Dissertations / Theses on the topic 'Vacuum processing'

Composite materials have traditionally been used in high-end aerospace parts and low-end consumer parts. The reason for this separation in markets is the wide gap in technology between pre-preg materials processed in an autoclave and chop strand fiberglass blown into an open mold. Liquid composite molding has emerged as a bridge between inexpensive tooling and large, technical parts. Processes such as vacuum infusion have made it possible to utilize complex layups of reinforcement materials in an open mold style set-up, creating optimal conditions for composites to penetrate many new markets with rapid innovation. Flow simulation for liquid composite molding is often performed to assist in process optimization, and requires the permeability of the reinforcement to be characterized. For infusion under a flexible membrane, such as vacuum infusion, or for simulation of a part with non-uniform thickness, one must test the permeability at various levels of compaction. This process is time consuming and often relies on interpolation or extrapolation around a few experimental permeability measurements. To accelerate the process of permeability characterization, a small number of methodologies have been previously presented in the literature, in which the permeability may be tested at multiple fiber volume contents in a single test. Some of the methods even measure the permeability over a continuous range of thicknesses, thus requiring no later interpolation of permeability values. A novel method is presented here for the rapid measurement of permeability over a continuous range of fiber volume content, in a single unidirectional vacuum infusion flow experiment. The thickness gradient across the vacuum bag, as well as the fluid pressure at several locations in the mold, were concurrently measured to calculate the fabric compressibility. An analytical flow model, which accounts for the compressibility, is then used by iterating the fitting constant in a permeability model until the predicted flow front progression matches empirical measurement. The method is demonstrated here for two reinforcement materials: 1) a fiberglass unbalanced weave and 2) a carbon bi-ax non-crimped fabric. The standard deviation of calculated permeabilities across the multiple infusion experiments for each material and flow orientation ranged from 12.8% to 29.7%. Validation of these results was performed by comparing the resulting permeability with multiple non-continuous permeability measurement methods.

The development of organic optoelectronics has progressed rapidly. These devices are now an essential part of our lives (e.g. mobile phone, computer, energy applications and touch-enabled applications). With increasing demand for mass production of low-cost materials, researchers are readily seeking new innovative materials to replace conventional materials based on polymers or small molecules. Metal oxides are one of the most interesting classes of materials, but their current processing is incompatible with organic systems and their application in this field requires new simplified methods of deposition. In this thesis, zinc acetate dihydrate (ZnAc2H2O) has been selected as a precursor for the formation of ZnO. It is inexpensive, has high volatility and demonstrates the oligomerisation of basic zinc acetate (BZA) in vacuum, which is known as a molecular model of ZnO. While there are limited reports of BZA films and powder in the literature, this is the first time that it is fully characterised. The BZA film is prepared on room temperature substrates, with and without pre-coating of 3,4,9,10-perylenetetracharboxylic dianhydride (PTCDA) using organic molecular beam deposition (OMBD), which convey high quality films with well-controlled film thickness and high purity. Contrasting the morphology of the two films, the growth mode for the former is known as “Frank-van-der-Merwe” whereas the latter is “Stranski-Krastanov”. This formation is critical since film orientation and morphology can dramatically alter device performance. A new method for processing metal oxide using small molecules at room temperature has been developed. This method depends on exposing small molecule film to vacuum ultraviolet (VUV) light, generating a photon energy of 7.2 eV (172 nm) via several degradation mechanisms. The effect of atmosphere and irradiation length are evaluated by altering the partial pressure of oxygen and adjusting the height of the sample stage during the VUV process, respectively. The presence of oxygen molecules inducing oxygen radicals and ozone plays a major role in the degradation reaction. This is significantly greater than the effect of irradiance. Finally, a new, room temperature method, VUV process, is used on two BZA films to explore whether this is suitable to the formation of ZnO. Both films exposed to VUV light under different atmospheric conditions show the formation of M-O-M species, with optimised results for high vacuum conditions. Varying the irradiation length results in further enhancement of M-O-M. Furthermore, the underlying PTCDA is preserved during UV exposure. This suggests that ZnO formation acts as an effective barrier layer protecting the underlying organic components.

A process has been developed to make the dielectric layer for organic thin-film transistors (OTFTs) in a roll-to-roll vacuum web coater environment. This dielectric layer combined with an organic semiconductor layer and metal layer deposited in vacuum allows a solvent-free process to make organic/inorganic multilayer structures for thin-film electronic devices on a flexible substrate at, potentially, high speed. The polymeric gate dielectric layers were fabricated by flash evaporation of acrylic monomers onto a polymer film with pre-patterned metal gates followed by radiation curing by electron beam, ultra-violent light (UV) or plasma. With a non-polar dielectric surface, charge carrier mobility (μ) of 1 cm²-V^-1s^-1; on/off curren ratio of 10⁸, sub-threshold swing (SS) of 0.3 V/decade and saturated output curve were routinely achieved in dinaphtho-[2,3-b:2'3'-f]thieno[3,2-b]thiophene (DNTT) transistors with dielectric layer of tripropylene glycol diacrylate (TPGDA) of ~400 nm. Apart from the TPGDA, monomer formulas including 1,6-Hexanediol diacrylate (HDDA) as well as several commercial acrylic resins have been used to make the dielectric layer. The highest areal capacitance of 41nF-cm^-2 was achieved with a pin-hole free film of less than 100 nm made of an acrylate mixture resin. A non-polar dielectric surface treatment layer has been developed based on flash evaporation of lauryl acrylate and HDDA mixture. The transistors with the buffer layer showed constant performance and a mobility fivefold greater than those of untreated samples. The effect of humidity, oxygen, and light during switching cycles of both pentacene and DNTT transistors were studied. Water and oxygen/illumination had a distinct effect on both pentacene and DNTT transistors. Oxygen leads to acceptor-like charge traps under illumination, which shifted the turn-on voltage (V_to) to more positive values. In contrast, water in transistors gave rise to donor-like charge traps, which shifted the V_to and the threshold voltage (V_T) more negatively. The DNTT devices showed good stability in dry air without encapsulation, while pentacene transistors degraded with either repeating measurement or long term storage. A DNTT transistor with a PS-coated TPGDA dielectric layer showed stable drain current (I_d) of ~105A under bias stress of the gate voltage (em>V_g) of -20V and the drain voltage (em>V_d) of -20V for at least 144 hours. The V_to shift after the stress was less than 5 V and was recoverable when the device was kept in dry air for a few days. Possible reasons for the V_to shift have been discussed.

