<p>Sintetisane su klasične alkidne smole polazeći od ricinolne kiseline, anhidrida ftalne<br />kiseline i tri poliola (glicerina, trimetilolpropana i etoksilovanog pentaeritritola), kao i<br />hiperrazgranati alkidi na osnovu ditrimetilolpropana, dimetilolpropionske kiseline i<br />ricinolne kiseline. Smole su karakterisane određivanjem hidroksilnog i kiselinskog broja,<br />viskoznosti, srednjih molskih masa i njihove raspodele. Struktura sintetisanih smola je<br />potvrđena infracrvenom spektroskopijom sa Furijeovom transformacijom (FTIR).<br />Sintetisani alkidi imaju veliki sadržaj hidroksilnih grupa, a mali kiselinski broj. Prisustvo<br />hidroksilnih grupa, kao krajnjih funkcionalnih grupa, omogućuje modifikaciju alkidnih<br />smola i dobijanje materijala različitih svojstava. Sintetisani alkidi su umrežavani sa<br />triizobutoksimetil i heksametoksimetil melaminskom smolom u cilju dobijanja umreženog materijala željene strukture i svojstava za primenu u premazima. Umrežavanje sme&scaron;a smola praćeno je FTIR spektroskopijom, dinamičko skanirajućom kalorimetrijom (DSC), reometrijom, kao i određivanjem sadržaja gela. Ispitivana su toplotna svojstva, dinamičkomehaničko pona&scaron;anje, fizičko-mehaničke karakteristike i hemijska otpornost filmova premaza. Umrežavanje sme&scaron;a smola teče uglavnom preko hidroksilnih i karboksilnih grupa alkida sa izobutoksimetil i metoksimetil grupama u melaminskim smolama. Sintetisane klasične alkidne smole u sme&scaron;i sa melaminskim smolama umrežavaju u temperaturnom opsegu od 90 do 170&nbsp;⁰C, a hiperrazgranati alkidi od 80 do 170&nbsp;⁰C, &scaron;to su uobičajene temperature u tehnologiji lakova koji umrežavaju &ldquo;pečenjem&ldquo;. Umreženi filmovi premaza su toplotno veoma stabilni, budući da početak razgradnje premaza započinje na temperaturama od 281 do 330 ⁰C. Potvrđeno je da postoji linearna zavisnost između modula izgubljene energije na 25 ⁰C, koji je mera viskoznog odgovora materijala, i tvrdoće premaza određene metodom klatna. Svi projektovani premazi, bez obzira na nesavr&scaron;enost nastale polimerne mreže, su pokazali zadovoljavajuća svojstva. Najbolja svojstva od klasičnih alkidnih premaza ima onaj na osnovu sme&scaron;e alkida sa etoksilovanim pentaeritritolom i heksametoksimetil melaminske smole. Kori&scaron;ćenje hiperrazgranatih alkidnih smola kao veziva u ekolo&scaron;ki prihvatljivim premazima ima prednost zbog manjeg sadržaja organskih rastvarača i manje viskoznosti u odnosu na klasične smole. Pretpostavljeno je da bi sme&scaron;e sintetisanih klasičnih i hiperrazgranatih alkida sa melaminskim smolama (maseni odnos 70:30) bile pogodne za primenu u industriji boja i lakova. Potvrđeno je da su sistemi alkid/melaminska smola veoma složeni. Dobijeni rezultati omogućuju da se objasni uticaj građe prekursora na strukturu nastale polimerne mreže, a time i na svojstva premaza.</p> / <p>Conventional alkyd resins based on ricinoleic acid, phthalic anhydride and three polyols (glycerin, trimethylolpropane or ethoxylated pentaerythritol), as well as hyperbranched alkyds based on ditrimethylolpropane, dimethylol propionic acid and ricinoleic acid were synthesized. Prepared alkyds were characterized by the determination of hydroxyl and acid numbers, viscosity, average molecular masses and molecular masses distribution. The structure of synthesized resins is confirmed by Fourier Transform Infrared Spectroscopy (FTIR). Obtained alkyd resins have high content of hydroxyl groups and low acid number. The presence of hydroxyl groups as functional end groups opens up a high potential for further chemical modifications and for obtaining materials with different properties. Synthesized alkyds were cured by triisobutoxymethyl- and hexamethoxymethyl melamine resins, in order to obtain crosslinked material with desired structure and properties for coating applications. Curing of the resin mixtures were examined by FTIR spectroscopy, dynamic scanning calorimety (DSC), rheometry and by the determination of gel content. Thermal properties, dynamic mechanical behavior, physico-mechanical characteristics and chemical resistance of coated films were determined. Curing of the resin mixtures proceeds via the reactions between hydroxyl and carboxyl groups of alkyds with isobutoxymethyl and metoxymethyl groups in melamine resins. Synthesized alkyd/melamine resin mixtures became cured in the temperature range from 80 to 170 0C, which is the usual temperature range employed in the baking enamel technology. Cured films are thermally very stable since the onset of films degradation starts at high temperatures (from 281 to 330 0C). It is confirmed that there is a linear dependence between the loss modulus at 25 0C, which is the measure of the material viscosity response, and the coating hardness determined by pendulum method. All projected coatings, despite of defects in the resulting polymer networks, show satisfying properties. Among the conventional systems coating based on mixture of alkyd with ethoxylated pentaerythritol and hexamethoxymethyl melamine resin show the best properties. Application of hyperbranched alkyd resins, as binders in environment friendly coatings has an advantage due to less content of organic solvent and lower viscosity, compared to conventional alkyd resins. It is supposed that the combination of synthesized conventional and hyperbranched alkyds with melamine resins (weight ratio of 70:30 based on dried mass) could be employed as new materials for the industrial preparation of baking enamels. It is confirmed that alkyd/melamine resin systems are very complex. Results obtained enable to explain the effect of precursor type on the structure of resulting polymer network, and thus, on the coating properties.</p>

