those polymers present at one of their extremities specific functional groups being able to couple with numerous biological molecules. Some collagen type peptides containing cellular recognition sites were grafted onto those extremities. The so-formed nanobiohybrid will permit cellular adhesion and proliferation favouring in fine tissue healing and regeneration. To evaluate new nanohybrid biological properties, titanate nanoribbons cytoxicity and aggregating power were determined by MTT tests, performed on two cell populations (fibroblasts and cardiomyocytes) and platelet aggregation tests (human blood). Finally, when used to promote healing process, the new nanobiohybrid was formulated in the form of sodium alginate hydrogel permitting a direct application on damaged tissues. To confirm the interest of this galenic form, initial in vivo tests were realized

Biodegradable hydrogels have become very promising materials for a number of biomedical applications, including tissue engineering and drug delivery. For optimal tissue engineering design, the mechanical properties of hydrogels should match those of native tissues as closely as possible because these properties are known to affect the behavior and function of cells seeded in the hydrogels. At the same time, high water-contents, large mesh sizes and well-tuned degradation rates are favorable for the controlled release of growth factors and for adequate transport of nutrients through the hydrogel during tissue regeneration. With these factors in mind, the goal of this research was to develop and investigate the behavior of injectable, biodegradable hydrogels with enhanced stiffness properties that persist even at high degrees of swelling. In order to do this, degradable functionalities were incorporated into photo-crosslinkable poly(ethylene glycol) and poly(acrylic acid) hydrogels, and these two components were used to make a series of double-network hydrogels. Synthesis of the precursor macromers, photopolymerization of the hydrogels, and structural parameters of the hydrogels were analyzed. The composition and the molecular weight between crosslinks (Mc) of the hydrogel components were varied, and the degradation, swelling, thermal and mechanical properties of the hydrogels were characterized over various time scales. These properties were compared to corresponding properties of the component single-network hydrogels.

Orientadores: Cecília Amélia de Carvalho Zavaglia, Ana Beatriz Albino Almeida
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica
Made available in DSpace on 2018-08-18T02:56:18Z (GMT). No. of bitstreams: 1 Feliciano_DanielleFerreira_M.pdf: 2215803 bytes, checksum: 78c936869613a6b313b028d4e7b84078 (MD5) Previous issue date: 2011
Resumo: Defeitos, doenças e acidentes que acometem a cartilagem articular para suportar às constantes solicitações mecânicas que estas regiões estão sujeitas, sendo indicada a utilização de estruturas viscoelástica resistente alto grau de atrito para preencher tais defeitos. Desta forma, foi selecionado o uso de hidrogéis para esta aplicação específica. Hidrogéis a base de poli(álcool vinilico) (PVAl) e polietileno glicol (PEG) apresentam propriedades mais adequadas, como biocompatibilidade, não estimulando reação imunológica ao organismo; baixa adesão de células sanguíneas, evitando coágulos; capacidade de absorção de água (intumecimento), proporcionando lubrificação do material e alto grau de transparência. O processo para obtenção desta blenda e formação de hidrogel foi realizado utilizando uma proporção de 1:9 (PEG:PVAl). O iniciador 2- hidroxi-4'-(2-hidroxietoxi)-2-metilpropiofenona foi adicionado à blenda, em 1% do volume total. È este iniciador, quando estimulado via temperatura, laser ou infravermelho, que irá desencadear as ligações intermacromoleculares de PEG-PVAl permitindo a formação de uma organização grafitizada da blenda dentro do hidrogel. Foi acompanhada a cinética de formação deste hidrogel através de reometria de placas, Espectroscopia de Infravermelho por Transformada de Fourier (FTIR) e Calorimetria Diferencial de Varredura (DSC). As amostras também foram devidamente caracterizadas quanto à condutividade térmica, densidade e absorção óptica. Observou-se que o iniciador ativou as ligações do grupo acetato do PVAl com as hidroxilas do PEG, resultando em formação de grupos ester. São estas ligações que caracterizam a formação do hidrogel grafitizado. Além disso, ocorreu a inversão do módulo viscoso em relação ao módulo de elasticidade, comprovando a reação de grafitização
Abstract: Defects, diseases and accidents that affect the articular cartilage can withstand constant mechanical stresses that they are subject, which indicated the use of viscoelastic structures resistant to high friction to fill these defects. In this way, the use was selected of hydrogels for this application it specifies. To base of I polished hydrogels polyvinyl alcohol (PVA) and polyethylene glycol (PEG) present more appropriate properties, biocompatibility, not stimulating reaction immunologically to the organism; low adhesion of blood cells, avoiding clots; capacity of absorption of water (swelling), providing lubrication of the material and high degree of transparency. The process for getting this blend and formation of hydrogel was carried out using a proportion of 1:9 (PEG:PVA). The initiator hidroxi 2-hidroxi-4 '-(2-hidroxietoxi)-2- metilpropiofenona was added to the blend, in 1 % of the total volume. This initiator, when stimulated he was seeing temperature, laser or infrared, what will be going to unleash the connections intermacromoleculares of PEG-PVA allowing the formation of an grafiting organization of the blend inside the hydrogel. There was accompanied the kinetic one of formation of this hydrogel through parallel plates rheometry, Fourier transform infrared spectroscopy (FTIR) and Differential scanning calorimetry (DSC). The samples also were characterized property as for the thermal condutivity, density and optical absorption. It noticed to itself that the initiator activated the connections of the group acetate of the PVA with the hydroxyl group of PEG, when ester is turning in formation of groups. It is these connections that characterize the formation of the hydrogel grafiting. Besides, it took place to inversion of the viscous module regarding the module of elasticity, proving the reaction of grafiting
Mestrado
Materiais e Processos de Fabricação
Mestre em Engenharia Mecânica

Gegenstand dieser Arbeit war die Synthese von thermisch schaltbaren Kammcopolymeren auf Basis von N-(Isopropylacrylamid) (NiPAAm) und Polyethylenglykolmakromonomeren (PEGMA). Die intensive Charakterisierung der aus diesen Copolymeren hergestellten Schichten und deren Anwendung als Zellkultursubstrate war ein weiteres Forschungsziel dieser Arbeit. Die mit Hilfe der neuartigen Schichten erhaltenen Zellkultursubstrate wurden anhand verschiedener adhärenter Zelllinien erfolgreich getestet. Alle getesten Zelltypen (Mausfibroblasten, humane Endothelzellen der Nabelschnurvene und humane korneale Endothelzellen) proliferierten auf den angebotenen Zellkultursubstraten bei 37°C und konnten durch senken der Temperatur geerntet werden.

Alors que l’éthique et la loi poussent la recherche à plus de sécurité, ainsi qu’à une moindre utilisation des animaux, il est devenu crucial de développer des systèmes in vitro d’une plus grande pertinence. Depuis la fin du XXe siècle, plusieurs systèmes ont fait leur apparition pour tenter de pallier les difficultés rencontrées, et notamment les « organes-sur-puces » (organ-on-chip systems). Ces systèmes microfluidiques de culture cellulaire avancés permettant de recréer certaines fonctions tissulaires grâce au contrôle très précis des conditions du microenvironnement cellulaire. Malgré les avancées de la bioingénierie et l’amélioration de nos méthodes de culture in vitro, la discipline est jeune et de nombreux progrès restent à faire. Les travaux présentés ici détaillent le développement d’un organe-sur-puce incluant une membrane d'hydrogel déformable et dégradable, aux propriétés physico-chimiques proches de tissus mous tels que les poumons ou les intestins. Cette puce semble pertinente pour accueillir des tissus barrières, composés de plusieurs types cellulaires, organisés de part et d'autre, ainsi qu'au sein de cette barrière, souvent soumise à des stimuli mécaniques. Durant ce doctorat, plusieurs objectifs ont été atteints : - Concevoir et fabriquer un organe-sur-puce incluant un hydrogel biocompatible et déformable, ainsi qu’un système microfluidique permettant le contrôle indépendant du flux et de la déformation de la membrane d’hydrogel. - Caractériser la déformation subie par l’hydrogel. - Cultiver dans la puce des cellules intestinales, formant un épithélium structuré en trois dimensions, et caractériser sa perméabilité à des molécules de tailles variées
Modern day ethics and laws call for more safety and use of fewer animals in biomedical research. It became crucial to develop novel in vitro devices of higher relevance. Since the end of the twentieth century, several systems have been proposed by researchers in attempts to palliate the shortcomings of current systems. Notably, organs-on-chip systems are specifically tailored to recapitulate tissue functions in a manner that remains easily accessible for the experimenter. Despite the significant improvements that were brought during the last century to in vitro cell and tissue culture systems, the field of bioengineering is still young and much progress remains to be done. The work presented here details the development of an organ-on-chip that includes a biocompatible and actuatable hydrogel membrane, with controlled physico-chemical properties. Such chip is relevant when hosting barrier tissues, which are composed of several cell types, disposed on each side of a barrier, as well as within its bulk, and are often submitted to mechanical stimuli. During this PhD, several objectives have been attained. Notably, we: - Designed and produced an organ-on-chip including a biocompatible and actuatable hydrogel layer, as well as a microfluidic system allowing the independent control of both flow and actuation. - Characterized the deformation of the hydrogel layer. - Cultured intestinal cells within the chip, which formed a three dimensionally structure epithelium, and characterized its apparent permeability to molecules of varying sizes