Thesis (MScEng)--University of Stellenbosch, 2001.<br>ENGLISH ABSTRACT: Current global trends in government, industry and popular OpInIOn indicate that recycling will become essential in the future. Vacuum pyrolysis is a new technology with many recycling applications that have not yet been investigated. This study is a contribution towards the better understanding of the vacuum pyrolysis process and also towards finding possible economically favourable recycling applications. A batch operated tube furnace, which allowed the controlled heating of different materials in a vacuum, was designed and built. The gases and vapours passed though a series of progressively colder vacuum traps, condensing the vapours for further study. The products from the process are charcoal, oil, an aqueous phase and noncondensable gases. The charcoal and oils' possible economic values (R2500- R5000/ton of charcoal, while the plant product oil can be sold as a low sulphur fuel, with a retail value of approximately R1.42 per litre) were determined along with the oils' chemical composition. Several possible feedstocks were studied, including intruder plant species, leather wastes, sewage sludge and a simplified representation of municipal solid waste. The three intruder plants studied were Kraalbos (Galenia africane), Scholtzbos (pteronia pallens) and Asbos (Psilocaolon absimile). These plants yielded 40%, 42% and 48% (charcoal per kilogram dry feedstock) respectively at their maximum oil yield temperatures of 380°C, 480°C and 450°C respectively. The maximum oil yields were 36%, 32% and 20% respectively (also on a dry feedstock basis). It was found that the plants with ash contents below 10% yielded commercially competitive charcoal, and that all of the plants yielded oils with heating values in the range of 24MJ/kg, containing several high value compounds. Asbos was the only plant that did not produce usable charcoal, as its ash content of 40% was double that of commercial charcoals. The leather wastes represent a previously unrecognised application of the technology that could bring huge financial rewards to the tanning industry and could provide a more environmentally friendly alternative to lined landfilling. The cost of landfilling for a medium sized tannery can be as high as RIOOO 000 a year. Apart from the volume reductions achieved (up to a factor 8) it was found that landfilling might be totally avoided if the chrome contained in the charcoal product could be extracted and reused. Sewage sludge was studied, as it is a hazardous waste that requires costly disposal in a lined landfill. It was revealed that volume reductions of up to a factor 3.5 were possible with corresponding charcoal and oil yields of 40% and 38% respectively at 500°C. It was also found that the charcoal product could be used as compost, which would then turn a costly waste into a commodity product. The oil from both the leather and sewage sludge had high energy values (26.7MJ/kg and 30.9MJ/kg respectively) and might either be sold as a bunker fuel or used in the process as a make-up heat source. The value of the oil depends on the problems posed by the oils' high nitrogen content (±5%-6%). A further study was also made of the co-pyrolysis of PVC and wood to determine the interaction between the feedstocks and as a simplified representation of municipal solid wastes. It was found that the HCI released from the PVC caused acid hydrolysis of the wood and led to lower charcoal (reduced from 32.6% to 29.7% on dry feedstock basis, at the maximum co-pyrolysis oil yield temperature of 460°C) and much higher oil yields (42.4% for the co-pyrolysis compared to 23.6% for the plant material at 460°C). An existing computer program (CEA by Gordan and McBride) was also employed in order to find explanations for some of the vacuum pyrolysis results. Although large specialist vacuum pyrolysis plants have been designed in the past (mostly to dispose of used tyre waste) it will be necessary to determine the process economics for small-scale applications if the technology is to be applied at the source of the problem. Overall vacuum pyrolysis appears to be a very promising technology that could solve many waste problems in an environmentally friendly and economically beneficial manner.<br>AFRIKAANSE OPSOMMING: Hedendaagse neigmgs in regenng, industrie en populêre opirue toon dat hergebruikstegnologieë al hoe meer noodsaaklik sal word in die toekoms. Vakuum pirolise is 'n nuwe tegnologie met vele moonlike hergebruik toepassings wat nog nie bestudeer is nie. Hierdie studie is 'n bydrae tot 'n dieper begrip van vakuum pirolise en ook tot die verdere soeke na nuwe toepassings vir die tegnologie. 'n Enkellading buis-oond, wat die beheerde verhitting van verskillende materiale in vakuum toegelaat het, is ontwerp en gebou. Die gevormde gasse en dampe het deur 'n progressief kouer reeks van vakuum valle beweeg waar dit vir verdere studie gekondenseer en opgevang is. Die produkte van die proses is houtskool, olie, 'n waterryke fase en nie-kondenseerbare gasse. Die houtskool en olie se moontlike waarde (R2500-R5000/ton houtskool, terwyl die plant produk olie verkoop kan word as 'n lae swael verhittings olie met 'n kleinmaat kommersieële verkoopswaarde van R1.42/1), saam met die chemiese samestelling van die olie fase, is bepaal. Die vakuum pirolise van verskeie moontlike voerstowwe is bestudeer, insluitende indringerplante, leerafval, rioolslyk en 'n vereenvoudigde voorstelling van munisipale afval. Die drie plant spesies wat bestudeer is, is: Kraalbos (Galenia africane), Scholtzbos (Pteronia pal/ens) en Asbos (Psilocaolon absimile). Die plante het opbrengste van 40%, 42% en 48% (houtskool per kilogram droë voerstof) onderskeidelik gelewer by elk van die plante se maksimum olie opbrengs temperature van 380°C, 480°C en 450°C onderskeidelik. Die maksimum olie opbrengste was 36%, 32%, 20% (olie per kilogram droë voerstof) vir die onderskeie plante. Daar is bevind dat die plante met as-inhoude van minder as 10% kommersieel kompeterende houtskool gelewer het. Dit is ook gevind dat die olie van al die plante verbrandingswaardes in die orde van 24MJ/kg lewer en dat die olies ook verskeie waardevolle chemikalieë bevat. Asbos was die enigste van die bestudeerde plante wat nie maklik bruikbare houtskool gelewer het nie. Die Asbos houtskool was minder bruikbaar as gevolg van die uiters hoë as-inhoude van tot 40% met gevolglike lae energie waarde. Die vakuum pirolise van leerafval is 'n toepassing wat nog nie voorheen ondersoek is nie. Dit kan moontlik lei tot groot finansiële voordele vir die leerlooi industrie en kan ook 'n meer omgewingsvriendelike alternatief tot belynde afval storting bied. Die koste verbonde aan die storting van leer afval van 'n medium grootte looiery kan tot R1000 000 per jaar beloop. Behalwe vir die volume verkleining behaal (tot 'n faktor 8), is daar ook gevind dat afvalstorting totaal vermy kan word as die hoë hoeveelheid chroom (12% van die houtskool) uit die houtskool verwyder en hergebruik kan word. Rioolslyk is ook bestudeer, siende dat dit ook 'n probleem afvalstof is wat teen groot koste gestort moet word. Die studie het getoon dat volume verkleinings van tot 'n faktor 3.5 en houtskool en olie opbrengste van onderskeidelik 40% en 38% by 500°C behaal kan word. 'n Ondersoek van die houtskool het getoon dat dit gebruik kan word as 'n kompos, wat dan sal beteken dat 'n probleem afvalstof verander word na 'n omgewingsvriendelike en ekonomies waardevolle produk. Die olie van beide die rioolslyk en leer het hoë energiewaardes (26.7MJ/kg en 30.9MJ/kg onderskeidelik) en kan verkoop word as verbrandingsolie of gebruik word in die vakuum pirolise proses as 'n hulp-hitte bron. Die gebruikswaarde van die olie sal baie afhang van die probleme wat deur die uiters hoë stikstof-inhoud (±5%-6%) veroorsaak gaan word. 'n Verdere studie van die ko-pirolise van PVC en hout is ook gedoen om die interaksie tussen die afvalstowwe te bestudeer en ook om as 'n vereenvoudigde voorstelling van munisipale afval te dien. Daar is gevind dat die HCI wat afkom as PVC verhit word, suur hidrolise van die houtstrukture veroorsaak en lei tot laer houtskool (verminder van 32.6% na 29.7% droë voerstofbasis, by die maksimum olie opbrengs temperatuur van 460°C) en veel hoër olie opbrengste (42.4% vir die kopirolise in vergelyking met 23.6% vir die plant materiaal by 460°C). 'n Studie van die energie wat verkry kan word uit die olie en houtskool het getoon dat 16% tot 28% meer energie verteenwoordig word deur die produkte per kilogram droë voerstof vir die ko-pirolise proses bo normale vakuum pirolise. Alhoewel groot spesialis vakuum pirolise aanlegte in die verlede ontwerp is (meestal vir die verwerking van gebruikte motor buitebande) sal dit nogstans noodsaaklik wees om die winsgewindheid van kleinermaat prosesse te bestudeer sodat vakuum pirolise by die oorsprong van die afvalstoftoegepas kan word. Dit blyk dat vakuum pirolise 'n baie belowende tegnologie IS wat verskeie afval probleme op 'n omgewingsvriendelike en ekonomies winsgewinde wyse kan oplos.

Honeycomb sandwich panels offer an extremely lightweight solution for aerospace structures. As efficiency demands increase, low-cost non-autoclave manufacturing solutions are sought for honeycomb and other composite structures. Vacuum-bag-only (VBO) manufacturing is one possible solution that relies on vacuum to remove all entrapped volatiles prior to cure, and then the differential pressure between the inside and outside of the vacuum bag consolidates the layers during cure. This technique can be very effective for monolithic laminates made with out-of-autoclave (OOA) prepregs, but honeycomb structures introduce two additional manufacturing nuisances. First, the core entraps up to 98 % of its volume during lay-up, and second, non-metallic cores readily absorb ambient moisture. Entrapped air and moisture can increase the honeycomb core pressure during processing, reducing part quality. Given that the honeycomb core pressure is crucial to achieving success in VBO manufacturing of honeycomb panels, a threefold approach was used in this thesis to study the transport phenomena that influence this behaviour. First, the transport phenomena of the constituent materials were characterized. Applying an impermeable boundary condition to the tool-side skin allowed for simple air permeability characterization of honeycomb skins by considering only the bag-side skin. An instrumented test fixture was used to measure the honeycomb core pressure during the pre-processing vacuum hold. The results revealed that a transverse interconnected pore space was required in OOA prepreg skins for gas evacuation to proceed in honeycomb panels. The same test fixture was used to characterize the honeycomb skin air permeability and honeycomb core moisture diffusivity during elevated temperature processing. The evolving skin air permeability and core diffusivity were observed to cause the honeycomb core pressure to increase during the temperature ramp and decrease during the temperature hold. Second, a process model was developed to predict honeycomb core pressure throughout the manufacturing process. The process model identified that the honeycomb core pressure can exceed the vacuum bag consolidation pressure due to the high core moisture adsorption and elevated temperature diffusivity. Choosing, or creating, a honeycomb skin with high air permeability was identified as a key process parameter to avoid exceeding the consolidation pressure. Finally, the material characterization and process modelling were successfully scaled to reproduce the honeycomb core pressure behaviour in holistic honeycomb panels. The in-situ honeycomb core pressure was measured throughout the manufacturing process in dual-skin honeycomb panels using embedded pressure sensors. The embedded pressure sensor response validated the material characterization assumptions and model simplifications used to predict the honeycomb core pressure during the VBO manufacturing process. Manufacturing honeycomb panels is a complex activity with many material and processing variables. A suitable skin material and bagging configuration was selected for VBO manufacturing of honeycomb panels by coupling transport phenomena modelling and tailored material characterization. This approach could be used to reduce manufacturing trial and error before scaling these materials to larger applications.<br>Les panneaux sandwich en nid d'abeille offrent une solution extrêmement légère pour les structures aérospatiales. Avec l'augmentation de la demande pour les structures en matériaux composites, les solutions de fabrication de ces structures hors de l'autoclave sont recherchées afin de réduire les coûts. La méthode de fabrication avec sac sous vide requiert une pompe à vide pour enlever tous les gaz piégés après le drapage des matériaux préimprégnés et créer le différentiel de pression entre l'intérieur et l'extérieur du sac à vide afin de consolider les couches de composite. Cette technique peut être très efficace pour les laminés monolithiques, mais les structures en nid d'abeille présentent deux difficultés supplémentaires lorsque des nids d'abeilles non métalliques sont utilisés. D'abord, le nid d'abeille contient 98% du volume d'air piégé pendant le drapage, et deuxièmement, les nids d'abeilles non métalliques absorbent l'humidité pendant leur manipulation. L'air emprisonné dans le nid d'abeilles et l'humidité va augmenter la pression pendant la mise en forme, et peuvent créer des défauts. Cette thèse est divisée en trois thèmes pour étudier et pour optimiser le processus de fabrication des panneaux de composite sandwich avec nid d'abeilles. Tout d'abord, une condition imperméable a été appliquée sur le côté de l'outil, ce qui permet une caractérisation simple des matériaux utilisés pour la mise en forme combinés avec les matériaux préimprégnés de côté de sac à vide. La perméabilité à l'air pour les matériaux préimprégnés a été mesurée durant l'évacuation de l'air avant la cuisson, révélant un degré significatif de l'anisotropie de perméabilité à l'air. Pendant la cuisson à température élevée, la perméabilité à l'air a évolué avec le cycle de cuisson. En outre, le coefficient de diffusion de l'humidité du nid d'abeille non métallique a été caractérisé par une fonction de la concentration d'humidité et de la température. Deuxièmement, un modèle a été développé pour prédire la pression dans le nid d'abeille pendant le processus de fabrication. Des cartes de processus ont été créées afin d'identifier les combinaisons de conditions de traitement pouvant augmenter la pression dans le nid d'abeille au-dessus de la pression de consolidation. Finalement, des panneaux ont été fabriqués avec un laminé sur le côté de l'outil ainsi que sur le côté du sac à vide. Des capteurs de pression ont été incorporés pour mesurer la pression dans le nid d'abeilles pendant le processus de fabrication. La caractérisation des matériaux et la modélisation des processus développées à partir d'expériences simples à petite échelle ont permis de reproduire avec succès le comportement complexe de la pression dans le nid d'abeilles des pièces de grandes dimensions.

