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.

(Table 1) Organic and inorganic geochemical analysis of Late Jurassic to Early Cretaceous black shale sediments from the Norwegian-Greenland Seaway

The Late Jurassic to Early Cretaceous (Volgian-Ryazanian) was a period of a second-order sea-level low stand, and it provided excellent conditions for the formation of shallow marine black shales in the Norwegian-Greenland Seaway (NGS). IKU Petroleum Research drilling cores taken offshore along the Norwegian shelf were investigated with geochemical and microscopic approaches to (1) determine the composition of the organic matter, (2) characterize the depositional environments, and (3) discuss the mechanisms which may have controlled production, accumulation, and preservation of the organic matter. The black shale sequences show a wide range of organic carbon contents (0.5-7.0 wt %) and consist of thermally immature organic matter of type II to II/III kerogen. Rock-Eval pyrolysis revealed fair to very good petroleum source rock potential, suggesting a deposition in restricted shallow marine basins. Well-developed lamination and the formation of autochthonous pyrite framboids further indicate suboxic to anoxic bottom water conditions. In combination with very low sedimentation rates it seems likely that preservation was the principal control on organic matter accumulation. However, a decrease of organic carbon preservation and an increase of refractory organic matter from the Volgian to the Hauterivian are superimposed on short-term variations (probably reflecting Milankovitch cycles). Various parameters indicate that black shale formation in the NGS was gradually terminated by increased oxidative conditions in the course of a sea-level rise.

Geochemical analysis at ODP Site 207-1261 from the Demerara Rise in the western equatorial Atlantic

A high-resolution geochemical record of a 120 cm black shale interval deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 (ODP Leg 207, Site 1261, Demerara Rise) has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo-redox conditions. High contents of organic matter, sulfur and redox-sensitive trace metals (Cd, Mo, V, Zn), as well as continuous lamination, point to deposition under consistently oxygen-free and largely sulfidic bottom water conditions. However, rapid and cyclic changes in deep ocean redox are documented by short-term (~15-20 ka) intervals with decreased total organic carbon (TOC), S and redox-sensitive trace metal contents, and in particular pronounced phosphorus peaks (up to 2.5 wt% P) associated with elevated Fe oxide contents. Sequential iron and phosphate extractions confirm that P is dominantly bound to iron oxides and incorporated into authigenic apatite. Preservation of this Fe-P coupling in an otherwise sulfidic depositional environment (as indicated by Fe speciation and high amounts of sulfurized organic matter) may be unexpected, and provides evidence for temporarily non-sulfidic bottom waters. However, there is no evidence for deposition under oxic conditions. Instead, sulfidic conditions were punctuated by periods of anoxic, non-sulfidic bottom waters. During these periods, phosphate was effectively scavenged during precipitation of iron (oxyhydr)oxides in the upper water column, and was subsequently deposited and largely preserved at the sea floor. After ~15-25 ka, sulfidic bottom water conditions were re-established, leading to the initial precipitation of CdS, ZnS and pyrite. Subsequently, increasing concentrations of H2S in the water column led to extensive formation of sulfurized organic matter, which effectively scavenged particle-reactive Mo complexes (thiomolybdates). At Site 1261, sulfidic bottom waters lasted for ?90-100 ka, followed by another period of anoxic, non-sulfidic conditions lasting for ~15-20 ka. The observed cyclicity at the lower end of the redox scale may have been triggered by repeated incursions of more oxygenated surface- to mid-waters from the South Atlantic resulting in a lowering of the oxic-anoxic chemocline in the water column. Alternatively, sea water sulfate might have been stripped by long-lasting high rates of sulfate reduction, removing the ultimate source for HS**- production.

Plásticos reforçados a base de tecidos híbridos: efeitos da anisotropia e geometria normativa na caracterização mecânica e da fratura

As most current studies, reinforced plastics have been, in recent years, a viable alternative in building structural elements of medium and large, since the lightness accompanied by high performance possible. The design of hybrid polymer composites (combination of different types of reinforcements) may enable structural applications thereof, facing the most severe service conditions. Within this class of composite materials, reinforced the underlying tissues hybrid high performance are taking space when your application requires high load bearing and high rigidity. The objective of this research work is to study the challenges in designing these fabrics bring these materials as to its mechanical characterization and fracture mechanisms involved. Some parameters associated with the process and / or form of hybridization stand out as influential factors in the final performance of the material such as the presence of anisotropy, so the fabric weave, the process of making the same, normative geometry of the specimens, among others. This sense, four laminates were developed based hybrid reinforcement fabrics involving AS4 carbon fiber, kevlar and glass 49-E as the matrix epoxy vinyl ester resin (DERAKANE 411-350). All laminates were formed each with four layers of reinforcements. Depending on the hybrid fabric, all the influencing factors mentioned above have been studied for laminates. All laminates were manufactured industrially used being the lamination process manual (hand-lay-up). All mechanical characterization and study of the mechanism of fracture (fracture mechanics) was developed for laminates subjected to uniaxial tensile test, bending in three and uniaxial compression. The analysis of fracture mechanisms were held involving the macroscopic, optical microscopy and scanning electron microscopy