Cardiovascular disease continues to be the leading cause of morbidity and mortality in the US and worldwide. Traditional treatments include vascular surgeries, such as angioplasty, stent placement, and vascular graft or vascular reconstruction. Of importance for this dissertation are the outcomes following vascular graft surgeries. More than 50% of vascular grafts fail within the first few years due to maladaptive responses, such as inflammation. There is a critical need to develop improved treatments to the traditional grafting procedures. One proposal to enhance outcomes is the use of cellularized, low modulus, synthetic poly(ethylene) glycol (PEG)-based biomaterials. PEG-based hydrogels have been shown to support the 3D growth and differentiation of vascular cells and may provide structural support for the vessel. A principal concern is that a growing percentage of individuals contain anti-PEG antibodies, including IgG antibodies. T cells are mediators of antibody production and play a major role in angiogenesis and in the development of arthrosclerosis. Therefore, studies to elucidate the T cell-PEG matrix interactions are needed to control and predict maladaptive responses. Here, an established murine D10-IL2, Th2 cell line, was used as a model of T lymphocyte activity to: 1) better understand the influence of PEG on T cell metabolism; 2) determine the consequence of an acute Th2 inflammatory microenvironment on the expression of pro-inflammatory responses in fibroblasts within the 3D matrix; and 3) investigate antigen presenting cell (APC)-independent T cell activation. This research demonstrated that Th2 cells experience a reversible suppression of mitochondrial membrane potential (ΔΨm) upon initial exposure to PEG. Data also suggested that T cells were susceptible to APC-independent activation during contact with the PEG matrix, as measured by an increase in IL4 and IL10 expression and the production of inflammatory cytokines (IGFBP-3, CTACK, MIP2, LIX). Additionally, this research led to the development of a bio-degradable PEG-based hydrogel system. This allowed for the investigation of aortic fibroblast cell responses to an acute inflammatory 3D microenvironment and demonstrated that the hydrogel system provided a limited protective barrier during inflammation. This research has public health benefits and has provided an improved understanding of the immunogenic nature of PEG.

Chronic wounds are a major financial and clinical burden causing the deaths of millions per year. Over expression of elastase is well documented as the main culprit that delays the normal wound repair process within chronic wounds. The aim of this thesis is to design a responsive chronic wound dressing based on the hydrogel polymer, PEGA (polyethylene glycol acrylamide) in the form of particles to mop-up excess elastase by exploiting polymer collapse in response to elastase hydrolytic activity within sample fluids mimicking the environment of chronic wounds. PEGA particles were functionalised with enzyme cleavable peptides (ECPs) containing charged residues. Upon cleavage the charge balance changes, causing polymer swelling and consequent elastase entrapment. The pH range of chronic wounds is reported in the range of 5.45 - 8.65. Due to its pI which is around 8.3, within this range elastase exist both in its cationic and anionic forms. To accommodate a hydrogel dressing that could selectively entrap excess elastase both in its cationic and anionic, oppositely charged ECPs were designed. In its cationic form, elastase was found to have a high preference of cleaving ECPs and penetrating into PEGA particles bearing negative charges. In contrast, in its anionic form the opposite effect was observed, wherein elastase preferred to cleave ECPs and penetrate PEGA particles bearing positive charges. The diffusion, accessibility and entrapment of elastase into functionalised PEGA particles was explored using various fluorescence microscopy techniques. Removal of the charged residue by elastase showed a reduction in particle swelling causing the pores of PEGA particles to become restricted. In this manner, cleaved PEGA particles prevented the accessibility of molecules with a molecular weight as low as 20 kDa into the cleaved PEGA particles. Since elastase has a molecular weight of 25.9 kDa the collapsing of the pores within PEGA particles entrapped elastase inside the interior of cleaved PEGA particles. In its cationic form (at pH 7.4) elastase was found to penetrate and become trapped more into both negative and positive PEGA particles compared to neutral particles. The negative particles were shown to trapped cationic elastase within 2 minutes compared to the positive particles. In contrast, the neutral particles failed to retain and encapsulate elastase as the fluorescence inside the neutral particles was found to decrease. Coinciding with these observations, after sample fluids containing elastase were treated with functionalised PEGA particles, the residual elastase activity in sample fluids was reduced more by the charged PEGA particles compared to neutral particles. The cell culture studies demonstrated that the elastase activity observed in human dermal fibroblasts (HDF) was also reduced more by the charged particles compared to the neutral particles. However, the positive particles were found to significantly reduced HDF-elastase activity compared to both the negative and neutral PEGA particles. Overall, this thesis exemplifies that on the basis of charge selective cleaving of ECPs coupled to PEGA particles can be exploited to selectively remove excess proteases such as elastase from sample fluids mimicking the environment of chronic wounds.

The electrolysis of water was evaluated as a potentially efficient, as a low cost means of hydrogen production. The theoretical energy, voltage, current, and energy efficiencies of water electrolysis were considered by using various catalyst materials used in the fabrication of membrane electrode assemblies used in low temperature water electrolysis systems. Traditionally, iridium based catalysts have shown to be the most suitable material for its use on electrocatalysis of water to form hydrogen. This study showed that a combination of various elements as a binary and or ternary mixture in the base catalyst that was applied to the anode and cathode by using the Adam’s method had shown to give comparatively good results to that of using iridium oxide on its own. These catalysts were characterized by cyclic voltammetry, at different temperatures (30oC-80oC) with a range of catalyst loading of 0.2-0.5 mg.cm-2 noble metals. The study showed that the Ir40Co40 mixture as an anode catalyst was found to show highest hydrogen efficiency of 73 percent with a relatively low over potential of 0.925V at higher temperature of 80oC. The mixture also showed to give the best electrocatalytic activity with a low Tafel slope of 30.1mV.dec-1. Whereas the Ir50Pt50 showed a comparatively lower hydrogen efficiency of 65 percent with a lower over potential of 0.6V at 50oC. Ternary mixed oxide of Ir20Ru40Co40 showed an even lower over potential of 0.5- 0.6V over a large range of temperatures with a low hydrogen efficiency of 44 percent but gave good electrocatalytic activity in terms of the Tafel slope analysis. On the other hand, mixtures with relatively cheaper material such as Nickel in binary mixture systems such as Pt50Ni50 as cathode catalyst was found to show promising performance of a relatively low over potential that was less than 1.4 V with a low hydrogen efficiency of 62.1 percent Ternary cathode catalyst materials such as Pt33Ni33Co33 exhibited good performance with higher hydrogen efficiency of 65.2 percent at lower over potential of 1.2 V and a higher Tafel slope of 133.9 mV.dec-1 at 80 0C.

Results on the development of Ni-based electrocatalysts for hydrogen evolution in an acidic medium are discussed in the thesis. This topic is of a great importance for the development of a PEM-type hydrogen generator, as a global initiative for the development of clean sustainable energy systems. A number of experimental techniques were used in research: linear dc polarization (Tafel), electrochemical impedance spectroscopy (EIS), potential-decay, inductively coupled plasma (ICP), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The first part of the thesis discusses the results on the influence of alloying nickel by left-hand side transition metals (Fe, Mo, W) on the electrocatalytic activity in hydrogen evolution, while the second part of the thesis discusses the results on the development of Ni electrocatalysts using conductive polymers, polypyrrole (PPY) and polyaniline (PANT) as catalysts pattering matrices. (Abstract shortened by UMI.)

The growing incidences of coronary artery bypass graft surgeries have triggered a need to engineer a viable small diameter blood vessel substitute. An ideal tissue engineered vascular graft should mimic the microenvironment of a native blood vessel, while providing the adequate compliance post-implantation. Current vascular graft technologies lack the ability to promote vascular ECM deposition, leading to a compliance mismatch and ultimately, graft failure. Hence, in order to engineer suitable vascular grafts, this thesis describes the synthesis and characterization of novel elastin mimetic peptides, EM-19 and EM-23, capable of promoting vascular ECM deposition within a poly(ethylene glycol) diacrylate (PEG-DA) hydrogel. By combining the material properties of a synthetic and bio-inspired polymer, a suitable microenvironment for cell growth and ECM deposition can be engineered, leading to improved compliance. As such, characterization of EM-19 and EM-23 was conducted in human vascular smooth muscle cell (SMC) cultures, and the peptides self-assembled with a growing elastic matrix. After grafting the peptides onto the surface of PEG-DA hydrogels, EM-23 increased SMC adhesion by 6000% over PEG-RGDS hydrogels, which have been the gold standard of cell adhesive PEG scaffolds. Moreover, EM-23 grafted surfaces were able to promote elastin deposition that was comparable to tissue cultured polystyrene (TCPS) surface even though TCPS had roughly 4.5 times more SMCs adhered. Once translated to a 3D model, EM-23 also stimulated increased elastin deposition and improved the mechanical strength of the scaffold over time. Moreover, degradation studies suggested that EM-23 may serve as a template that not only promotes ECM deposition, but also allows ECM remodeling over time. The characterization studies in this thesis suggest that this peptide is an extremely promising candidate for improving vascular ECM deposition within a synthetic substrate, and that it may be beneficial to incorporate EM-23 within polymeric scaffolds to engineer compliant vascular grafts.

