Réaction d’amination intramoléculaire de liens C-H à partir de N-mésyloxycarbamates catalysée par des complexes de rhodium et d’autres métaux de transition : s ynthèse verte d’oxazolidinones

La réaction d’amination de liens C-H, impliquant la transformation directe d’un lien C-H en lien C-N constitue une approche synthétique d’avenir pour la préparation de composés azotés. L’application de cette stratégie de manière intramoléculaire apparaît comme une approche puissante pour la synthèse de composés hétérocycliques. En particulier, les oxazolidinones, carbamates cycliques à cinq chaînons, constituant une nouvelle classe d’antibiotiques très prometteuse, pourraient être synthétisées par cette méthode. Il y a moins d’une dizaine d’années, notre groupe de recherche a travaillé sur le développement de méthodologies utilisant des espèces nitrènes métalliques pour l’amination intra et intermoléculaire. Les N-tosyloxycarbamates, en présence d’une base et d’un catalyseur dimère de rhodium (II) tétracarboxylate sont les précurseurs de ces espèces nitrènes métalliques, capables de faire l’insertion de liens C(sp3)-H. Dans ces travaux de thèse, nous avons travaillé sur le développement d’une méthode plus « verte » d’amination intramoléculaire. Les N-mésyloxycarbamates, plus légers que leurs homologues N-tosyloxycarbamates, ont été identifiés comme d’excellents précurseurs de nitrènes. La méthodologie développée ne nécessite que 3 mol % de dimère de rhodium Rh2(tpa)4 et de 1,5 équivalents de solution aqueuse saturée de K2CO3, le tout dans l’acétate d’éthyle et donne de bons rendements de cyclisation. Une étude de l’étendue réactionnelle a été effectuée, montrant la tolérance et les limitations de notre système catalytique : les hétéroatomes ne posent pas de problèmes hormis l’atome d’azote, qui doit être protégé afin de garantir la transformation. En outre, nous avons constaté que les liens C-H aliphatiques secondaires sont moins réactifs que les liens tertiaires. Après avoir tenté de développer des conditions réactionnelles spécifiques aux liens C-H non activés, nous avons montré la possibilité d’aminer des liens C-H propargyliques de manière chimiosélective ; la triple liaison C-C peut ensuite être dérivatisée efficacement, donnant accès à la formule saturée correspondante ainsi qu’à d’autres motifs. Dans un désir de substituer les complexes de rhodium par d’autres complexes de métaux plus abondants et moins dispendieux, nous nous sommes tournés, dans un premier temps, vers les complexes de fer et par la suite, vers les pinceurs de nickel. Les phtalocyanines de fer ont été identifiées comme étant de bons catalyseurs de l’amination intramoléculaire de N-mésyloxycarbamates. Le chlorure de phtalocyanine de fer (III), en présence d’un sel de AgBF4 et de K2CO3, dans le 1,1,2,2-tétrachloroéthane anhydre, permet l’obtention de la 4-phenyloxazolidin-2-one avec 63% de rendement. En outre, il est possible d’atteindre un rendement de 49% à partir du même substrat N-mésyloxycarbamate, par catalyse avec un pinceur de nickel de type POCN, en présence d’un sel de mésylate. Des indices sur le mécanisme des ces deux transformations ont pu être recueillis lors de la courte étude de ces systèmes.

Réaction d’amination intramoléculaire de liens C-H à partir de N-mésyloxycarbamates catalysée par des complexes de rhodium et d’autres métaux de transition : s ynthèse verte d’oxazolidinones

