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Self-Consolidating concrete (SCC), a highly flowable concrete, is gaining wide acceptance in the concrete industries due to a higher productivity, lower energy consumption, improved working environment and increase quality. SCC is susceptible to segregation and therefore a balance between flow-ability and stability is required. The absence of a comprehensive SCC mixture composition design guidelines merits investigating the effects of SCC mixture variables on the properties affecting its performance, namely flow and stability. An experimental and analytical study were carried out to study the influence of 5 design variables, namely water to binder ratio (w/b), percent addition of silica fume (SF), percent addition of Ground Granulated Blast Furnace Slag (GGBFS), bulk volume of coarse aggregates and binder content, on the workability and rheology of SCC. Workability measurements, specifically the slump flow, T50, L-Box and segregation column, and rheological properties, namely plastic viscosity, yield stress, and thixotropy were measured to evaluate SCC’s performance. A revised modified Bingham model was proposed to adequately account for the linear and non-linear responses of the concrete flow. It postulates that the flow is divided into a linear and non-linear part. The revised model is found to provide more consistent and precise estimate of the rheological properties. Using regression analyses, yield stress and plastic viscosity models that account for the statistically significant variables were derived from experimental test data. Yield stress is found to depend on the bulk volume fraction of the coarse aggregate, Silica Fume content, High Range Water Reducing Agent (HRWRA) and Viscosity Modifying Agent (VMA), and plastic viscosity on w/b, HRWRA and Average Paste Thickness (APT). / Thesis / Master of Applied Science (MASc)

A small scale, highly accurate elongational viscometer was developed explicitly for the rheological investigation of well characterized polyethylene samples. Elongational stress growth measurements as well as dynamic shear experiments demonstrated that the rheological response of molten polyethylene was sensitive to both molecular weight distribution and shear modification. The effects of molecular weight distribution and shear modification were rationalized from a molecular point of view. A model is proposed which is based on the concept of a molecular network and incorporates polymer chain entanglement disruption and regeneration. Direct observations of polymeric semicrystalline morphologies in a copolyester by scanning electron microscopy were made possible by the development of a novel chemical etch. Spherulitic textures were consistent with classic spherulite growth mechanisms and structure theories. Uniaxial deformation of a single spherulite was successfully studied in a model system consisting of isolated spherulites embedded in an amorphous polymer matrix. By isolating the spherulite, the mechanical influence of surrounding and often impinging spherulites found in most semicrystalline polymers on the mechanical response of an individual spherulite was avoided. The mechanical response of the amorphous matrix was characterized and found to correlate with the effectiveness of a cold draw neck in elongating an embedded spherulite. The observed mechanism and morphology of isolated spherulite deformation were rationalized within the context of existing theories of spherulite-to-microfibrillar transitions. Optically active poly(L-lactic acid) and racemic poly(lactic acid) were synthesized in a ring opening polymerization scheme with stannous octoate as a catalyst and lactic acid as a molecular weight controlling initiator. Binary polymer blends composed of these isomeric polymer pairs were found to be miscible at 40,000 molecular weight and immiscible at 120,000 molecular weight. Strain hardening and the level of strain induced crystallization which occurred in the biaxial deformation of poly(lactic acid) blend films were found to be contingent on the concentration of optically active poly(L-lactic acid). Temperature, molecular weight, and biaxial strain rate were also found to have an influence on strain hardening and strain induced crystallization of these thermodynamically ideal polymer blends. / Ph. D.