Wind-hydrogen systems for remote area power supply are an early niche application of sustainable hydrogen energy. Optimal direct coupling between a wind turbine and an electrolyser stack is essential for maximum electrical energy transfer and hydrogen production. In addition, system costs need to be minimised if wind-hydrogen systems are to become competitive. This paper investigates achieving near maximum power transfer between a fixed pitched variable-speed wind turbine and a Proton Exchange Membrane (PEM) electrolyser without the need for intervening voltage converters and maximum power point tracking electronics. The approach investigated involves direct coupling of the wind turbine with suitably configured generator coils to an optimal series-parallel configuration of PEM electrolyser cells so that the I-V characteristics of both the wind turbine and electrolyser stack are closely matched for maximum power transfer. A procedure for finding these optimal con figurations and hence maximising hydrogen production from the system is described. For the case of an Air 403 400 W wind turbine located at a typical coastal site in south-eastern Australia and directly coupled to an optimally configured 400 W stack of PEM electrolysers, it is estimated that up to 95% of the maximum achievable energy can be transferred to the electrolyser over an annual period. The results of an extended experiment to test this theoretical prediction for an actual Air 403 wind turbine are reported. The implications of optimal coupling between a PEM electrolyser and an aerogenerator for the performance and overall economics of wind-energy hydrogen systems for RAPS applications are discussed.

en Español:
Se propone un modelo de FC basado en ecuaciones electroquímicas para predicción del exceso de oxígeno y de la temperatura de la pila, permitiendo además una conexión circuital con la carga. Así mismo, se presenta una técnica de modelado basada en Fuzzy, orientada a la emulación, obteniendo gran precisión con carga computacional reducida. Usando este último modelo se diseña e implementa un emulador. Estos modelos y el sistema de emulación fueron validados usando un sistema experimental.
Adicionalmente, diferentes topologías de sistemas de potencia basados en FC se proponen y analizan, obteniendo un criterio de selección dependiendo de la aplicación. Así mismo, se presentan criterios de control para una operación segura y eficiente del sistema. Finalmente, se proponen una metodología para la caracterización de los puntos óptimos de operación, y una estructura de control para operar en esas condiciones óptimas, siendo validados en un sistema experimental representativo del estado del arte.
in English:
A new FC modeling approach based on electrochemical equations for thermal and oxygen excess ration prediction with a circuit-based load connection is introduced. A fuzzy-based modeling technique is also proposed for emulation purposes, it reproducing the fuel cell dynamics with a high accuracy and a short computational time. The implementation of a fuel cell emulation system, based on this model, is described and analyzed. The models and the emulation system are experimentally validated by using a benchmark fuel cell system.
Different topologies for fuel cell-auxiliary storage devices interaction are also proposed and analyzed, thus giving an architecture selection criterion based on the load profile. Controllers, dynamic constrains and control objectives are designed for a safe and efficient fuel cell operation. Finally, a methodology for the identification of the fuel cell optimal operation conditions has been proposed, and a control strategy for operating in that optimal profile is introduced and validated.

A stand-alone power system is an autonomous system that supplies electricity to the user load without being connected to the electric grid. This kind of decentralized system is frequently located in remote and inaccessible areas. The purpose of this thesis is the modelling and simulation of a solar hydrogen hybrid power system to supply the typical residential electric customers in stand alone. It couples a photovoltaic (PV) generator, an alkaline water electrolyzer, a storage gas tank, a proton exchange membrane fuel cell (PEMFC), and power conditioning units (PCU) to give different system topologies. The overall mathematical model was obtained by integrating between their various subsystems models derived from literature. The system is intended to be an environmentally friendly solution since it tries maximizing the use of a renewable energy source. The results of the simulations showed that the hydrogen is one of the future energy storage mediums by using both TRNSYS software and HOMER software.

Contestualmente al processo di decarbonizzazione del settore energetico mondiale, risulta necessario individuare soluzioni alternative in grado di consentire l’abbattimento delle emissioni climalteranti. L’idrogeno può assumere un ruolo chiave nel raggiungimento di questi obiettivi: grazie al Power to Hydrogen è infatti possibile intraprendere la conversione dei settori “hard to abate” e stoccare ingenti quantità di energia, cooperando inoltre alla stabilizzazione della rete elettrica. Con il presente elaborato si intende approfondire la tematica idrogeno, tramite l’analisi di potenzialità, limiti ed applicazioni presenti e future. A seguito della descrizione dei principali metodi di produzione, vengono considerate le tecnologie di generazione a basso impatto ambientale e, in particolare, l’elettrolisi dell’acqua. In accordo con i progetti di “Hydrogen Valley” e con il recente PNRR pubblicato dal Governo Italiano, particolare interesse è stato rivolto al territorio dell’Emilia Romagna, con l’obiettivo di individuare informazioni relative a realtà industriali coinvolte nella produzione e/o nell’utilizzo di idrogeno, con valutazioni attinenti a volumi interessati e potenzialità future. La trattazione dei risultati ottenuti confluisce nella descrizione tecnica delle attività riscontrate di maggiore interesse, ed assume espressione conclusiva nell’elaborazione di un caso di studio specifico, rispetto al quale è condotta un’analisi tecnico-economica volta a valutare la sostituzione di “idrogeno grigio” con un impianto di autoproduzione di “idrogeno verde”, basato sullo sfruttamento di risorse rinnovabili. La competitività economica di una soluzione di tale natura consentirebbe la realizzazione di una delle prime realtà nazionali adibite alla produzione industriale di idrogeno a basso impatto ambientale e dunque consentirebbe l’implementazione di sinergie e connessioni tra le attività, presenti e future, coinvolte nella catena del valore dell’idrogeno.

La première partie de cette thèse est dédiée à la modification de polyélectrolytes pour former des films de multicouche de polyélectrolytes (PEM) ayant des propriétés d’adhésion de protéine et de cellules bien contrôlées et modifiables par étirement. L’acide polyacrylique a été modifié avec des groupes latéraux phosphorylcholine (PC) à des taux de 25 % (PAA-PC) ou avec des chaînes oligo(éthylène oxyde) terminées par la biotine : (EO)nBiotine (n = 0, 3, 9 et 18) avec de taux de modification de 1, 5, 10 ou 25 %. Des PEM incorporant ces polymères lient spécifiquement la streptavidine et repoussent tout autre protéine. Les propriétés d’adsorption et la sélectivité de ces PEM ont été mesurées par microbalance à quartz. Sur un substrat de PDMS étirables, on a construit des PEM terminés par un PAA portant des RGD recouvert par deux couches contenant PAA-PC. Au repos, seuls les PC sont exposés et inhibent l’adhésion cellulaire ; sous étirement, les groupes RGD sous-jacents sont exposés et déclenchent l’adhésion de fibroblastes.La deuxième partie est consacrée à l‘étude d’acide polyméthacrylique modifié hydrophobiquement avec des chaînes alkyle liées par des esters à la chaîne principale. 3 chaînes différentes ont été greffées : -C12H25 ; -C18H35 et C4H8-OOC- C11H23 avec des taux de 1, 5 and 10 %. Ces polymères sont associatifs et forment des hydrogels dans des tampons physiologiques pour des taux de modifications de 5% et des concentrations supérieures à 4% en poids. Ces gels ont été caractérisés par des mesures rhéologiques. Leur incubation avec des lipases provoque une baisse de leur viscosité, interprétable par une coupure des esters. Quand les gels faits à partir du PAA-C12 sont incubés avec une culture de Pseudomonas aeruginosa, la viscosité baisse également, ce qui montre que les chaînes sont également coupées in vivo
The first part of this thesis is dedicated to the modification of polyelectrolytes to form polyelectrolyte films with controlled and stretch responsive cell and protein adsorption properties. Poly(acrylic acid) (PAA) was modified with side phosphorylcholine groups (PC) at rates of 25 % or with oligo(ethylene oxide) chains ended by biotin ((EO)nBiotin, (n =0, 3, 9 and 18) at 1, 5, 10 and 25 % modification rates. Polyelectrolytes multilayer films (PEM) containing these polyelectrolytes bind selectively streptavidin but repel all other proteins. The adsorption properties and selectivity were measured by quartz crystal microbalance. On a stretchable PDMS substrate, we have built PEM ended by PAA bearing RGD, covered by two PAA-PC layers on the top. Under rest, only the PC groups are exposed and prevent cell adhesion; when the film is stretched, the underlying RGD groups are exposed, and trigger adhesion of fibroblasts.The second part was consecrated to the study of poly(methacrylic acid) hydrophobically modified with alkyl chains connected through an ester moiety to the main chain. Three different chains were grafted -C12H25; -C18H35 and -C4H8- OOC-C11H23 with a rate of 1, 5 and 10 %. These polymers associate in water and form hydrogels in physiological buffer, for modification rates higher than 5 % and polymer concentrations higher than 4 wt. %. The gels were characterized by rheology. Their incubation with lipases resulted in a decrease of their viscosity, which could be interpreted by the cleavage of the hydrophobic side chains, by rheological tests. When the gels with PAA-C12 were incubated with a culture of Pseudomonas aeruginosa, their viscosity decreased, which shows that alkyle chains are also cleaved in vivo