Coatings are frequently applied on gas turbine components inorder to restrict surface degradation such as corrosion andoxidation of the structural material or to thermally insulatethe structural material against the hot environment, therebyincreasing the efficiency of the turbine. However, in order toobtain accurate lifetime expectancies and performance of thecoatings system it is necessary to have a reliableunderstanding of the mechanical properties and failuremechanisms of the coatings. In this thesis, mechanical and fracture behaviour have beenstudied for a NiAl coating applied by a pack cementationprocess, an air-plasma sprayed NiCoCrAlY bondcoat, a vacuumplasma-sprayed NiCrAlY bondcoat and an air plasma-sprayed ZrO2+ 6-8 % Y2O3topcoat. The mechanical tests were carried out ata temperature interval between room temperature and 860oC.Small punch tests and spherical indentation were the testmethods applied for this purpose, in which existing bending andindentation theory were adopted for interpretation of the testresults. Efforts were made to validate the test methods toensure their relevance for coating property measurements. Itwas found that the combination of these two methods givescapability to predict the temperature dependence of severalrelevant mechanical properties of gas turbine coatings, forexample the hardness, elastic modulus, yield strength, fracturestrength, flow stress-strain behaviour and ductility.Furthermore, the plasma-sprayed coatings were tested in bothas-coated and heat-treated condition, which revealedsignificant difference in properties. Microstructuralexamination of the bondcoats showed that oxidation with loss ofaluminium plays an important role in the coating degradationand for the property changes in the coatings. Keywords:small punch test, miniaturised disc bendingtests, spherical indentation, coatings, NiAl, APS-NiCoCrAlY,VPS-NiCrAlY, mechanical properties

No description available.

Stable single-unit recordings from the nervous system using microelectrode arrays can have significant implications for the treatment of a wide variety of sensory and movement disorders. However, the long-term performance of the implanted neural electrodes is compromised by the formation of glial scar around these devices, which is a typical consequence of the inflammatory tissue reaction to implantation-induced injury in the CNS. The glial scar is inhibitory to neurons and forms a barrier between the electrode and neurons in the surrounding brain tissue. Therefore, to maintain long-term recording stability, reactive gliosis and other inflammatory processes around the electrode need to be minimized. This work has succeeded in the development of neural electrode coatings that are capable of sustained release of anti-inflammatory agents while not adversely affecting the electrical performance of the electrodes. The effects of coating methods, initial drug loadings on release kinetics were investigated to optimize the coatings. The physical properties of the coatings and the bioactivity of released anti-inflammatory agents were characterized. The effect of the coatings on the electrical property of the electrodes was tested. Two candidate anti-inflammatory agents were screened by evaluating their anti-inflammatory potency in vitro. Finally, neural electrodes coated with the anti-inflammatory coatings were implanted into rat brains to assess the anti-inflammatory potential of the coatings in vivo. This work represents a promising approach to attenuate astroglial scar around the implanted silicon neural electrodes, and may provide a promising strategy to improve the long-term recording stability of silicon neural electrodes.