Nine 1B/1R translocated soft red winter wheat (SRWW) varieties and six non-1B/1R varieties from two crop years (1995-1996 and 1996-1997), grown in two Virginia locations (Warsaw and Blacksburg), were studied to evaluate the effects of the 1R rye chromosome on soft wheat flour quality and baking performance. The presence of the 1B/1R chromosomal translocation in wheat has been reported to provide disease resistance, but produce sticky doughs. The 1995-1996 and 1996-1997 SRWW flours were subjected to farinograph analysis and dough stickiness testing. Dough stickiness was determined by the Schwarzlaff-Shepherd Dough Stripping Method. Wheat samples from 1995-1996 were also analyzed for protein, ash, and moisture content, alkaline water retention capacity (AWRC), cookie diameter, tensile stress and strain, and by ¹³C nuclear magnetic resonance (¹³C-NMR) spectroscopy techniques. Significant (p = 0.0001) negative correlations were found between AWRC and cookie diameter of SRWWs grown in Warsaw and Blacksburg. Location was found to exert a significant effect on AWRC, cookie diameter and stickiness (p < 0.05). Farinograph data revealed that mixing characteristics of SRWW were affected significantly by variety, crop year and location (p < 0.05). In some cases the 1B/1R varieties had lower breakdown rates, longer departure times (DT) and lower mixing tolerance index (MTI), than their non-1B/1R counterparts. There was a significant difference (p = 0.0133) in the stickiness of 1B/1R and non-1B/1R samples from Blacksburg. However no such difference was found in the corresponding Warsaw samples (p = 0.9826), indicating that location exerted a significant effect on stickiness. Two flour samples exhibiting stickiness (one with and one without 1B/1R) and two non-sticky samples (one with and one without the 1B/1R) were fractionated into gluten, starch and water-solubles (WS) in order to determine if the sticky dough factor resided in the 1B/1R and / or non-1B/1R WS. The peel time of the interchanged samples, as in the case of 'Massey' flour combined with the WS from VA52-22, increased to 79 seconds from the 30 seconds originally observed in the Massey flour. However when gluten and starch fractions from a non-sticky, non-1B/1R sample,VA54-21, were mixed with WS from VA54-211 (sticky, 1B/1R), the peel time went from 18 in the original flour to 8 seconds. Tensile measurements showed dough stress was not significantly affected by the presence or absence of 1B/1R (p = 0.7057). However, dough strain was lower in 1B/1R translocated SRWWs (p = 0.0048). A ¹³C-NMR spectra failed to show differences amongst selected 1B/1R and non-1B/1R dough samples. Proton relaxation time (T1-rho-[H]) - a ¹³C-NMR technique, indicated that water did not exert a significant influence on the molecular dynamics within the dough samples of Massey (non-1B/1R), VA54-211 (1B/1R) and VA52-22 (1B/1R). However, the non-sticky, non-1B/1R sample (VA54-21) had a higher proton relaxation time at 62 ppm which may indicate the size of starch-protein particles in VA54-21 doughs were larger and less flexible than in the other three doughs. / Ph. D.

Northeast Japan experienced an approximately constant, compressional deformation during the last 5 million years resulting from the steady subduction of the Pacific plate. Because the direction of the maximum compression axis is approximately perpendicular to the strike of the island arc, 2-D finite-element modeling can be used to examine the deformation over time of the island-arc lithosphere. The model geometry is based on geophysical and geological data, and each model run requires an assumed rheology and interplate coupling. Novel to our modeling is the ability to include erosion/deposition loading and the creation of strike-slip faults, based on a dynamically-applied fracture criterion. The criterion for acceptability is how well a model matches observed present-day topography, gravity, and seismicity patterns. Results given below are for models that satisfy this criterion. The long-term effective elastic thickness is 10 km in the inner arc, increasing to about 50 km near the trench. The effective elastic thickness in the inner arc is therefore much smaller than the about 30 km short-term elastic thickness estimated from seismological data. The viscosity of the lower crust is on the order of 1022 Pa s or less. The strength of interplate coupling off Sanriku is about two to four times greater than off Miyagi, and there is about twice as strong a coupling at greater depths. The relative strength of coupling correlates well with the observed interplate seismicity. Hence the inferred weaker coupling off Miyagi indicates a lack of seismogenic potential -- a low probability for large earthquakes in that region, not just a long return cycle. The same modeling procedure was also applied to southwest Japan. The viscosity of the lower crust is not more than 1021 Pa s, and the elas tic thickness is about 10 km. The calculated strength of interplate coupling for southwest Japan is about 1.5 times greater than for the off-Sanriku region in northeast Japan, which correlates well with the fact that there have been great (M>8) earthquakes in the Nankai Trough region, but none that large in the off-Sanriku region. / Ph. D.

