Polymer Process Partitioning: Extruding Plastic Pipe

When plastic pipe is solidified, it proceeds through a long cooling chamber. Inside this chamber, inside the hollow extrudate, the plastic is molten, and this inner surface solidifies last. Sag, the flow due to the self-weight of the molten plastic, then happens in this cooling chamber, and sometimes, thickened regions (called knuckles) arise in the lower quadrants, especially of large diameter thickwalled pipes. To compensate for sag, engineers normally shift the die centerpiece downward. This thesis focuses on the consequences of this decentering. Specifically, when the molten polymer is viscoelastic, as is normally the case, a downward lateral force is exerted on the mandrel. Die eccentricity also affects the downstream axial force on the mandrel. These forces govern how rigidly the mandrel must be attached (normally, on a spider die). We attack this flow problem in eccentric cylindrical coordinates, using the Oldroyd 8-constant constitutive model framework. Specifically, we revise the method of Jones (1964), called polymer process partitioning. We estimate both axial and lateral forces. We develop a corresponding map to help plastics engineers predict the extrudate shape, including extrudate knuckles. From the mass balance over the postdie region, we then predict the shape of the extrudate entering the cooling chamber. We further include expressions for the stresses in the extruded polymer melt. We include detailed dimensional worked examples to show process engineers how to use our results to design pipe dies, and especially to suppress extrudate knuckling.

Provenance of Holocene Calcareous Aeolianites, Eastern South Australia

The southeastern coast of South Australia contains a spectacular and world-renown suite of Quaternary calcareous aeolianites. This study is focused on the provenance of components in the Holocene sector of this carbonate breach-dune succession. Research was carried out along seven transects from ~30 meters water depth offshore across the beach and into the dunes. Offshore sediments were acquired via grab sampling and SCUBA. Results indicate that dunes of the southern Lacepede and Otway coasts in particular are mostly composed of modern invertebrate and calcareous algal allochems. The most numerous grains are from molluscs, benthic foraminifera, coralline algae, echinoids, and bryozoans. These particles originate in carbonate factories such as macroalgal forests, rocky reefs, seagrass meadows, and low-relief seafloor rockgrounds. The incorporation of carbonate skeletons into coastal dunes, however, depends on a combination of; 1) the infauna within intertidal and nearshore environments, 2) the physical characteristics of different allochems and their ability to withstand fragmentation and abrasion, 3) the wave and swell climate, and 4) the nature of aeolian transport. Most aeolian dune sediment is derived from nearshore and intertidal carbonate factories. This is particularly well illustrated by the abundance of robust infaunal bivalves that inhabit the nearshore sands and virtual absence of bryozoans that are common as sediment particles in water depths > 10mwd. Thus, the calcareous aeolianites in this cool-water carbonate region are not a reflection of the offshore marine shelf factories, but more a product of shallow nearshore-intertidal biomes.

Swellable polymer films containing Au nanoparticles for point-of-care therapeutic drug monitoring using surface-enhanced Raman spectroscopy

Large (10 × 10 cm) sheets of surface-enhanced Raman spectroscopy (SERS) active polymer have been prepared by stabilising metal nanoparticle aggregates within dry hydroxyethylcellulose (HEC) films. In these films the aggregates are protected by the polymer matrix during storage but in use they are released when aqueous analyte droplets cause the films to swell to their gel form. The fact that these "Poly-SERS" films can be prepared in bulk but then cut to size and stored in air before use means that they provide a cost effective and convenient method for routine SERS analysis. Here we have tested both Ag and Au Poly-SERS films for use in point-of-care monitoring of therapeutic drugs, using phenytoin as the test compound. Phenytoin in water could readily be detected using Ag Poly-SERS films but dissolving the compound in phosphate buffered saline (PBS) to mimic body fluid samples caused loss of the drug signal due to competition for metal surface sites from Cl^- ions in the buffer solution. However, with Au Poly-SERS films there was no detectable interference from Cl^- and these materials allowed phenytoin to be detected at 1.8 mg L^-1, even in PBS. The target range of detection of phenytoin in therapeutic drug monitoring is 10-20 mg L^-1. With the Au Poly-SERS films, the absolute signal generated by a given concentration of phenytoin was lower for the films than for the parent colloid but the SERS signals were still high enough to be used for therapeutic monitoring, so the cost in sensitivity for moving from simple aqueous colloids to films is not so large that it outweighs the advantages which the films bring for practical applications, in particular their ease of use and long shelf life.

