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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.

The effect of molecular weight on the dispersion of relatively polar montmorillonite (MMT) in non polar, unmodified high density polyethylene (HDPE) was examined. Polymer layered silicate (PLS) nanocomposites were compounded using three unmodified HDPE matrices of differing molecular weight and an organically modified MMT in concentrations ranging from 2 wt% to 8 wt% via single screw extrusion. The weight average molecular weights of the HDPE matrices used in this study ranged from 87,000 g/mol to 460,000 g/mol. X-ray diffraction (XRD), mechanical testing, dynamic mechanical thermal analysis (DMTA), as well as dynamic and capillary rheometry were performed on the nanocomposites. Nanocomposites generated from the high molecular weight (HMW) HDPE matrix exhibited increased intercalation of the MMT as shown by XRD as well as greater improvements in the Young's modulus compared to nanocomposites generated from both the low (LMW) and middle molecular weight (MMW) matrices. This was attributed to higher shear stress imparted to MMT during compounding from the more viscous matrix facilitating their separation and orientation during injection molding. DMTA showed that the torsional response of the HMW nanocomposites was not as great compared to their LMW and MMW counterparts as observed from a lower percentage enhancement in the storage modulus (Gâ ) and estimated heat distortion temperature (HDT) due to anisotropy in mechanical properties. Dynamic rheology indicated that a percolated network did not exist in any of the nanocomposites as shown by no change in the terminal behavior of Gâ upon addition of clay. / Master of Science

High density polyethylene (HDPE) is a widely used plastic but it is also a combustible material. One way of reducing flammability is to add fillers, such as magnesium hydroxide (Mg(OH)2). However, this has a deleterious effect on the mechanical properties of composites. It has been found that one possible method of restoring mechanical properties is to modifY the filler particles with coating agents, such as stearic acid. In the present work, this idea was taken a stage further with the use of various metal stearates (e.g. magnesium stearate, calcium stearate, and zinc stearate) for modifying filler. The fillers examined were magnesium hydroxide and calcium carbonate. A filler loading of 40% w/w was used in all samples. Samples were moulded into a variety of shapes for mechanical testing. Such tests included, tensile, flexural, and impact testing. To obtain deeper understanding of the effect of the coating agents on the fillers, a variety of fundamental tests were carried out. These included Diffuse Reflectance FTIR (DRIFT), Thermal Analysis using a DSC cell, Xray Diffraction (XRD), contact angle measurement. Unfilled HDPE, uncoated filled-HDPE, and coated filled-HDPE were compared using uncoated filled-HDPE as a base line. Uncoated filled-HDPE is more brittle than unfilled HPDE. Surface modification of filler improves the toughness properties. Comparing coated filled-compounds, stearic acid and zinc stearate caused a small improvement, magnesium stearate improved the properties significantly with calcium carbonate while calcium stearate gave the best results for coating magnesium hydroxide. One monolayer coating gave the best compound properties compared to other degrees of coating. Although, tensile/flexural strength was not greatly affected elongation at yield, extension at maximum load, and impact properties increased significantly. DSC was used to observe the disappearance and conversion of coating agents as coating proceeded. X-ray diffraction showed the effect of injection moulding on the orientation of the filler and polymer. During coating of the filler particles, XRD and DSC were used to follow incorporation of stearate particles to produce the monolayer coverage. Surface free energy results showed that surface modification of filler resulted in the reduction of hydrophilicity of filler leading to tougher composites compared with uncoated filled-compounds.