In an effort to synthesize macromolecules comprising both covalent and non-covalent bonding to tune ultimate physical properties, a variety of methodologies and functionalization strategies were employed. First, protected functional initiation, namely 3-[(N-benzyl-N-methyl)amino]-1-propyllithium and 3-(t-butyldimethylsilyloxy)-1-propyllithium, in living anionic polymerization of isoprene was used to yield well-defined chain end functional macromolecules. Using both initiating systems, polymers with good molar mass control and narrow molar mass distributions were obtained and well-defined chain end functionality was observed. There was no observed effect on the polymer microstructure from the polar functionality in the initiator, with ~92% 1,4- and 8% 3,4-enchainment observed in each case. Further investigation of the 3-[(N-benzyl-N-methyl)amino]-1-propyllithium initiated polyisoprenes proved that facile deprotection was not possible and residual catalyst was not removable from the polymer. However, polymers initiated with 3-(t-butyldimethylsilyloxy)-1-propyllithium were quantitatively hydrogenated and deprotected under relatively mild conditions to yield hydroxyl functional macromolecules in several architectures, including linear and star-shaped. Excellent conversion from arm polymer to star polymer was observed and well-defined macromolecules were obtained. Subsequently, a series of non-functional, hydroxyl functional, and 2-ureido-4[1H]-pyrimidone (UPy) chain end functional linear and star-shaped poly(ethylene-co-propylene)s were synthesized and characterized. The melt phase properties were investigated using melt rheology and the effect of macromolecular topology and multiple hydrogen bond functionality was investigated. Linear UPy functional poly(ethylene-co-propylene)s exhibited increased viscosity and shear thinning onset at lower frequencies than non-functional polymers of similar molar mass due to interaction of the multiple hydrogen bonding groups. Star-shaped UPy functional poly(ethylene-co-propylene)s showed inhibition to terminal flow and the absence of a zero shear viscosity in melt rheological characterization, indicative of a network like structure imparted from the multiple hydrogen bonding interactions. In addition, the living anionic polymerization of D3 was controlled using the functionalized initiators3-[(N-benzyl-N-methyl)amino]-1-propyllithium and 3-(t-butyldimethylsilyloxy)-1-propyllithium. Good molar mass control and narrow molar mass distributions were observed. In contrast to the polyisoprene homopolymers, facile deprotection of the 3-(t-butyldimethylsilyloxy)-1-propyllithium was not possible due to the acid sensitivity of the poly(dimethylsiloxane) backbone. However, facile deprotection of the protected secondary amine was achieved through hydrogenolysis and well-defined terminal amine functionalized poly(dimethylsiloxane) was synthesized, which are then amenable to further functionalization reactions. In contrast to the well-defined polymers synthesized using living anionic polymerization, free radical polymerizations was used to synthesize free radical copolymers with broader polydispersities and pendant UPy groups. These copolymers were compared with a simple dimeric hydrogen bonding carboxylic acid containing copolymer. Melt rheological characterization revealed that, at similar concentrations, the effect of the UPy group was much greater than the carboxylic acid, and broadened plateau moduli and increased viscosity for the UPy containing polymers were observed, while the acid containing polymer exhibited similar results to a non-functional control. The dynamic viscosity was observed to increase systematically with increasing UPyMA incorporation and the quadruple hydrogen bonding interactions were observed to dissociate between ~80-150 °C. / Ph. D.