La réaction d’amination de liens C-H, impliquant la transformation directe d’un lien C-H en lien C-N constitue une approche synthétique d’avenir pour la préparation de composés azotés. L’application de cette stratégie de manière intramoléculaire apparaît comme une approche puissante pour la synthèse de composés hétérocycliques. En particulier, les oxazolidinones, carbamates cycliques à cinq chaînons, constituant une nouvelle classe d’antibiotiques très prometteuse, pourraient être synthétisées par cette méthode. Il y a moins d’une dizaine d’années, notre groupe de recherche a travaillé sur le développement de méthodologies utilisant des espèces nitrènes métalliques pour l’amination intra et intermoléculaire. Les N-tosyloxycarbamates, en présence d’une base et d’un catalyseur dimère de rhodium (II) tétracarboxylate sont les précurseurs de ces espèces nitrènes métalliques, capables de faire l’insertion de liens C(sp3)-H. Dans ces travaux de thèse, nous avons travaillé sur le développement d’une méthode plus « verte » d’amination intramoléculaire. Les N-mésyloxycarbamates, plus légers que leurs homologues N-tosyloxycarbamates, ont été identifiés comme d’excellents précurseurs de nitrènes. La méthodologie développée ne nécessite que 3 mol % de dimère de rhodium Rh2(tpa)4 et de 1,5 équivalents de solution aqueuse saturée de K2CO3, le tout dans l’acétate d’éthyle et donne de bons rendements de cyclisation. Une étude de l’étendue réactionnelle a été effectuée, montrant la tolérance et les limitations de notre système catalytique : les hétéroatomes ne posent pas de problèmes hormis l’atome d’azote, qui doit être protégé afin de garantir la transformation. En outre, nous avons constaté que les liens C-H aliphatiques secondaires sont moins réactifs que les liens tertiaires. Après avoir tenté de développer des conditions réactionnelles spécifiques aux liens C-H non activés, nous avons montré la possibilité d’aminer des liens C-H propargyliques de manière chimiosélective ; la triple liaison C-C peut ensuite être dérivatisée efficacement, donnant accès à la formule saturée correspondante ainsi qu’à d’autres motifs. Dans un désir de substituer les complexes de rhodium par d’autres complexes de métaux plus abondants et moins dispendieux, nous nous sommes tournés, dans un premier temps, vers les complexes de fer et par la suite, vers les pinceurs de nickel. Les phtalocyanines de fer ont été identifiées comme étant de bons catalyseurs de l’amination intramoléculaire de N-mésyloxycarbamates. Le chlorure de phtalocyanine de fer (III), en présence d’un sel de AgBF4 et de K2CO3, dans le 1,1,2,2-tétrachloroéthane anhydre, permet l’obtention de la 4-phenyloxazolidin-2-one avec 63% de rendement. En outre, il est possible d’atteindre un rendement de 49% à partir du même substrat N-mésyloxycarbamate, par catalyse avec un pinceur de nickel de type POCN, en présence d’un sel de mésylate. Des indices sur le mécanisme des ces deux transformations ont pu être recueillis lors de la courte étude de ces systèmes.

Age determination of sediment cores of the southeastern Weddell Sea, Antarctica

On the continental margin of the southeastern Weddell Sea, Antarctica, several channel-ridge systems can be traced on the eastern side of the Crary Fan. Swath mapping of the bathymetry reveals three southwest-northeast trending ridges up to 300 m high with channels on their southeastern side. The structures occur on a terrace of the continental slope in water depths of 2000 - 3300 m. We carried out sedimentological studies on cores from three sites. Two of the studied cores are from ridges, one is from the northwestern part of the terrace. The stratigraphy of the recovered sediments is based on accelerator mass spectrometer 14C determinations, stable oxygen and carbon isotopes analyses and paleomagnetic measurements. The sediments represent a period from the last glacial maximum (LGM) to recent time. They are composed predominantly of terrigenous components. We distinguish four different sedimentary facies and assign them to processes controlling sedimentation. Microlaminated muds and cross-stratified coarse-silty sediments originated from contour currents. Bioturbated sediments reflect the increasing influence of hemipelagic sedimentation. Structureless sediments with high contents of ice-rafted debris characterize slumps. The inferred contour currents shaping the continental slope during the LGM were canalized within the channels and supplied microlaminated mud to the western sedimentary ridges due to deflection to the left induced by the Coriolis force. The lamination of the sediments is attributed to seasonal variations of current velocities. The thermohaline bottom currents were directed to the northeast and hence opposite to the Weddell Gyre. Cross-stratified coarse-silty contourites on the ridges are intercalated with the muds and indicate spillover of faster thermohaline flows. Average sedimentation rates on the terrace of the continental slope were unusually high (250 cm/ka) during the LGM, indicating active growth phases of the Crary Fan during glacial intervals. A substantial environmental change at 19.5 - 20 ka is documented in the sediments by a gradual change from lamination to bioturbation. During the recent interglacial, bioturbated sediments were deposited in all parts of the terrace. Because of a reduction of the contour current velocities (4-7 cm/s), the water masses of the Weddell Gyre, supplying fine-grained sediments from northeast, gain a greater influence on sedimentation on the continental slope. Higher percentages of microfossils indicate enhanced biogenic productivity. Increased iceberg activity is documented by greater amounts of ice-rafted debris. The interglacial sedimentation rates decrease to a few cm/ka and indicate that the Crary Fan became relatively sediment-starved during interglacial intervals.