[EN] Articular cartilage is a tissue with low capacity for self-restoration due to its avascularity and low cell population. It is located on the surface of the subchondral bone covering the diarthrodial joints. Degeneration of articular cartilage can appear in athletes, in people with genetic degenerative processes (osteoarthritis or rheumatoid arthritis) or due to a trauma; what produces pain, difficulties in mobility and progressive degeneration that finally leads to joint failure. Self-restoration is only produced when the defect reaches the subchondral bone and bone marrow mesenchymal stem cells (MSCs) invade the defect. However, this new formed tissue is a fibrocartilaginous type cartilage and no a hyaline cartilage, which finally leads to degeneration. Transplantation of autologous chondrocytes has been proposed to regenerate articular cartilage but this therapy fails mainly to the absence of a material support (scaffold) for the adequate stimulation of cells. Matrix-induced autologous chondrocyte implantation uses a collagen hydrogel as scaffold for chondrocytes; however, it does not have the adequate mechanical properties, does not provide the biological cues for cells and regenerated tissue is not articular cartilage but fibrocartilage. Different approaches have been done until now in order to obtain a scaffold that mimics better articular cartilage properties and composition. Hydrogels are a good option as they retain high amounts of water, in a similar way to the natural tissue, and can closely mimic the composition of natural tissue by the combination of natural derived hydrogels. Their three-dimensionality plays a critical role in articular cartilage tissue engineering to maintain chondrocyte function, since monolayer culture of chondrocytes makes them dedifferentiate towards a fibroblast-like phenotype secreting fibrocartilage. Recently, injectable hydrogels have attracted attention for the tissue engineering of articular cartilage due to their ability to encapsulate cells, injectability in the injury with minimal invasive surgeries and adaptability to the shape of the defect. Following this new approach we aimed at synthesizing two new families of injectable hydrogels based on the natural protein gelatin for the tissue engineering of articular cartilage. The first series of materials consisted on the combination of injectable gelatin with loose reinforcing polymeric microfibers to obtain injectable composites with improved mechanical properties. Our results demonstrate that there is an influence of the shape and distribution of the fibers in the mechanical properties of the composite. More importantly bad fiber-matrix interaction is not able to reinforce the hydrogel. Due to this, our composites were optimized by improving matrix-fiber interaction through a hydrophilic grafting onto the microfibers, with very successful results. The second series of materials were inspired in the extracellular matrix of articular cartilage and consisted of injectable mixtures of gelatin and hyaluronic acid. Gelatin molecules in the mixtures provided integrin adhesion sites to cells, and hyaluronic acid increased the mechanical properties of gelatin. This combination demonstrated ability for the differentiation of MSCs towards the chondrocytic lineage and makes these materials very good candidates for the regeneration of articular cartilage. The last part of this thesis is dedicated to the synthesis of a non-biodegradable material with mechanical properties, swelling and permeability similar to cartilage. This material intends to be used as a platform in a bioreactor in which the typical loads of the joint are simulated, so that the hydrogels or scaffolds would fit in the recesses in the platform. The function of the platform is to simulate the effect of the surrounding tissue on the scaffold after implantation and could reduce animal experimentation by simulating in vivo conditions.
[ES] El cartílago articular es un tejido con baja capacidad de auto-reparación debida a su avascularidad y baja población celular. Se encuentra en la superficie del hueso subcondral cubriendo las articulaciones. La degeneración del cartílago articular puede aparecer en atletas, en personas con procesos genéticos degenerativos o debido a un trauma; lo que produce dolor, dificultades en la movilidad y degeneración progresiva que lleva al fallo de la articulación. La auto-reparación sólo se produce cuando el defecto alcanza el hueso subcondral y las células madre (MSCs) de la médula ósea invaden el defecto. Sin embargo, este nuevo tejido es un cartílago de tipo fibrocartilaginoso y no un cartílago hialino, el cual finalmente lleva a la degeneración. El trasplante de condrocitos autólogos ha sido propuesto para regenerar el cartílago articular pero esta terapia falla principalmente por la ausencia de un material soporte (scaffold) que estimule adecuadamente a las células. El implante de condrocitos autólogos mediante un hidrogel de colágeno no tiene las propiedades mecánicas apropiadas, no proporciona las señales biológicas a las células y el tejido regenerado no es cartílago articular sino fibrocartílago. Se han realizado diferentes enfoques para obtener un scaffold que mimetice mejor las propiedades y la composición del cartílago articular. Los hidrogeles son una buena opción ya que retienen elevadas cantidades de agua, de forma similar al tejido natural, y pueden imitar de cerca la composición del tejido natural mediante la combinación de derivados de hidrogeles naturales. Su tridimensionalidad juega un papel crítico para mantener la función de los condrocitos, ya que el cultivo en monocapa de los condrocitos hace que desdiferencien hacia un fenotipo similar al fibroblasto secretando fibrocartílago. Los hidrogeles inyectables han acaparado la atención en la ingeniería tisular de cartílago articular debido a su capacidad para encapsular células, su inyectabilidad en el daño con cirugías mínimamente invasivas y su adaptabilidad a la forma del defecto. Siguiendo este nuevo enfoque hemos sintetizado dos nuevas familias de hidrogeles inyectables basados en la proteína natural gelatina para la ingeniería tisular del cartílago articular. La primera serie de materiales combina una gelatina inyectable con microfibras poliméricas sueltas de refuerzo para obtener composites inyectables con propiedades mecánicas mejoradas. Nuestros resultados demuestran que hay una influencia de la forma y la distribución de las fibras en las propiedades mecánicas del composite. Además, la mala interacción entre las fibras y la matriz no es capaz de reforzar el hidrogel. Debido a esto, nuestros composites han sido optimizados mediante la mejora de la interacción fibra-matriz a través de un injerto hidrófilo sobre las microfibras, con resultados muy exitosos. La segunda serie de materiales se ha inspirado en la matriz extracelular del cartílago articular y ha consistido en mezclas inyectables de gelatina y ácido hialurónico. Las moléculas de gelatina proporcionan los dominios de adhesión mediante integrinas a las células, y el ácido hialurónico aumenta las propiedades mecánicas de la gelatina. Esta combinación ha demostrado la habilidad para la diferenciación de MSCs hacia el linaje condrocítico y convierte a estos materiales en buenos candidatos para la regeneración del cartílago articular. La última parte de esta tesis se dedica a la síntesis de un material no biodegradable con propiedades mecánicas, hinchado y permeabilidad similar al cartílago. Este material pretende ser empleado como plataforma en un biorreactor en el que se simulan las cargas típicas de las articulaciones, de forma que los scaffolds encajarían en los huecos de la plataforma. Su función es simular el efecto del tejido circundante en el scaffold después de su implantación y podría reducir la experimentación anim
[CAT] El cartílag articular es un teixit amb baixa capacitat d'auto-reparació deguda a la seua avascularitat i baixa població cel·lular. Es troba en la superfície de l'ós subcondral cobrint les articulacions. La degeneració del cartílag articular pot aparèixer en atletes, en persones amb processos genètics degeneratius o degut a un trauma; produeix dolor, dificultats a la mobilitat i degeneració progressiva que finalment porta a la fallida de l'articulació. L'auto-reparació es produeix quan el defecte arriba fins a l'ós subcondral i les cèl·lules mare (MSCs) de la medul·la òssia envaeixen el defecte. No obstant això, aquest nou teixit format es un cartílag de tipus fibrocartilaginós i no un cartílag hialí, el qual finalment porta a la degeneració. El transplantament de condròcits autòlegs ha sigut proposat per a regenerar el cartílag articular però aquesta teràpia falla principalment per la absència d'un material de suport (scaffold) que estimuli adequadament a les cèl·lules. L'implant de condròcits autòlegs en un hidrogel de col·lagen per als condròcits no té les propietats mecàniques apropiades, no proporciona les senyals biològiques a les cèl·lules i el teixit regenerat no és cartílag articular sinó fibrocartílag. Diferents enfocs han sigut realitzats fins ara per a obtenir un scaffold que mimetitzi millor les propietats i la composició del cartílag articular. Els hidrogels son una bona opció ja que retenen elevades quantitats d'aigua, de forma similar al teixit natural, i poden imitar acuradament la composició del teixit natural mitjançant la combinació d'hidrogels naturals. La seua tridimensionalitat juga un paper crític per a mantenir la funció dels condròcits, ja que el cultiu en monocapa dels condròcits fa que aquests desdiferencien cap a un fenotip similar al fibroblàstic secretant fibrocartílag. Recentment, els hidrogels injectables han acaparat l'atenció en l' enginyeria tissular de cartílag articular degut a la seua capacitat per a encapsular cèl·lules, la seua injectabilitat en el dany amb cirurgies mínimament invasives i la seua adaptabilitat a la forma del defecte. Seguint aquesta nova aproximació hem sintetitzat dues noves famílies d'hidrogels injectables basats en la proteïna natural gelatina per a l'enginyeria tissular del cartílag articular. La primera sèrie de materials combina una gelatina injectable amb microfibres polimèriques soltes de reforç per a obtenir compòsits injectables amb propietats mecàniques millorades. Els nostres resultats demostren que hi ha una influència de la forma i la distribució de les fibres en les propietats mecàniques del compòsit. Més importantment, la mala interacció entre les fibres i la matriu no és capaç de reforçar l'hidrogel. Degut a això, els nostres compòsits han segut optimitzats mitjançant la millora de la interacció fibra-matriu a traves d'un empelt hidròfil sobre les fibres, amb resultats molt exitosos. La segona sèrie de materials està inspirada en la matriu extracel·lular del cartílag articular i ha consistit en mescles injectables de gelatina i àcid hialurònic. Les molècules de gelatina proporcionen els dominis d'adhesió mitjançant integrines a les cèl·lules, i l'àcid hialurònic augmenta les propietats mecàniques de la gelatina. Esta combinació ha demostrat l'habilitat per a la diferenciació de MSCs cap al llinatge condrocític i converteix a aquests materials en bons candidats per a la regeneració del cartílag articular. L'última part d'aquesta tesi és dedicada a la síntesi d'un material no biodegradable amb propietats mecàniques, inflat i permeabilitat similar al cartílag. Aquest material pretén ser utilitzat com a plataforma a un bioreactor que simula les cargues típiques de les articulacions, de manera que els hidrogels o scaffolds encaixarien als buits de la plataforma. La seua funció es simular l'efecte del teixit circumdant al scaffold després d
Poveda Reyes, S. (2016). Protein-based injectable hydrogels towards the regeneration of articular cartilage [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/61392
TESIS
Premiado

