Universiẗat, Diss., 2002--Bayreuth. / Erscheinungsjahr an der Haupttitelstelle: 2002.

Made available in DSpace on 2014-06-11T19:27:12Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-04-20Bitstream added on 2014-06-13T19:35:01Z : No. of bitstreams: 1 oliveira_acm_me_guara.pdf: 813696 bytes, checksum: 291a32b0707aad7bbcf67e98ead0311c (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O presente trabalho aborda as condições de reticulação do polímero termoplástico polietileno e, para isso, foram avaliadas diferentes temperaturas de processo (60 e 90°C), bem como diferentes tempos de permanência em imersão em banho termostatizado (1, 3, 6 e 9 horas). Esta avaliação foi realizada a partir dos ensaios de teores de gel e fator de uptake, de massa específica, de calorimetria exploratória diferencial (DSC), de análise termogravimétrica (TGA), de espectrofotometria no infravermelho com transformada de Fourier (FT-IR) e de ensaios de tração. Desta forma, o grau de reticulação do polietileno de baixa densidade reticulado em água, foi correlacionado com sua morfologia, com seu desempenho térmico e mecânico. Os resultados mostraram que o teor de gel do polietileno reticulado aumentou com o aumento da temperatura e do tempo de exposição desta matriz polimérica em água, sendo que, este aumento ocorreu de forma significativa até 3 horas de exposição, não sendo observados ganhos significativos na formação de ligações cruzadas após este período / The present work deals with the crosslink conditions of polyethylene polymer using different process temperatures (60 and 90°C). For this different water immersion times in thermostated bath (1, 3, 6 and 9 hours) have been analyzed by using gel content and uptake factor, density tests, dynamic scanning calorimetric analyses (DSC), thermogravimetric analysis (TGA), infrared spectroscopy (FT-IR) and tensile tests. This way, it was evaluated the degree of crosslinking of low density polyethylene crosslinked into water, and these parameters were correlated with the morphology and its thermal and mechanical performance. According to found results, it was observed that the gel content of polyethylene crosslinked increased with increasing of exposition temperature and time of this polymeric matrix in water, therefore, this increase was significantly up to 3 hours of exposition, not being observed significant gains in crosslinking density after this time

A variety of modified minerals have been screened to determine their effectiveness as agents for the catalytic transformation of the thermally generated off gases arising from the pyrolysis of the polyolefinic plastic High Density Polyethylene (HDPE). This polymer has been shown to degrade through a series of known mechanisms to yield a hydrocarbon product mixture consisting of an homologous series of saturated and unsaturated hydrocarbons which include alk-1-enes, n-alkanes, alk-x-enes and a-w-dienes. Modification treatments have been wide ranging having included activation of the parent mineral by means of pillaring, ion exchange and acid activation. The activated products have been characterised by XRD, XRF, TGA and vibrational spectroscopy. Moreover, evolved gas analysis has been employed to perform catalytic screening runs on these modified minerals. In particular, attention has been paid to the activity of these materials in respect of the formation of potentially fuel applicable hydrocarbons, namely those exhibiting high octane ratings, including aromatics and branched aliphatics from the feedstock species present in the HDPE pyrolysate gas mixture. Pillared clays (PILC's) have proven ineffective in this role as a consequence of their poor reproducibility and lack of selectivity towards the formation of single ring aromatics. Likewise, ion exchange has been found to influence strongly the catalytic behaviour of previously acid activated clays, with autotransformed samples offering dehydrocyclisation (DHC) activity at levels significantly greater than seen with some ion exchanged samples, particularly protons. Acid activated metakaolinites have demonstrated poor selectivity in terms of aromatic formation, although total DHC activity is good. Metakaolin also gave rise to appreciable activity in respect of the formation of the single ring aromatics selected for monitoring in this work. Isomerisation activity was prevalent over these materials, but coking levels were high. Acid activated smectites represent the most suitable candidates to fulfil the role of single step fuel generation from the transformation of the gas stream resulting from HDPE pyrolysis. It has been found that careful control over the chemical and physical properties of acid activated clays can be achieved through consideration of the severity of the activation parameters chosen to induce modification. In addition, the nature of the activated product is strongly dependant on the nature of the base clay. In particular, acid activated beidellites have been shown to exhibit high levels of surface acidity as determined through the thermal desorption of cyclohexylamine. These materials consequently give rise to respectable activity and selectivity in terms of the formation of highly octane rated methyl substituted single ring aromatics, principally trimethylbenzene. In contrast, acid activated montmorillonites have been seen to offer lower levels of total surface acidity and have been shown to be active in promoting skeletal isomerisation reactions to yield branched aliphatics, again, highly octane rated. This activity variation has been attributed to the formation of highly Bronsted acidic silanol containing Surface Localised Acid Pools (SLAP's) on the exposed surfaces of the former as a consequence of the isomorphous substitution patterns observed in the tetrahedral sheets of beidellites.

