This dissertation works towards the larger objective of identifying and assessing the key features of molecular structure that lead to desired polymer processing performance with an ultimate goal of being able to tailor-make specific macromolecules that yield the desired processing response. A series of eight well-characterized, high-density polyethylene (HDPE) resins, with varying degrees of sparse long chain branching (LCB) content, is used to study the effect of both LCB content and distribution on the rheological and commercial processing response using the Pom-pom constitutive relationship. A flow instability known as ductile failure in extensional flow required the development a novel technique known as encapsulation in order to carry out shear-free rheological characterization. Ductile failure prevents the rheological measurement of transient stress growth at higher strains for certain strain-hardening materials. This reduces the accuracy of nonlinear parameters for constitutive equations fit from transient stress growth data, as well as their effectiveness in modeling extensionally driven processes such as film casting. An experimental technique to overcome ductile failure called encapsulation in which the material that undergoes ductile failure is surrounded by a resin that readily deforms homogeneously at higher strains is introduced. A simple parallel model is shown to calculate the viscosity of the core material. The effect of sparse long chain branching, LCB, on the film-casting process is analyzed at various drawdown ratios. A full rheological characterization in both shear and shear-free flows is also presented. At low drawdown ratios, the low-density polyethylenes, LDPE, exhibited the least degree of necking at distances less than the HDPE frostline. The sparsely-branched HDPE resins films had similar final film-widths that were larger than those of the linear HDPE. As the drawdown ratio was increased, film width profiles separated based on branching level. Small amounts of LCB were found to reduce the amount of necking at intermediate drawdown ratios. At higher drawdown ratios, the sparsely-branched HDPE resins of lower LCB had content film-widths that mimicked that of the linear HDPE, while the sparsely-branched HDPE resins of higher LCB content retained a larger film width. Molecular structural analysis via the Pom-pom constitutive model suggested that branching that was distributed across a larger range of backbone lengths serve to improve resistance to necking. As the drawdown ratio increased, the length of the backbones dominating the response decreased, so that the linear chains were controlling the necking behavior of the sparsely-branched resins of lower LCB content while remaining in branched regime for higher LCB content HDPEs. Other processing variables such as shear viscosity magnitude, extrudate swell, and non-isothermal processing conditions were eliminated as contributing factors to the differences in the film width profile. The effect of sparse long chain branching, LCB, on the shear step-strain relaxation modulus is analyzed using a series of eight well-characterized, high-density polyethylene (HDPE) resins. The motivation for this work is in assessing the ability of step-strain flows to provide specific information about a material's branching architecture. Fundamental to this goal is proving the validity of relaxation moduli data at times shorter than the onset of time-strain separability. Strains of 1% to 1250% are imposed on materials with LCB content ranging from zero to 3.33 LCB per 10,000 carbon atoms. All materials are observed to obey time-strain separation beyond some characteristic time, Ï k. The presence of LCB is observed to increase the value of Ï k relative to the linear resin. Furthermore, the amount of LCB content is seen to correlate positively with increasing Ï k. The behavior of the relaxation modulus at times shorter than Ï k is investigated by an analysis of the enhancement seen in the linear relaxation modulus, G0(t), as a function of strain and LCB content. This enhancement is seen to 1) increase with increasing strain in all resins, 2) be significantly larger in the sparsely-branched HDPE resins relative to the linear HDPE resin, and 3) increase in magnitude with increasing LCB content. The shape and smoothness of the damping function is investigated to rule out the presence of wall-slip and material rupture during testing. The finite rise time to impose the desired strain is carefully monitored and compared to the Rouse relaxation time of the linear HDPE resins studied. Sparse LCB is found to increase the magnitude of the relaxation modulus at short times relative to the linear resin. It is shown that these differences are due to variations in the material architecture, specifically LCB content, and not because of mechanical anomalies. / Ph. D.