Total organic carbon content and redox-sensitiv trace metal concentrations of selected late Cenoman claystones from DSDP Hole 93-603B

The Cenomanian/Turonian (C/T) intervals at DSDP Sites 105 and 603B from the northern part of the proto-North Atlantic show high amplitude, short-term cyclic variations in total organic carbon (TOC) content. The more pronounced changes in TOC are also reflected by changes in lithology from green claystones (TOC<1%) to black claystones (TOC>1%). Although their depositional history was different, the individual TOC cycles at Sites 105 and 603B can be correlated using stable carbon isotope stratigraphy. Sedimentation rates obtained from the isotope stratigraphy and spectral analyses indicate that these cycles were predominately precession controlled. The coinciding variations in HI, OI, delta13Corg and the abundance of marine relative to terrestrial biomarkers, as well as the low abundance of lignin pyrolysis products generated from the kerogen of the black claystones, indicate that these cyclic variations reflect changes in the contribution of marine organic matter (OM). The cooccurrence of lamination, enrichment of redox-sensitive trace metals and presence of molecular fossils of pigments from green sulfur bacteria indicate that the northern proto-North Atlantic Ocean water column was periodically euxinic from the bottom to at least the base of the photic zone (<150 m) during the deposition of the black claystones. In contrast, the green claystones are bioturbated, are enriched in Mn, do not show enrichments in redox-sensitive trace metals and show biomarker distributions indicative of long oxygen exposure times, indicating more oxic water conditions. At the same time, there is evidence (e.g., abundance of biogenic silica and significant 13C-enrichment for OC of phytoplanktic origin) for enhanced primary productivity during the deposition of the black claystones. We propose that increased primary productivity periodically overwhelmed the oxic OM remineralisation potential of the bottom waters resulting in the deposition of OM-rich black claystones. Because the amount of oxygen used for OM remineralisation exceeded the amount supplied by diffusion and deep-water circulation, the northern proto-North Atlantic became euxinic during these periods. Both Sites 105 and 603B show trends of continually increasing TOC contents and HI values of the black claystones up section, which most likely resulted from both enhanced preservation due to increased anoxia and increased production of marine OM during oceanic anoxic event 2 (OAE2).

Benthic foraminiferal assemblages in ODP Hole 167-1017E

A strong oxygen-minimum zone (OMZ) currently exists along the California margin because of a combination of high surface-water productivity and poor intermediate-water ventilation. However, the strength of this OMZ may have been sensitive to late Quaternary ocean-circulation and productivity changes along the margin. Although sediment-lamination strength has been used to trace ocean-oxygenation changes in the past, oxygen levels on the open margin are not sufficiently low for laminations to form. In these regions, benthic foraminifera are highly sensitive monitors of OMZ strength, and their fossil assemblages can be used to reconstruct past fluctuations. Benthic foraminiferal assemblages from Ocean Drilling Program Site 1017, off Point Conception, exhibit major and rapid faunal oscillations in response to late Quaternary millennial-scale climate change (Dansgaard-Oeschger cycles) on the open central California margin. These faunal oscillations can be correlated to and are apparently synchronous with those reported from Santa Barbara Basin. Together they represent major fluctuations in the strength of the OMZ which were intimately associated with global climate change-weakening, perhaps disappearing, during cool periods and strengthening during warm periods. These rapid, major OMZ strength fluctuations were apparently widespread on the Northeast Pacific margin and must have influenced the evolution of margin biota and altered biogeochemical cycles with potential feedbacks to global climate change.

