Thesis (Ph. D.)--Institute of Paper Chemistry, 1965. / Includes bibliographical references (p. 107-109).

Drilled shafts are cast-in-place concrete, deep foundation elements that require high levels of quality control to ensure the borehole does not become unstable either during excavation or during concreting. Bentonite slurry is a popular choice among state DOT officials nationwide to maintain borehole stability as it has a long history with reasonable load carrying performance. However, specifications developed to replicate successful shaft construction are largely based on empirical data. Further, as slurry construction is a blind process, the final as-built shaft is rarely visually inspected and much of the perceived concrete flow and slurry interaction with rebar and the soil interface are largely unverified. This thesis presents the wide range of nationwide specifications for slurry viscosities (upper and lower) and notes that in only one case out of a hundred (50 states with an upper and lower viscosity limit) is there a rational basis for setting the limit. To this end, the objective of this thesis was to provide compelling evidence to support or dispute present upper viscosity limits. The study was part of a larger scope to show the effects of high viscosity slurry on concrete / soil interface and rebar bond. However, this thesis addresses only the latter via large scale testing to show concrete flow patterns, the build-up of bentonite slurry on rebar, and the degradation of rebar pull-out capacity as a function of bentonite slurry viscosity. Pull-out test results from 126 specimens, comprised of No. 8 rebar embedded in 42in diameter shafts, showed that rebar bond degraded as much as 70%#37; and more when in the presence of bentonite slurry that conformed to most state viscosity specifications (40 to 90 sec/qt). Visual inspection which is rarely possible on drilled shafts showed convincingly that the concrete that flowed through the cage to form the cover concrete does not fully encapsulate the rebar. In most cases a void/crease was formed reflecting the cage grid and which would provide a pathway from the soil pore water directly to the reinforcing steel. While present specifications nationwide dictate bentonite slurry ranges from a minimum of 28 to a maximum of 60 sec/qt, the study findings indicate that only viscosity levels of 30 sec/qt and below are reasonable from both a bond and durability stand point. As pure water has a viscosity of 26 sec/qt, this leaves only a very slight window of acceptability which is unlikely to provide sufficient lateral borehole stability.

Delivery of protein therapeutics is restricted to intravenous infusions due to protein-dependent problems including low solubilities, high viscosities, and physical instabilities. The ability to inject high concentrations of proteins via subcutaneous injections would increase accessibility and compliance. Large particles of a protein in a non-aqueous solvent can decrease the viscosity over a solution of equally concentrated individual protein molecules. The lower viscosity of a particle suspension is due to decreased surface area resulting in reduced electroviscous effects, solvation and deviations of the particle shape from a spherical geometry. Additional studies show that aqueous-based dispersions of antibody nanoclusters can be formed by increasing the attractive interactions between protein molecules using the excluded volume effects of extrinsic crowding agents. These novel, equilibrium, nanoclusters are maintained by a balance of highly attractive interactions and weak electrostatic repulsive interactions near the protein’s pI. These protein nanoclusters are ideal for subcutaneous delivery as they have low interactions between the colloids, are reversible in nature, and dissolve rapidly upon dilution in a buffer media. Through in vivo mouse studies, the bioavailability of a monoclonal antibody in the dispersion is prolonged and higher doses can be administered versus a solution. Overall, these studies with high concentration, low viscosity subcutaneous injections of protein therapeutics open new opportunities in biotechnology. For oral delivery of itraconzole, controlled flocculation of individual polymerically-stabilized nanoparticles is used to increase supersaturation. Flocculation of these nanoparticles is achieved by desolvating the polymer by changing the pH. The flocculated dispersions can then be easily filtered. The final amorphous powder maintains high supersaturation with simulated stomach and small intestine conditions and improves bioavailability of itraconazole, over the commercial product, Sporanox®. / text