Rheological and processing behavior of a number of linear low-density polyethylene(LLDPE)/low-density polyethylene (LDPE) blends was studied with emphasis on the effects of long chain branching. First, a linear low-density polyethylene (LL3001.32) was blended with four LDPE's having distinctly different molecular weights. At high LDPE weight fractions, DSC melting thermograms have shown three different polymer phases; two for the pure components and a third melting peak of co-crystals. Different rheological techniques were used to check the thermo rheological behavior of all blends in the melt state and the effect of long chain branching. It was found that all blends are miscible in the melt state at small LDPE concentrations. The elongational behavior of the blends was studied using a uniaxial extensional rheometer, SER. The blends exhibit strain hardening behavior at high rates of deformation even at LDPE concentrations as low as 1%, which suggests the strong effect of branching added by the LDPE component. On the other hand, shear rheology was found to be insensitive to detect addition of small levels of LDPE up to lwt%. The second set of blends prepared and studied consisted of two Ziegler-Natta LLDPE's (LL3001.32 and Dowlex2045G) and two metallocene LLDPE's(AffinityPL1840 and Exact 3128) blended with a single LDPE. In DSC melting thermograms, it was observed that blends with metallocence LLDPE's exhibit a single melting peak at all compositions; whereas the Ziegler-Natta blends exhibit three melting peaks at certain compositions. It was found also that the metallocene LLDPE's are miscible with the LDPE at all concentrations. On the other hand, the Ziegler-Natta LLDPE's were found to be miscible with LDPE only at small LDPE concentrations. The processing behavior of all blends with emphasis on the effects of long chain branches was also studied in capillary extrusion. The critical shear stresses for the onset of sharkskin and gross melt fracture are slightly delayed with the addition of LDPE into LLDPE. Furthermore, the amplitude of the oscillations in the stick-slip flow regime, known as oscillating melt fracture, were found to scale with the weight fraction of LDPE. Amounts as low as 1 wt% LDPE have a significant effect on the amplitude of pressure oscillations. These effects are clearly due to the presence of LCB. It is suggested that the magnitude of oscillations in the oscillating melt fracture flow regime can be used as a method capable to detect low levels of LCB. Finally, the sharkskin and stick-slip polymer extrusion instabilities of a linear low-density polyethylene were studied as a function of the type of die geometry. The critical wall shear stress for the onset of flow instabilities, the pressure and flow rate oscillations, and the effects of geometry and operating conditions on the instabilities are presented for a LLDPE. It was found that sharkskin and stick-slip instabilities were present in the capillary and slit extrusion. However, stick-slip and sharkskin in annular extrusion are absent at high ratios of the inside to outside diameter of the annular die. This observation also explains the absence of these instabilities in polymer processing operations such as film blowing. These phenomena are explained in terms of the surface to volume ratio of the extrudates. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

Due to the nature of gas-solid fluidized beds, providing continuous contacts between fluidizing particles and between particles and the reactor wall, the occurrence of electrostatic charges is unavoidable. In the polyethylene industry, electrostatics is a major problem. Large amounts of electrostatic charges are generated causing polyethylene and catalyst particles to adhere to the reactor wall, forming sheets. Particle sheets can break off and block the distributor plate, causing long shutdown periods for clean-up which result in economic loss due to decreased production and higher maintenance costs. The overall purpose of the project of which this thesis is part of is to help industry in minimizing this problem by examining the mechanisms underlying this phenomenon. Towards this goal, an experimental technique for the measurement of the degree of wall fouling and its charge distribution was previously developed and implemented in an atmospheric system with a column of 0.102 m in diameter. This technique was extended in this thesis to a pilot-scale unit (0.154 m in diameter) designed to be capable of operating at pressures and temperatures up to 2 600 kPa and 100°C respectively and gas velocities up to 1 m/s, which are operating conditions of industrial polyethylene reactors. Preliminary experiments showed that increasing the operating pressure from 101 kPa to 401 kPa almost doubled the amount of polyethylene wall fouling due to the higher bubble rise velocity at this pressure, enhancing charge generation within the fluidized bed. Changing the particle size distribution by removing particles smaller than 250 μm had no significant effect on the extent of the wall fouling. Increasing the column diameter from 0.102 m to 0.154 m decreased wall fouling due to the lower column wall area per mass of particles. Overall, particle-particle contacts generated positively and negatively charged particles, but did not produce a net charge in the bed due to the negligible elutriation. However, particle-wall contacts produced a net charge. The formation of the wall layer was due to the image force created by the net charge and the layering effect created by the attraction between oppositely charged particles.

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No / The deformation behavior of a particular grade of high-density polyethylene prepared in a number of different ways has been examined. The samples all have an initially isotropic crystalline texture but differ in the levels of network preorientation surviving as a legacy of the melt processing history. Measurements of shrinkage and shrinkage force have been used to characterize this network, and the results suggest that the density of active chains is much lower than found in the main molecular network operating during solid-state drawing. The subnetwork properties vary depending on the level of extrusion and rate of cooling experienced during processing, with those entanglements surviving in the oriented melt at the point of crystallization having a long relaxation time. The presence of this subnetwork can lead to the suppression of necking during subsequent solid-state deformation. The implication is that simple processing procedures can be devised to remove or control the instability associated with necking.