Horizontal directional drilling is increasingly used to install pipes without costs and disruptions associated with conventional ‘cut and cover’ installations. This technique, which was developed by industrial innovators, feature complex soil and pipe response which is not well understood. The success of this operation depends on knowledge of the pulling forces applied, level of ground disturbance, ground expansion or fracture from mud pressure, and the effect of the pulling operation on the pipes. Tensile stresses in the pipe vary with time during and after installation, and along the pipe. This applies especially to polymer pipes where the stresses during insertion and those over the service life of the pipe may influence its performance. The main objective of this study is to model the short term and long term response of pipes installed using horizontal directional drilling and to investigate the effect of the time dependent behaviour of polymer pipes, as well as other installation variables on the performance of the pipe during and after installation. The mechanical behaviour of high density polyethylene used to manufacture a significant portion of pipes installed using horizontal directional drilling is investigated and two sophisticated constitutive models are developed to simulate the time-dependent behaviour of high density polyethylene. The interaction between the pipe and the surrounding soil during horizontal directional drilling installations is also investigated and modelled. A FORTRAN algorithm is developed to calculate the short and long term response of elastic and polymeric pipes installed using horizontal directional drilling. The program uses the HDPE constitutive models as well as the pipe-soil interaction model developed in the study. After evaluation, the developed program is employed in a parametric study on the sensitivity of short term and long term pipe response to different parameters, including the effect of overstressing the pipe during installation. As Multiaxial modeling is necessary for accurate analysis of some applications including the swagelining method, a uniaxial constitutive model developed in the current study is generalized to a multi-axial model that can simulate the response to biaxial stress-strain fields. The multi-axial model is implemented in a finite element code and its performance in simulating multiaxial stress-strain fields is evaluated. / Thesis (Ph.D, Civil Engineering) -- Queen's University, 2008-06-12 18:03:43.501

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

Polymeric materials are widely used in diverse applications. However, a major weakness in the majority of the thermoplastic polymers is their lack of ability to resist fire. Most of the chemicals and additives currently used to improve fire retardancy have deleterious effects on the environment. This research focuses on developing an environmentally safe and effective fire-retardant system for high density polyethylene (HDPE), using cellulose nanocrystals (CNCs) and zinc oxide (ZnO). The effect of CNCs coated with nano ZnO has been investigated for improving the fire resistance properties of the HDPE. Improved dispersion of CNCs into HDPE matrix was achieved by employing maleic anhydride as a coupling agent. It was found that addition of CNCs-ZnO can introduce a reasonable level of flame retardancy in HDPE matrix in addition to improving the maximum tensile strength and elongation at break.

Oxidative processes are linked to a number of major disease states as well as the breakdown of many materials. Of particular importance are reactive oxygen species (ROS), as they are known to be endogenously produced in biological systems as well as exogenously produced through a variety of different means. In hopes of better understanding what controls the behavior of ROS, researchers have studied radical chemistry on a fundamental level. Fundamental knowledge of what contributes to oxidative processes can be extrapolated to more complex biological or macromolecular systems. Fundamental concepts and applied data (i.e. interaction of ROS with polymers, biomolecules, etc.) are critical to understanding the reactivity of ROS. A detailed review of the literature, focusing primarily on the hydroxyl radical (HO•) and hydrogen atom (H•) abstraction reactions, is presented in Chapter 1. Also reviewed herein is the literature concerning high density polyethylene (HDPE) degradation. Exposure to treated water systems is known to greatly reduce the lifetime of HDPE pipe. While there is no consensus on what leads to HDPE breakdown, evidence suggests oxidative processes are at play. The research which follows in Chapter 2 focuses on the reactivity of the hydroxyl radical and how it is controlled by its environment. The HO• has been thought to react instantaneously, approaching the diffusion controlled rate and showing little to no selectivity. Both experimental and calculational evidence suggest that some of the previous assumptions regarding hydroxyl radical reactivity are wrong and that it is decidedly less reactive in an aprotic polar solvent than in aqueous solution. These findings are explained on the basis of a polarized transition state that can be stabilized via the hydrogen bonding afforded by water. Experimental and calculational evidence also suggest that the degree of polarization in the transition state will determine the magnitude of this solvent effect. Chapter 3 discusses the results of HDPE degradation studies. While HDPE is an extremely stable polymer, exposure to chlorinated aqueous conditions severely reduces the lifetime of HDPE pipes. While much research exists detailing the mechanical breakdown and failure of these pipes under said conditions, a gap still exists in defining the species responsible or mechanism for this degradation. Experimental evidence put forth in this dissertation suggests that this is due to an auto-oxidative process initiated by free radicals in the chlorinated aqueous solution and propagated through singlet oxygen from the environment. A mechanism for HDPE degradation is proposed and discussed. Additionally two small molecules, 2,3-dichloro-2-methylbutane and 3-chloro-1,1-di-methylpropanol, have been suggested as HDPE byproducts. While the mechanism of formation for these products is still elusive, evidence concerning their identification and production in HDPE and PE oligomers is discussed. Finally, Chapter 4 deals with concluding remarks of the aforementioned work. Future work needed to enhance and further the results published herein is also addressed. / Ph. D.