Organic photovoltaics have attracted considerable research and commercial interest due to their lightness, mechanical flexibility and low production costs. There are two main approaches for the fabrication of organic solar cells – solution and vacuum processing. The former relies on morphology control in polymer-fullerene blends resulting from natural phase separation in these systems. The latter takes advantage of solvent-free processing allowing highly complex multi-junction architectures similar to inorganic solar cells. This work aims to combine the benefits of both by depositing conjugated polymers using vacuum thermal evaporation. By employing this unconventional approach it aims to enhance the efficiency of organic photovoltaics through increased complexity of the thin-film architecture while improving the nanoscale morphology control of the individual active layers. The thesis explores the vacuum thermal deposition of polythiophenes, mainly poly(3-hexylthiophene) (P3HT) and side-group free poly(thiophene) (PTh). A variety of chemical techniques, such as NMR, FT-IR, GPC, DSC and TGA, are used to examine the effect of heating on chemical structure of the polymers. Optimal processing parameters are identified and related to the resulting thin-film morphology and charge transport properties. Efficient photovoltaic devices based on polythiophene donors and fullerene acceptors are fabricated. Materials science techniques AFM, XRD, SEM, TEM and MicroXAM are used to characterize topography and morphology of the thin films, and UV-Vis, EQE, I-V and C-V measurements relate these to the optical and electronic properties. The results of the study show that polymer side groups have a strong influence on molecular packing and charge extraction in vacuum-deposited polymer thin films. Unlike P3HT, evaporated PTh forms highly crystalline films. This leads to enhanced charge transport properties with hole mobility two orders of magnitude higher than that in P3HT. The effect of molecular order is demonstrated on polymer/fullerene planar heterojunction solar cells. PTh-based devices have significantly better current and recombination characteristics, resulting in improved overall power conversion efficiency (PCE) by 70% as compared to P3HT. This confirms that the chemical structure of the molecule is a crucial parameter in deposition of large organic semiconductors. It is also the first-ever example of vacuum-deposited polymer photovoltaic cell. Next, vacuum co-deposited PTh:C60 bulk heterojunctions with different donor-acceptor compositions are fabricated, and the effect of post-production thermal annealing on their photovoltaic performance and morphology is studied. Co-deposition of blended mixtures leads to 60% higher photocurrents than in thickness-optimized PTh/C60 planar heterojunction counterparts. Furthermore, by annealing the devices post-situ the PCE is improved by as much as 80%, achieving performance comparable to previously reported polythiophene and oligothiophene equivalents processed in solution and vacuum, respectively. The enhanced photo-response is a result of favourable morphological development of PTh upon annealing. In contrast to standard vacuum-processed molecular blends, annealing-induced phase separation in PTh:C60 does not lead to the formation of coarse morphology but rather to an incremental improvement of the already established interpenetrated nanoscale network. The morphological response of the evaporated PTh within the blend is further verified to positively differ from that of its small-molecule counterpart sexithiophene. This illustrates the morphological advantage of polymer-fullerene combination over all other vacuum-processable material systems. In conclusion, this processing approach outlines the conceptual path towards the most beneficial combination of solution/polymer- and vacuum-based photovoltaics. It opens up a fabrication method with considerable potential to enhance the efficiency of large-scale organic solar cells production.

This thesis discusses vacuum deposited organic solar cells. It focuses on the investigation of new donor molecules blended with the standard electron acceptor C60. These donor-acceptor heterojunctions form the photoactive system of organic solar cells. In addition, the influence of the processing conditions on the morphology of the blend layers is investigated, as the morphology is crucial for an efficient generation of free charge carriers upon photon absorption. Bulk heterojunction solar cells with the donor DTDCTB are deposited at different substrate temperatures. We identify three substrate temperature regimes, discriminated by the behavior of the fill factor (FF ) as a function of the blend layer thickness. Devices deposited at RT have a maximum FF between 50 and 70 nm blend thickness, while devices deposited at 110 °C have a monotonically decreasing FF. At Tsub=85 °C, the devices have an S-kinked current-voltage curve. Grazing incidence wide angle X-ray scattering measurements show that this peculiar behavior of the FF is not correlated with a change in the crystallinity of the DTDCTB, which stays amorphous. Absorption measurements show that the average alignment of the molecules inside the blend also remains unchanged. Charge extraction measurements (OTRACE) reveal a mobility for the 110 °C device that is an order of magnitude higher than for the RT device. The difference in mobility can be explained by a higher trap density for the RT samples as measured by impedance spectroscopy. Despite slightly higher carrier lifetimes for the RT device obtained by transient photovoltage measurements, its mobility-lifetime product is still lower than for the 110 °C devices. Based on DTDCTB, three new donor materials are designed to have a higher thermal stability in order to achieve higher yields upon material purification using gradient sublimation. For PRTF, the thermal stability is increased demonstrated by a higher yield upon sublimation. However, all new materials have a reduced absorption as compared to DTDCTB, which limits the short current density, and the FF is more sensitive to an increase of the blend layer thickness. The highest power conversion efficiency is achieved for a PRTF:C60 solar cell with 3.8%. Interestingly, PRTF:C60 solar cells show exceptionally low nonradiative voltage losses of only 0.26 V. Another absorber molecule is the push-pull chromophore QM1. Scanning electron microscope (SEM) measurements show a growth of the molecule in nanowires on several substrates. The nanowires have lengths up to several micrometers and are several tens of nanometers wide. The formation of the nanowires is accompanied by a strong blue shift (650 meV) of the thin film absorption spectrum in comparison to the absorption in solution, which is attributed to H-aggregation of the molecules. Furthermore, the thin film absorption onset reaches up to 1100 nm, making the material a suitable candidate for a near infrared absorber in organic solar cells. For a solar cell in combination with C60, a power conversion efficiency of 1.9% was achieved with an external quantum efficiency of over 19% for the spectral range between 600 and 1000 nm. The method of “co-evaporant induced crystallization” as a means to increase the crystallinity of blend layers without increasing the substrate temperature during the deposition is investigated. Mass spectrometry (LDI-ToF-MS) measurements show that polydimethylsiloxane (PDMS), which is used as a co-evaporant, decomposes during the evaporation and only lighter oligomers evaporate. Quartz crystal microbalance (QCM) measurements prove that the detection of PDMS saturates at higher amounts of evaporated material. LDI-ToF-MS measurements show further that the determination of the volatilization temperature by QCM measurements is highly error prone. The method was applied to zinc phthalocyanine (ZnPc) :C60 solar cells, accepting the insertion of PDMS into the blend layer. Diffraction (GIXRD) measurements show a large increase in crystallinity. ZnPc:C60 solar cells produced by applying the method reveal a similar behavior as solar cells processed at a higher substrate temperature.

Out-of-autoclave manufacturing processes for composite materials are increasing in importance for aerospace and automotive industries. Vacuum Infusion processes are leading the push to move out of the autoclave. An understanding of the various process parameters associated with resin infusion is necessary to produce quality product. Variance in compaction, resin, and vacuum pressures are studied, concentrating on developing a compaction pressure profile as it relates to fiber volume fraction. The purpose of this research is twofold: (1) to show and quantify the existence of a resin pressure gradient in compression testing using rigid tooling, and (2) to use measured test data to validate and improve resin flow simulation models. One-dimensional compression tests revealed a pressure gradient across the diameter of the compression tool. The pressure gradient follows trends consistent with Darcy's Law. Compression tests revealed fabric hysteresis during compaction as shown in previous studies. Fiber compaction pressure was found to not be directly equal to compressive forces of the Instron when resin is present in the system. The relationship between Instron, resin and compaction pressures is defined. The compression study was used to validate previously developed flow simulation models. Resin pressures are critical to developing an accurate two-dimensional radial flow simulation for low permeability fabrics. It is feasible to determine final fiber volume fraction at a given compaction pressure.