Hydrogen gas (H2), that is not produced from fossil oil or natural gas, is expected to become a cornerstone in the energy transition strategy in Europe. The recent years, technological and economic advances in the electrolyzer area, along with political and corporate support, have put H2 at the forefront of many countries’ climate change agenda. Consequently, green H2 is poised to play a large role in the coming energy transition to combat climate change. The possible advantages of integrating H2 production with a combined heat and power plant, or CHP, is investigated in this study. More precisely, the water electrolysis is carried out based on the purified flue gas condensate water and excess heat is recovered as district heating. A comparison of today’s three most common electrolyzer technologies was made, where Proton Exchange Membrane, or PEM, technology was chosen for this project, mainly for its high purity of H2 gas, robust construction, and the ability to run it as a fuel cell. Based on a mass and energy balance, a model including the integration of a PEM with a generic CHP plant was developed. The model was made modifiable, making it possible to change governing parameters, to be able to investigate different possible scenarios. Production flows, losses and other relevant data was calculated from the model. Operational data for the PEM electrolyzer were collected from several manufacturers where a mean value of the data was used as a base-case for the calculations. Based on literature and consulting experts, several assumptions were made, for example the selling price of H2 and the price for electricity. From the base-case were two cases made: a linear and non-linear case. The linear case uses the same input data each year for 20 years, while the non-linear case uses a changing input data each year for 20 years. Calculations were based on an electrolyzer size of 1,4 MW, where auxiliary equipment consumed additional 0,04 MW, resulting in a total energy consumption of 1,44 MW. An operational temperature of 80°C was assumed along with an operational pressure of 5 and 30 bar for the anode and cathode respectively. This resulted in an H2 production flow of 26 kg/h, a process water requirement of 0,2 m3/h, and a possible heat recovery amount of 0,34 MWh with a relevant temperature for the use in district heating. The study shows that the condensate-water at E.ON could provide for ~4000 hours of operation in the wintertime. To enable full operation all year around, a purchase of tap water would be necessary. The economical calculations resulted in an H2 production cost of 53 SEK/kg for the linear case and 58 SEK/kg for the non-linear case. The linear case showed a positive internal rate of return, or IRR, of 1,7%, while the non-linear case resulted in IRR < -25%. A sensitive analysis was made to examine governing parameters. The results of the sensitivity analysis showed that the largest driving variables, that significantly affect the IRR, are the price for electricity and the selling price for H2. The largest OPEX cost was found to be the price of electricity. The results showed that it is feasible to produce H2 at E.ON Örebro in a resource efficient way under certain circumstances, correlated to the electricity and H2 market. With a low electricity price and a selling price of ~50 SEK/kg for H2, good profitability is expected.  It is also clear that future work should focus the areas of O2 usage, infrastructure, and market investigation for a more definitive conclusion.

L'infarto miocardico rappresenta al giorno d'oggi una delle principali cause di moralità in tutto il mondo e le tradizionali strategie terapeutiche non risultano essere particolarmente efficienti ed efficaci nel ripristinare la funzionalità del miocardio infartuato. In alternativa alle tradizionali terapie, le innovative strategie terapeutiche, quali cardiopatch impiantabili e gli idrogel iniettabili, garantiscono ottimi standard in termini di proprietà meccaniche, elettroconduttive, vitalità e proliferazione cellulare. Sebbene entrambi gli approcci risultino particolarmente efficaci, l'applicazione di un singolo sistema potrebbe portare ad una efficacia terapeutica limitata. Una possibile soluzione, in ottica futura, potrebbe essere quella di combinare entrambe le terapie e ottenere così i vantaggi di entrambi i sistemi

Hydrogen is considered one of the means by which to store energy coming from renewable and intermittent power sources. With the growing capacity of renewable energy sources, a storage system is required to not waste energy. PEM electrolysis provides a sustainable solution for the production of hydrogen and is well suited to couple with energy sources such as solar and wind. This work reports the development of simulation software to estimate the performance of a proton exchange membrane electrolyzer working at atmospheric or low pressure conditions connected to a solar energy source. The electrolyzer is defined from a validated reference semi-empirical model, which allows for simulating the electrochemical, thermal and H2 output flow behaviours with enough precision for engineering applications. An algorithm for a fitting procedure to characterize commercial products, and functions for power modulation have been implemented. A series of simulations have been carried on, starting from real photovoltaic data of input power, and the output values have been discussed, with particular attention to output flow rate, thermal behaviour and the cooling demand in order to preserve the operation of the electrolyzer.

The work in this thesis addresses the improvement of electrocatalyst performance in hydrogen PEM fuel cells. An agglomerate model for a catalyst layer was coupled with a one dimensional macroscale model in order to investigate the fuel cell performance. The model focuses on the agglomerate scale and the characteristic length in this study was 0.4 µm. The model was validated successfully with the experimental data. Based on the analysis of variance method at a 99% confidence level, the variation in the average fuel cell voltage was significantly sensitive to that in the volume fraction of electrolyte in an agglomerate. The effect of changing electrolyte film thickness was observed to have a significant impact only in the mass transport limited region, whereas the effect of changing agglomerate radius was found over the entire range of current density. An analysis comparing the effect of agglomerate shape at a constant platinum loading, a constant characteristic length and assuming the semi-finite structure was suitable for this study. Sphere, cylinder and slab agglomerate geometries were considered. The behaviour of the utilisation effectiveness was discovered to be strongly affected by the agglomerate shape. The improvement in the utilisation effectiveness was non-linear with current density. The advantage of the slab geometry in distributing reactant through the agglomerate volume was reduced and consequently the increase in utilisation effectiveness for slab-like agglomerates diminishes in the high current density region. At 0.85 Acm−2, the maximum improvement of the catalyst utilisation effectiveness in slab was 27.8% based on the performance in sphere. The improvement in fuel cell maximum power density achieved using slab-like agglomerate was limited to around 3%. The improvement in the overall fuel cell performance by changing the agglomerate shape was not significant. To achieve significant improvements in fuel cell performance will require changes to other features of the catalyst layer.

Recently, the role of hydrogen sulphide (H2S) a well known toxic gas with reducing properties has received a great interest. It has been found that H2S is produced in consistent quantity in the mammalian tissues and it exerts several physiological effects that suggest its role as a regulating mediator. H2S is involved in the regulation of the muscular tone, of the myocardial contractility, in the inflammatory processes, in the neurotransmission and in insulin secretion. Reduced levels of H2S were observed in several animal models of artery and pulmonary hypertension, damages of gastric mucosa and hepatic cirrhosis. Exogenous H2S inhibits inflammation, improves cardiac dysfunctions associated to ischemia/reperfusion and reduces the gastric damage induced by anti-inflammatory drugs. On the other hand, if not properly controlled and in excessive doses, endogenous H2S may contribute to tissue inflammation through stimulation of related converting enzymes (CBA and CBS). H2S has also an active role in the redox imbalance processes. In particular this gas mediator influences the activation of cellular inflammatory processes interacting with signalling mechanisms, transcription factors and neutralizing ROS. Moreover it has been reported that it has cytoprotective properties due to GSH production in several tissues. On this basis, it is clear the utility of molecules capable to modulate the plasma and tissue concentration of H2S especially in pathologies characterised by disorders of GSH homeostasis and increase of oxidative stress as it happens in neurodegenerative diseases, cystic fibrosis and other severe lung pathologies, but also in cardiovascular diseases (such as metabolic syndrome) etc. An interesting and innovative approach is the synthesis of hybrid molecules that combine the structure of a known drug with a sulfurated moiety able to in vivo slowly release H2S. Therefore, the purpose of this thesis was the synthesis of hybrid compounds active in neurodegenerative diseases (PD), such as sulfurated derivatives of L-DOPA and H2S-releasing drugs active on the peripheral circulatory system, such as sulfurated derivatives of phosphodiesterase 5 (PDE-5) inhibitors, in order to improve the efficacy and tolerability of the parent compound. Cysteine hybrid compounds coupled to dithiolethiones, addressed to treatment of specific metabolic conditions such as hyperhomocysteinemia, were also synthesized. The pharmacological studies conducted until now show that the H2S-releasing drugs, described in this thesis, by in vivo H2S releasing and modulating, have important antioxidant, anti-inflammatory and cytoprotective properties, while maintaining the pharmacological profile of the original drug. These data confirm the potential usefulness of new compounds in the treatment of many different diseases in which there is an inflammatory and / or a redox imbalance component.