<p>Coatings are frequently applied on gas turbine components inorder to restrict surface degradation such as corrosion andoxidation of the structural material or to thermally insulatethe structural material against the hot environment, therebyincreasing the efficiency of the turbine. However, in order toobtain accurate lifetime expectancies and performance of thecoatings system it is necessary to have a reliableunderstanding of the mechanical properties and failuremechanisms of the coatings.</p><p>In this thesis, mechanical and fracture behaviour have beenstudied for a NiAl coating applied by a pack cementationprocess, an air-plasma sprayed NiCoCrAlY bondcoat, a vacuumplasma-sprayed NiCrAlY bondcoat and an air plasma-sprayed ZrO₂+ 6-8 % Y₂O₃topcoat. The mechanical tests were carried out ata temperature interval between room temperature and 860oC.Small punch tests and spherical indentation were the testmethods applied for this purpose, in which existing bending andindentation theory were adopted for interpretation of the testresults. Efforts were made to validate the test methods toensure their relevance for coating property measurements. Itwas found that the combination of these two methods givescapability to predict the temperature dependence of severalrelevant mechanical properties of gas turbine coatings, forexample the hardness, elastic modulus, yield strength, fracturestrength, flow stress-strain behaviour and ductility.Furthermore, the plasma-sprayed coatings were tested in bothas-coated and heat-treated condition, which revealedsignificant difference in properties. Microstructuralexamination of the bondcoats showed that oxidation with loss ofaluminium plays an important role in the coating degradationand for the property changes in the coatings.</p><p><b>Keywords:</b>small punch test, miniaturised disc bendingtests, spherical indentation, coatings, NiAl, APS-NiCoCrAlY,VPS-NiCrAlY, mechanical properties</p>

As ligas de alumínio vêm sendo amplamente usadas nas indústrias aeronáuticas e automobilísticas por suas propriedades mecânicas superiores às do metal puro. Entretanto, como as propriedades de corrosão dessas ligas variam, sendo piores do que as do alumínio puro, surge a necessidade de estudos de diferentes métodos de proteção contra a corrosão. O uso de coberturas protetoras é uma alternativa para diminuir os processos corrosivos e, desta maneira, aumentar a vida útil desses materiais. Das coberturas de conversão existentes, as mais usadas ainda são à base de cromo, porém o cromo tem se mostrado danoso ao meio ambiente e à saúde humana. Por outro lado, as coberturas de conversão à base de óxidos de cério, ambientalmente mais corretas e menos nocivas, já têm sido usadas com sucesso para este propósito. Ademais, partindo do consenso sobre o bom desempenho da polianilina (PAni) em proteger metais oxidáveis contra a corrosão, inclusive o alumínio e suas ligas, o presente estudo propõe o desenvolvimento de proteção anticorrosiva de ligas de alumínio pela combinação de camadas de conversão à base de óxidos de cério associada com camadas de PAni nas ligas de alumínio das séries AA1xxx e AA6xxx. A combinação de camadas duplex surge como uma alternativa promissora por: (i) possibilitar a formação de pontos de ancoragem sobre a superfície, promovidos pelas camadas de conversão à base de óxidos de cério, para a posterior deposição de PAni; (ii) ampliar o uso das camadas de conversão à base de óxidos de cério isoladamente ou combinadas com PAni e (iii) promover o melhor sinergismo na proteção contra a corrosão das ligas de alumínio e de outros materiais pela associação e maior interação desses sistemas. / Aluminium alloys have been widely used in automobile and aircraft industries for their superior mechanical properties to the pure metal. However, as the corrosion properties of these alloys vary, being worse than those of pure aluminium, there is a need for studies of different methods of corrosion protection. The use of protective coverings appears as an alternative to reduce the corrosion process and thereby increase the useful life of these materials. Conversion of existing coverage, the most used are still based on chrome, but chrome has proven harmful to the environment and human health. Furthermore, coverage of cerium-based conversion, more environmentally friendly and healthy, have already been successfully used for this purpose. Furthermore, based on the consensus on the proper performance of polyaniline (PAni) to protect oxidizable metals against corrosion, including aluminium and its alloys, this study proposes the development of corrosion protection of aluminium alloys by combining layers of cerium conversion associated with layers of polyaniline on aluminium alloys AA1xxx and AA6xxx series. The combination of double layers arises as a promising alternative, which may: (i) facilitating formation of anchor points on the surface, driven by layers of cerium conversion, for the subsequent deposition of PAni (ii) expand the use of cerium conversion coatings alone or combined with PAni and (iii) promote synergy in protection against corrosion of aluminium alloys and other materials by the association and greater interaction of these systems.