Time-lapse seismic is proving to be a valuable method for monitoring subsurface pressure changes and fluid movements in producing hydrocarbon reservoirs. This case study aims to show the importance of multicomponent seismic data in time-lapse monitoring as shear wave splitting proves to be a highly sensitive diagnostic for monitoring hydrocarbon production. The investigated 4D, 3C land seismic data are from Vacuum Field, New Mexico, USA with a fractured dolomite forming the reservoir of interest. In 1995,<i> </i>over a period of two months, two seismic surveys were acquired before and after a pilot tertiary recovery program of CO₂-injection in a single well. The pore fluid pressure in the reservoir increased significantly from a ‘normal’ pressure of 10.6 MPa to an ‘overpressure’ of 17 MPa. CO₂is a highly compressible fluid at these pressures and therefore decreases the bulk modulus of the reservoir fluid. After the application of a data processing sequence that aims to preserve anisotropy and maximise repeatability, the interval time analysis of the reservoir interval shows a significant 10% change in shear-wave anisotropy and a 3% decrease in the <i>P</i>-interval velocities to the south and east of the CO₂-injection well. The fast shear wave becomes the slowest after the injection. Further, the rms-amplitudes of the shear-wave parallel to the maximum horizontal stress direction decrease in the area of the anisotropy anomaly after injection. In 1997 and 1998 two further surveys were acquired one year apart in Vacuum Field during a major CO₂-injection program. Due to repeatability issues these data are analysed separately. Small pore fluid pressure increases of up to 1.4 MPa in the reservoir led to velocity decreases of generally less than 2% in <i>P </i>and in shear. In order to interpret the observations several 1D models incorporating both saturation and pressure changes are matched to the data in the vicinity of the injection well. Due to the high stiffness of the dolomitic reservoir rock the saturation changes have little effect on the seismic velocities.

Vacuum-Assisted Resin Transfer Molding (VARTM) processes are becoming promising technologies in the manufacturing of primary composite structures in the aircraft industry as well as infrastructure. A great deal of work still needs to be done on efforts to reduce the costly trial-and-error methods of VARTM processing that are currently in practice today. A computer simulation model of the VARTM process would provide a cost-effective tool in the manufacturing of composites utilizing this technique. Therefore, the objective of this research was to modify an existing three-dimensional, Resin Film Infusion (RFI)/Resin Transfer Molding (RTM) model to include VARTM simulation capabilities and to verify this model with the fabrication of aircraft structural composites. An additional objective was to use the VARTM model as a process analysis tool, where this tool would enable the user to configure the best process for manufacturing quality composites. Experimental verification of the model was performed by processing several flat composite panels. The parameters verified included flow front patterns and infiltration times. The flow front patterns were determined to be qualitatively accurate, while the simulated infiltration times over predicted experimental times by 8 to 10%. Capillary and gravitational forces were incorporated into the existing RFI/RTM model in order to simulate VARTM processing physics more accurately. The theoretical capillary pressure showed the capability to reduce the simulated infiltration times by as great as 6%. The gravity, on the other hand, was found to be negligible for all cases. Finally, the VARTM model was used as a process analysis tool. This enabled the user to determine such important process constraints as the location and type of injection ports and the permeability and location of the high-permeable media. A process for a three-stiffener composite panel was proposed. This configuration evolved from the variation of the process constraints in the modeling of several different composite panels. The configuration was proposed by considering such factors as: infiltration time, the number of vacuum ports, and possible areas of void entrapment.<br>Ph. D.

Clostridium sporogenes PA 3679 spores were inoculated into a meat-vegetable mixture before extrusion, cooking, and vacuum packaging into "stewsticks" to simulate Clostridium botulinum growth. The experiment was a 3 x 5 x 2 x 3 factorial which determined the influence of pH, water activity, initial spore load, and storage period on spore survival. Spore levels decreased throughout storage for all treatments. Spore levels decreased linearly (P = 0.02) as water activity increased, in samples that were heated to kill vegetative cells and activate spores. Other significant interactions of heat-treated samples were observed with inoculum level (P < 0.01) and storage time (P < 0.01). Spore levels in stored products were also significantly affected by water activity* inoculum level (P = 0.03), pH * time, water activity* time (P = 0.01), inoculum level * time (P < 0.01), and water activity * inoculum levels * time (P < 0.01). The interaction between pH * water activity * time tended towards significance (P = 0.06). Most probable number estimates in nonheated samples accounted for naturally occurring viable cells and spores, and added spores and were significantly affected by the main effects of inoculum level (P < 0.01) and time (P < 0.01). The two-way interactions of water activity * inoculum level (P = 0.04), pH * inoculum level (P < 0.01),water activity * time (P < 0.01), and three-way interaction of pH * inoculum level * time (P = 0.03) were significant. Spore levels approached 102, or less (compared to an inoculum level of 106 spores per gram) due to the effects of many treatments. Some stewstick packages were observed to become "gassy" or "loose" during storage. Subsequently the stewstick packages were used to isolate microorganisms that were able to grow at water activities of 0.96-0.86, in glycerol-adjusted Rogosa agar, and were acid tolerant to pH 4.4-4.2. One produced gas in pure culture, and some produced indole. These bacteria were not destroyed by heating to 74°C for at least 30 minutes, and lowered the pH in the stewstick during storage. In conclusion, in all stewstick samples, regardless of pH or Aw, inoculated clostridial spore levels decreased during storage, apparently because spores germinated and vegetative cells subsequently died. Thus, if stewsticks are cooked to 74°C throughout, have a Aw ≤ 0.86 and pH ≤ 4.8, they appear to be safe.

The main aim of this thesis is to gain an improved understanding of the use and limitations of flax fibres as a reinforcement for thermoplastic composites manufactured by the vacuum forming process. The effect of process variables on void content and on mechanical properties of flax fibre/polypropylene composites has been investigated. An isothermal vacuum forming process has been studied and the following process parameters varied : consolidation time; fibre volume fraction; moisture content; reinforcement stacking sequence. The thermal degradation of untreated and alkaline treated flax fibres and its effect on the composite properties has been investigated using fourier transform infrared spectrometry (FTIR) and thermogravimetry (TG) techniques. Characterisation of the micro structure of failure surfaces following tensile testing of the composites has also been observed using scanning electron microscopy (SEM). The results of the investigation show that an increase in consolidation time at temperature and/or a reduction in fibre volume fraction reduces void content, as expected . By contrast and in spite of the reduction in voidage levels, mechanical tests show that an increase in consolidation time reduces ultimate tensile strength (UTS), strain to failure and impact strength of the composite. This reduction in properties is attributed to increased thermal degradation of the flax fibres and consequently the composite. Degradation manifests itself as hemicellulose and pectin decomposition in the fibres, particularly at low heating rates. Alkaline treatment was investigated as a potential method of improving the thermal stability of the fibres by reducing the low thermal stability hemicellulose and pectin components. Furthermore, such treatment improves the surface roughness of the fib res and results in an improved consolidation due to the reduction in void content. However, these positive effects did not significantly improve composite strength because of an apparent reduction in reinforcement volume fraction resulting from reduced fibre volume.

Vacuum assisted resin transfer molding (VARTM) is a low cost resin infusion process being developed for the manufacture of composite structures. VARTM is being evaluated for the manufacture of primary aircraft structures, including foam sandwich composite materials. One of the benefits of VARTM is the ability to resin infiltrate large or complex shaped components. However, trial and error process development of these types of composite structures can prove costly and ineffective. Therefore, process modeling of the associated flow details and infiltration times can aide in manufacturing design and optimization. The purpose of this research was to develop a process using VARTM to resin infiltrate stitched and unstitched dry carbon fiber preforms with polymethacrylimide foam cores to produce composite sandwich structures. The infiltration process was then used to experimentally verify a three-dimensional finite element model for VARTM injection of stitched sandwich structures. Using the processes developed for the resin infiltration of stitched foam core preforms, visualization experiments were performed to verify the finite element model. The flow front progression as a function of time and the total infiltration time were recorded and compared with model predictions. Four preform configurations were examined in which foam thickness and stitch row spacing were varied. For the preform with 12.7 mm thick foam core and 12.7 mm stitch row spacing, model prediction and experimental data agreed within 5%. The 12.7 mm thick foam core preform with 6.35 mm row spacing experimental and model predicted data agreed within 8%. However, for the 12.7 mm thick foam core preform with 25.4 mm row spacing, the model overpredicted infiltration times by more 20%. The final case was the 25.4 mm thick foam core preform with 12.7 mm row spacing. In this case, the model overpredicted infiltration times by more than 50%. This indicates that the model did not accurately describe flow through the needle perforations in the foam core and could be addressed by changing the mesh elements connecting the two face sheets.<br>Master of Science

This thesis investigates the application of plasma immersion ion implantation (PIII) to polymers. PIII requires that a high negative potential be applied to the surface of the material while it is immersed in a plasma. This presents a problem for insulating materials such as polymers, since the implanting ions carry charge to the surface, resulting in a charge accumulation that effectively neutralises the applied potential. This causes the plasma sheath at the surface to collapse a short time after the potential is applied. Measurements of the sheath dynamics, including the collapsing sheath, are performed using an electric probe. The results are compared to theoretical models of the plasma sheath based on the Child-Langmuir law for high voltage sheaths. The theoretical model predicts well the sheath dynamics for conductive substrates. For insulating substrates the model can account for the experimental observations if the secondary electron coefficient is modified, justified on the basis of the poly-energetic nature of the implanting ions. If a conductive film is applied to the insulator surface the problem of charge accumulation can be avoided without compromising the effectiveness of PIII. The requirement for the film is that it be conductive, yet transparent to the incident ions. Experimental results are presented which confirm the effectiveness of the method. Theoretical estimates of the surface potential show that a film of the order of 5nm thickness can effectively circumvent the charge accumulation problem. Efforts to produce and characterise such a film form the final two chapters of this thesis. The optimal thickness is determined to be near the percolation threshold, where a marked increase in conductivity occurs. Spectroscopic ellipsometry is shown to be an excellent method to determine the film thickness and percolation threshold non-invasively. Throughout this work cathodic vacuum arcs are used to deposit thin films and as a source of metal plasmas. The design and construction of a pulsed cathodic vacuum arc forms a significant part of this thesis. Investigations of the cathode spots and power supply requirements are presented.