Tailored conductivity in ion implanted polyetheretherketone

Ion implantation can be used to confer electrical conductivity upon conventional insulating polymers such as polyetheretherketone (PEEK). We have implanted PEEK films using three different types of ion implantation: conventional inert gas and metal ion implantation, and ion beam mixing. We have applied a number of analytical techniques to compare the chemical, structural and electrical properties of these films. The most effective means of increasing electrical conductivity appears to be via ion beam mixing of metals into the polymer, followed by metal ion implantation and finally, inert gas ion implantation. Our results suggest that in all cases, the conducting region corresponds to the implanted layer in the near surface to a depth of similar to750 Angstrom (ion beam mixed) to similar to5000 Angstrom (metal ion). This latter value is significantly higher than would be expected from a purely ballistic standpoint, and can only be attributed to thermal inter-diffusion. Our data also indicates that graphitic carbon is formed within the implant region by chain scission and subsequent cross-linking. All ion implanted samples retained their bulk mechanical properties, i.e. they remained flexible. The implant layers showed no signs of de-lamination. We believe this to be the first comparative study between different implantation techniques, and our results support the proposition that soft electronic circuitry and devices can be created by conductivity engineering with ion beams. (C) 2004 Elsevier B.V. All rights reserved.

Production of phenol-formaldehyde resin composites

The main objective of this work was to examlne the various stages of the production of industrial laminates based on phenol-formaldehyde resins, with a view of suggesting ways of improving the process economics and/or the physical properties of the final product. Aspects of impregnation, drying, and lamination were investigated. The resins used in all experiments were ammonia-catalysed. Work was concentrated on the lamination stage since this is a labour intensive activity. Paper-phenolic lay-ups were characterised in terms of the temperatures experienced during cure, and a shorter cure-cycle is proposed, utilising the exothermic heat produced during pressing of 25.5 mm thick lay-ups. Significant savings in production costs and improvements in some of the physical properties have been achieved. In particular, water absorption has been reduced by 43-61%. Work on the drying stage has shown that rapid heating of the wet impregnated substrate results in resin solids losses. Drying at lower temperatures by reducing the driving force leads to more resin (up to 6.5%) being retained by the prepregs and therefore more effective use of an expensive raw material. The impregnation work has indicated that residence times above 6 seconds in the varnish bath enhance the insulation resistance of the final product, possibly due to improved resin distribution and reduction in water absorption. In addition, a novel process which involves production of laminates by in situ polymerisation of the phenolic resin on the substrate has been examined. Such a process would eliminate the solvent recovery plant - a necessary stage in current industrial processes. In situ polymerisation has been shown to be chemically feasible.

Improving the solubility and dissolution of poorly soluble drugs by salt formation and the consequent effect on mechanical properties

The bioavailability of BCS II compounds may be improved by an enhanced solubility and dissolution rate. Four carboxylic acid drugs were selected, which were flurbiprofen, etodolac, ibuprofen and gemfibrozil. The drugs were chosen because they are weak acids with poor aqueous solubility and should readily form salts. The counterions used for salt formation were: butylamine, pentylamine, hexylamine, octylamine, benzylamine, cyclohexylamine, tert-butylamine, 2-amino-2-methylpropan­2-ol, 2-amino-2-methyl propan-1,3-ol and tromethamine. Solubility was partially controlled by the saturated solution pH with the butylamine counterion increasing the solution pH and solubility and dissolution to the greatest extent. As the chain length increased, solubility was reduced due to the increasing lipophilic nature of the counterion. The benzylamine and cyclohexylamine counterions produced crystalline, stable salts but did not improve solubility and dissolution significantly compared to the parent compound. The substitution of hydroxyl groups to tert-butylamine counterions produced an increase in solubility and dissolution. AMP2 resulted in the most enhanced solubility and dissolution compared to the parent drug but using the tris salt did not further improve solubility due to a very stable crystal lattice structure. The parent drugs were very difficult to compress due to orientation effects and lamination. Compacts were prepared of each parent drug and salt and their modulus of elasticity values were measured using a three-point bend (Young’s modulus, E0) were extrapolated to zero porosity and compared. Compressibility and E0 were improved with the butylamine, tert-butylamine, cyclohexylamine and AMP2 counterions. The most significant improvement in compression and E0 was with the AMP2 salts. Mechanical properties were related to the hydrogen bonding within the crystal lattice structure for the gemfibrozil salt series.