Anodisation is a surface treatment process, commonly used to form a protective oxide coating on the surface of metals like aluminium. Anodised coatings, being grown out of the base metal have excellent interface strength but are porous and brittle. Porosity of the coating reduces the hardness and the brittle nature of the oxide induces cracking. In practice, the pores are typically filled with organic dye and sealed. Under certain controlled electrochemical conditions, anodisation results in a highly ordered hexagonal porous structure in pure aluminium. In this work, we explore the possibility of using this ordered porous alumina to form a novel metal nanocomposite as a tribological coating. By optimizing the nonporous structure and tuning the electrodeposition process, we uniformly filled the ordered pores with copper. We have measured the hardness of the resulting ordered and aligned nanocomposite. We explore the possibility of using this composite coating for tribological applications by carrying out some preliminary reciprocating wear test. Ordered porous alumina layer is formed by a two-step anodisation process. By optimizing the anodisation conditions, we control the thickness of the coating and the pore size. The interface of the porous structure and aluminium substrate is defined by a non-conducting dense barrier oxide layer. However, to deposit metal into the pores, a conducting path should be established through the barrier layer. One possibility is to etch out the bottom of the pores at the cost of the interface strength and losing out on the main advantage of anodised coatings. To be able to fill metal without this sacrifice, we utilised the dendritic structure in the barrier layer formed by a step-wise reduction of voltage towards the end of anodisation process. Optimisation of this dendritic structure led to uniform deposition of metal into pores, achieved by pulsed electrodeposition. In pulse lectrodeposition, a positive pulse is applied to remove accumulated charge near to the bottom of pores, followed by a negative pulse to deposit metal and a delay to allow diffusion of ions. By optimising the pulse shape and duration, we have achieved uniform growth of metal into pores. Further, monitoring the deposition current helped us to identify and control different phases of growth of the nanowire. The properties of the porous alumina and the nanocomposite were measured by nanoindentation. The deformation characteristics were obtained by observing the indents in a FE-SEM. We find that dendritic modification of interface has very little effect on the hardness of the porous alumina layer. We also found that the porous alumina deformed either by compaction or by forming circumferential and radial cracks. When copper is filled in the nano pores, the hardness increased by 50% and no circumferential cracks were found up to the load of 10 mN for a film thickness of about 1 µm. Coefficient of friction of the coating reciprocated against steel in dry condition is found to be around 0.4. Minimal wear was observed from the SEM images of wear track. In summary, a novel nanocomposite coating with ordered porous alumina as matrix embedded with aligned metal nano rods has been developed. This was achieved by optimally modifying the barrier layer without sacrificing the interfacial strength. Uniform coating has been achieved over an area of 10 mm x 10 mm. The coating is found to have high hardness and high wear resistance.

The diploma thesis is focused on the study of the thermal sprayed coating consisting of the NiCrAlY alloy bond layer and the partially stabilized zirconium oxide (8YSZ) top layer on the AZ91 magnesium alloy. The theoretical part deals with the structure of the alloy AZ91, NiCrAlY and partially stabilized zirconia. Furthermore, the methods of thermal spraying and the function and properties of thermal barrier coatings are summarized. The experimental part deals with the characterization of the thermal sprayed coating and the AZ91 alloy in terms of elemental, structural and phase composition. Optical and electron microscopy, EDS and XRD analysis were used for characterization. Electrochemical properties were investigated in~3.5% sodium chloride solution by potentiodynamic polarization. The mechanical properties (hardness, coefficient of friction) of the substrate and coating were measured using a hardness tester and tribological tests.