Solar photovoltaic modules provide clean electricity from sunlight but will not be able to compete on an open market until the cost of the electricity they produce is comparable to that produced by traditional methods. At present, modules based on crystalline silicon wafer solar cells account for nearly 90% of photovoltaic production capacity. However, it is anticipated that the ultimate cost reduction achievable for crystalline silicon solar cell production will be somewhat limited and that thin film solar cells may offer a cheaper alternative in the long term. The highest energy conversion efficiencies reported for thin film solar cells have been for devices based around chalcopyrite Cu(In, Ga)(Se, S)2 photovoltaic absorbers. The most efficient Cu(In, Ga)(Se, S)2 solar cells contain absorber layers deposited by vacuum co-evaporation of the elements. However, the cost of ownership of large area vacuum evaporation technology is high and may be a limiting factor in the cost reductions achievable for Cu(In, Ga)(Se, S)2 based solar cells. Therefore, many alternative deposition methods are under investigation. Despite almost thirty companies being in the process of commercialising these technologies there is no consensus as to which deposition method will lead to the most cost effective product. Non-vacuum deposition techniques involving powders and chemical solutions potentially offer significant reductions in the cost of Cu(In, Ga)(Se, S)2 absorber layer deposition as compared to their vacuum counterparts. A wide range of such approaches has been investigated for thirty years and the gap between the world record Cu(In, Ga)(Se, S)2 solar cell and the best devices containing non-vacuum deposited absorber layers has closed significantly in recent years. Nevertheless, no one technique has demonstrated its superiority and the best results are still achieved with some of the most complex approaches. The work presented here involved the development and investigation of a new process for performing one of the stages of non-vacuum deposition of Cu(In, Ga)(Se, S)2 absorber layers. The new process incorporates copper into an initial Group III-VI precursor layer, e.g. indium gallium selenide, through an ion exchange reaction performed in solution. The ion exchange reaction requires only very simple, low-cost equipment and proceeds at temperatures over 1000°C lower than required for the evaporation of Cu under vacuum. In the new process, indium (gallium) selenide initial precursor layers are immersed in solutions containing Cu ions. During immersion an exchange reaction occurs and Cu ions from the solution exchange places with Group III ions in the layer. This leads to the formation of an intimately bonded, laterally homogeneous copper selenide – indium (gallium) selenide modified precursor layer with the same morphology as the initial precursor. These modified precursor layers were converted to single phase chalcopyrite CuInSe2 and Cu(In, Ga)Se2 by annealing with Se in a tube furnace system. Investigation of the annealing treatment revealed that a series of phase transformations, beginning at low temperature, lead to chalcopyrite formation. Control of the timing of the Se supply was demonstrated to prevent reactions that were deemed detrimental to the morphology of the resulting chalcopyrite layers. When vacuum evaporated indium (gallium) selenide layers were used as initial precursors, solar cells produced from the absorber layers exhibited energy conversion efficiencies of up to 4%. While these results are considered promising, the devices were characterised by very low open circuit voltages and parallel resistances. Rapid thermal processing was applied to the modified precursor layers in an attempt to further improve their conversion into chalcopyrite material. Despite only a small number of solar cells being fabricated using rapid thermal processing, improvements in open circuit voltage of close to 150mV were achieved. However, due to increases in series resistance and reductions in current collection only small increases in solar cell efficiency were recorded. Rapid thermal processing was also used to demonstrate synthesis of single phase CuInS2 from modified precursor layers based on non-vacuum deposited indium sulphide. Non-vacuum deposition methods provide many opportunities for the incorporation of undesirable impurities into the deposited layers. Analysis of the precursor layers developed during this work revealed that alkali atoms from the complexant used in the ion exchange baths are incorporated into the precursor layers alongside the Cu. Alkali atoms exhibit pronounced electronic and structural effects on Cu(In, Ga)Se2 layers and are beneficial in low concentrations. However, excess alkali atoms are detrimental to Cu(In, Ga)Se2 solar cell performance and the problems encountered with cells produced here are consistent with the effects reported in the literature for excess alkali incorporation. It is therefore expected that further improvements in solar cell efficiency might be achieved following reformulation of the ion exchange bath chemistry.

Le monde fait face à des enjeux climatiques et énergétiques qui impliquent l’utilisation de biomasse, au même titre que d’autres énergies renouvelables, comme des moyens de production d’énergie. Parmi les voies envisagées, l’addition d’huile de pyrolyse au sein de procédés de raffinage déjà existants présenterait l’avantage d’une mise en place rapide et d’une modification structurelle limitée. L’unité de craquage catalytique en lit fluidisé (FCC), valorisant les fractions pétrolières les plus lourdes, est l’unité la plus à même de valoriser des charges biosourcées. Cependant, les premiers tests ont pu révéler la présence de certains freins, tels que l’immiscibilité des charges fossiles et biosourcées, impliquant la mise en place de deux systèmes d’injection indépendants, ou encore une plus forte désactivation des catalyseurs de craquage. Sur ce dernier point, la présence de larges fragments lignocellulosiques, volumineux et riches en oxygène, perturbe le fonctionnement des catalyseurs de FCC. Leur encombrement étant suspecté de limiter leur accès aux sites acides, responsables du craquage catalytique, l’addition de mésopores aux cristaux de zéolites microporeux est une voie de recherche intéressante. Parallèlement à cela, la préparation de matériaux à porosité hiérarchisée, c’est-à-dire alliant l’agencement de plusieurs niveaux de porosité, se développe depuis quelques années. Ces matériaux rentrent parfaitement dans le cadre de l’amélioration de l’accessibilité aux sites acides. Ces travaux de thèse visent ainsi à définir l’impact que peut avoir un processus de hiérarchisation de la porosité sur le craquage catalytique d’un mélange de charges pétrolières fossiles avec une huile de pyrolyse de biomasse. Dans cette optique, une zéolite Y - couramment utilisée pour le craquage catalytique - a été hiérarchisée conformément aux protocoles déjà disponibles dans la littérature. Les caractéristiques structurelles de quatre matériaux ont ensuite été définies, aidant ainsi à la compréhension d’études du transfert diffusionnel, du craquage de molécules modèles et du craquage de charges réelles réalisées par la suite et présentées dans ce manuscrit de thèse<br>Fluid Catalytic Cracking (FCC) gasoline represents one third of the global gasoline pool. In order to meet objectives regarding increased renewable share in transportation fuels, the production of a hybrid bio/fossil fuel by co-refining biomass pyrolysis liquids with crude oil fractions in an oil refinery is an achievable approach. Oxygenated molecules, typical of the bio-feedstock, are present in liquids produced from biomass pyrolysis. Because large lignocellulosic fragments could strongly adsorb on the FCC zeolite surface, they may not access catalytic sites or could diffuse very slowly in the microporous network. Hence, for high oxygenated molecule content, co-refining may lead to severe changes in product quality, such as a higher aromaticity, coke and residual oxygenates in the hybrid fuels that are produced. To adjust the reactivity of FCC catalysts towards bio-oil, four Y zeolites with well controlled hierarchical mesoporous – microporous network have been investigated. They mainly vary by the characteristics of the secondary mesoporous network (pore size, mesoporous volume) while their globally similar acidity displays some changes in nature (Lewis/Brønsted). The impact of hierarchical porous structures combined with changes in acidity is studied on catalytic activity and selectivity (e.g., coke formation). The issue of diffusion limitation in line with acidity changes are discussed based on Zero Length Column (ZLC) measurements, pyridine adsorption measurements, catalytic cracking of n-hexane and co-processing of vacuum gas oil and bio-oil in micro-activity test unit

Current methods to reduce the native microbiota and potential pathogens on spices include steam treatments and ethylene oxide (EtO) fumigation. The objectives of this research were to identify the effectiveness of a lab-scale steam apparatus and a commercial EtO process on the inactivation of Salmonella enterica or Enterococcus faecium NRRL B-2354 inoculated whole black peppercorns and cumin seeds. Peppercorns and cumin seeds were inoculated with Salmonella or Enterococcus and processed in a lab-scale steam apparatus at 16.9 PSIA and two references temperatures (165°F and 180°F) and in a commercial ethylene oxide fumigation chamber using a standard commercial EtO fumigation process. Cells were enumerated by serial dilution and plating onto TSA with a thin overlay of selective media. Inoculation preparation influenced inactivation of Salmonella on peppercorns with greater reductions reported for TSA-grown cells compared to within a biofilm. To achieve an assured 5-log reduction of TSA-inoculated Salmonella on peppercorns exposure for 125s and 100s at 165°F and 180°F, respectively is required. For cumin seeds temperatures of 165°F for 110s were needed or 65s at 180°F to assure 5 log reduction. EtO fumigation significantly reduced both microorganisms on both spices (p<0.05), however significant variation existed between bags in the same process run. Reductions of Enterococcus were comparable or less than that of Salmonella under the majority of conditions, however a direct linear relationship cannot be used to compare the microbes. This study demonstrates that the effectiveness of Enterococcus faecium NRRL B-2354 as a surrogate for Salmonella can vary between spices and processes.<br>Master of Science in Life Sciences

Shape memory alloys when deformed can produce strains as high as 8%. Heating results in a phase transformation and associated recovery of all the accumulated strain, a phenomenon known as shape memory. This strain recovery can occur against large forces, resulting in their use as actuators. The goal of this project is to lower the operating temperature range of shape memory alloys in order for them to be used in cryogenic switches, seals, valves, fluid-line repair and self-healing gaskets for space related technologies. The Ni-Ti-Fe alloy system, previously used in Grumman F-14 aircrafts and activated at 120 K, is further developed through arc-melting a range of compositions and subsequent thermo-mechanical processing. A controlled atmosphere arc-melting facility and vertical vacuum quench furnace facility was commissioned to fabricate these alloys. The facility can create a vacuum of 10-7 Torr and heat treat samples up to 977 &deg;C. High purity powders of Ni, Ti and Fe in varying ratios were mixed and arc-melted into small buttons weighing 0.010 kg to 0.025 kg. The alloys were subjected to solutionizing and aging treatments. A combination of rolling, electro-discharge machining and low-speed cutting techniques were used to produce strips. Successful rolling experiments highlighted the workability of these alloys. The shape memory effect was successfully demonstrated at liquid nitrogen temperatures through a constrained recovery experiment that generated stresses of over 40 MPa. Differential scanning calorimetry (DSC) and a dilatometry setup was used to characterize the fabricated materials and determine relationships between composition, thermo-mechanical processing parameters and transformation temperatures.<br>M.S.M.S.E.<br>Department of Mechanical, Materials and Aerospace Engineering;<br>Engineering and Computer Science<br>Materials Science and Engineering

