Thesis (M.S.)--University of Alabama at Birmingham, 2010. / Title from PDF t.p. (viewed July 19, 2010). Includes bibliographical references (p. 67-70).

The surface functionalisation of polyethylene and polypropylene by industrial and laboratory scale corona treatments and by laboratory flame treatment was studied. The surface sensitive techniques of X-ray photoelectron spectroscopy (XPS), attenuated total reflection infra-red spectroscopy (FTIR-ATR), contact angle measurement and electron microscopy (SEM and TEM) were employed. Corona and flame treatments resulted in incorporation of oxygen only into the surfaces of both polyethylene and polypropylene, resulting in improved surface wettabilities. A variety of oxygen functional groups were introduced by the two treatments. The industrial and laboratory scale treatments of both polymers were found to be similar in terms of the oxygen concentrations incorporated and surface wettabilities achieved. The presence of significant amounts of chain scission products were indicated on corona treated surfaces, while only minimal quantities were indicted on flame treated surfaces. This was attributed to their volatilisation during flame treatment. Introduction of sulfur dioxide into the flame and corona regions during treatment resulted in significant improvements in surface wettability. Incorporation of sulfur and nitrogen resulted from the presence of sulfur dioxide. A possible mechanism involving the formation of sulfonic acid groups and ammonium sulfonate groups was suggested. An oxidation depth model developed for use with variable take-off angle XPS showed that significantly deeper oxidation occurred in the presence of sulfur dioxide. Corona treatment was more effective in improving surface wettabilities than flame treatment, this being attributed to heat induced functional group reorientation during flame . treatment for polyethylene and to differences in surface chemistry resulting from the two treatments in the case of polypropylene. The surface wettability of poly ethylene was more readily improved than the surface wettability of polypropylene after all the treatments investigated. A method for estimating functional group concentrations using chemical derivatisation and contact angle measurement was developed. Functional group estimates for flame treated polyethylene were found to be in good agreement with chemical derivatisation used in conjunction with XPS measurements.

No

A novel on-line capillary rheometer (OLR) was used to examine the shear and extensional characteristics of polyolefin melts during twin screw extrusion (TSE). Comparisons with off-line rheometry were made using a twin-bore capillary rheometer and a modular in-line slit die rheometer (ILR) provided in-line rheometry comparisons. Both capillary rheometers were controlled via PCs running dedicated software, and the extrusion line and ELR were fully instrumented allowing real-time process monitoring to be carried out by IBM compatible PCs via data acquisition hardware and software. The prototype OLR was developed by the re-design of several key features including an instrumented transfer section and capillary die block which facilitated the use of various die geometries. Shear and extensional on-line rheometry of three polyethylenes (linear and branched), and four molecular weight grades of polypropylene were examined, and a direct comparison with off-line capillary rheometry showed a good correlation. The effect of a high loading of filler on two of the polyethylenes was investigated. In-line shear stress and entry pressure measurements showed a reasonable correlation with on-line rheometry. A study of entry flows in the OLR using capillary dies approaching orifice showed non-linearities occurred at very low capillary length to diameter(L:D) ratios, and this was repeatable using off-line rheometry. Predicted zero length entry pressures (Po) were used to estimate apparent extensional viscosity using a number of standard models. Melt instability and capillary wall slip were also investigated using on-line rheometry. Melt pressure and temperature in the twin screw extruder and OLR were monitored at various process conditions to examine the ability of the OLR to condition melt during testing, and the effect of OLR testing on extrusion conditions. Pressure variation in the extruder, OLR and off-line rheometer were compared in order to quantify process noise. The effect of OLR testing on melt rheology and polymer molecular weight were examined using off-line rheometry and gel permeation chromatography(GPC).

<p> The effect of capillary dimensions on the die swell of molten polymers is investigated. Low and high density polyethylene, polypropylene, polystyrene are used to make investigation It is found the die swell decreases vii th L/D. The plot of die swell index (d/D) vs. L/D has the shape of anexponential decay curve. </p> <p> Bagley's decaying equation is used to fit the data. The effect of Deborah number on die swell phenomenon is also studied. 'I'he relationship between the recoverable shear strains of infinitely long capillary and the one with dimensions ratio L/D is obtained. This relationship could be used to estima te the die swell of short capillary from its value at equilibrium and polymer characteristics. </p> / Thesis / Master of Engineering (MEngr)

No / The in-line development of crystalline morphology and orientation during melt extrusion of low density polyethylene (LDPE) tape at nil and low haul-off speeds has been investigated using Small-Angle X-Ray Scattering (SAXS). The processing parameters, namely haul-off speed and distance down the tape-line have been varied and the resulting crystalline morphology is described from detailed analysis of the SAXS data. Increasing haul-off speed increased orientation in the polymer tape and the resulting morphology could be described in terms of regular lamellar stacking perpendicular to the elongation direction. In contrast, under nil haul-off conditions the tape still showed some orientation down the tape-line, but a shish-kebab structure prevails. The final lamellae thickness (similar to 50 angstrom) and bulk crystallinity (similar to 20%), were low at, for all processing conditions investigated, which is attributed to the significant short-chain branching in the polymer acting as point defects limiting lamellae crystal growth. (C) 2013 Elsevier Ltd. All rights reserved.