Geochemical analysis at ODP Site 207-1259 from the Demerara Rise in the western equatorial Atlantic

Organic carbon-rich shales deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 were drilled during ODP Leg 207 at Demerara Rise. We present integrated high-resolution geochemical records of core intervals from ODP Sites 1259 and 1261 both from nannofossil biozone CC14. Our results reveal systematic variations in marine and detrital sediment contribution, depositional processes, and bottom water redox conditions during black shale formation at two locations on Demerara Rise in different paleo-water depths. A combination of redox proxies (Fe/S, P/Al, C/P, redox-sensitive/sulfide-forming trace metals Mn, Cd, Mo, Ni, V, Zn) and other analytical approaches (bulk sediment composition, P speciation, electron microscopy, X-ray diffraction) evidence anoxic to sulfidic bottom water and sediment conditions throughout the deposition of black shale. These extreme redox conditions persisted and were periodically punctuated by short-termed periods with less reducing bottom waters irrespective of paleo-water depth. Sediment supply at both sites was generally dominated by marine material (carbonate, organic matter, opal) although relationships of detrital proxies as well as glauconitic horizons support some influence of turbidites, winnowing bottom currents and/or variable detritus sources, along with less reducing bottom water at the proposed shallower location (ODP Site 1259). At Site 1261, located at greater paleo-depth, redox fluctuations were more regular, and steady hemipelagic sedimentation sustained the development of mostly undisturbed lamination in the sedimentary record. Strong similarities of the studied deposits exist with the stratigraphic older Cenomanian-Turonian OAE2 black shale sections at Demerara Rise, suggesting that the primary mechanisms controlling continental supply and ocean redox state were time-invariant and kept the western equatorial Atlantic margin widely anoxic over millions of years.

Enhanced 3-Dimensional Carbon Nanotube Based Anodes for Li-ion Battery Applications

A prototype 3-dimensional (3D) anode, based on multiwall carbon nanotubes (MWCNTs), for Li-ion batteries (LIBs), with potential use in Electric Vehicles (EVs) was investigated. The unique 3D design of the anode allowed much higher areal mass density of MWCNTs as active materials, resulting in more amount of Li+ ion intake, compared to that of a conventional 2D counterpart. Furthermore, 3D amorphous Si/MWCNTs hybrid structure offered enhancement in electrochemical response (specific capacity 549 mAhg-1). Also, an anode stack was fabricated to further increase the areal or volumetric mass density of MWCNTs. An areal mass density of the anode stack 34.9 mg/cm2 was attained, which is 1,342% higher than the value for a single layer 2.6 mg/cm2. Furthermore, the binder-assisted and hot-pressed anode stack yielded the average reversible, stable gravimetric and volumetric specific capacities of 213 mAhg-1 and 265 mAh/cm3, respectively (at 0.5C). Moreover, a large-scale patterned novel flexible 3D MWCNTs-graphene-polyethylene terephthalate (PET) anode structure was prepared. It generated a reversible specific capacity of 153 mAhg-1 at 0.17C and cycling stability of 130 mAhg-1 up to 50 cycles at 1.7C.

Design, development, and analysis of hybrid metal-composite tube for industrial application

In the aerospace, automotive, printing, and sports industries, the development of hybrid Carbon Fiber Reinforced Polymer (CFRP)-metal components is becoming increasingly important. The coupling of metal with CFRP in axial symmetric components results in reduced production costs and increased mechanical properties such as bending, torsional stiffness, mass reduction, damping, and critical speed compared to the single material-built ones. In this thesis, thanks to a novel methodology involving a rubbery/viscoelastic interface layer, several hybrid aluminum-CFRP prototype tubes were produced. Besides, an innovative system for the cure of the CFRP part has been studied, analyzed, tested, and developed in the company that financed these research activities (Reglass SRL, Minerbio BO, Italy). The residual thermal stresses and strains have been investigated with numerical models based on the Finite Element Method (FEM) and compared with experimental tests. Thanks to numerical models, it was also possible to reduce residual thermal stresses by optimizing the lamination sequence of CFRP and determining the influence of the system parameters. A novel software and methodology for evaluating mechanical and damping properties of specimens and tubes made in CFRP were also developed. Moreover, to increase the component's damping properties, rubber nanofibers have been produced and interposed throughout the lamination of specimens. The promising results indicated that the nanofibrous mat could improve the material damping factor over 77% and be adopted in CFRP components with a negligible increment of weight or losing mechanical properties.