Le procédé Cold Spray (CS) ou projection à froid a été largement étudié en raison de son rendement de projection et de la conservation des propriétés du matériau de départ. Donc, ce procédé a montré des avantages évidents sur la fabrication de différents dépôts à base de cuivre et de ses alliages par rapport à d'autres techniques, comme l’électrodéposition, le Laser Cladding ou la projection thermique. Parmi les alliages de cuivre, le laiton s’implante dans les domaines de l'architecture ou de l'industrie. Malheureusement, aujourd’hui force est de constater qu’il n’existe que très peu de travaux sur les revêtements en laiton qui ne sont réalisés d’ailleurs que par électrodéposition et par aucune autre méthode d’élaboration limitant sérieusement leur utilisation dans de nombreuses applications.Cette thèse s’est appliquée à élaborer des revêtements de laiton et des composites à matrice laiton. La poudre d'alliage de laiton Muntz de composition Cu60Zn40, présentant une résistance à la corrosion parmi les meilleures, a été choisie comme matériau de base des revêtements. Deux méthodes de projection permettant d’éviter les phénomènes d’oxydation ont été sélectionnées : la projection à froid et la projection basse pression. La comparaison entre les deux procédés sur les microstructures, phases, textures, propriétés mécaniques, comportements à l’usure et en corrosion du revêtement Cu60Zn40 a été étudié. De plus, les recherches de ce travail ont porté sur l’optimisation du revêtement par le post-traitement de friction malaxage et par ajout de différents renforts céramiques. Les effets du post-traitement par friction malaxage sur les microstructures, phases, textures, et propriétés mécaniques et les effets des types de renfort et de leurs quantités dans les revêtements composites sur les microstructures, les phases, les propriétés mécaniques et thermiques et les comportements à la corrosion ont été analysés. Les gains de performance obtenus à la fin de cette étude sont finalement concrétisés par la réparation d’une pièce endommagée en Cu60Zn40 avec l’étude des microstructures interfaciales entre le revêtement composite Cu60Zn40 et le substrat Cu60Zn40 ainsi que la détermination des propriétés mécaniques et des comportements tribologiques<br>Cold Spray (CS) has been widely investigated owing to its high deposition efficiency and retention of the properties of starting materials. Thus, this process has shown obvious advantages over the fabrication of different copper-based deposits and its alloys over other techniques, such as electroplating, Laser Cladding or thermal spraying. As one of the main copper alloys, brass is implanted in the fields of architecture or industry. Nevertheless, nowadays it is clear that there is very little work on brass coatings, and they were mainly made by electroplating and any other deposition methods, which has severely limits their uses in many applications.This study was applied to develop the brass coatings and its composites. The Muntz brass alloy powder of Cu60Zn40, which shows the best corrosion resistance, was selected to manufacture the brass coatings. Two projection methods were used, i.e. Cold Spraying and Vacuum Plasma Spraying (VPS), avoiding the oxidation. The comparison study of spraying processes on the microstructures, the phases, the textures, the mechanical properties, and the wear and corrosion behaviors of the Cu60Zn40 coatings was carried out. In addition, this work also focused on the optimization of the coatings either by applying the post-treatment of friction stir processing (FSP), or by adding different ceramic reinforcements. The effects of FSP on the microstructures, the phases, the textures and the mechanical properties of coating and the effects of reinforcement types and their amounts in composite coatings on the microstructures, the phases, the mechanical and thermal properties and the corrosion behaviors were revealed. At the end of this study, the obtained performance will ultimately be realized by repairing the damaged part of Cu60Zn40 alloy, and the studies on the interfacial microstructures between the Cu60Zn40 composite coating and the Cu60Zn40 substrate as well as the mechanical properties and the tribological behaviors between were performed

Le but de ces mesures est de determiner certaines caracteristiques d'un milieu physique par utilisation d'une source de rayonnement (neutron ou gamma) et des techniques appropriees de traitement du signal (moyennage, transformee de fourier). Grace a un systeme de modulation de la source, la transformee de fourier permet d'extraire le signal du bruit de fond (provenant soit du systeme de mesure, soit du milieu physique). Les applications etudiees sont la mesure du taux de vide dans la branche chaude d'un rep par transmission gamma modulee et la mesure de quantite de matieres fissiles dans les usines de retraitement par utilisation d'une source de neutrons

This thesis describes the design, manufacture and characterisation of thick vacuum plasma sprayed tungsten (W) coatings on steel substrates. Fusion is a potentially clean, sustainable, energy source in which nuclear energy is generated via the release of internal energy from nuclei. In order to fuse nuclei the Coulomb barrier must be breached - requiring extreme temperatures or pressures – akin to creating a ‘star in a box’. Tungsten is a promising candidate material for future fusion reactors due to a high sputtering threshold and melting temperature. However, the large coefficient of thermal expansion mismatch with reactor structural steels such as the low activation steel Eurofer’97 is a major manufacturing and in-service problem. A vacuum plasma spraying approach for the manufacture of tungsten and tungsten/steel graded coatings has been developed successfully. The use of graded coatings and highly textured 3D interface surfi-sculpt substrates has been investigated to allow the deposition of thick plasma sprayed tungsten coatings on steel substrates. Finite element models have been developed to understand the residual stresses that develop in W/steel systems and made use of experimental measurements of coating thermal history during manufacture and elastic moduli measured by nano-indentation. For both the graded and surfi-sculpt coating, the models have been used to understand the mechanism of residual stress redistribution and relief in comparison with simple W on steel coatings, particularly by consideration of stored strain energy. In the case of surfi-sculpt W coatings, the patterned substrate gave rise to regular stress concentrating features, and allowed 2mm thick W coatings to be produced reproducibly without delamination. Preliminary through thickness residual stress measurements were compared to model predictions and provided tentative evidence of significant W coating stress relief by regulated coating segmentation.

The purpose of this dissertation was to realize two studies to evaluate the nutritional value of diets containing full-fat soybean processed by vacuum (FFSvac) or by steam (FFSstm) and of FFSvac and FFSstm for broilers and pigs. The study 1 evaluated the digestibility of diets, of soybeans and the metabolism of broilers fed with diets containing processed full-fat soybean. The experimental design was completely randomized with five treatments (control diet - CD, CD with isometric substitution of 40% FFSvac or FFSstm; diet with FFSvac and diet with FFSstm). The N intake was 23 and 20% less (P<0.01) to the broilers fed with diets containing FFSvac or FFSstm in relation to control group. The excretion, digestibility and absorption of N were not influenced (P>0.05) by the diets. The excretion of energy was 19 and 22% less (P<0.01) to the broilers fed with FFSvac in the diet in relation to control group and those fed with FFSstm in the diet. The diet with FFSvac enhanced (P<0.01) the digestibility and the metabolization of energy. The apparent metabolizable energy corrected for retention of N (MEn) was 12% higher (P<0.01) to the one fed of diet with FFSstm and similar to control diet. The dry matter, protein and ether extract digestibles, the apparent metabolizable energy and MEn were similar (P>0.05) for full-fat soybean processed by vacuum or by steam. The digestibility and absorption of N are not influenced by diets containing full-fat soybean processed by vacuum or by steam. The vacuum processing for full-fat soybean improves the digestibility of gross energy and the apparent metabolizable energy of diets. For the studied soybean types, the digestible nutrients, the apparent metabolizable energy and corrected to nitrogen retention are similar. The study 2 evaluated the digestibility of diets, of soybeans and the metabolism of pigs fed with diets containing processed full-fat soybean. The experimental design was completely randomized with five treatments (control diet - CD, CD with isometric substitution of 40% FFSvac or FFSstm; diet with FFSvac and diet with FFSstm) and four replications with one animal. The intake, urinary excretion of energy and digestible and metabolizable energy were not influenced (P>0.05) by the type of FFS processing. The animals fed diet containing FFSvac excreted 56% more energy (P<0.05) in their feces than animals fed the control diet. The digestion and N metabolism were not influenced (P>0.05) by the type of FFS processing. The digestibility of P, the fecal and the retained P did not differ (P>0.05) between the diets. For FFS, the digestible contents of protein and energy were 10.4 and 4.0% higher (P<0.01) with vacuum processing. The processed soybean does not affect the digestibility of diets neither the metabolism of pigs, except the digestibility of gross energy, which is reduced. The vacuum processing improves the digestible contents of protein and energy of full-fat soybean.<br>O objetivo desta dissertação foi realizar dois estudos para avaliar o valor nutricional de dietas contendo soja integral processada a vácuo (SIvac) ou a vapor (SIvap) e da SIvac e SIvap para frangos de corte e suínos. O estudo 1 avaliou a digestibilidade das dietas, das sojas e o metabolismo de frangos de corte alimentados com dietas contendo soja integral processada. O delineamento experimental foi inteiramente casualizado, com cinco tratamentos (dieta controle - DC; DC com substituição isométrica de 40% de SIvac ou SIvap; dieta com SIvac e dieta com SIvap). A ingestão de N foi 23 e 20% menor (P<0,01) para as aves alimentadas com dietas com SIvac ou SIvap em relação ao grupo controle. A excreção, digestibilidade e absorção do N não foram influenciadas (P>0,05) pelas dietas. A excreção de energia foi 19 e 22% menor (P<0,01) para as aves alimentadas com SIvac na dieta em relação ao grupo controle e àquele alimentado com dieta com SIvap. A dieta com SIvac melhorou (P<0,01) a digestibilidade e a metabolização da energia. A energia metabolizável aparente corrigida para retenção de N (EMn) foi 12% superior (P<0,01) à da dieta com SIvap e similar a da dieta controle. A matéria seca, proteína e extrato etéreo digestíveis, as energias metabolizável aparente e EMn foram semelhantes (P>0,05) para a soja integral processada a vácuo ou a vapor. A digestibilidade e a absorção do nitrogênio não são influenciadas por dietas contendo soja integral processada a vácuo ou a vapor. O processo a vácuo para a soja integral melhora a digestibilidade da energia bruta e a energia metabolizável aparente das dietas. Para os tipos de soja estudados, os nutrientes digestíveis, a energia metabolizável aparente e corrigida para retenção de nitrogênio são similares. O estudo 2 avaliou a digestibilidade das dietas, das sojas e o metabolismo de suínos alimentados com dietas contendo soja integral processada. O delineamento experimental foi inteiramente casualizado, com cinco tratamentos (dieta controle - DC; DC com substituição isométrica de 40% de SIvac ou SIvap; dieta com SIvac e dieta com SIvap) e quatro repetições de um animal. A ingestão, excreção urinária de energia e energias digestível e metabolizável das dietas não foram influenciadas (P>0,05) pelo processamento da soja. Os animais alimentados com dieta contendo SIvac excretaram 56% mais energia (P<0,05) nas fezes que os alimentados com a dieta controle. A digestão e o metabolismo do N não foram influenciados (P>0,05) pelo tipo de processamento da soja. A digestibilidade do P, o P fecal e absorvido não diferiram (P>0,05) entre as dietas. Para a soja integral, os teores digestíveis de proteína e energia foram 10,4 e 4,0% superiores (P<0,01) com o processamento a vácuo. A soja processada não altera a digestibilidade das dietas nem o metabolismo de suínos, exceto a digestibilidade da energia bruta, que é reduzida. O processamento a vácuo melhora os teores digestíveis de proteína e energia da soja integral para suínos.