The occurrence of deformation in plastic bottles is a common problem in the bottling industry where bottles are blow molded, hot filled at high temperatures and sealed. Plastics have unique properties that make it difficult to predict when and why such changes may occur. The root cause of such deformation is unknown by many bottle producers and recent attempts have been made to minimize the occurrence of such defects. The purpose of this research is to determine which variables involved in the bottle production process influence bottle shape. Earlier variables that were tested included both blow molding resin and total bottle sidewall thickness. The result of changing these variables did not create a decrease in defects. The use of an Ishikawa fishbone diagram identified hot filling temperature a major variable that influences final bottle shape. This research summarizes the results of a series of tests that were developed to observe the effect of hot filling temperature on final bottle shape. A positive correlation between sidewall deflection and liquid hot filling temperature was observed. A series of tensile tests were also developed to analyze the strength of various regions of a blow molded bottle. An early Pareto Analysis determined that the parting line is more susceptible to defects than any other region of the bottle. This weakness was confirmed after the tensile tests proved that there is a statistically significant difference between measurements on the sidewall and parting line (pvalue < .001). The results of this thesis highlight the consequences of arbitrarily choosing a filling temperature with little understanding of the bottle's strength at high temperatures. Plastic bottle producers and hot filling companies should unite to determine the appropriate hot filling temperature before bottles are molded and filled.

The aim of this study is to develop a combined experimental and analytical framework for accelerated lifetime estimates of semi-crystalline plastic pipes which is sensitive to changes in structure, orientation, and morphology introduced by processing conditions. To accomplish this task, high-density polyethylene (HDPE) is chosen as the exemplary base material. As a new accelerated test protocol, several characterization tests were planned and conducted on as-manufactured HDPE pipe segments. Custom fixtures are designed and developed to admit uniaxial characterization tests. The yield behavior of the material was modeled using two hydrostatic pressure modified Eyring equations in parallel to describe the characterization test data collected in axial tension and compression. Subsequently, creep rupture failure of the pipes under hydrostatic pressure is predicted using the model. The model predictions are validated using the experimental creep rupture failure data collected from internal pressurization of pipes using a custom-designed, fully automatic test system. The results indicate that the method allows the prediction of pipe service lifetimes in excess of 50 years using experiments conducted over approximately 10 days instead of the traditional 13 months. The analytical model is joined with a commercial finite element package to allow simulations including different thermal-mechanical loading conditions as well as complicated geometries. The numerical model is validated using the characterization test data at different temperatures and deformation rates. The results suggest that the long-term performance of the pipe is dominated by the plastic behavior of the material and its viscoelastic response is found to play an insignificant role in this manner. Because of the potential role of residual stresses on the long-term behavior, the residual stress across the wall thickness is measured for three geometrically different HDPE pipes. As expected, the magnitude of tensile and compressive residual stresses are found to be greater in pipes with thicker walls. The effect of the residual stress on the long-term performance of the pipes is investigated by including the residual stress measurements into the numerical simulations. The residual stress slightly accelerates the failure process; however, for the pipe geometries examined, this acceleration is insignificant. / Doctor of Philosophy / The use of plastic pipes to carry liquids and gases has greatly increased in recent decades, primarily because of their moderate costs, long service lifetimes, and corrosion resistance compared with materials such as corrugated steel and ductile iron. Before these pipes can be effectively used, however, designers need the capability to quickly predict the service lifetime so that they can choose the best plastic material and pipe design for a specific application. This capability also allows manufacturers to modify materials to improve performance. The aim of this study is to develop a combination of experiments and models to quickly predict the service lifetime of plastic pipes. High-density polyethylene (HDPE) was chosen as the plastic material on which the model was developed. Several characterization tests are planned and conducted on as-manufactured HDPE pipe segments. The yielding behavior of the material is modeled and the lifetime predictions are evaluated. The predictions are validated by experimental data captured during pipe burst tests conducted in the lab. The results indicate that the method allows the accurate prediction of pipe service lifetimes in excess of 50 years using experiments conducted over approximately 10 days instead of the traditional 13 months, resulting in significant savings in time (and consequently costs) and making it possible to introduce new materials into production more rapidly.