The prediction of vibration in large electric machines

This thesis reports the development of a reliable method for the prediction of response to electromagnetically induced vibration in large electric machines. The machines of primary interest are DC ship-propulsion motors but much of the work reported has broader significance. The investigation has involved work in five principal areas. (1) The development and use of dynamic substructuring methods. (2) The development of special elements to represent individual machine components. (3) Laboratory scale investigations to establish empirical values for properties which affect machine vibration levels. (4) Experiments on machines on the factory test-bed to provide data for correlation with prediction. (5) Reasoning with regard to the effect of various design features. The limiting factor in producing good models for machines in vibration is the time required for an analysis to take place. Dynamic substructuring methods were adopted early in the project to maximise the efficiency of the analysis. A review of existing substructure- representation and composite-structure assembly methods includes comments on which are most suitable for this application. In three appendices to the main volume methods are presented which were developed by the author to accelerate analyses. Despite significant advances in this area, the limiting factor in machine analyses is still time. The representation of individual machine components was addressed as another means by which the time required for an analysis could be reduced. This has resulted in the development of special elements which are more efficient than their finite-element counterparts. The laboratory scale experiments reported were undertaken to establish empirical values for the properties of three distinct features - lamination stacks, bolted-flange joints in rings and cylinders and the shimmed pole-yoke joint. These are central to the preparation of an accurate machine model. The theoretical methods are tested numerically and correlated with tests on two machines (running and static). A system has been devised with which the general electromagnetic forcing may be split into its most fundamental components. This is used to draw some conclusions about the probable effects of various design features.

Theoretical modelling of the sulcated spring

Replacement of the traditional coil spring with one of more fibre-reinforced plastic sulcated springs is a future possibility. Spring designers of metallic coil springs have design formulae readily available, and software packages specific to coil spring design exist. However, the sulcated spring is at the prototype stage of development, so literature on these springs is very sparse. The thesis contains information on the market for sulcated springs, and their advantages and disadvantages. Literature on other types of fibre reinforced plastic springs has also been reviewed. Design software has been developed for the sulcated spring along similar lines to coil spring design software. In order to develop the software, a theoretical model had to be developed which formed the mathematical basis for the software. The theoretical model is based on a choice of four methods for calculating the flexural rigidity; beam theory, plate theory, and lamination theory assuming isotropic and orthoropic material properties. Experimental results for strain and spring stiffness have been compared with the theoretical model, and were in good agreement. Included in the design software are the results of experimental work on fatigue, and design limiting factors to prevent or warn against impractical designs. Finite element analysis has been used to verify the theoretical model developed, and to find the better approximation to the experimental results. Applications and types of assemblies for the sulcated spring were discussed. Sulcated spring designs for the automotive applications of a suspension, clutch and engine valve spring were found using the design computer software. These sulcated spring designs were within or close to the space of the existing coil spring and yield the same performance. Finally the commercial feasibility of manufacturing the sulcated spring was assessed and compared with the coil spring, to evaluate the plausibility of the sulcated spring replacing the coil spring eventually.

Enhanced zinc oxide and graphene nanostructures for electronics and sensing applications

