Defects in polyethylene film are often caused by contaminant particles in the polymer melt. In this research, particle properties obtainable from in-line melt monitoring, combined with processing information, are used to predict film defect properties. “Model” particles (solid and hollow glass microspheres, aluminum powder, ceramic microspheres, glass fibers, wood particles, and cross-linked polyethylene) were injected into low-density polyethylene extruder feed. Defects resulted when the polyethylene containing particles was extruded through a film die and stretched by a take-up roller as it cooled to form films 57 to 241mm in thickness. Two off-line analysis methods were further developed and applied to the defects: polarized light imaging and interferometric imaging. Polarized light showed residual stresses in the film caused by the particle as well as properties of the embedded particle. Interferometry enabled measures of the film distortion, notably defect volume. From the images, only three attributes were required for mathematical modeling: particle area, defect area, and defect volume. These attributes yielded two ”primary defect properties”: average defect height and magnification (of particle area). For all spherical particles, empirical correlations of these properties were obtained for each of the two major types of defects that emerged: high average height and low average height defects. Analysis of data for non-spherical particles was limited to showing how, in some cases, their data differed from the spherical particle correlations. To help explain empirical correlations of the primary defect properties with film thickness, a simple model was proposed and found to be supported by the high average height defect data: the “constant defect volume per unit particle area” model. It assumes that the product of average defect height and magnification is a constant for all film thicknesses. A numerical example illustrates how the methodology developed in this work can be used as a starting point for predicting film defect properties in industrial systems. A limitation is that each prediction yields two pairs of primary defect property values, one pair for each defect type. If it is necessary to identify the dominant type, then measurement of a length dimension of sufficient defects in the film is required.

Defects in polyethylene film are often caused by contaminant particles in the polymer melt. In this research, particle properties obtainable from in-line melt monitoring, combined with processing information, are used to predict film defect properties. “Model” particles (solid and hollow glass microspheres, aluminum powder, ceramic microspheres, glass fibers, wood particles, and cross-linked polyethylene) were injected into low-density polyethylene extruder feed. Defects resulted when the polyethylene containing particles was extruded through a film die and stretched by a take-up roller as it cooled to form films 57 to 241mm in thickness. Two off-line analysis methods were further developed and applied to the defects: polarized light imaging and interferometric imaging. Polarized light showed residual stresses in the film caused by the particle as well as properties of the embedded particle. Interferometry enabled measures of the film distortion, notably defect volume. From the images, only three attributes were required for mathematical modeling: particle area, defect area, and defect volume. These attributes yielded two ”primary defect properties”: average defect height and magnification (of particle area). For all spherical particles, empirical correlations of these properties were obtained for each of the two major types of defects that emerged: high average height and low average height defects. Analysis of data for non-spherical particles was limited to showing how, in some cases, their data differed from the spherical particle correlations. To help explain empirical correlations of the primary defect properties with film thickness, a simple model was proposed and found to be supported by the high average height defect data: the “constant defect volume per unit particle area” model. It assumes that the product of average defect height and magnification is a constant for all film thicknesses. A numerical example illustrates how the methodology developed in this work can be used as a starting point for predicting film defect properties in industrial systems. A limitation is that each prediction yields two pairs of primary defect property values, one pair for each defect type. If it is necessary to identify the dominant type, then measurement of a length dimension of sufficient defects in the film is required.

