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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.

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.

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.

Safripol is a South African polymer company producing mainly high density polyethylene and polypropylene for the South African market. Safripol used to be part of a global chemical company Dow Chemicals. Dow Chemical's divested in South Africa in 2006 and Safripol lost all the advantages of being part of a global corporate enterprise. The company is faced with a unique situation in that it is receiving monomer from Sasol, which is also its main competitor in the polymer market. The price of monomer and its low availability is putting pressure on Safripol's product margins, with a negative effect on the company's sustainability. The above was also defined as the research problem that threatens to undermine the company's competitive edge in the polymer market. It was clear from this research study that monomer and specifically propylene was the biggest burning point for Safripol regarding the price and availability thereof. Research into the South African polymer market has shown that Safripol will lose significant market share if the company is not showing additional growth in the market. The research problem is investigated through interviews, monomer availability investigations, plant capacity increasing and potential technology partner's discussions. A specific scenario planning process was also followed to help Safripol identify potential present and future scenarios that the company can investigate. The research problem was addressed by developing a strategy for Safripol to address the research objectives. Recommendations were done regarding the following: 1) Recommendations for additional propylene supply. 2) Recommendations to increase the polypropylene plant capacity. 3) Recommendations with regards to technology partners. 4) Recommendations regarding the scenario planning process. / Thesis (M.Ing. (Development and Management Engineering))--North-West University, Potchefstroom Campus, 2011. (Mag eers in 2014 gepubliseer word)

Safripol is a South African polymer company producing mainly high density polyethylene and polypropylene for the South African market. Safripol used to be part of a global chemical company Dow Chemicals. Dow Chemical's divested in South Africa in 2006 and Safripol lost all the advantages of being part of a global corporate enterprise. The company is faced with a unique situation in that it is receiving monomer from Sasol, which is also its main competitor in the polymer market. The price of monomer and its low availability is putting pressure on Safripol's product margins, with a negative effect on the company's sustainability. The above was also defined as the research problem that threatens to undermine the company's competitive edge in the polymer market. It was clear from this research study that monomer and specifically propylene was the biggest burning point for Safripol regarding the price and availability thereof. Research into the South African polymer market has shown that Safripol will lose significant market share if the company is not showing additional growth in the market. The research problem is investigated through interviews, monomer availability investigations, plant capacity increasing and potential technology partner's discussions. A specific scenario planning process was also followed to help Safripol identify potential present and future scenarios that the company can investigate. The research problem was addressed by developing a strategy for Safripol to address the research objectives. Recommendations were done regarding the following: 1) Recommendations for additional propylene supply. 2) Recommendations to increase the polypropylene plant capacity. 3) Recommendations with regards to technology partners. 4) Recommendations regarding the scenario planning process. / Thesis (M.Ing. (Development and Management Engineering))--North-West University, Potchefstroom Campus, 2011. (Mag eers in 2014 gepubliseer word)

Made available in DSpace on 2015-04-01T12:17:42Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 15897135 bytes, checksum: 47ccae1f15e072aad07f5eb733587b9f (MD5) Previous issue date: 2014-03-21 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This research have the aim of prepare mixture of high density polyethylene (HDPE) and chitosan (CS) with and without compatibilizers agents. To this, have developed in laboratory, powders by two different methods, precipitation and evaporation. It was used like compatibilizers agents on mixture HDPE/CS. They are chemically modified chitosan with the ammonium alkil organic salt codified as (CS+MA)evap, (CS+MA)prec and the chemically modified clay AN with the respectives samples codified as AN(CS+MA)evap e AN(CS+MA)prec. Next, the HDPE/CS mixture with different proportion 90/10, 80/20, 70/30 and 60/40 in weight fractions with and without compatibilizers, respectively was prepared by internal mixer torque rheometry Haake, operating at 170°C, 60 rpm for 10 min. Every samples was analysed morphologically, thermically and mechanically. Was observed in the differents compositions of MIXTURE that when we decrease the chitosan proportion of the mixture HDPE/CS we have a discrete increase on the crystallinity percentage and an increase on the thermal stability. The FTIR results pointing to absence on interation between both components of mistute HDPE/CS, indicating immiscibility of mixture the obtained analyses by MEV of the fracture surface of mixture 80/20 HDPE/CS for different compositions showing a weak interfacial adhesion. However, the addiction of compatibilizer agent, specially the chemically modified clay AN(CS+MA)prec resulted in greater tendency in the interaction between the components HDPE/CS as consequence of better dispersion of chitosan on HDPE. / A pesquisa teve como objetivo preparar misturas de polietileno de alta densidade (PEAD) e quitosana (CS) sem e com agentes compatibilizantes. Para tanto, foram desenvolvidos em nosso laboratório, pós por dois diferentes métodos, precipitação e evaporação, visando usá-los como agentes compatibilizantes nas misturas PEAD/CS, sendo eles: quitosana modificada quimicamente com o sal orgânico alquil amônio (MA) codificadas como (CS+MA)evap e (CS+MA)prec e a argila AN modificada quimicamente com as respectivas amostras, codificadas como AN(CS+MA)prec e AN(CS+MA)evap. Em seguida, as misturas de PEAD/CS com diferentes proporções 90/10, 80/20, 70/30 e 60/40 em frações mássicas, respectivamente, sem e com agentes compatibilizantes foram preparadas num misturador interno do reômetro de torque Haake, operando a 170°C, 60rpm por 10min. Todas as amostras foram analisadas morfologicamente e caracterizadas termicamente e mecanicamente. Observa-se nas diferentes composições das misturas que à medida que se diminui o teor de quitosana nas misturas PEAD/CS tem-se discreto aumento no grau de cristalinidade assim como aumento na estabilidade térmica das mesmas. Os resultados de FTIR apontam ausência de interação entre ambos os componentes da mistura PEAD/CS, indicando imiscibilidade das mesmas. As análises obtidas por microscopia eletrônica de varredura das superfícies de fratura das misturas 80/20 PEAD/CS para diferentes composições mostraram fraca adesão interfacial. Entretanto, a adição de agentes compatibilizantes, especialmente, a argila modificada quimicamente AN(CS+MA)prec resultou numa maior tendência a interação entre os componentes PEAD/CS como consequência de uma melhor dispersão da quitosana no PEAD.

Submitted in fulfilment of the Degree of Master of Engineering in Chemical Engineering, Durban University of Technology, Durban, South Africa, 2017. / A pertinent issue facing the materials industry is that of the lifespan of materials when exposed to certain solvents/ environments. Limitations to the applications of materials require further research into understanding their failure mechanisms and how such problems can be addressed in terms of re-engineering such materials to be more durable. PVC and HDPE are two common polymers used extensively in industrial applications. Gibbs ensemble Monte Carlo simulations were used to simulate systems of PVC and HDPE with methanol, respectively. The temperatures used in this work were 25, 30 and 40 oC and all systems were at atmospheric pressure. Laboratory tests were used to complement simulations for analysis purposes. Results showed an increase in temperature resulted in a decrease in the overall clustering in both polymers although PVC displayed a greater decrease than HDPE. Linear clustering dominated over other forms of clustering with increases in temperature, with dimers being the most prevalent topology type. The results of this study suggest that the presence of chlorine atoms in PVC may not directly affect clustering of absorbed methanol, and their effect may instead be indirect by means of altering the accessible free volume within the polymer. Swelling was also investigated in the simulated systems and it was found that PVC displayed a greater degree of swelling than HDPE despite its lower rate of clustering. The effect of cluster radius on the cluster analysis was also considered. / M