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 boundary layer effect on viscosity and injection molding studies in radial and unidirectional flows were investigated for liquid crystalline (ethylene terephthalate) using Instron model 3211 capillary rheometer. Two copolyesters of PET modified with 60 and 80 mole percent parahydroxy benzoate were examined. Melt viscosities were measured as a function of temperature and wall shear rates. Mold filling characteristics were investigated by introducing different fluid pigments into the melt before injection. Molecular orientation of the molded parts was studied by measuring the shrinkage of the microtomed samples at various temperatures, injection speeds, and cavity thicknesses for these two molds. For PET/60 mole % PHB, the viscosity was found to be some function of the capillary diameter, showing a marked decrease with decreasing capillary diameter at 275 C; this possible phenomenon is not found in most polymer melts. During mold filling stage, fluid pigments indicated that these liquid crystalline melts flow and split in the core before they approach the flow front. Molecular orientation studies showed that high shrinkage across the flow direction than that measured along the flow direction. Studies also indicated that there existed a relative maximum molecular orientation away from the surface of the parts, corresponding to the shear zone. As the cavity thickness decreases or injection speed increases, this relative maximum peak moves to the surface of the molded parts. / Master of Science

Mine influenced waters (MIW) pose a broad range of potential environmental impacts, which often also carry financial and social consequences. MIWs are often high in solids content, and can have highly acidic or alkaline pH and high contents of metals or other problematic constituents (e.g., traces of chemicals used in minerals processing or water treatment). Acid mine drainage (AMD) is a common type of MIW characterized by low pH. Release of untreated MIWs like AMD to surface waters, for example, can lead to problems such as a sedimentation and siltation, undesirable changes in pH and/or precipitation of metals and salts, and addition of particular stressors for various aquatic organisms. As such, these waters are frequently captured and treated on-site in systems requiring extensive piping. Polyethylene (PE) pipes are popular in mining, including MIW, applications because they are chemically inert, and have relatively low costs, low density, and high flexibility. However, PE material is susceptible to abrasion. To combat this problem and offer a single pipe option for a variety of mining applications, Gerodur MPM Kunststoffverarbeitung GmbH and Co. KG.(Gerodur) has developed a novel liner for PE pipes. The liner is made of a rubber-like material that is resistant to mechanical abrasion by slurries or high-solids waters, but its susceptibility to mineral scale buildup has not been specifically evaluated. In order to evaluate scale buildup on the lined PE versus traditional PE pipe material, two studies were undertaken and are reported in this thesis. A short-term field study was conducted in the Reiche Zeche underground mine in Freiberg, Germany – an inactive lead-zinc mine. Water quality varies considerably between different zones in this mine, but is characterized by very high dissolved solids, which is typical for AMD. For this study, the pipe materials were exposed to waters in six locations for three weeks; and were then analyzed for weight gain and scale composition. Results showed that there was only a marginal difference in the scale build up when comparing the two piping materials. In a follow-up study in the laboratory, the two pipe materials were exposed over a total of 16 weeks to three idealized AMD water qualities: an untreated AMD made to simulate the most extreme condition observed in the field study, the same AMD following passive treatment (i.e., neutral pH), and the same AMD following active treatment (i.e., slightly basic pH). Exposure was done in pipe-loop apparatuses such that samples could be subjected to different flow and sedimentation conditions (i.e., gentle mixing only on the sides of the water reservoir, gentle mixing and sedimentation on the bottom of the reservoir, and constant flow and possible sedimentation within the pipe-loop tubing itself). Results of this study indicated that factors such as water chemistry and flow velocity had significant effect on the quantity and chemistry of scale. However, there was very little difference in propensity for scale build up between the two materials. This liner was designed in an effort to resist mechanical abrasion. Because scale build up is not exacerbated by the liner, it may provide a means for uniform applications across mines with contiguous abrasive and scale prone waters. That is, it could eliminate the need to have various specialized piping materials on a site to handle these problems individually, streamlining the pumping and piping network installation and operation. / Master of Science