No

The primary reason for incorporating pigments into plastic materials is to impart the desired colour to finished articles. Some pigments however, may interact with the polymer leading to unexpected deleterious effects. Organic pigments, especially phthalocyanines, are favourable for their brilliant shade but are also well known for causing part distortion or warpage. This causes problems in parts which require good dimensional stability such as crates, containers, trays, caps and closures. Despite that, there are not many published studies on the root cause and mechanism of warpage induced by the pigment. Hence, the objective of this research is to study the influence of such pigments on the dimensional stability, crystallisation behaviour and morphology of polyethylenes in order to have a better understanding on the mechanism of warpage, which could possibly lead to a solution in overcoming this problem.

SOLUTION AND MELT BEHAVIOUR OF HIGH-DENSITY POLYETHYLENE - Successive Solution Fractionation mechanism - Influence of the molecular structure on the flow In the field of polyethylene characterization, one of the most challenging research topic is certainly an accurate molecular structure determination of industrial products, in terms of molar mass distribution (MMD), corresponding average-molar masses and molecular architecture (branching nature, content and heterogeneity). Solution to this long-term problem necessarily calls for a multi-disciplinary approach. Therefore, respective advantages of molecular structure characterization in solution and in the melt are exploited. In solution, chromatographic and spectroscopic methods allow determination of MMD, average branching content and intermolecular heterogeneity within their detection limits. Rheological testing in the melt could be a very powerful molecular structure investigation tool, due to its extreme sensitivity to high molar mass (MM) tailing or long chain branching (LCB) traces. But when the rheological tests results are in hand, we often still wonder what kind of molecular structure gives rise to such results. Indeed, melt signal depends on MM, MMD and LCB presence. MMD determination and LCB quantification by melt approach is impossible as long as respective effects of these molecular parameters are not clearly quantified. The general purpose of the present work is to contribute to a better molecular structure characterization of high-density polyethylene by developing, in a first time, a preparative fractionation method able to provide narrow-disperse linear and long chain branched samples, essential to separate concomitant effects of MM, MMD and LCB on rheological behaviour. Once such model fractions isolated, influence of MM and LCB on both shear and elongational flow behaviours in the melt is studied. /Dans le domaine du polyéthylène, un des sujets de recherche les plus investigués à l'heure actuelle est la détermination précise de la structure moléculaire de résines industrielles, en termes de distribution des masses molaires (MMD), de masses molaires moyennes correspondantes et d'architecture moléculaire (nature, teneur et hétérogénéité). La résolution de cette problématique nécessite une approche multi-disciplinaire, afin d' exploiter simultanément les avantages d'une caractérisation en solution et à l'état fondu. En solution, certaines méthodes chromatographiques et spectroscopiques permettent de déterminer une MMD, une teneur moyenne en branchement et leur distribution, dans leurs limites de détection. La mesure du comportement rhéologique à l'état fondu pourrait s'avérer un formidable outil de caractérisation de la structure moléculaire en raison de son extrême sensibilité à certains détails moléculaires, tels que la présence de traces de LCB ou de très hautes masses molaires (MM). Malheureusement, le signal rhéologique dépend de manière conjointe de la MM, MMD et de la présence ou non de LCB, de telle sorte que la détermination d'une MMD ou d'une teneur en LCB par cette voie est impossible aussi longtemps que les effets respectifs de ces paramètres moléculaires sur le comportement rhéologique n'ont pas été clairement et distinctement établis. L'objectif global de cette thèse est de contribuer à une meilleure caractérisation de la structure moléculaire du polyéthylène haute densité en développant, dans un premier temps, une méthode préparative de fractionnement capable de produire des échantillons, linéaires ou branchés, à MMD la plus étroite possible, indispensables en vue de séparer les effets concomitants de la MM, MMD et LCB sur le comportement rhéologique à l'état fondu. Une fois de tels objets modèles isolés, l'influence de la MM et du LCB sur le comportement rhéologique, en cisaillement et en élongation, sera étudié.