The broad objective of my research is to investigate the physical characteristics and interactions of macromolecules and nanoparticles, and the corresponding effects on their phase separation behavior using static and dynamic light scattering (SLS & DLS). Light scattering provides a non-invasive technique for monitoring the in-situ behavior of solutes in solution, including solute interactions, sizes, shapes, aggregation kinetics and even rheological properties of condensed phases. Initially, we investigated lysozyme solutions for the presence of preformed aggregates and clusters that can distort the kinetics of protein crystal nucleation studies in this important model system for protein crystallization. We found that both undersaturated and supersaturated lysozyme solutions contained population of large, pre-existing protein aggregate. Separating these clusters and analyzing their composition with gel chromatography indicated that these clusters represented pre-formed lysozyme aggregates, and not extrinsic protein contamination. We investigated the effect of chaotropic versus kosmotropic ions (water structure breakers vs. structure makers) on the hydration layer and hydrodynamic interactions of hen egg white lysozyme. Surprisingly, neither chaotropic nor kosmotropic ions affected the protein hydration layer. Salt-effects on direct and hydrodynamic protein interactions were determined as function of the solutions ionic strength and temperature. Using both static and dynamic light scattering, we investigated the nucleation of gold nanoparticles forming from supersaturated gold sols. We observed that two well separated populations of nuclei formed essentially simultaneously, with sizes of 3nm vs. several tens of nanometer, respectively. We explore the use of lysozyme as tracer particle for diffusion-base measurements of electrolyte solutions. We showed that the unusual stability of lysozyme and its enhanced colloidal stability enable viscosity measurement of salts solutions at high salt concentration, over a wide range of pH values and temperatures for the common tracer particle polystyrene flocculates. We applied dynamic light scattering to measure the viscoelastic responses of polystyrene probe particles embedded in solutions and gels of two different polymers: polyacrylamide (PAAm) and poly-N-isopropylacrylamide (poly-NiPAAm).

When a rigid shaft such as a jacked pile or the sleeve of a cone penetrometer penetrates soil, the soil mass at the shaft tip fails. This failed soil mass flows around the shaft surface and creates a disturbed soil zone. The soil in this zone, which is at a failure or critical state (CS), flows and behaves like a viscous fluid. During continuous penetration, the shaft surface is subjected to an additional viscous shear stress above the static shear stress (interfacial solid friction). The total resistance on the shaft in motion is due to the static and viscous shear components. Current methods of calculating the penetration resistance in soils are based on static interfacial friction, which determine the force required to cause failure at the shaft-soil interface and not the viscous drag. The main aim of this research is to understand the viscous soil resistance on penetrating shafts in clays.This research consists of two components. First, a theoretical analysis based on creeping flow hydrodynamics is developed to study the viscous drag on the shaft. The results of this analysis reveal that the size of the CS zone, the shear viscosity of the soil and velocity of the shaft influence the viscous drag stress. Large increases in viscous drag occur when the size of the CS zone is less than four times the shaft radius.Second, a new experimental procedure to estimate the shear viscosity of clays with water contents less than the liquid limit is developed. Shear viscosity is the desired soil parameter to estimate viscous drag. However, there is no standard method to determine shear viscosity of clays with low water contents (or Liquidity Index, LI). Soils can reach CS for water contents in the plastic range (LI<1) and exhibit viscous behavior. The fall cone test is widely used to interpret the index (liquid and plastic limit) and strength properties of clays. In this study the existing analysis of the fall cone test is reexamined to discern the viscous drag as the cone penetrates the soil. This reexamination shows that the shear viscosity of clays with low water contents (LI<1.5) can be estimated from time-penetration data of the fall cone. Fall cone test results on kaolin show that the shear viscosity decreases exponentially with an increase in LI.The results of this research can be used to understand practical problems such as jacked piles in clays, cone penetrometer sleeve resistance and advancement of casings in soil for drilling or tunneling operations.

No description available.

No description available.

