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The purpose of this study is to identify and quantify factors governing extrudate swell and melt fracture. In the first part, the factors which control the extrudate swell of carbon black (N330) filled styrene-butadiene rubber (SBR) compounds at various states-of-mix were investigated. State-of-mix is quantified by effective filler volume fraction (EFVF), based on an estimate of the amount of rubber immobilised in the carbon black agglomerates. Extrudate swell was found to be dominated by recoverable strain and relaxation time, which are controlled by EFVF. In contrast, shear rate and the rubber-carbon black tridimensional transient network were not found to influence extrudate swell significantly. In the second part, melt fracture of the rubber compounds was investigated in terms of surface texture wavelength. The longer the wavelength, the greater the severity of the surface disruption. It was found that wavelength was controlled strongly by state-of mix (or by EFVF). In addition, a mechanism for melt fracture of the compounds studied has been proposed, based on average energy at the extrudate surface (t.E). Lastly, the influences of additives; paraffinic processing oil, stearic acid or a mixture of predominantly calcium fatty acid soaps on extrudate swell and melt fracture were investigated. For the rubber compounds with paraffinic processing oil or stearic acid, EFVF was found to play an important role in extrudate swell. The mixture of fatty acid soaps was shown to reduce significantly extrudate swell due to the presence of wall slip. The influence of the fatty acid soaps on extrudate swell is more noticeable for extrudates obtained from long dies, in which flow is dominated by shear. The major factors shown to exert a significant influence on melt fracture for the compounds with paraffinic processing oil or stearic acid are EFVF and green strength of the extrudate. Wall slip, promoted by a mixture of fatty acid soaps, was also found to decrease the melt fracture severity, particularly for long dies in which shear stresses are dominant.

Thesis (Ph.D.) -- University of Rhode Island, 2007 / Typescript. Includes bibliographical references (leaves 178-184).

abstract: Volcanic devolatilization is one of the major processes in the global nitrogen cycle. Past studies have often estimated the magnitude of this flux using volcanic emission measurements, which are limited to currently active systems and sensitive to atmospheric contamination. A different methodological approach requires appropriate analytical parameters for nitrogen analysis in silicate glasses by secondary ion mass spectrometry (SIMS), which have not yet been established. To this end, we analyze various ion implanted basaltic and rhyolitic glasses by SIMS. We demonstrate that water content significantly affects the ion yields of 14N+ and 14N16O−, as well as the background intensity of 14N+ and 12C+. Application of implant-derived calibrations to natural samples provide the first reported concentrations of nitrogen in melt inclusions. These measurements are from samples from the Bishop Tuff in California, the Huckleberry Ridge Tuff of the Yellowstone Volcanic Center, and material from the Okaia and Oruanui eruptions in the Taupo Volcanic Center. In all studied material, we find maximum nitrogen contents of less than 45 ppm and that nitrogen concentration varies positively with CO2 concentration, which is interpreted to reflect partial degassing trend. Using the maximum measured nitrogen contents for each eruption, we find that the Bishop released >3.6 x 1013 g of nitrogen, the Huckleberry Ridge released >1.3 x 1014 g, the Okaia released >1.1 x 1011 g of nitrogen, the Oruanui released >4.7 x 1013 g of nitrogen. Simple calculations suggest that with concentrations such as these, rhyolitic eruptions may ephemerally increase the nitrogen flux to the atmosphere, but are insignificant compared to the 4 x 1021 g of nitrogen stored in the atmosphere. / Dissertation/Thesis / Masters Thesis Geological Sciences 2016

Made available in DSpace on 2014-06-12T15:49:36Z (GMT). No. of bitstreams: 2 arquivo5263_1.pdf: 10272836 bytes, checksum: 6b376d934755a2dba22f7fba5ee09e14 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2006 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Foi descoberto um sistema mel-spinning para produção de fitas metálicas. O sistema consiste essencialmente de um forno de radio-freqüência, operando com 8kVA de potência e em 450 kHz, o qual é utilizado para fundir a liga precursora e um volante de cobre usado para resfriamento da liga fundida...