The frequent use of high-density polyethylene pipes over the last decades has been possible because these pipes are lightweight, corrosion resistant, unlikely to have leaks, and are low cost. The chain structure of the polymer, the extrusion and cooling conditions, the resulting morphology and the ambient conditions all play an important role in the pipe's performance. A new generation of high density polyethylene resins has improved the performance of pipes, but brought new challenges to their testing and characterization. There is a need to understand the rheological behavior of the resins, their processing, and their associated properties in a finished pipe. The rheological behavior of the resins was studied to characterize the effect of high molecular weight tails in a bimodal molecular weight distribution. The use of cone-and-plate and parallel-plate geometries in a rheometer provided simple flow that characterized the steady and dynamical response of the polymer melts. The rheological measurements detected differences in the resins: the resin with higher molecular weight tail showed increased zero shear-rate viscosity, a much slower relaxation of stresses and a resin that more readily deviates from linear viscoelastic behavior. The rheology of the resins allowed modeling their flow through different extrusion dies. The flow channels for pipe dies are thick, so velocities and shear rates are low. Using a different die had a larger impact in shear rates and stresses compared to using different resins. The resin with higher molecular weight shows much higher shear stresses for the same die and temperature, which makes processing harder. The flow of a fluid through a pipe causes constant stress, which at long enough times is one the reasons for pipe failure. Tests that characterize the service lifetime of pipes take long times and are expensive. Dynamical mechanical analysis allows characterizing the viscoelastic properties of the pipe and creep testing confirms that shift factors work for viscoelastic properties measured inde-pendently. For the characterized pipes, one hour of testing at 80 °C is equivalent to a month of test-ing at 25 °C. This works characterizes pipes made from two resins and two different dies. The meas-urements showed that the pipes were statistically the same. / Doctor of Philosophy / The use of high-density polyethylene pipes has thrived over the last decades. This has been possible because these pipes are lightweight, corrosion resistant, unlikely to have leaks, and are low cost. The structure of the polymer and the manufacturing process both affect the pipe's performance. A new generation of high density polyethylene resins has improved the performance of the pipes, but brought new challenges to their testing and characterization. There is a need to understand the flow characteristics of the resins and their properties as a finished pipe. The flow behavior of the polymers in simple geometries gave insights into the polymer's structure. A higher molecular weight resin showed increased resistance to flow and deviated from ideal behavior more readily. These flow characteristics let one model certain aspects of the manufacturing process. Pipe manufacturing is a slow process because of the high resistance to flow of the polymer. Changing the processing equipment, and to a minor degree changing the resins, had an important impact in the manufacturing process. The tests that characterize the service lifetime of pipes take long times and are expensive. When pipes have fluids flowing at high pressures, it takes decades for them to fail. There are viscoelastic tests that allow much quicker characterization of pipes and help predict their long term behavior. This works characterizes pipes made from two resins and two different dies. This works characterizes pipes made from two resins and two different dies. The measurements showed that the pipes were statistically the same.