The process of creating an efficacious malaria vaccine is complex due to the characteristics of the disease that are directly related to the responsible parasite. In the disease-vaccine interaction several aspects need to be taken into account to improve and understand the vaccine and for that reason different types of data need to be analyzed. Current assays technology allows analyzing several proteins simultaneously with a small blood volume. The combination of the medium throughput dataset of some assays and the small sample size of some malaria studies may hinder the use of classical statistical methods. In the context of low number of observations and medium or high number of variables the support vector machines (SVM) models are a powerful tool to analyze sparse data, i.e., data in which the number of predictors is larger or approximately equal to the number of observations, especially when handling binary outcomes. However, biomedical research often involves analysis of time-to-event outcomes. Several methods have been tested in the literature to deal with censored data into the SVM framework. Most of these methods are based on a support vector regression (SVR) approach and results found in the literature suggest no significant differences with Cox proportional hazards model and kernel Cox regression. Another perspective is a SVM for binary classification, however, almost no work has been done into this approach: only SVM learning using privileged information and SVM with uncertain classes have been described. This PhD thesis aims to propose alternative methods and extensions to the ones existing in the binary classification framework, specifically, proposing a conditional survival approach for weighting censored observations, a semi-supervised SVM with local invariances perspective and evaluating a weighted SVM model. Another important aspect in biomedical research is to identify the relevance of the variables in a model, i.e., which variables are important related to the response variable. In the SVM framework most of the work done is related to linear kernels, however, the main advantage of SVM is using non-linear kernels. This PhD thesis aims to propose three approaches based on the Recursive Feature Elimination (RFE) algorithm to rank variables based on non-linear SVM and SVM for survival analysis. Moreover, the proposed algorithms are focused on interpretation and visualization of each one the RFE iterations, allowing to identify relevant variables associated with the response variable and among predictor variables. After evaluating all proposed methods in a simulation study under several scenarios, a real dataset applying these methods has been analyzed: the Mal067 data aims to identify immune responses correlated with protection from malaria that were elicited by the malaria RTS,S vaccine and by natural immunity. All SVM for survival analysis methods have been implemented in R, since neither R packages nor R functions have been found.<br>El procés de crear una vacuna eficaç contra la malària és complex degut a les característiques del paràsit responsable. Les tècniques de laboratori actuals permeten analitzar moltes proteïnes simultàniament amb molt poc volum de sang, això, juntament amb la poca grandària mostral de molts estudis de malària fa que els mètodes estadístics clàssics no siguin adequats. Les màquines de suport vectorial (SVM) són una eina molt potent per tractar aquest tipus de dades en el context de poques observacions i moltes variables, moltes vegades, però, la recerca està enfocada en variables resposta temps fins a esdeveniment. Gran part de la recerca feta a la literatura en aproximar els mètodes SVM a dades de supervivència està enfocada des de la perspectiva de SVM per regressió. Una altra perspectiva molt poc desenvolupada i avaluada és la de SVM per classificació binària. En aquesta tesi proposem extensions i mètodes alternatius basats en SVM per classificació binària, específicament, proposant una ponderació de les dades censurades basada en la supervivència condicionada, una perspectiva semi-supervisada de SVM amb invariàncies locals i l’avaluació de SVM ponderant les observacions censurades. Un aspecte important en la recerca biomèdica és la identificació de la rellevància de variables en el model, és a dir, quines variables són importants en relació a la variable resposta. En el context de SVM, gran part de la recerca està enfocada a kernels lineals, però el gran avantatge dels SVM és la possibilitat d’utilitzar kernels no lineals. En aquesta tesi proposem tres aproximacions basades en l’algoritme recursiu d’eliminació de característiques (RFE) per ordenar variables, des d’una perspectiva de kernels no lineals i SVM per l’anàlisi de supervivència. A més, els mètodes proposats permeten ser interpretats i visualitzats a cada iteració de l’algoritme RFE, permeten identificar la rellevància de les variables predictores amb respecte la variable resposta i l’associació entre variables predictores. Després d’avaluar tots els mètodes proposats per SVM amb dades censurades i rellevància de variables, mitjançant simulacions, s’han analitzat les dades reals de l’estudi Mal067 que estudia correlats de protecció contra la malària induïts per la vacuna RTS,S.

碩士<br>國立彰化師範大學<br>電機工程學系<br>101<br>The objective of this thesis is to compare the advantages, disadvantages, characteristics, and appropriate applications of various product surface decoration processing methods, those are, for example, printing, spraying, screen printing, heat transfer, water transfer printing, electroplating and in-mold decoration process of in-mold labeling, in mold rolling, and in mold film technologies. A new curved decorative vacuum machine is developed. Based on the curved decorative vacuum machining process. The electrical control system of the machine consists of a programmable controller, a man-machine interface, a pressure detector, and electromagnetic switches. By a pneumatic component drive and mechanism, the film material printed with pattern or text is heated to its softening point, and then the image film is adhered to the surface of plastic or metal products using a vacuum and atmospheric pressure drape approach to form a three-dimensional surface decorative effect. This process technology can give excellent visual and tactile surface of the product, and improve the pollution generated in the conventional machining process phenomenon.

One of heavy oils upgrading processes is hydroconversion. As it is a complex process involving many chemical reactions, the mathematical model of hydroconversion process often has more kinetic parameters than can be estimated from the data. In this thesis, a model for hydroconversion processing of vacuum residue is proposed. It is proved that the model is structurally identifiable, but shown that it is inestimable and good parameter estimates may be impossible to obtain even if the model fit is good. As a proof to the model inestimability, it is shown that literature data can be fitted using a subset of only three (of seven) parameters. To improve parameter estimability, a method is proposed for designing additional experiments. The method is based on designing experiments that provide data that is complementary (in an appropriate sense) to existing data. The approach is illustrated using the hydroconversion model. For the hydroconversion model, using two additional experiments provides a good balance between parameter estimation and experimental effort.<br>Process Control

碩士<br>大葉大學<br>機械工程學系碩士班<br>92<br>The geometric design method of the rotor of dual-screw type vacuum pump is to combine several arcs or curves with the collinear principle of midpoints and continuous points of any two adjacent curves to form the contour of an male rotor. Then, the contour of female screw rotor conjugated with the male screw rotor is created through converting matrix and meshing equations. The object of this thesis is to construct a physical model of the screw rotor manufactured by the tools whose geometric contours are already designed with the Unigraphics CAD/ CAM software. Different processing modes are employed to program the path of tools and the processing parameters. Once the simulation results show that interference and undercut are avoided, NC codes will be produced through postprocessor and delivered to the machine to manufacture the screw rotor. Generally, the rotors of the screw vacuum pumps in mass production are processed by CNC rotor machine as milling and grinding works can be completed at the same time. However, product development concerns about the expense of the preproduction arrangements to order the forming multiple-cutting-edge tools of special outline curves and to manufacture the diamond-grinding wheel. In order to save development time and reduce production costs, two different kinds of processing techniques are employed for this research to analyze the feasibility of production method of the product development. First, install the turning tools and tool holders processed by CNC wire electric discharge machine in the CNC lathe. Then, the forming tool method is selected to process the PE plastics rotor. Second, a CNC five-axis machine is used to process the aluminum alloy (6061) rotor by the carving and milling process method. Finally, the helical grooves in two rotors are assembled and tested to ensure that the rotors can be operated smoothly.