The 8-9 million year old volcanic complex of Oxnadalur is host to large-volume basalt flows, small and large volume rhyolite ash and lava flows, and a gabbroic intrusion. Both the plagioclase and pyroxene phenocrysts of the basalt are larger in size in the younger flows. The rhyolite ashes contain no primary crystals, but numerous basalt xenoliths and pumice fragments. The rhyolite lava flows are banded, with only the oldest containing phenocrysts of sanidine and plagioclase. One rhyolite flow is a mingled hybrid of two glasses, each containing plagioclase, pyroxene, and hornblende. Whole rock major and trace element analyses indicate a mixing trend among all of the units in the complex; yet abundant xenoliths in the ashes make this less data less dependable. In situ major and trace element analyses were performed via electron microprobe show two distinct populations in the variation diagrams, with the basalts and rhyolites separated by a compositional gap. Electron microprobe analyses also show that the plagioclase of the basalts and the gabbro are normally zoned with distinct calcic cores and sodic rims; this is also true for the mingled hybrid flow. Rare earth element analyses done via laser ablation inductively coupled plasma mass spectrometry, show that the phenocrysts are enriched in the light and depleted in the heavy rare earth elements. Rare earth element abundances in the glasses have a trend similar to that of ocean island basalt rather than that of mid ocean ridge basalt. Plagioclase geothermometry and amphibole geobarometry indicate that the magma chambers were replenished by new batches of melt and may have existed at a shallow level in the crust just prior to being erupted. Oxygen isotope ratios are depleted compared to those of typical mid ocean ridge basalts, typically indicating that the source melt was partially melted from a hydrothermally altered layer in the crust. As the δ18O values are whole rock, the depletion may be the result of any sub solidus interaction with low δ18O water. The data indicate that multiple shallow reservoirs evolved separately, with limited communication while being intruded by new magma throughout the lifespan of the complex.

<p> A high-pressure nitrogen-driven viscometer has been used to study the melt fracture of polystyrene. The polystyrene samples used differed in molecular weight and molecular weight distribution. The weight average molecular weight (Mw) ranged from 97,200 to 1.8 x 10^6 and the distribution breadth (Mw/Mn) from 1.06 to 9.21. Results obtained indicate that the critical shear stress varies linearly with 1/Mw, increases slightly with temperature and is independent of the polydispersity of polymers. This type of behaviour is satisfactorily explained in terms of Graessley's entanglement theory.</p> / Thesis / Master of Engineering (MEngr)