Zinc oxide and graphene nanostructures are important technological materials because of their unique properties and potential applications in future generation of electronic and sensing devices. This dissertation investigates a brief account of the strategies to grow zinc oxide nanostructures (thin film and nanowire) and graphene, and their applications as enhanced field effect transistors, chemical sensors and transparent flexible electrodes. Nanostructured zinc oxide (ZnO) and low-gallium doped zinc oxide (GZO) thin films were synthesized by a magnetron sputtering process. Zinc oxide nanowires (ZNWs) were grown by a chemical vapor deposition method. Field effect transistors (FETs) of ZnO and GZO thin films and ZNWs were fabricated by standard photo and electron beam lithography processes. Electrical characteristics of these devices were investigated by nondestructive surface cleaning, ultraviolet irradiation treatment at high temperature and under vacuum. GZO thin film transistors showed a mobility of ∼5.7 cm2/V·s at low operation voltage of <5 V and a low turn-on voltage of ∼0.5 V with a sub threshold swing of ∼85 mV/decade. Bottom gated FET fabricated from ZNWs exhibit a very high on-to-off ratio (∼106) and mobility (∼28 cm2/V·s). A bottom gated FET showed large hysteresis of ∼5.0 to 8.0 V which was significantly reduced to ∼1.0 V by the surface treatment process. The results demonstrate charge transport in ZnO nanostructures strongly depends on its surface environmental conditions and can be explained by formation of depletion layer at the surface by various surface states. A nitric oxide (NO) gas sensor using single ZNW, functionalized with Cr nanoparticles was developed. The sensor exhibited average sensitivity of ∼46% and a minimum detection limit of ∼1.5 ppm for NO gas. The sensor also is selective towards NO gas as demonstrated by a cross sensitivity test with N2, CO and CO2 gases. Graphene film on copper foil was synthesized by chemical vapor deposition method. A hot press lamination process was developed for transferring graphene film to flexible polymer substrate. The graphene/polymer film exhibited a high quality, flexible transparent conductive structure with unique electrical-mechanical properties; ∼88.80% light transmittance and ∼1.1742Ω/sq k sheet resistance. The application of a graphene/polymer film as a flexible and transparent electrode for field emission displays was demonstrated.

Desenvolvimento de um painel sanduíche com carga de particulado oriundo de resíduo lignocelulósico para aplicação em produtos na área de equipamentos de proteção

This work aims to study and investigate the use of a hybrid composite polymer formed with blanket aramid (Kevlar 29) fiber blanket flax fiber and particulate dry endocarp of coconut (Cocos nucifera Linn), using as matrix an epoxy resin based thermoset for use in areas of protective equipment. Besides such material is used an aluminum plate, joined to the composite by means of glue based on epoxy and araldite commercial. The manufacturing process adopted was manual lamination (Hand Lay Up) to manufacture the hybrid composite. After the composite is prepared, an aluminum plate is subjected to pressure and glued to cure the adhesive. Layers of veil will also be used to separate the particulate from the linen blanket layer without disturbing the alignment of the fibers of the blankets. To characterize the mechanical and physical behavior was manufactured a plate of 800 x 600 mm of the hybrid composite, which were removed specimens for tests of water absorption to saturation; density; impact test (Charpy) and two test specimens for ballistic testing 220 mm x 200 mm to make a comparative study between the dry state and saturated water absorption and thus see the ballistic performance of these two conditions. The test was applied to make a comparative study of fracture in these two conditions, caused by penetrating ballistic missile (38 and 380). To test the impact (Charpy) will analyze the absorbed energy, fracture appearance and lateral contraction, also in dry condition and saturation of absorbed water, thereby analyzing situations where the impact load is relevant, such as bumps and shocks produced by stone, metal or wooden bars among others. The proposed configuration, along with the tests, has the purpose, application in the fields of equipment against ballistic impact, such as helmets; bullet proof vests; shields; protective packaging and other items to be identified in this research.

Influência da absorção de umidade no comportamento mecânico nos compósitos poliméricos híbridos Kevlar/vidro quando imerso em água do mar e petróleo

The polymer matrix composite materials are being used on a large scale in the most different industrial fields such as aerospace, automotive, oil, among others, since the industrial perspectives is currently working with materials which have a good mechanical performance at high service life and cost / benefit. Thus, the determination of the mechanical properties is indispensable for the characterization of waste resulting in greater expansion of this type of material. Thus, this work will be obtained three plates laminated with tereftálica polymeric matrix reinforced by a bidirectional woven E-glass and kevlar both industrially made, where the plates are manufactured by manual lamination process (hand lay-up), all laminates have five enhancement layers, the first hybrid laminate will consist of bidirectional woven E-glass fiber, kevlar fiber interspersed with layers, is formed by the second bidirectional woven kevlar fiber at the ends of the laminate (two layers), and in the center the glass fiber fabric (three layers), the third plate is composed of only the bidirectional woven E-glass fiber. Then were prepared specimens (CP) by standard, to determine the mechanical properties of tensile and bending in three points. After fabrication of the specimens, they were immersed in oil and seawater. After that, there was a comparison of the mechanical properties for the test condition in the dry state. Showing that there was a considerable increase in the properties studied because the effect of hybridization in laminates.