Butt fusion welding process is an extensively used method of joining for high density polyethylene (HDPE) pipe. With the increasing number of HDPE resin and pipe manufacturers and the diversity of industries utilising HDPE pipes, a wide range of different standards have evolved to specify the butt fusion welding parameters with inspection and testing methods, to maintain quality and structural integrity of welds. There is a lack of understanding and cohesion in these standards for the selection of welding parameters; effectiveness, accuracy, and selection of the test methods and; correlation of the mechanical properties to the micro and macro joint structure. The common standards (WIS 4-32-08, DVS 2207-1, ASTM F2620, and ISO 21307) for butt fusion welding were used to derive the six welding procedures. A total of 48 welds were produced using 180 mm outer diameter SDR 11 HDPE pipe manufactured from BorSafe™ HE3490-LS black bimodal PE100 resin. Three short term coupon mechanical tests were conducted. The waisted tensile test was able to differentiate the quality of welds using the energy to break parameter. The tensile impact test due to specimen geometry caused the failure to occur in the parent material. The guided side bend specimen geometry proved to be too ductile to be able to cause failures. A statistical t-test was used to analyse the results of the short term mechanical tests. The circumferential positon of the test specimen had no impact on their performance. Finite element analysis (FEA) study was conducted for the long term whole pipe tensile creep rupture (WPTCR) test to find the minimum length of pipe required for testing based on pipe geometry parameters of outer diameter and SDR. Macrographs of the weld beads supplemented with heat treatment were used to derive several weld bead parameters. The FEA modelling of the weld bead parameters identified the length to be a key parameter and provided insight into the relationship between the geometry of the weld beads and the stresses in the weld region. The realistic bead geometry digitised using the macrographs contributed a 30% increase in pipe wall stress due to the stress concentration effect of the notches formed between the weld beads and the pipe wall. The circumferential position of the weld bead had no impact on the pipe wall stresses in a similar manner to the results of the different mechanical tests. IV Nanoindentation (NI) and differential scanning calorimetry (DSC) techniques were used to study the weld microstructure and variation of mechanical properties across the weld at the resolutions of 100 and 50 microns, respectively. NI revealed signature 'twin-peaks and a valley' distribution of hardness and elastic modulus across the weld. The degrees of crystallinity obtained from DSC followed the NI pattern as crystallinity positively correlates with the material properties. Both techniques confirm annealing of the heat affected zone (HAZ) material towards the MZ from the parent material. The transmission light microscopy (TLM) was used to provide dimensions of the melt zone (MZ) which displays an hour glass figure widening to the size of the weld bead root length towards the pipe surfaces. Thermal FEA modelling was validated using both NI and TLM data to predict the HAZ size. The HAZ-parent boundary temperature was calculated to be 105 ⁰C. The 1st contribution of the study is to prove the existence of a positive correlation between the heat input calculated from FEA and the energy to break values obtained from the waisted tensile test. The 2nd contribution providing the minimum length of pipe for WPTCR based on the pipe dimensions. The 3rd contribution is the recommendation for the waisted tensile test with the test using the geometry designed to minimise deformation of the loading pin holes. The 4th contribution related the weld bead parameters to pipe wall stresses and the effect of notches as stress concentrators. The 5th contribution is a new method of visualising a welding procedure that can be used to not only compare the welding procedures but also predict the size of the MZ and the HAZ. The 6th contribution of the study is the proposal of new weld bead geometry that consist of the MZ bounded by the HAZ, for butt fusion welded joints of HDPE pipes.

Adhesion, heterogeneous catalysis, electrochemistry, and many other important processes and properties are driven by interactions at surfaces and interfaces. Vibrational sum frequency generation spectroscopy (VSFG) is an increasingly popular analytical technique because it can provide information about the nature and physical orientation of functional groups at these surfaces and interfaces. Analysis of VSFG data can be complicated by the presence of SFG signal that is not associated with a resonant vibration. This nonresonant sum frequency generation (NR-SFG) signal can interfere with the resonant signal and influence the detected spectrum. Methods have been developed to remove NR-SFG signal; however, these methods tend to be complicated and expensive. In fact many SFG practitioners do not have the ability to remove NR-SFG signal components, and systems designed to remove NR-SFG signal contributions may not be able to do so for some materials. We have worked to help develop a better understanding of NR-SFG. As part of this work, a better understanding of the temporal and phase behavior of NR-SFG signal has been developed, based on the behavior of NR-SFG signal from Si(111) wafers. This work calls into question some assumptions underlying nonresonant suppression methods based on time-domain detection. A new method for nondestructively testing (NDT) materials has been developed that uses nonresonant second harmonic generation, the degenerate form of SFG. This new NDT technology has the potential to detect several forms of material damage, such as aluminum sensitization, and plastic deformation of materials, which are largely invisible to current NDT technologies. Methods for extracting functional group orientation from VSFG data that contains NR-SFG contributions are also demonstrated and used to investigate how the surface of high density polyethylene changes in response to mechanical deformation. This work shows that the inability to remove NR-SFG contributions from VSFG spectra does not mean that these instruments cannot be used to make important discoveries. It simply means that NR-SFG contributions must be properly understood and accounted for during experimental design, and kept in mind during the analysis of VSFG spectra.