Due to the limited regenerative capacity of the central nervous system (CNS) upon injury, regenerative medicine and tissue engineering strategies show great promise for treatment. These aim to restore tissue functions by combining principles of cell biology and engineering, using biomaterial scaffolds which can help in recapitulating the 3D environment of the brain and improving cell survival after grafting. Stroke and TBI are severe forms of disruptions of brain architecture, and two of the leading causes of mortality and morbidity worldwide, as no effective treatments are available. Several studies report how neural stem cells (NSCs) are able to improve functional recovery upon transplantation. However, the efficacy of these treatments is limited because of the mortality these cells are subject to after transplantation. In this context, the transplantation of mesenchymal cells (MSCs) has shown beneficial effects by secreting molecules and factors that help in the healing process. In this study, we tested alginate-based hydrogels as candidates to support human NSCs and MSCs transplantation into the brain, in the view of exploiting the beneficial effects of both and analyzing whether their combined use could have a synergistic effect. In the first part, we studied the suitability of alginate-based scaffolds for the three-dimensional encapsulation and culture of hNSCs and hMSCs. We analyzed their ability to support cell survival, and we evaluated whether changes in their concentration or modifications with ECM molecules could influence cell viability. We showed that the best survival conditions are found when using an RGDs-functionalized alginate scaffold at a low concentration (0.5% w/v). We then worked on the identification of the best conditions for MSCs culture and the definition of coculture conditions. Since serum is necessary for MSCs, but it is reported to induce glial differentiation of NSCs, we explored two different experimental setups. On one hand, we investigated the feasibility to exploit biomaterials to create "compartmentalized" cocultures that would at least partially retain serum. In parallel, we positively observed that MSCs can survive, proliferate and maintain their stemness even in absence of serum, supporting the hypothesis that the use of “compartmentalized” coculture systems would likely be exploitable for MSCs culture. Finally, we tested the reported beneficial effects of MSCs in our 3D culture system, in which NSCs do not show a great viability. Encapsulated NSCs were cultured on an MSCs monolayer, and we analyzed cell survival, proliferation, differentiation and stemness retention. Gene expression analyses highlighted that NSCs maintain stemness characteristics, but we were not able to observe any improvement in NSCs survival in coculture, with respect to standard culture. In the last part of the project we decided to test our system for tissue engineering approaches, exploiting axotomized brain organotypic slices (OSCs). We evaluated the presence of cells 7 days after transplantation, their integration in the OSCs and glial response. Preliminary results suggest that the biomaterial does not cause activation of glial cells, although stem cells do not seem to migrate out of scaffold and integrate into the brain slice.

Due to the limited regenerative capacity of the central nervous system (CNS) upon injury, regenerative medicine and tissue engineering strategies show great promise for treatment. These aim to restore tissue functions by combining principles of cell biology and engineering, using biomaterial scaffolds which can help in recapitulating the 3D environment of the brain and improving cell survival after grafting. Stroke and TBI are severe forms of disruptions of brain architecture, and two of the leading causes of mortality and morbidity worldwide, as no effective treatments are available. Several studies report how neural stem cells (NSCs) are able to improve functional recovery upon transplantation. However, the efficacy of these treatments is limited because of the mortality these cells are subject to after transplantation. In this context, the transplantation of mesenchymal cells (MSCs) has shown beneficial effects by secreting molecules and factors that help in the healing process. In this study, we tested alginate-based hydrogels as candidates to support human NSCs and MSCs transplantation into the brain, in the view of exploiting the beneficial effects of both and analyzing whether their combined use could have a synergistic effect. In the first part, we studied the suitability of alginate-based scaffolds for the three-dimensional encapsulation and culture of hNSCs and hMSCs. We analyzed their ability to support cell survival, and we evaluated whether changes in their concentration or modifications with ECM molecules could influence cell viability. We showed that the best survival conditions are found when using an RGDs-functionalized alginate scaffold at a low concentration (0.5% w/v). We then worked on the identification of the best conditions for MSCs culture and the definition of coculture conditions. Since serum is necessary for MSCs, but it is reported to induce glial differentiation of NSCs, we explored two different experimental setups. On one hand, we investigated the feasibility to exploit biomaterials to create "compartmentalized" cocultures that would at least partially retain serum. In parallel, we positively observed that MSCs can survive, proliferate and maintain their stemness even in absence of serum, supporting the hypothesis that the use of “compartmentalized” coculture systems would likely be exploitable for MSCs culture. Finally, we tested the reported beneficial effects of MSCs in our 3D culture system, in which NSCs do not show a great viability. Encapsulated NSCs were cultured on an MSCs monolayer, and we analyzed cell survival, proliferation, differentiation and stemness retention. Gene expression analyses highlighted that NSCs maintain stemness characteristics, but we were not able to observe any improvement in NSCs survival in coculture, with respect to standard culture. In the last part of the project we decided to test our system for tissue engineering approaches, exploiting axotomized brain organotypic slices (OSCs). We evaluated the presence of cells 7 days after transplantation, their integration in the OSCs and glial response. Preliminary results suggest that the biomaterial does not cause activation of glial cells, although stem cells do not seem to migrate out of scaffold and integrate into the brain slice.

Actuellement, l'hydrogène est considéré comme un vecteur d'énergie prometteur. Cependant, il est préalablement produit par une électrolyse, une photo-catalyse, ou des procédés thermochimiques, biologiques. En suit une étape de stockage/conditionnement se réalisant par une compression, une liquéfaction, une physisorption ou une chimisorption. Enfin, la conversion quand elle est électrochimique et a lieu dans les piles à combustible. L'hydrogène remplit les principales caractéristiques pour atteindre les performances requises comme vecteur énergétique efficace, mais sa faible densité volumique reste un point faible. L’étape de compression reste nécessaire et doit avoir un rendement énergétique élevé. De plus, la purification est également essentielle notamment pour des applications comme la mobilité.Le but de ce travail est d'étudier les dispositifs à électrolyte type membrane polymère (PEM : proton exchange membrane) que l’on retrouve fréquemment dans la filière hydrogène. Plus précisément, l'électrolyse de l'eau (PEMWE, Proton exchange Membrane Water Electrolysis) pour la production d'hydrogène et le compresseur/concentrateur électrochimique d'hydrogène (EHC, Eletrochemical Hydrogen Compressor) pour le stockage et la purification de l'hydrogène. Dans un premier temps, une étude préliminaire a été réalisée à l'aide d'un modèle adimensionnel analytique en régime permanent. Ce dernier a été appliqué aux cellules d'électrolyse fonctionnant avec un gradient de pression important. Cette approche permet l'estimation des performances à l'aide de trois nombres adimensionnels qui sont régi par la cinétique électrochimique au niveau de la couche active et le transport de matière dans la membrane. Les nombres adimensionnels sont : (i) un nombre de type Wagner à l’anode et à la cathode qui représente le rapport entre la conductivité protonique et la cinétique électrochimique au niveau de la couche active. (ii) un nombre similaire au module de Thiele au niveau des couches actives qui décrit la conductivité protonique effective et la densité de courant opérationnel, (iii) un rapport sans dimension décrivant le processus de transport de l'eau à travers la membrane. Le modèle a été appliqué à l'électrolyse de l'eau et le modèle est en bonne adéquation avec les résultats expérimentaux.Dans un second temps, une étude expérimentale de compression et de purification à l'aide d'une cellule EHC a été mise en œuvre. Lors de ces tests, la compression a été effectuée entre 0 et 30 bars pour différentes températures et humidité relative. De plus, une mesure par spectroscopie d'impédance électrochimique (SIE) a permis de caractériser la cellule EHC. Ces expériences ont été menées pour deux alimentations : hydrogène pur et un mélange d'hydrogène/azote. Grâce à l'analyse d'entropie des résultats expérimentaux et la caractérisation post mortem à l'aide de l'imagerie MEB et des spectres IRTF, il a été constaté que l'azote n'est pas inerte lors du processus électrochimique. De manière surprenante, le N2 peut conduire à la dégradation de la membrane due à la synthèse locale de NH3. Enfin, un modèle de spectroscopie d'impédance électrochimique (SIE) a été développé. La SIE est une méthode de caractérisation puissante qui inclue à la fois des approches théoriques et expérimentales en décrivant les différents processus physiques et électrochimiques dans un système complexe. Le modèle analytique monodimensionnel développé en régime dynamique permet de caractériser les phénomènes prenant place aux électrodes d’une cellule EHC. Cette méthode permet de mettre en évidence les processus limitants et de prédire les artefacts
Currently, hydrogen is considered as a promising energy carrier. However, it needs to be produced first using electrolysis, photo catalysis, thermochemical or biological processes. Then hydrogen is stored by compression, liquefaction, physisorption or chemisorption. Lastly, the conversion process occurs, which is based on using it as a product or a reactant in an application like Fuel Cells. Hydrogen fulfils the main characteristics to achieve the performance required for efficient energy carrier, but its low volume density remains a weak point. An extremely high energy-efficient compression is a necessary step. On the other hand, hydrogen purification step is also essential for several applications as mobility.The aim of this work is to investigate the Polymer Electrolyte Membrane (PEM) devices for hydrogen energy carrier. Specifically, PEM Water Electrolysis (PEMWE) for hydrogen production and Electrochemical Hydrogen Compressor/Concentrator (EHC) for hydrogen storage. First, a preliminary study was carried out using a dimensionless analytical steady state model of PEM electrolysis cells operating with large pressure gradient. This approach enables the estimation of performance using three dimensionless parameters that governed the electrochemical reaction at the catalyst layer and the mass transport through the membrane. The dimensionless numbers are: (i) a Wagner like numbers at the anode and cathode side which is the ratio between the protonic conductivity and the electrochemical kinetic at the catalyst layer, (ii) a number similar to Thiele modulus at the catalyst layers that describes the effective protonic conductivity and the operational current density, (iii) a dimensionless ratio describing the water transport process through the membrane. The model was applied to the PEMWE and it was in good agreement with the experimental data. Secondly, hydrogen compression and purification experiments were conducted using an EHC. During these tests, the compression was performed between 0 and 30 bars for different temperatures and relative humidity. In addition, an electrochemical impedance spectroscopy (EIS) measurement was also performed. These experiments ran on both pure hydrogen and hydrogen/nitrogen mixture. After the data entropy analysis and the postmortem characterization using FTIR and SEM imaging it was found that the azote is not a benign component for this application. Surprisingly, the N2 can lead to the degradation of the membrane due to local NH3 synthesis. Finally, an electrochemical impedance spectroscopy (EIS) model was developed. The EIS is a strong characterization method which inclines both theoretical and experimental approaches by modelling the different physics and electrochemical process into a very complexed system. The one-dimensional analytical model describes the electrochemical kinetics of the cell in EIS regime. This method allows to highlight the limiting process and to predict the artefacts