Polyethylene pipes and epoxy or polyurethane linings are increasingly used in drinking water infrastructure. As a recent introduction to the water industry, there are still many unknowns about how polymers will behave in the distribution system specifically relating to sorption and desorption of chemical contaminants. This study is in response to a spill of 4-methylcyclohexane methanol (MCHM) that occurred in January 2014 contaminating the drinking water of nine counties in West Virginia. This study investigated sorption and desorption of the odorous chemical MCHM into polymer drinking water infrastructure and granular activated carbon (GAC). Experiments for sorption of non-polar toluene and polar 1-butanol were conducted as a comparison for MCHM sorption. Additionally, a brief odor analysis was done on the ability of activated carbon to remove odor from contaminated water and on leaching of MCHM from pipe material into clean water. The results show that MCHM diffusion and solubility in polyethylene pipe materials is low. Solubility in polyethylene ranged from 0.003-0.008 g/cm3 and was more similar to the polar contaminant n-butanol than the non-polar contaminant toluene. Desorption experiments indicated that MCHM sorbed to polyethylene diffused back into water at levels that produced odor. MCHM diffused very quickly into epoxy; its solubility was similar to polyethylene pipe. MCHM caused the polyurethane lining to swell and deform. Granular activated carbon effectively sorbed MCHM to below its odor threshold. The sorption properties of MCHM indicate the potential for contamination of infrastructure and the desorption indicates subsequent recontamination of drinking water. / Master of Science

Results of an experimental test program are presented to determine the bursting strength of polyethylene terephthalate film and fabric cylinders containing axial silts of various lengths. The results demonstrate that the fabric material is superior to the film material as regards residual strength in the presence of a slit. It is shown that the strength-weight ratio of the fabric cylinders is approximately twice that of the film cylinders, largely due to the strength advantage of fiber over film. The results are compared with the predicted bursting strength obtained from two different semiempirical analyses, one based on notch strength analysis and the other employing fracture mechanics concepts. The comparison demonstrates that large errors can result from the application of the notch-strength analysis yields a scatter band which is consistent with the data scatter and follows the trend of the data. / Master of Science

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.

Yes / Many drug molecules can be directly used as nanomedicine without the requirement of any inorganic or organic carriers such as silica and liposome nanostructures. This new type of carrier-free drug nanoparticles (NPs) has great potential in clinical treatment because of its ultra-high drug loading capacity and biodegradability. For practical applications, it is essential for such nanomedicine to possess robust stability and minimal premature release of therapeutic molecules during circulation in the blood stream. To meet this requirement, herein, we develop GSH-responsive and crosslinkable amphiphilic polyethylene glycol (PEG) molecules to modify carrier-free drug NPs. These PEG molecules can be cross-linked on the surface of the NPs to endow them with greater stability and the cross-link is sensitive to intracellular environment for bio-responsive drug release. With this elegant design, our experimental results show that the liberation of DOX from DOX-cross-linked PEG NPs is dramatically slower than that from DOX-non-cross-linked PEG NPs, and the DOX release profile can be controlled by tuning the concentration of the reducing agent to break the cross-link between PEG molecules. More importantly, in vivo studies reveal that the DOX-cross-linked PEG NPs exhibit favorable blood circulation half-life (>4 h) and intense accumulation in tumor areas, enabling effective anti-cancer therapy. We expect this work will provide a powerful strategy for stabilizing carrier-free nanomedicines and pave the way to their successful clinical applications in the future. / The National Basic Research Program of China (2013CB933500, 2012CB932400), National Natural Science Foundation of China (61422403), Natural Science Foundation of Jiangsu Province (BK20131162), QingLan Project, Collaborative Innovation Center of Suzhou Nano Science and a Project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

O trabalho propõe procedimentos para a avaliação da degradação mecânica de reservatórios de polietileno para água potável expostos às intempéries nas edificações brasileiras. Tais procedimentos envolvem a comparação das propriedades mecânicas antes e após a exposição acelerada de corpos de prova retirados de reservatórios de polietileno em equipamento Weather-OMeter (WOM). Demonstra-se que esses procedimentos reproduzem a degradação provocada pela natureza, por comparação dos resultados obtidos na exposição acelerada até 10 800 horas em WOM com três anos de exposição natural em Piracicaba (SP). / O trabalho propõe procedimentos para a avaliação da degradação mecânica de reservatórios de polietileno para água potável expostos às intempéries nas edificações brasileiras. Tais procedimentos envolvem a comparação das propriedades mecânicas antes e após a exposição acelerada de corpos de prova retirados de reservatórios de polietileno em equipamento Weather-OMeter (WOM). Demonstra-se que esses procedimentos reproduzem a degradação provocada pela natureza, por comparação dos resultados obtidos na exposição acelerada até 10 800 horas em WOM com três anos de exposição natural em Piracicaba (SP).

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.