Elintarvikepakkauskartongin vettyminen

Elintarviketeollisuudessa tärkeimpiä pakkausmateriaaleja ovat erilaiset kartonkipakkaukset ja erityisesti niiden kuljetuksessa käytettävät aaltopahvipakkaukset. Aaltopahvilta vaadittavia ominaisuuksia ovat muun muassa puristuslujuus ja kosteudenkestävyys. Elintarvikekäyttöön tarkoitetuilla aaltopahveilla on myös tiettyjä vaatimuksia niissä käytettävistä yhdisteistä. Erilaiset kuitumateriaalit käyttäytyvät vettyessään eri tavalla ja niistä voi liueta yhdisteitä pakattavaan elintarvikkeeseen. Työn tavoitteena oli selvittää vettymiseen vaikuttavia tekijöitä ja veden vaikutus aaltopahvin rakenteeseen. Havaittiin, että ligniiniä tai uuteaineita sisältävä mekaanisesti valmistettu kartonkimateriaali ei sido vettä yhtä paljon kuin kemiallisesti valmistettu tai valkaistu kartonki. Aaltopahvissa tapahtuvan kapillaariabsorptio sai veden nousemaan pääasiassa aallotuskartonkiin. Vesi imeytyi korkeammalle puolikemiallisesti valmistetuissa aaltopahveissa kuin keräyskartonkipahveissa, jotka eivät myöskään turvonneet yhtä voimakkaasti. Työssä kartoitettiin myös elintarvikekäyttöä rajoittavia liukoisia yhdisteitä, jotka löytyivät paperiteollisuudessa yleisesti käytetyistä liimoista. Tällaisia yhdisteitä olivat märkälujaliimojen formaldehydiyhdisteet ja polyamidoamiini-epikloorihydriinihartsi. Keräyskartongin joukossa olevat raskasmetallit rajoittavat myös niiden käyttöä elintarvikepakkauksissa.

Comparison and validation of physical wave parameterizations in spectral wave models

Recent developments in the physical parameterizations available in spectral wave models have already been validated, but there is little information on their relative performance especially with focus on the higher order spectral moments and wave partitions. This study concentrates on documenting their strengths and limitations using satellite measurements, buoy spectra, and a comparison between the different models. It is confirmed that all models perform well in terms of significant wave heights; however higher-order moments have larger errors. The partition wave quantities perform well in terms of direction and frequency but the magnitude and directional spread typically have larger discrepancies. The high-frequency tail is examined through the mean square slope using satellites and buoys. From this analysis it is clear that some models behave better than the others, suggesting their parameterizations match the physical processes reasonably well. However none of the models are entirely satisfactory, pointing to poorly constrained parameterizations or missing physical processes. The major space-time differences between the models are related to the swell field stressing the importance of describing its evolution. An example swell field confirms the wave heights can be notably different between model configurations while the directional distributions remain similar. It is clear that all models have difficulty in describing the directional spread. Therefore, knowledge of the source term directional distributions is paramount in improving the wave model physics in the future.

Wind Waves in the Arctic Seas: Envisat and AltiKa Data Analysis

Wind-generated waves in the Kara, Laptev, and East-Siberian Seas are investigated using altimeter data from Envisat RA-2 and SARAL-AltiKa. Only isolated ice-free zones had been selected for analysis. Wind seas can be treated as pure wind-generated waves without any contamination by ambient swell. Such zones were identified using ice concentration data from microwave radiometers. Altimeter data, both significant wave height (SWH) and wind speed, for these areas were further obtained for the period 2002-2012 using Envisat RA-2 measurements, and for 2013 using SARAL-AltiKa. Dependencies of dimensionless SWH and wavelength on dimensionless wave generation spatial scale are compared to known empirical dependencies for fetch-limited wind wave development. We further check sensitivity of Ka- and Ku-band and discuss new possibilities that AltiKa's higher resolution can open.