<p>With the extreme increases in power density of electronic devices, the contact thermal resistance imposed at interfaces between mating solids becomes a major challenge in thermal management. This contact thermal resistance is mainly caused by micro-scale surface asperities (roughness) and wavy profile of surface (nonflatness) which severely reduce the contact area available for heat conduction. High contact pressures (1~100 MPa) can be used to deform the surface asperities to increase contact area. Besides, a variety of conventional thermal interface materials (TIM), such as greases and pastes, are used to improve the contact thermal conductance by filling the remaining air gaps. However, there are still some applications where such TIMs are disallowed for reworkability concerns. For example, heat must be transferred across dry interfaces to a heat sink in pluggable opto-electronic transceivers which needs to repeatedly slide into / out of contact with the heat sink. Dry contact and low contact pressures are required for this sliding application.</p> <p>This dissertation presents a metallized micro-spring array as a surface coating to enhance dry contact thermal conductance under ultra-low interfacial contact pressure. The shape of the micro-springs is designed to be mechanically compliant to achieve conformal contact between nonflat surfaces. The polymer scaffolds of the micro-structured TIMs are fabricated by using a custom projection micro-stereolithography (μSL) system. By applying the projection scheme, this method is more cost-effective and high-throughput than other 3D micro-fabrication methods using a scanning scheme. The thermal conductance of polymer micro-springs is further enhanced by metallization using plating and surface polishing on their top surfaces. The measured mechanical compliance of TIMs indicates that they can deform ~10s μm under ~10s kPa contact pressures over their footprint area, which is large enough to accommodate most of surface nonflatness of electronic packages. The measured thermal resistances of the TIM at different fabrication stages confirms the enhanced thermal conductance by applying metallization and surface polishing. Thermal resistances of the TIMs are compared to direct metal-to-metal contact thermal resistance for flat and nonflat mating surfaces, which confirms that the TIM outperforms direct contact. A thin layer of soft polymer is coated on the top surfaces of the TIMs to accommodate surface roughness that has a smaller spatial period than the micro-springs. For rough surfaces, the polymer-coated TIM has reduced thermal resistance which is comparable to a benchmark case where the top surfaces of the TIM are glued to the mating surface. A polymer base is designed under the micro-spring array which can provide the advantages for handling as a standalone material or integration convenience, at the toll of an increased insertion resistance. Through-holes are designed in the base layer and coated with thermally conductive metal after metallization to enhance thermal conductance of the base layer; a thin layer of epoxy is applied between the base layer and the working surface to reduce contact thermal resistance exposed on the base layer. Cycling tests are conducted on the TIMs; the results show good early-stage reliability of the TIM under normal pressure, sliding contact, and temperature cycles. The TIM is thermally demonstrated on a pluggable application, namely, a CFP4 module, which shows enhanced thermal conductance by applying the TIM. </p> To further enhance the potential mechanical compliance of microstructured surfaces, a stable double curved beam structure with near-zero stiffness composed of intrinsic negative and positive stiffness elastic elements is designed and fabricated by introducing residual stresses. Stiffness measurements shows that the positive-stiffness single curved beam, which is the same as the top beam in the double curved beam, is stiffer than the double curved beam, which confirms the negative stiffness of the bottom beam in the double curved beam. Layered near zero-stiffness materials made of these structures are built to demonstrate the scalability of the zero-stiffness zone.

Hydrogen production by PEM-Water electrolysis is an environmentally benign and promising approach to store excess energy from renewable energy sources but facing drawbacks of high costs, mainly due to a harsh cell-environment. The aim of my Master Thesis was to reduce the costs of the most expensive cell component, the bipolar plate by surface engineering. Thin films of Ti, Zr and alloys thereof, as well as Nb and W have been vapor deposited by either cathodic arc deposition or magnetron sputtering in an industrial scale coating system. The nitrides, carbides, and pure metals from the previously mentioned transition metals were investigated by crosscut adhesion tests, interfacial contact resistance, electrochemical corrosion tests, scanning electron microscopy and energy dispersive X-ray spectroscopy. Highly promising thin film materials have been developed to functionalize the bipolar plates, enabling significant cost reductions of the PEMWE-cell.