Correlazioni tra proprietá reologiche, struttura e processabilitá di blend di LLDPE/LDPE

Polymer blends constitute a valuable way to produce relatively low cost new materials. A still open question concerns the miscibility of polyethylene blends. Deviations from the log-additivity rule of the newtonian viscosity are often taken as a signature of immiscibility of the two components. The aim of this thesis is to characterize the rheological behavior in shear and elongation of five series of LLDPE/LDPE blends whose parent polymers have been chosen with different viscosity and SCB content and length. Synergistic effects have been measured for both zero shear viscosity and melt strength. Both SCB length and viscosity ratio between the components have been found to be key parameters for the miscibility of the pure polymers. In particular the miscibility increases with increasing SCB length and with decreasing the LDPE molecular weight and viscosity. This rheological behavior has significant effects on the processability window of these blends when the uni or biaxial elongational flows are involved. The film blowing is one of the processes for which the synergistic effects above mentioned can be crucial. Small scale experiments of film blowing performed for one of the series of blends has demonstrated that the positive deviation of the melt strength enlarges the processability window. In particular, the bubble stability was found to improve or disappear when the melt strength of the samples increased. The blending of LDPE and LLDPE can even reduce undesired melt flow instability phenomena widening, as a consequence, the processability window in extrusion. One of the series of blends has been characterized by means of capillary rheometry in order to allow a careful morphological analysis of the surface of the extruded polymer jets by means of Scanning Electron Microscopy (SEM) with the aim to detect the very early stages of the small scale melt instabilty at low shear rates (sharksin) and to follow its subsequent evolution as long as the shear rate was increased. With this experimental procedure it was possible to evaluate the shear rate ranges corresponding to different flow regions: smooth extrudate surface (absence of instability), sharkskin (small scale instability produced at the capillary exit), stick-slip transition (instability involving the whole capillary wall) and gross melt fracture (i.e. a large scale "upstream" instability originating from the entrance region of the capillary). A quantitative map was finally worked out using which an assessment of the flow type for a given shear rate and blend composition can be predicted.

Analysis of cumulative effects of multiple stressors on saltmarshes and consideration of management options

Natural systems face pressures exerted by natural physical-chemical forcings and a myriad of co-occurring human stressors that may interact to cause larger than expected effects, thereby presenting a challenge to ecosystem management. This thesis aimed to develop new information that can contribute to reduce the existing knowledge gaps hampering the holistic management of multiple stressors. I undertook a review of the state-of-the-art methods to detect, quantify and predict stressor interactions, identifying techniques that could be applied in this thesis research. Then, I conducted a systematic review of saltmarsh multiple stressor studies in conjunction with a multiple stressor mapping exercise for the study system in order to infer potential important synergistic stressor interactions. This analysis identified key stressors that are affecting the study system, but also pointed to data gaps in terms of driver and pressure data and raised issues for potentially overlooked stressors. Using field mesocosms, I explored how a local stressor (nutrient availability) affects the responses of saltmarsh vegetation to a global stressor (increased inundation) in different soil types. Results indicate that saltmarsh vegetation would be more drastically affected by increased inundation in low than in medium organic matter soils, and especially in estuaries already under high nutrient availability. In another field experiment, I examined the challenges of managing co-occurring and potentially interacting local stressors on saltmarsh vegetation: recreational trampling and smothering by deposition of excess macroalgal wrack due to high nutrient loads. Trampling and wrack prevention had interacting effects, causing non-linear responses of the vegetation to simulated management of these stressors, such that vegetation recovered only in those treatments simulating the combined prevention of both stressors. During this research I detected, using molecular genetic methods, a widespread presence of S. anglica (and to a lesser extent S. townsendii), two previously unrecorded non-native Spartinas in the study areas.