This thesis is concerned with the development of engineering technologies that facilitate melt spinning of carbon fiber precursors in both an environmentally sound and cost effective manner. More specifically, methods were developed to avoid a degradative process in acrylonitrile copolymers (typically used in textiles and as carbon fiber precursors) that occurs as melt spinning temperatures are approached. The following set of analyses was developed to define the rheological properties required for a melt processable acrylic copolymer suitable for use as a carbon fiber precursor, and accordingly facilitated development of a processing window: measurement of steady shear viscosity as a function of both temperature and time, measurement of the magnitude of the complex viscosity (|η*|) as a function of temperature using a temperature sweep, and measurement of the angular frequency dependence of |η*|. Through a systematic screening process, the following properties were identified to afford melt spinnable acrylic precursors suitable for conversion to carbon fibers: emulsion polymerization, 85-88 mole % acrylonitrile, 11-14 mole % methyl acrylate, 1 mole % acryloyl benzophenone, intrinsic viscosity < 0.6 dL/g, steady shear viscosity ≤ 1000-2000 Pa*s at a shear rate (γ) of 0.1 s⁻¹, viscosity increases ≤ 45% over a period of 1800 seconds at 200-220°C and γ=0.1 s⁻¹. Use of the rheological analyses assisted in development of a melt spinnable carbon fiber precursor, which resulted in carbon fibers possessing a tensile strength and modulus of approximately 1.0 and 120 GPa, respectively. A second approach was evaluated using carbon dioxide (CO₂) to plasticize AN copolymers to an extent that facilitates processing at reduced temperatures, below where thermal degradation is significant. A batch saturation method to absorb CO₂ in AN copolymers was developed. Differential scanning calorimetry and thermogravimetric analyses were used to measure the glass transition temperature (T_g) reduction and amount of absorbed CO₂ (respectively). A pressurized rheometer and measurement procedure was designed to obtain viscosity measurements of saturated AN copolymers. Up to 6.7 wt. % CO₂ was found to absorb into a 65 mole % AN copolymer with the saturation method used, resulting in a 31°C glass transition temperature (T_g) reduction, 60% viscosity reduction, and 30°C potential processing temperature reduction. It was found that CO₂ can absorb into copolymers containing up to 90 mole % AN (with the absorption methods used) with the following results (for a 90/10 mole % AN/MA copolymer): 3.0 wt. % uptake, 27°C T_g reduction, 56% viscosity reduction, and potential processing temperature reduction of 9°C. Via estimates of the required pressure, sealing fluid flow rate, and length of a pressure chamber to prevent foaming of the saturated polymer melt during extrusion, melt spinning of saturated AN copolymers appears feasible. / Ph. D.

Linear thermoplastic polyesters are commonly used in high volume applications such as food containers, films and textile fibers. The physical and mechanical properties of these materials are well documented and are a function of chemical structure and morphology (e.g. semi-crystalline, amorphous, etc.). Polyesters, as are many organic polymers, are quite flammable. Polydimethylsiloxane homopolymer exhibits low mechanical strength and, even at high molecular weight, exists as a viscous fluid rubbery gum due to its low glass transition temperature of approximately -123°C. However, one of the many attractive properties of this polymer is its relatively low flammability and if properly designed, organic "sand-like" silicates are produced in oxidizing atmospheres at elevated temperatures (e.g. 500-700°C). This thesis discusses the synthesis and characterization of novel, high molecular weight cycloaliphatic and aromatic polyester/ poly(dimethylsiloxane) segmented copolymers. The cycloaliphatic copolymers were synthesized via a melt process using a high trans content 1,4 dimethylcyclohexanedicarboxylate, and 1,4 butanediol or cyclohexanedimethanol, while the partially aromatic systems were synthesized using dimethyl terephthalate and butanediol. Primary and secondary aminopropyl terminated poly(dimethylsiloxane) oligomers of controlled molecular weight were endcapped with excess diester to form an amide linked diester terminated oligomer. The latter was then incorporated into the copolymer via melt transesterification to afford a multiphase segmented copolymer. Selected compositions showed enhanced ductility and hydrophobic surface modification. The polysiloxane segment was effeciently incorporated into the copolymers and was unaffected by the transesterification catalyst under typical reaction conditions. The homopolymers and copolymers were characterized by solution, thermal, and mechanical, and surface techniques. The segmented copolymers were demonstrated to be microphase separated as determined by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and transmission electron microscopy. The surface of the copolymers was enriched with the polysiloxane segment as evidenced by contact angle analysis. Thermal gravimetric analysis of the segmented copolymers containing identical amounts of PDMS, but varying in the primary or secondary nature of their amide linkages, exhibited quantitatively identical char yields and weight loss behavior. The segmented copolymers exhibited char yields in air superior to those of their respective homopolymers. Additionally, aromatic poly(tetramethyleneoxide) (PTMO) based polyether/polyester segmented copolymers were modified with poly(dimethylsiloxane). DMA revealed an apparent shift (higher Tg) of the PTMO segment reflecting an increase in phase mixing with the "hard" polyester segment, possibly induced by the hydrophobic PDMS phase. / Master of Science