The implications of chain topology and intermolecular interactions on the electrospinning process were investigated for linear and randomly branched polymers. Empirical correlations were developed based on solution rheological measurements that predict the onset of electrospun fiber formation and average fiber diameter. In particular, for neutral, non-associating polymer solutions, the minimum concentration required for fiber formation was the entanglement concentration (Ce), and uniform, bead-free fibers were formed at 2 to 2.5 Ce. This was attributed to entanglement couplings stabilizing the electrospinning jet and preventing the Raleigh instability. Moreover, the influence of molar mass and degree of branching on electrospun fiber diameter was eliminated when the polymer concentration was normalized with Ce, and the fiber diameter universally scaled with C/Ce to the 2.7 power. Polymers modified with quadruple hydrogen bonding groups were investigated to determine the role of intermolecular interactions on the solution rheological behavior and the electrospinning process. In nonpolar solvents, the hydrogen bonding functionalized polymers displayed significant deviation from the electrospinning behavior for neutral solutions due to the strong intermolecular associations of the multiple hydrogen bonding groups. The predicted electrospinning behavior was recovered when the hydrogen bonding interactions were screened with a polar solvent. Moreover, it was observed that branching and multiple hydrogen bonding afforded significant processing advantages compared to functionalized, linear analogs of equal molar mass. For example, branched chains in the unassociated state possessed a larger Ce compared to the linear chains, which indicated a lower entanglement density of the former. However, in the associated state the linear and branched chains possessed nearly equivalent Ce values, suggesting a similar entanglement density. Thus, the branched polymers displayed significantly lower viscosities in the unassociated state compared to linear polymers, while still retaining sufficient entanglements in the associated state due to the reversible network structure of the multiple hydrogen bond sites. The solution rheological and processing behavior of polyelectrolyte solutions was also investigated to discern the role of electrostatic interactions on electrospun fiber formation. In particular, the polyelectrolyte solutions formed nano-scale electrospun fibers with an average fiber diameter 2 to 3 orders of magnitude smaller than neutral polymer solutions of equivalent viscosity and C/Ce. This was attributed to the very high electrical conductivity of the polyelectrolyte solutions, which imparted a high degree of charge repulsion in the electrospinning jet and increased the extent of plastic stretching in the polymer filament. In fact, the average diameter of the polyelectrolyte fibers under certain conditions was less than 100 nm, which makes them good candidates for protective clothing applications due to their high specific surface area. Moreover, the neutral polymer solution electrospinning behavior was recovered after the addition of NaCl, which screened the electrostatic charge repulsions along the polyelectrolyte main chain. Finally, electrospun, biocompatible phospholipid membranes were produced from solutions of entangled worm-like lecithin micelles. This is the first example of successfully electrospinning low molar mass, amphiphilic compounds into uniform fibers. Electrospinning the phospholipid worm-like micelles into nonwoven fibrous mats will afford direct engineering of bio-functional, high surface area membranes without the use of multiple synthetic steps, complicated electrospinning setups, or post processing surface treatments. / Ph. D.

Fat bloom in chocolates is the gray-white discoloration and dullness that can occur on the surface of the confectionery. Fat bloom is a common quality defect that can result from temperature fluctuations during storage. Chocolates candies with peanuts or other nut fillings are more prone to fat bloom compared to plain chocolates, due to a release of incompatible nut oils into the chocolate matrix. The overall goal of this study was to determine if differences in triacylglycerol (TAG) composition and rheological properties of high, medium, and normal oleic peanuts influence fat bloom formation. All three peanut varieties showed high concentrations of triolein. Normal oleic peanuts had a slightly higher trilinolein than high and medium oleic peanuts, which contained trilinolein in trace amounts. Peanut pastes from the three peanut varieties all had a minimum apparent yield stress, and all pastes showed varying degrees of shear thinning. The apparent yield stress of high and normal oleic pastes was higher than the apparent yield stress of medium oleic paste. The absolute value of the flow index behavior was 1 for the high oleic peanut paste, suggesting friction in the experimental apparatus, even with use of Teflon plates. The peanut chocolate candies took around 45 days for significant dulling of the chocolates with temperature cycling between 26-29 °C approximately every 26 hours. Optical microscopy scans showed differences in glossiness and surface textural attributes of the unbloomed and bloomed peanut chocolate confectionery. Consumer evaluation showed some differences in the glossiness and significant differences in surface texture of unbloomed and bloomed chocolates. A majority (62%) of the survey respondents had seen whitish discoloration in chocolates and 40% of the respondents thought this is because the chocolate had grown old. / Ph. D.