The evolution of rhyolitic lava from effusion to cessation of activity is poorly understood. Recent lava dome eruptions at Unzen, Colima, Chaiten and Soufrière Hills have vastly increased our knowledge on the changes in behaviour of active domes. However, in ancient domes, little knowledge of the evolution of individual extrusion events exists. Instead, internal structures and facies variations can be used to assess the mechanisms of eruption. Rhyolitic magma rising in a conduit vesiculates and undergoes shear, such that lava erupting at the surface will be a mix of glass and sheared vesicles that form a permeable network, and with or without phenocryst or microlites. This foam will undergo compression from overburden in the shallow conduit and lava dome, forcing the vesicles to close and affecting the permeable network. High temperature, uniaxial compression experiments on crystal-rich and crystal-poor lavas have quantified the evolution of porosity and permeability in such environments. The deformation mechanisms involved in uniaxial deformation are viscous deformation and cracking. Crack production is controlled by strain rate and crystallinity, as strain is localised in crystals in crystal rich lavas. In crystal poor lavas, high strain rates result in long cracks that drastically increase permeability at low strain. Numerous and small cracks in crystal rich lavas allow the permeable network to remain open (although at a lower permeability than undeformed samples) while the porosity decreases. Flow bands result from shear movement within the conduit. Upon extrusion, these bands will become modified from movement of lava, and can therefore be used to reconstruct styles of eruption. Both Ngongotaha and Ruawahia domes, from Rotorua caldera and Okataina caldera complex (OCC) respectively, show complex flow banding that can be traced to elongated or aligned vents. The northernmost lobe at Ngongotaha exhibits a fan-like distribution of flow bands that are interpreted as resulting from an initial lava flow from a N – S trending fissure. This flow then transitioned into intrusion of obsidian sheets directly above the conduit, bound by wide breccia zones which show vertical movement of the sheets. Progressive intrusions then forced the sheets laterally, forming a sequence of sheets and breccia zones. At Ruawahia, the flow bands show two types of eruption; long flow lobes with ramp structures, and smaller spiny lobes which show vertical movement and possible spine extrusion. The difference is likely due to palaeotopography, as a large pyroclastic cone would have confined the small domes, while the flow lobes were unconfined and able to flow down slope. The vents at Ruawahia are aligned in a NE – SW orientation. Both domes are suggested to have formed from the intrusion of a dyke. The orientations of the alignment or elongation of vents at Ngongotaha and Ruawahia can be attributed to the overall regional structure of the Taupo Volcanic Zone (TVZ). At Ngongotaha, the N – S trending elongated vent is suggested to be controlled by a N – S trending caldera collapse structure at Rotorua caldera. The rest of the lobes at Ngongotaha, as well as other domes at Rotorua caldera, are controlled by the NE – SW trending extensional regional structure or a NW – SE trending basement structure. The collapse of Rotorua caldera, and geometry of the deformation margin, are related to the interplay of these structures. At Ruawahia, the NE – SW trending vent zone is parallel to the regional extension across the OCC, as shown by the orientation of intrusion of the 1886AD dyke through the Tarawera dome complex. The NE – SW trending regional structures observed at both Rotorua caldera and Okataina caldera complex are very similar to each other, but differ from extension within the Taupo rift to the south. Lava domes, such as Ngongotaha, that are controlled by this structure show that the ‘kink’ in the extension across Okataina caldera complex was active across Rotorua caldera during the collapse at 240 ka, and possibly earlier. This study shows the evolution of dyke-fed lava domes during eruption, and the control of regional structures in the location and timing of eruption. These findings improve our knowledge of the evolution of porosity and permeability in a compacting lava dome, as well as of the structures of Rotorua caldera, the longevity of volcanic activity at dormant calderas and the hazard potential of dyke-fed lava domes.

The viscosity and density of bis(8-methylnonyl) benzene-1,2- dicarboxylate {diisodecyl phthalate (DIDP)}, with a nominal viscosity at T = 298 K and p = 0.1 MPa of 87 mPa•s, have been measured at temperatures from (298.15 to 423.15) K and pressures from (0.1 to 70) MPa. A vibrating wire viscometer, with a wire diameter of about 0.15 mm, was utilised for the viscosity measurements and the results have an expanded uncertainty, (k = 2), including the error arising from the pressure measurement, of between ±(2 and 2.5) % The density was determined with two vibrating tube densimeters one for operation at p≈0.1 MPa with an expanded uncertainty (k = 2) of about ±0.1 %, the other that used at pressures up to 70 MPa, with an estimated expanded uncertainty (k = 2) of about ±0.3 %. Measurements of density and viscosity were performed on three samples of DIDP each with different purity stated by the supplier and as a function of water mass fraction. The measured viscosity and density are represented by interpolating expressions with differences between the experimental and calculated values that are comparable with the expanded (k = 2) uncertainties. The obtained viscosities at p = 0.1 MPa agree with values reported in the literature within the combined expanded (k = 2) uncertainties of the measurements while our densities differ by no more than 1.5 %. Viscosity data at p > 0.1 MPa deviate systematically from the literature values in the range of -10 % to 10 %. An apparatus capable of simultaneously measuring the solubility of a gas dissolved in a liquid and the viscosity and the density of the resulting mixture over a wide temperature and pressure range was constructed and tested. Preliminary results have been reported.

Thesis (Ph.D.)--University of Tulsa, 1993. / Includes bibliographies.