With this research, we work towards the overall objective of customizing polymer molecules in terms of their molecular structure to optimize processing performance. The work includes analysis of the rheology in shear and shear-free flows for sparsely long-chain branched, LCB, polyethylene, PE, resins; determination of the consistency of the molecular based constitutive model, the pom-pom model; for these flows, and evaluation of the same PE resins in film-casting. As we progress towards molecular systems with defined molecular structural characteristics, we transition from a linear low density polyethylene, LLDPE, based series of PE resins to a high density polyethylene, HDPE, based series of PE resins, each with materials of varying degrees of sparse LCB. Evaluation of the shear step-strain rheology for the series of LLDPE-based PE resins allows for the assessment of any inadequacies associated with the step-strain experiments and the ability of the K-BKZ analog of the pom-pom constitutive model to predict step-strain rheological behavior. Finite rise time and wall slip are addressed to ensure the accuracy of the experimental step-strain measurements and eliminated as factors contributing to the stress relaxation moduli response. Analysis of the K-BKZ analog of the pom-pom constitutive model includes comparisons between experimental stress relaxation moduli and predictions from the model using pom-pom model parameters determined from extensional rheology. The results show inconsistencies in the model predictions, where the predictions fail to capture the short time behavior and accurately dampen at larger strains. Pom-pom model parameters are determined using the K-BKZ analog of the pom-pom constitutive model and fitting the stress relaxation moduli. These results are qualitatively consistent indicating that branching occurs on the longest backbone segments, but the values appear to be unrealistic with respect to the molecular theory. Analysis of film-width reduction or necking during film-casting for the series of LLDPE-based resins determines whether uniaxial extensional rheological characteristics, in particular strain-hardening, that are a result of LCB influence the film-necking properties. At the lowest drawdown ratio necking is observed to be reduced with increasing LCB, and thus strain-hardening characteristics. At the higher drawdown ratios it is observed that LCB no longer reduces necking and the curves merge to the results found for linear PE, except in the case of LDPE, which shows reduced necking at all drawdown ratios. Furthermore, comparisons of film necking are also made to separate the effects of molecular weight distribution, MWD, and LCB. The results indicate that both broadening the MWD and the addition of sparse LCB reduce the degree of necking observed. It is established that film necking is more significantly reduced by LCB than by broadening the MWD. Analysis of the uniaxial extensional and dynamic shear rheology with the pom-pom constitutive model reveals that a distribution of branches along shorter relaxation time modes is important in reducing necking at higher drawdown ratios. Factors such as shear viscosity effects, extrudate swell, and non-isothermal behavior were eliminated as contributing factors because of the similar shear viscosity curves, N1 curves, and activation energies among the sparsely LCB PE resins. The same experimental concepts have been extended to the series of HDPE-based resins, but the lack of adequate uniaxial extensional data prevents a thorough analysis with respect to uniaxial extensional characteristics. Regardless, in the context of step-strain rheology, the results were found to be similar with those of the LLDPE-based series of resins, where a distinctive shape at short times was observed for any of the PE resins possessing some level of LCB that was not apparent in the linear PE resins. Film-casting revealed similar results to those of the LLDPE-based materials as well, but a broader spectrum of drawdown ratios revealed greater insight into how the distribution of branching controls the film-casting response. At low drawdown ratios all materials exhibit the same necking behavior. At intermediate drawdown ratios separation occurs where the linear PE resins experiences the most drastic necking, the sparsely LCB PE resins show reduced necking, and the LDPE shows an even greater reduction in necking. Progression then to the higher drawdown ratios results in similar necking behavior for the linear and sparsely LCB PE resins and greatly reduced necking for the LDPE. These results support the idea that to reduce necking the backbone segments that dominate the film-casting behavior must contain some level of LCB. / Ph. D.

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.

No description available.

No description available.

Bioplastic research has become more diverse and different types of research on bioplastic production have been conducted from fruits and vegetable waste, for example, orange waste. The wastes that come from oranges contain more than just vitamins, it has soluble sugars, starch, hemicellulose, cellulose, and pectin. The intention of this project was to study the possibility to produce bio-composite films from orange waste, after removing the soluble sugars. It was also to analyze the properties of the material by tensile strength, visual observation, and to find a methodology that suits this study. An ultrafine grinder was used to mechanically separate the cellulose fibres, with the intention to compare the fibrillation cycles on the properties of the bio-composite films. A total of 30fibrillation cycle was performed. In addition, different film casting strategies were performed and evaluated. The primary plan was to produce a biofilm without the use of chemicals. After the observing the results three new routes for the methodology was developed where the usage of chemicals was be included. The citric acid was used as a solvent for pectin and glycerol was used as a plasticizer. In the first method, different concentration of citric acid and glycerol were added and observed. The combination which gave uniformed films that contained 0.3 g of citric and 0.375 g of glycerol for a 75 ml hydrogel. The second method was to infuse citric acid before grinding the orange waste suspension. Lastly, the third method was to bleach the orange waste before grinding. The films that were produced gave interesting results and from the tensile testing implied that an impact was made on the strength by every fibrillation. The amount of glycerol was consistent throughout the project, but by adding different amount of citric acid gave the films differentIIproperties. The same happened when changing the mould of the film. The best values of the films were from the 30th fibrillation, gave the mean value of 31.6 MPa in tensile strength, and had a strain in elongation at 6.1 %. The tensile strength and elongation had increased drastically compared the fifth fibrillation which had 9.8 MPa and 7.6%.