Coagent Modified Polypropylene Prepared by Reactive Extrusion: A New Look Into the Structure-Property Relations of Injection Molded Parts

Peroxide-mediated reactive extrusion of linear isotactic polypropylene (L-PP) was conducted in the presence of trimethylolpropane trimethacrylate (TMPTMA) and triallyl trimesate (TAM) coagents, using a twin screw extruder. The resulting coagent-modified polypropylenes (CM-PP) had higher viscosities and elasticities, as well as increased crystallization temperature compared to PP reacted only with peroxide (DCP-PP). Additionally, deviations from terminal flow, and strain hardening were observed in PP modified with TAM, signifying the presence of long chain branching (LCB). The CM-PP formulations retained the modulus and tensile strength of the parent L-PP, in spite of their lower molar mass and viscosities, whereas their elongation at break and the impact strength were better. This was attributed to the finer spherulitic structure of these materials, and to the disappearance of the skin-core layer in the injection molded specimens.

Simulating Granite Emplacement and Deformation with Centrifuge Analogue Modelling

The Greater Himalayan leucogranites are a discontinuous suite of intrusions emplaced in a thickened crust during the Miocene southward ductile extrusion of the Himalayan metamorphic core. Melt-induced weakening is thought to have played a critical role in strain localization that facilitated the extrusion. Recent advancements in centrifuge analogue modelling techniques allow for the replication of a broader range of crustal deformation behaviors, enhancing our understanding of large hot orogens. Polydimethylsiloxane (PDMS) is commonly used in centrifuge experiments to model weak melt zones. Difficulties in handling PDMS had, until now, limited its emplacement in models prior to any deformation. A new modelling technique has been developed where PDMS is emplaced into models that have been subjected to some shortening. This technique aims to better understand the effects of melt on strain localization and potential decoupling between structural levels within an evolving orogenic system. Models are subjected to an early stage of shortening, followed by the introduction of PDMS, and then a final stage of shortening. Theoretical percentages of partial melt and their effect on rock strength are considered when adding a specific percentage of PDMS in each model. Due to the limited size of the models, only PDMS sheets of 3 mm thickness were used, which varied in length and width. Within undeformed packages, minimal surface and internal deformation occurred when PDMS is emplaced in the lower layer of the model, showing a vertical volume increase of ~20% within the package; whereas the emplacement of PDMS into the middle layer showed internal dragging of the middle laminations into the lower layer and a vertical volume increase ~30%. Emplacement of PDMS results in ~7% shortening for undeformed and deformed models. Deformed models undergo ~20% additional shortening after two rounds of deformation. Strain localization and decoupling between units occur in deformed models where the degree of deformation changes based on the amount of partial melt present. Surface deformation visible by the formation of a bulge, mode 1 extension cracks and varying surface strain ellipses varies depending if PDMS is present. Better control during emplacement is exhibited when PDMS is added into cooler models, resulting in reduced internal deformation within the middle layer.

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.