Fabricação e caracterização de um compósito hibrido com resíduo lignocelulósico

This work aims to manufacture and characterize a hybrid plastic composite with the matrix isophthalic polyester resin base and having as reinforcing glass fiber and the dry endocarp of coconut (Coco nucifera Linn) in the form of particles as filler. The composite was made industrially in Tecniplas Industry and Trade LTDA. in the form of plate, and was manufactured process made by the manual lamination (Hand Lay Up). From the plate they were prepared test specimens for testing density, water absorption, uniaxial traction in dry and wet states, and testing of bending, as well as studies on the behavior of the generated fractures, macroscopic and microscopic, in mechanical tests through. All tests were performed in order to find the most viable applications the hybrid composite manufactured. The tensile and bending tests were analyzed last tensile properties, elasticity and deformation module. After the studies, it is observed that the percentage moisture absorbed was 3.03%. The presence of moisture in the tensile test meant a decrease of 19.77% from last stand, and 5.26% in the elastic modulus. For bending tests gave an average value of 69.13 MPa flexural strength. The results show the application of hybrid composite studied in lightweight structures, indoors, which require low / medium performance traction demands, and which involve flexural requests.

(Table1) Frequency of well defined bioturbation in sediments of the Eckernförder Bay, Western Baltic Sea

The lamination and burrowing patterns in 17 box cores were analyzed with the aid of X-ray photographs and thin sections. A standardized method of log plotting made statistical analysis of the data possible. Several 'structure types' were established, although it was realized that the boundaries are purely arbitrary divisions in what can sometimes be a continuous sequence. In the transition zone between marginal sand facies and fine-grained basin facies, muddy sediment is found which contains particularly well differentiated, alternating laminae. This zone is also characterized by layers rich in plant remains. The alternation of laminae shows a high degree of statistical scattering. Even though a small degree of cyclic periodicity could be defined, it was impossible to correlate individual layers from core to core across the bay. However, through a statistical handling of the plots, zones could be separated on the basis of the number of sand layers they contained. These more or minder sandy zones clarified the bottom reflections seen in the records of the echograph from the area. The manner of facies change across the bay, suggests that no strong bottom currents are effective in the Eckernförde Bay. The marked asymmetry between the north and south flanks of the profile can be attributed to the stronger action of waves on the more exposed areas. Grain size analyses were made from the more homogeneous units found in a core from the transition-facies zone. The results indicate that the most pronounced differences between layers appear in the silt range, and although the differences are slight, they are statistically significant. Layers rich in plant remains were wet-sieved in order to separate the plant detritus. This was than analyzed in a sediment settling balance and found to be hydrodynamically equivalent to a well-sorted, finegrained sand. A special, rhythmic cross-bedding type with dimensions in the millimeter range, has been named 'Crypto-cross-lamination' and is thought to represent rapid sedimentation in an area where only very weak bottom currents are present. It is found only in the deepest part of the basin. Relatively large sand grains, scattered within layers of clayey-silty matrix, seem to be transported by flotation. Thin section examination showed that the inner part of Eckernförder Bay carbonate grains (e. g. Foraminifera shells) were preserved throughout the cores, while in the outer part of the bay they were not present. Well defined tracks and burrows are relatively rare in all of the facies in comparision to the generally strongly developed deformation burrowing. The application of special measures for the deformation burrowing allowed to plot their intensity in profile for each core. A degree of regularity could be found in these burrowing intensity plots, with higher values appearing in the sandy facies, but with no clear differences between sand and silt layers in the transition facies. Small sections in the profiles of the deepest part of the bay show no bioturbation at all.