This work is concerned with a better understanding of the influences that sparse long-chain branching has on the rheological and processing behavior of commercial metallocene polyethylene (mPE) resins. In order to clarify these influences, a series of six commercial polyethylenes was investigated. Four of these resins are mPE resins having varying degrees of long-chain branching and narrow molecular weight distribution. The remaining two resins are deemed controls and include a highly branched low-density polyethylene and a linear low-density polyethylene. Together, the effects of long-chain branching are considered with respect to the shear and extensional rheological properties, the melt fracture behavior, and the ability to accurately predict the flow through an abrupt 4:1 contraction geometry. The effects that sparse long-chain branching (M_branch > M_c) has on the shear and extensional rheological properties are analyzed in two separate treatments. The first focuses on the shear rheological properties of linear, sparsely branched, and highly branched PE systems. By employing a time-molecular weight superposition principle, the effects of molecular weight on the shear rheological properties are factored out. The results show that as little as 0.6 LCB/10⁴ carbons (<1 LCB/molecule) significantly increases the zero-shear viscosity, reduces the onset of shear-thinning behavior, and increases elasticity at low deformation rates when compared to linear materials of equivalent molecular weight. Conversely, a high degree of long-chain branching ultimately reduces the zero-shear viscosity. The second treatment focuses on the relationship between long-chain branching and extensional strain-hardening behavior. In this study, the McLeish-Larson molecular constitutive model is employed to relate long-chain branching to rheological behavior. The results show that extensional strain hardening arises from the presence of LCB in polyethylene resins, and that the frequency of branching in sparsely branched metallocene polyethylenes dictates the degree of strain hardening. This observation for the metallocene polyethylenes agrees well with the proposed mechanism for polymerization. The presence of long-chain branching profoundly alters the melt fracture behavior of commercial polyethylene resins. Results obtained from a sparsely branched metallocene polyethylene show that as few as one long-chain branch per two molecules was found to mitigate oscillatory slip-stick fracture often observed in linear polyethylenes. Furthermore, the presence and severity of gross melt fracture was found to increase with long-chain branching content. These indirect effects were correlated to an early onset of shear-thinning behavior and extensional strain hardening, respectively. Conversely, linear resins exhibiting a delayed onset of shear-thinning behavior and extensional strain softening were found to manifest pronounced slip-stick fracture and less severe gross melt fracture. The occurrence of surface melt fracture appeared to correlate best with the degree of shear thinning arising from both molecular weight distribution and long-chain branching. The ability to predict the flow behavior of long-chain branched and linear polyethylene resins was also investigated. Using the benchmark 4:1 planar contraction geometry, pressure profile measurements and predictions were obtained for a linear and branched polyethylene. Two sets of finite element method (FEM) predictions were obtained using a viscoelastic Phan-Thien/Tanner (PTT) model and an inelastic Generalized Newtonian Fluid (GNF) model. The results show that the predicted profiles for the linear PE resin were consistently more accurate than those of the branched PE resin, all of which were within 15% of the measured vales. Furthermore, the differences in the predictions provided by the two constitutive models was found to vary by less than 5% over the range of numerical simulations obtained. In the case of the branched PE resin, this range was very narrow due to loss of convergence. It was determined that the small differences between the PTT and GNF predictions were the result of the small contraction ratio utilized and the long relaxation behavior of the branched PE resin, which obscured the influence of extensional strain hardening on the pressure predictions. Hence, it was expected that numerical simulations of the 4:1 planar contraction flow for the mildly strain hardening metallocene polyethylenes would not be fruitful. / Ph. D.