The first part of this essay aims at investigating the already available and promising technologies for the biogas and bio-hydrogen production from anaerobic digestion of different organic substrates. One strives to show all the peculiarities of this complicate process, such as continuity, number of stages, moisture, biomass preservation and rate of feeding. The main outcome of this part is the awareness of the huge amount of reactor configurations, each of which suitable for a few types of substrate and circumstance. Among the most remarkable results, one may consider first of all the wet continuous stirred tank reactors (CSTR), right to face the high waste production rate in urbanised and industrialised areas. Then, there is the up-flow anaerobic sludge blanket reactor (UASB), aimed at the biomass preservation in case of highly heterogeneous feedstock, which can also be treated in a wise co-digestion scheme. On the other hand, smaller and scattered rural realities can be served by either wet low-rate digesters for homogeneous agricultural by-products (e.g. fixed-dome) or the cheap dry batch reactors for lignocellulose waste and energy crops (e.g. hybrid batch-UASB). The biological and technical aspects raised during the first chapters are later supported with bibliographic research on the important and multifarious large-scale applications the products of the anaerobic digestion may have. After the upgrading techniques, particular care was devoted to their importance as biofuels, highlighting a further and more flexible solution consisting in the reforming to syngas. Then, one shows the electricity generation and the associated heat conversion, stressing on the high potential of fuel cells (FC) as electricity converters. Last but not least, both the use as vehicle fuel and the injection into the gas pipes are considered as promising applications. The consideration of the still important issues of the bio-hydrogen management (e.g. storage and delivery) may lead to the conclusion that it would be far more challenging to implement than bio-methane, which can potentially “inherit” the assets of the similar fossil natural gas. Thanks to the gathered knowledge, one devotes a chapter to the energetic and financial study of a hybrid power system supplied by biogas and made of different pieces of equipment (natural gas thermocatalitic unit, molten carbonate fuel cell and combined-cycle gas turbine structure). A parallel analysis on a bio-methane-fed CCGT system is carried out in order to compare the two solutions. Both studies show that the apparent inconvenience of the hybrid system actually emphasises the importance of extending the computations to a broader reality, i.e. the upstream processes for the biofuel production and the environmental/social drawbacks due to fossil-derived emissions. Thanks to this “boundary widening”, one can realise the hidden benefits of the hybrid over the CCGT system.

Biomass-fuelled proton exchange membrane fuel cells (PEMFCs) offer asolution for replacing fossil fuel for hydrogen production. Through using thebiomass-derived hydrogen as fuel, PEMFCs may become an efficient andsustainable energy system for small and medium-sized enterprises. The aim ofthis thesis is to evaluate the performance and potential applications of biomassfuelledPEMFC systems which are designed to convert biomass to electricity andheat. Biomass-fuelled PEMFC systems are simulated by Aspen plus based ondata collected from experiments and literature.The impact of the quality of the hydrogen-rich gas, anode stoichiometry, CH4content in the biogas and CH4 conversion rate on the performance of the PEMFCis investigated. Also, pinch technology is used to optimize the heat exchangernetwork to improve the power generation and thermal efficiency.For liquid and solid biomass, anaerobic digestion (AD) and gasification (GF),respectively, are relatively viable and developed conversion technologies. ForAD-PEMFC, a steam reformer is also needed to convert biogas to hydrogen-richgas. For 100 kWe generation, the GF-PEMFC system yields a good technicalperformance with 20 % electrical efficiency and 57 % thermal efficiency,whereas the AD-PEMFC system only has 9 % electrical efficiency and 13 %thermal efficiency. This low efficiency is due to the low efficiency of theanaerobic digester (AD) and the high internal heat consumption of the AD andthe steam reformer (SR). For the environmental aspects, the GF-PEMFC systemhas a high CO2 emissions offset factor and the AD-PEMFC system has anefficient land-use.The applications of the biomass-fuelled PEMFC systems are investigated on adairy farm and an olive oil plant. For the dairy farm, manure is used as feedstockto generate biogas through anaerobic digestion. A PEMFC qualified for 40 %electrical efficiency may generate 360 MWh electricity and 680 MWh heat peryear to make a dairy farm with 300 milked cows self-sufficient in a sustainableway. A PEMFC-CHP system designed for an olive oil plant generating annual 50000 m3 solid olive mill waste (SOMW) and 9 000 m3 olive mill waste water(OMW) is simulated based on experimental data from the Biogas2PEM-FCproject1. After the optimization of the heat exchanger network, the PEMFC-CHP  system can generate 194 kW electricity which corresponds to 62 % of the totalelectricity demand of the olive oil plant.The economic performance of the PEMFC and biogas-fuelled PEMFC areassessed roughly including capital, operation & maintenance (O&M) costs of thebiogas plant and the PEMFC-CHP, the cost of heat and electricity, and the valueof the digestate as fertilizer.

QC 20151109

The thesis is focused to hydrogen usage in the aviation. There are shown existing types of fuel cells and hydrogen storage possibilities. Main part of the thesis is conceptual design of small UAV with hydrogen fuel cell, which will show potential of hydrogen power system.

L'objectif principal de cette thèse est de concevoir, mettre en œuvre et comparer différentes stratégies de gestion de l'énergie et approches d'optimisation pour un système hybride impliquant l'intégration de l'énergie marémotrice flottante avec la production de l'hydrogène vert. Pour atteindre les objectifs, les composants individuels du système sont d'abord modélisés. Les capacités annuelles de performance du système de la centrale d'énergie marémotrice ont ensuite été obtenues à l'aide des profils quotidiens fréquents au poste d'amarrage de Fall of Warness dans les îles Orcades. Les modes de fonctionnement transitoires des électrolyseurs à membrane échangeuse de protons, lorsqu'elles sont soumises à l'énergie de la centrale hydrolienne, ont été analysés sur la base d'une (RBA) stratégie de gestion de l'énergie basée sur des règles. Plus tard, une évaluation préliminaire du coût de production d'hydrogène est effectuée sur la base de différentes conditions de demande quotidienne d'hydrogène et de profils de marée quotidiens. En outre, une approche d'optimisation dans le but de maximiser le profit d'exploitation du système tout en assurant un fonctionnement optimal et suffisant des deux électrolyseurs sous des contraintes réelles du système, est formulée en donnant la priorité à la production d'hydrogène par l'énergie marémotrice. Le problème d'optimisation est résolu à l'aide d'un algorithme génétique basé sur un problème non linéaire à entiers mixtes. Une analyse coûts-avantages complète basée à la fois sur les coûts fixes-variables et sur les facteurs de coûts actualisés est réalisée pour analyser le fonctionnement technico-environnemento-économique optimal d'un système hybride d'énergie marémotrice-éolienne-hydrogène connecté au réseau. Les résultats ont été comparés aux résultats de l'approche basée sur des règles. Les bénéfices annuels dans l'approche d'optimisation ont été estimés supérieurs de 41,5 % par rapport à ceux de la RBA. De plus, d'un point de vue environnemental, les meilleurs résultats d'optimisation étaient supérieurs d’environ 47 % par rapport aux résultats de la RBA en termes de réduction des émissions de carbone. Un électrolyseur dynamique capable de fonctionner à deux fois sa puissance nominale pendant une durée limitée s'avère particulièrement avantageux lorsqu'il est couplé à l'énergie marémotrice qui est de nature cyclique avec des périodes prévisibles de production d'énergie élevée et faible. Enfin, il est conclu que l'approche d'optimisation des coûts fixes-variables est relativement simple dans l'estimation des coûts. Au contraire, bien que des résultats légèrement meilleurs soient obtenus dans le cas de l'approche par coût actualisé, il est nécessaire d'avoir une meilleure connaissance préalable du fonctionnement du système pour estimer finement les facteurs de coût actualisé. Le modèle proposé peut être utilisé comme un outil générique pour l'analyse de la production d'hydrogène dans différents contextes et il est particulièrement applicable dans les sites à fort potentiel d'énergie verte avec des installations de réseau limitées
The overarching aim of this thesis is to design, implement and compare different energy management strategies and optimisation approaches for a hybrid system involving floating tidal stream energy integration with green hydrogen production. Towards reaching the objectives, the individual system components are modelled initially. The annual system performance capabilities of the tidal stream energy plant are then obtained using frequently occurring daily profiles at the Fall of Warness berth in the Orkney Islands, Scotland. The transitionary operating modes of two polymer electrolyte membrane electrolyser units, when subjected to the energy from the tidal stream plant are analysed based on a rule-based approach energy management strategy. Later, a preliminary evaluation of the hydrogen production cost is assessed based on different daily hydrogen demand and daily tidal profile conditions. Further, an optimisation approach with the objective to maximise the system operating profit ensuring optimal and sufficient operations of both the electrolyser units under real system constraints, is formulated with priority for tidal energy powered hydrogen production. The optimisation problem is solved using a genetic algorithm based on the mixed integer non-linear problem. A comprehensive cost-benefit analysis based on fixed-variable costs and levelised costs factors is performed to analyse the optimal techno-enviro-economic operation of a hybrid grid connected tidal-wind-hydrogen energy system. The outcomes are compared against the rule-based approach results. The annualised profits in the optimisation approach are estimated to be 41.5% higher compared to the rule-based approach. Further, from an environmental view, the best optimisation results are approximately 47% higher than the rule-based approach results in terms of carbon emission reductions. A dynamic electrolyser capable of working at twice of its nominal power rating for limited duration, resulted particularly advantageous when coupled with tidal energy which is cyclic in nature with predictable periods of high and low power generation. Finally, it was determined that the fixed cost (FC) optimisation approach is relatively simple in terms of cost estimation. On the contrary, while the levelised cost (LC) approach yields slightly better results, it necessitates a greater prior knowledge of system operations to reasonably estimate the cost factors. The proposed method can be used as a generic tool for electrolytic hydrogen production analysis under different contexts, with preferable application in high green energy potential sites with constrained grid facilities