This thesis discusses vacuum deposited organic solar cells. It focuses on the investigation of new donor molecules blended with the standard electron acceptor C60. These donor-acceptor heterojunctions form the photoactive system of organic solar cells. In addition, the influence of the processing conditions on the morphology of the blend layers is investigated, as the morphology is crucial for an efficient generation of free charge carriers upon photon absorption. Bulk heterojunction solar cells with the donor DTDCTB are deposited at different substrate temperatures. We identify three substrate temperature regimes, discriminated by the behavior of the fill factor (FF ) as a function of the blend layer thickness. Devices deposited at RT have a maximum FF between 50 and 70 nm blend thickness, while devices deposited at 110 °C have a monotonically decreasing FF. At Tsub=85 °C, the devices have an S-kinked current-voltage curve. Grazing incidence wide angle X-ray scattering measurements show that this peculiar behavior of the FF is not correlated with a change in the crystallinity of the DTDCTB, which stays amorphous. Absorption measurements show that the average alignment of the molecules inside the blend also remains unchanged. Charge extraction measurements (OTRACE) reveal a mobility for the 110 °C device that is an order of magnitude higher than for the RT device. The difference in mobility can be explained by a higher trap density for the RT samples as measured by impedance spectroscopy. Despite slightly higher carrier lifetimes for the RT device obtained by transient photovoltage measurements, its mobility-lifetime product is still lower than for the 110 °C devices. Based on DTDCTB, three new donor materials are designed to have a higher thermal stability in order to achieve higher yields upon material purification using gradient sublimation. For PRTF, the thermal stability is increased demonstrated by a higher yield upon sublimation. However, all new materials have a reduced absorption as compared to DTDCTB, which limits the short current density, and the FF is more sensitive to an increase of the blend layer thickness. The highest power conversion efficiency is achieved for a PRTF:C60 solar cell with 3.8%. Interestingly, PRTF:C60 solar cells show exceptionally low nonradiative voltage losses of only 0.26 V. Another absorber molecule is the push-pull chromophore QM1. Scanning electron microscope (SEM) measurements show a growth of the molecule in nanowires on several substrates. The nanowires have lengths up to several micrometers and are several tens of nanometers wide. The formation of the nanowires is accompanied by a strong blue shift (650 meV) of the thin film absorption spectrum in comparison to the absorption in solution, which is attributed to H-aggregation of the molecules. Furthermore, the thin film absorption onset reaches up to 1100 nm, making the material a suitable candidate for a near infrared absorber in organic solar cells. For a solar cell in combination with C60, a power conversion efficiency of 1.9% was achieved with an external quantum efficiency of over 19% for the spectral range between 600 and 1000 nm. The method of “co-evaporant induced crystallization” as a means to increase the crystallinity of blend layers without increasing the substrate temperature during the deposition is investigated. Mass spectrometry (LDI-ToF-MS) measurements show that polydimethylsiloxane (PDMS), which is used as a co-evaporant, decomposes during the evaporation and only lighter oligomers evaporate. Quartz crystal microbalance (QCM) measurements prove that the detection of PDMS saturates at higher amounts of evaporated material. LDI-ToF-MS measurements show further that the determination of the volatilization temperature by QCM measurements is highly error prone. The method was applied to zinc phthalocyanine (ZnPc) :C60 solar cells, accepting the insertion of PDMS into the blend layer. Diffraction (GIXRD) measurements show a large increase in crystallinity. ZnPc:C60 solar cells produced by applying the method reveal a similar behavior as solar cells processed at a higher substrate temperature.

碩士<br>國立中興大學<br>材料工程學系所<br>94<br>In this study, the Ag18PbSbTe20 thermoelectric alloy was prepared for various smelting time and various cooling time by using vibration vacuum smelting. The effects of smelting time and cooling time on thermoelectric properties, microstructures and compositions of the AgPb18SbTe20 alloy were studies. The results of thermoelectric properties show that the optimal electrical conductivity is 4.95× 10² (Ω-cm)‾¹ for specimens smelted 14 hours and cooled from 850℃ to 450℃ for 40 hours. The electrical conductivity increase with the amount of Ag increasing in matrix. The optimal Seebeck coefficient is 268 (μV/K) for specimens smelted for 14 hours and cooled for 80 hours. As the amount of impurities in the semiconductive PbTe phase increases, the Seebeck coefficient increases. The lowest of thermal conductivity is 1.58 (W/K•m) for specimen smelted for 14 hours and cooled for 40 hours. In the microstructural aspect, the major phase of AgPb18SbTe20 is PbTe phase. Precipitates at some conditions. The amount of doping Ag and Sb atom in the precipitates and matrix affects the thermoelectric properties of AgPb18SbTe20 alloy greatly. The optimum parameters of AgPb18SbTe20 alloy by smelting are smelting time of 14 hours and cooling time of 40 hours at this condition that the best figure of merit is 0.056.

Superheated steam (SS) drying of distillers’ spent grain (DSG) is a more energy efficient alternative to conventional hot air drying. SS drying at sub-atmospheric pressure (also referred to as low pressure) can prevent burning and lowering the quality of the food product. The objective of this study was to design, fabricate, and test a SS drying system that could operate at sub-atmospheric pressure for drying DSG. After the custom designed system was constructed, major problems associated with the system were identified. A number of tests were carried out and modifications were made to the system to resolve technical problems. Distillers’ spent grain was then successfully dried using the system under various levels of temperature from 95 to 115°C and pressure of either -25 or -20 kPa, with a SS velocity from 0.100 to 0.289 m/s.

碩士<br>大同大學<br>材料工程學系(所)<br>98<br>The vacuum brazing of Cemented Tungsten Carbide (WC-Ni) and structural alloy steel using Cu-9Sn braze alloy has been studied. The microstructure observation, hardness and the shear strength of the brazed joint, the effect of the brazing time, interface reaction of filler and different Ni content in the cermet on the joint behavior have been discussed in the article. The experimental results show that the max shear strength of the joints, 361±13 MPa was derived at 1080°C 15 min. The SEM micrographs showed that many tiny white-spot precipitates were observed in the grain boundaries of the brazed zone and EPMA analysis evidenced that the precipitates were composed of Sn-Ni. The experimental results also manifested that the wettability of WC-Ni/SNCM439 and Cu-9Sn/SNCM439 joints were better than that of the WC-Co/KDA1. After four hours slurry erosion test, the mass loss of WC-Ni/SNCM439 joints was more than those of WC-Co/KDA1 joints have been proved.

博士<br>國立清華大學<br>材料科學工程學系<br>95<br>In this thesis, the 90o-bend filtered cathodic vacuum arc (FCVA) technology was employed to deposit the chromium carbide films on the steel (AISI D2). This investigation was to compare various conditions which including the deposition temperature, the substrate bias voltage and the C2H2/Ar flow. The micro-structures, mechanical properties, corrosion behavior and optical properties of the chromium carbide film are thoroughly discussed. The uniform and dense of the chromium carbide films have been successfully synthesized using our FCVA system. The chromium carbide is transformed from amorphous to crystallized phase, as the negative substrate bias voltage increases from -50 to -550 V at 500 ℃.Moreover, the crystallized Cr23C6 phase appears as the negative substrate bias voltage further increases. A compact and dense Cr3C2 film with the fibrous structure of Cr23C6 was successfully prepared. The Cr3C2 coated steel has a relatively high nanohardness and excellent adhesion compare with the amorphous chromium carbide. The corrosion resistance of the Cr3C2 coated steel is owing to the establishment of a defects-free microstructure. No pitting corrosion was observed on the Cr3C2 coated steel. The corrosion behaviors of cryst-Cr3C2/steel and a-CrC/steel were investigated further. All samples was measured and the results obtained from electrochemical impedance spectroscopy (EIS) simulated by the equivalent circuit to interpret the corrosion mechanism of the cryst-Cr3C2/steel and a-CrC/steel were compared. The results indicated that the cryst-Cr3C2/steel more effectively isolates the defects than dose a-C:Cr/steel in saline environment. The cathodoluminescence spectra of the DLC:Cr films are evident in the visible region, thereby shifting the red emission to 1.99 eV. The orange emission at 2.03 eV also appears due to transitions between chromium-related electron levels and σ* states. Additionally, the peak at 2.10 eV likely results from the defective structures in the DLC:Cr films. The effect of Cr doping changed DLC band structure and its consequent cathodoluminescence property.

No<br>A comparison has been made between compaction, sintering, microstructural and mechanical properties of the 6061 aluminium alloy prepared via premixed elemental (EL) and prealloyed (PA) powders (as received and degassed) with and without additions of sintering aids and various solid and/or liquid lubricants. Both EL and PA powders were cold pressed at different pressures, ranging from 250 to 770 MPa, and sintered under vacuum in the range 580-640°C for 30-120 min. and then under pure nitrogen atmosphere for comparison. Vacuum degassing of the PA powder provided better compressibility and thus higher green densities than those for the as received PA or the premixed EL powder compacts pressed at compaction pressures ¿340 MPa. Near full sintered densities of ~98%TD were obtained for both EL and PA 6061 Al alloys. Degassed PA Al with 0·6 wt-% paraffin wax (PW) or with only 0·12 wt-%Pb addition as sintering aid and no lubricant, and premixed EL with only 0·12 wt-%Pb addition and no lubricant gave the best optimum properties. It became apparent that additions of some solid lubricants such as lithium stearate (LS) and acrawax to both the premixed EL and PA powders provided reasonable green densities, but had deleterious effect on sintered densities and microstructures, particularly under vacuum sintering. Heating data curves during the sintering cycle, revealed formation of both transient and persistent liquid phases for the EL and mainly supersolidus liquid phase sintering (SLPS) mechanism for the PA. Tensile properties of the degassed, vacuum or nitrogen sintered PA Al alloy in T6 condition were higher than those of the equivalent alloy prepared by EL mixing with the former giving a tensile strength of 330 MPa and 6-8% elongation to failure, which are similar to those of the commercial (wrought) 6061 Al alloys.