Filament-based material extrusion (MatEx) additive manufacturing has garnered huge interest in both academic and industrial communities. Moreover, there is an increasing need to expand the material catalog for MatEx to produce end use parts for a wide variety of functional applications. Current approaches towards MatEx of semicrystalline thermoplastics are in their nascent stage with fiber reinforcements being one of the most common techniques. MatEx of commodity semicrystalline thermoplastics has been investigated but most of the current methods are extremely material and machine specific. The goal of this dissertation is to enable MatEx of semicrystalline polymers with mechanical properties approaching that of injection molded parts. Tailored molecular architectures of blends that can control the crystallization kinetics from the melt state are investigated. By modifying the crystallization time window, the time during which chain diffusion can occur across the deposited layers is prolonged, which allows for a stronger bond between layers. Such differences in the crystallization process impact the z-axis adhesion and residual stress state, which directly affect mechanical properties and warpage in the printed parts. The impact of blend composition on polymer chain diffusion, crystallization profiles, and print properties resulting from the repeated non-uniform thermal history in filament based MatEx is studied. The melt flow behaviour is characterized using rheology and its effect on the interlayer adhesion of printed parts and print precision is explored. The extent of polymer chain re-entanglement post deposition on the printer bed is quantitatively determined using interrupted shear rheology protocols. Tensile bars are printed and mechanically characterized to analyze the tensile performance of the printed parts. Correlating the rheological findings with the mechanical performance of the printed parts provides valuable insights into the complex interlayer welding process during MatEx and is critical to improving existing machine designs and feedstocks in order to achieve printed parts with properties approaching their injection molded counterparts. The results will be essential in identifying optimal processing conditions to maximize material specific printed part performance as well as highlight the associated limitations to enable MatEx of next generation materials. / Doctor of Philosophy / Compared to traditional subtractive manufacturing techniques, additive manufacturing (AM) has the potential to transform modern manufacturing capabilities due to its unique advantages including design flexibility, mass customization, energy efficiency, and economic viability. The filament-based material extrusion (MatEx), also referred to as fused filament fabrication (FFF), employing thermoplastic polymers (and composites) has emerged as one of the most common AM modality for industrial adoption due to its operational simplicity. However, the widespread application of MatEx has been limited due to the lack of compatible materials, anisotropic mechanical properties, and lack of quality assurance. Most of the research on FFF has been performed on amorphous polymers with almost negligible levels of crystalline content such as polylactic acid (PLA) and acrylonitrile-butadiene-styrene (ABS). Semicrystalline polymers are an attractive choice for FFF feedstocks compared to the amorphous ones due to their improved thermal resistance, toughness, and deformability. However, processing semicrystalline polymers using FFF is challenging due to the volumetric shrinkage encountered during crystallization from the melt state. This results in the buildup of significant levels of residual stresses at temperatures lower than the crystallization temperature of the polymer resulting in warpage of the printed parts. The research presented in this dissertation aims to address the aforementioned challenges by characterizing semicrystalline polymer feedstocks under conditions representative of the multiphysics encountered during a typical FFF process. Several strategies to limit shrinkage and warpage are discussed that involve tuning the thermal profile and crystallization kinetics during printing. The former is achieved by addition of thermally conductive carbon fiber reinforcements while the latter is realized by blending amorphous resins or low crystallinity polymers to the semicrystalline polymer matrix. The fibers results in a more homogenous temperature distribution during printing while the incorporation of the resins modify the rate of crystallization; both of which play a pivotal role in reducing the residual stress build-up and hence minimizing the warpage during printing. The printability of the materials is investigated based on the shear- and temperature dependent viscous response of the polymers. The printed parts with fiber reinforcements exhibit high levels of mechanical anisotropy compared to the blends with the resins, likely due to differences in polymer chain mobility at the interface. The tensile properties of the printed polymer blends are slightly inferior to those obtained using traditional manufacturing techniques; however, properties close to 90-95% of injection molded properties are recovered through a simple post-processing thermal annealing step. The obtained results will assist in optimizing the processing parameters and feedstock formulation in order to consistently produce printed parts with minimal defects and tailored mechanical properties for functional applications.