In this thesis, solar-hydrogen Stand-Alone Power System (SAPS) which is planned to be built for the emergency room of a hospital is designed. The system provides continuous, off-grid electricity during the whole period of a year without any external electrical power supply. The system consists of Photovoltaic (PV) panels, Proton Exchange Membrane (PEM) based electrolyzers, PEM based fuel cells, hydrogen tanks, batteries, a control mechanism and auxiliary equipments such as DC/AC converters, water pump, pipes and hydrogen dryers. The aim of this work is to investigate the optimal system configuration and component sizing which yield to high performance and low cost for different user needs and control strategies. TRNSYS commercial software is used for the overall system design and simulations. Numerical models of the PV panels, the control mechanism and the PEM electrolyzers are developed by using theoretical and experimental data and the models are integrated into TRNSYS. Overall system models include user-defined components as well as the default software components. The electricity need of the emergency room without any shortage is supplied directly from the PV panels or by the help of the batteries and the fuel cells when the solar energy is not enough. The pressure level in the hydrogen tanks and the overall system efficiency are selected as the key design parameters. The major component parameters and various control strategies affecting the hydrogen tank pressure and the system efficiency are analyzed and the results are presented.

Fuel cells based Micro Combined Heat and Power (micro-CHP) systems maintain good efficiencies for small size plants and at partial load making them suitable for domestic applications. High Temperature Polymer Electrolyte Membrane (HT-PEM) fuel cells are a promising technology for micro-CHP system, especially thanks to their high CO tolerance that allows the use of fuels other than hydrogen. Nevertheless, cost, performance and degradation issues are still to be overcome to fully achieve commercialization. Regarding performance degradation, operating conditions strongly affect their durability. The purpose of this research is to determine how the degradation issues for HT-PEM fuel cells, installed in micro-CHP systems, can be handled to make the system become suitable for long term operation, in terms of performance. To do so, a specific methodology has been developed for experimental testing and modelling of performance degradation of HT-PEM fuel cells for use on micro-CHP systems. Data of 8 Membrane Electrode Assemblies (MEAs) operated with different accelerated ageing tests have been collected and compared with literature. In order to assess the cell performance, Polarization Curves (PC), Electro Impedance Spectroscopy (EIS) and Cyclic Voltammetry (CV) have been recorded during the ageing tests. As expected, voltage degradation was strongly influenced by operating conditions. The voltage decay rate at 200 mA/cm2 was found to be about 30 µV/h for constant load operation, 34 µV/h for triangular load cycle ([0.01 – 0.5]V), 45 µV/h for triangular load cycle with permanence at OCV ( [0 – 0.5]V - 2s OCV), 81 µV/h for Start/Stop cycles, while for constant permanence at OCV a wide variability of the degradation rate has been encountered. In order to analyse the nano-morphological evolution of the catalyst layer on large portions of the MEA, Small Angle X-Ray Scattering (SAXS) has been carried out. The SAXS results showed a mean size increase of the platinum nanoparticles up to 130% when the MEA is subjected to load cycles. SAXS data has then been compared with data obtained by Transmission Electron Microscopy (TEM) analysis confirming the catalyst particles growing trend. The experimental data collected during this research activity allowed to identify the performance degradation of the fuel cell over different load conditions and allowed to infer a performance degradation model that has then been implemented in a CHP system process simulation model. Stack degradation has been shown to be still an issue that hampers the full exploitation of the technology, but, in CHP configuration, heat production can partially compensate electrical energy loss due to degradation and its detrimental effect can be mitigated choosing some operational control strategies and increasing the size of the stack, even if this affects system cost. Finally, the model can be a valuable tool for conducting sensitivity analysis and find optimal size of system components taking into account the system performance degradation over time. In the future this model could be upgraded introducing different degradation behaviour for each operational condition encountered during the lifetime of the CHP-system.

The main objective of this research was to develop efficient CuIn1-xGaxS2 (CIGS2)/CdS thin film solar cells for photoelectrochemical (PEC) water splitting to produce very pure hydrogen and oxygen. Efficiencies obtained using CIGS2 have been lower than those achieved using CuInSe2 and CuIn1-xGaxSe2. The basic limitation in the efficiencies is attributed to lower open circuit voltages with respect to the bandgap of the material. Presently, the main mechanism used to increase the open circuit voltage of these copper chalcopyrites (CuInSe2 and CuInS2) is the addition of gallium. However, addition of gallium has its own challenges. This research was intended to (i) elucidate the advantages and disadvantages of gallium addition, (ii) provide an alternative technique to the photovoltaic (PV) community to increase the open circuit voltage which is independent of gallium additions, (iii) develop highly efficient CIGS2/CdS thin film solar cells and (iv) provide an alternative material in the form of CIGS2/CdS thin film solar cells and an advanced technology in the form of a multiple bandgap tandem for PEC water splitting. High gallium content was achieved by the incorporation of a highly excess copper composition. Attempts to achieve high gallium content produced reasonable but not the best solar cell performance. Few solar cells developed on a molybdenum back contact and an ITO/MoS2 transparent conducting back contact showed a PV conversion efficiency of 7.93% and 5.97%, respectively. The solar cells developed on the ITO/MoS2 back contact form the first generation CIGS2/CdS thin film solar cells and 5.97% is the first ever reported efficiency on an ITO/MoS2 transparent back contact. Reasons for the moderate performance of these solar cells were attributed to significant porosity and remnants of unsulfurized CuGa alloy in the bulk of CIGS2. This was the first attempt to a detailed study of materials and device characteristics of CIGS2/CdS thin film solar cells prepared starting with a highly excess copper content CIGS2 layer. Next, excess copper composition of 1.4 (equivalent to gallium content, x = 0.3) was chosen with the aim to achieve the best efficiency. The open circuit voltage was enhanced by depositing an intermediate layer of intrinsic ZnO between CdS and ZnO:Al layers. The systematic study of requirements for such a layer and further optimization of its thickness to achieve a higher open circuit voltage (which is the greatest challenge of the scientific community) forms an important scientific contribution of this research. The PV parameters for CIGS2/CdS thin film solar cell as measured officially at the National Renewable Energy Laboratory were: open circuit voltage of 830.5 mV, short circuit current density of 21.88 mA/cm2, fill factor of 69.13% and photovoltaic conversion efficiency of 11.99% which sets a new world record for CIGS2 cells developed using sulfurization and the open circuit voltage of 830.5 mV has become the "Voc champion value". New PEC setups with the RuS2 and Ru0.99Fe0.01S2 photoanodes were developed. RuS2 and Ru0.99Fe0.01S2 photoanodes were more stable in the electrolyte and showed better I-V characteristics than the RuO2 anode earlier used. Using two CIGS2/CdS thin film solar cells, a PEC efficiency of 8.78% was achieved with a RuS2 anode and a platinum cathode. Results of this research constitute a significant advance towards achieving practical feasibility and industrially viability of the technology of PEC hydrogen generation by water splitting.
Ph.D.
Department of Mechanical, Materials and Aerospace Engineering;
Engineering and Computer Science
Materials Science and Engineering

Fuel cell system models are key tools for automotive fuel cell system engineers to properly size components to meet design parameters without compromising efficiency by over-sizing parasitic components. A transient fuel cell system level model is being developed that includes a simplified transient thermal and parasitics model. Model validation is achieved using a small 1.2 kW fuel cell system, due to its availability. While this is a relatively small stack compared to a full size automotive stack, the power, general thermal behavior, and compressor parasitics portions of the model can be scaled to any number of cells with any size membrane area. With flexibility in membrane size and cell numbers, this model can be easily scaled to match full automotive stacks of any size. The electrical model employs a generalized polarization curve to approximate system performance and efficiency parameters needed for the other components of the model. General parameters of a stackâ s individual cells must be known to scale the stack model. These parameters are usually known by the time system level design begins. The thermal model relies on a lumped capacity approximation of an individual cell system with convective cooling. From the thermal parameters calculated by the model, a designer can effectively size thermal components to remove stack thermal loads. The transient thermal model was found to match experimental data well. The steady state and transient sections of the curve have good agreement during warm up and cool down cycles. In all, the model provides a useful tool for system level engineers in the early stages of stack system development. The flexibility of this model will be critical for providing engineers with the ability to look at possible solutions for their fuel cell power requirements.
Master of Science