Thesis (Ph. D.)--Columbia University, 1934. / Vita. Bibliography: p. 45-46.

Thesis (Ph. D.)--Columbia University, 1931. / Vita. Caption title: The effect of certain electrolytes on the stability of Bredig gold sols. eContent provider-neutral record in process. Description based on print version record. Bibliography: p. 27.

Thesis (Ph. D.)--Columbia University, 1931. / Vita. Caption title: The effect of certain electrolytes on the stability of Bredig gold sols. Bibliography: p. 27.

Thesis--Hannover. / In Periodical Room.

Thesis (Ph. D.)--University of Michigan, 1934. / From Physical reviw, v.46, October 1, 1934.

Thesis (Ph. D.)--Oregon Graduate Center, 1988.

This project studied the production of barium sulphate nanoparticles through inhibition of crystal growth, during precipitation, by different surfactants. Barium sulphate is the pure form of the ore baryte, which due to its high density and softness, is the most commonly used additive used to increase the density of drilling fluids. A non-agglomerating, stable nano-scale dispersion of barium sulphate particles would have significant technical and commercial impact in the drilling fluids industry. This thesis tested the possibility of precipitating barium sulphate and restricting its crystal growth with inhibitors, creating nanoparticles. Six inhibitors were tested; dodecanoic acid, palmitic acid, stearic acid, adamantane carboxylic acid, methylnonanoic acid and a mixture of phosphate esters known commercially as Fazewet. Precipitated, inhibited barium sulphate was characterised using powder XRD, DRIFT FTIR and solid-state NMR (SSNMR). All inhibitors were shown to form single-phase, orthorhombic barium sulphate crystals proving that the inhibitors affect only the surfaces of precipitated crystals and do not enter the crystal lattice. FTIR allowed the relative adsorbed concentration of each inhibitor to be assessed. The results indicate that adsorbed inhibitor increases with increasing inhibitor concentrations but that their attachment is not proportional to the concentration. In most cases concentrations of 0.1mol l-1 of inhibitor were sufficient to saturate the crystal surface. SSNMR also agreed with this although the sample size was too small, due to equipment restrictions, to make definitive conclusions. Through the use of the Debye-Scherrer equation, the crystallite size was calculated and showed that at concentrations of 0.2mol l-1 all inhibitors other than palmitic acid produced nano-scale (< 100nm) crystallites. Further analysis showed that further reductions could be achieved through precipitation in an alkaline pH environment, with the application of mechanical shear and by using adding 50% v/v of ethanol. iv Laser diffraction particle size analysis showed that the dominant factor in reducing particle size distribution was inhibitor concentration. The volume-based PSD used by the laser diffraction system was considered to distort excessively the particle sizes present and so analysis switched to dynamic light scattering. DLS showed that dodecanoic acid, palmitic acid and stearic acid, despite forming nano-scale crystallites, could not produce a nano-scale dispersion of barium sulphate and as such were unsuitable for use in drilling fluids. Stable nano-scale dispersions were found to have been formed when inhibited with adamantane carboxylic acid, methylnonanoic acid and Fazewet. DLS also confirmed that dispersed particle size rather than simply crystallite size could be reduced with an alkaline pH and high mechanical shear. Concentration was still the dominant effect, however with the smallest particles sizes (ZAvg) being observed at concentrations of 0.6mol l-1. The particle sizes for the three modifiers were approaching that of the crystallite size, suggesting that some further reduction is possible, but large reductions are unlikely. All three inhibitors produced sub 100nm ZAvgs, with the smallest produced by methylnonanoic acid of 43nm. Spherical nanoparticles were observed through the use of ESEM and TEM. Due to equipment time restrictions only 0.2mol l-1 treatment levels could be examined, but ESEM showed apparent nanoparticle clusters, later confirmed using pixel count and SFDA methods. TEM analysis showed discrete particles as small as 3nm, indicating that the lower limit for achievable particle size may be lower than PSD measurements would suggest. The results indicate that adamantane carboxylic acid, methylnonanoic acid and Fazewet sufficiently inhibit crystal growth to be potential candidates for the production of barium sulphate nanoparticles. These three inhibitors produce a barium sulphate dispersion that is stable and nano-scale even after drying and redispersion.

M.Sc. (Chemistry) / Barium titanate (BaTi03) is an important material in the electronics industry as a result of its excellent dielectric properties. It has been the subject of many studies since its initial discovery, which have focussed on a wide variety of different aspects, including its synthesis, the identification of the crystal structures of its various phases, and also attempts to determine the various factors that could explain its unusual electrical properties. Since barium titanate has been studied by this wide range of disciplines, the information regarding this material is scattered over many sources. This study contains a literature survey of some of the significant work on barium titanate, in order to collect, and order, the available data into a coherent picture of the state of knowledge pertaining to the crystal structure, syntheses and electric properties of the material. From this study, it was clear that there was a distinct lack of consistent findings with respect to the identification of the tetragonal phase crystal structure. The tetragonal phase is the requisite one since it is ferroelectric, although the cubic phase also plays a significant role when the material is in the form of a very fine powder. The exact influence of the small particle size is also shown to be the object of much debate amongst the scientific community. Another area of inquiry which has attracted much attention in the past is that of the synthesis of barium titanate. The synthesis of a pure phase of barium titanate requires an intimate mixture of components which is not obtained using the standard solid-state method of synthesis, thus resulting in researchers switching to solvent-based methods of preparation. The present study also contains a summary of several of these published methods, from which four suitable methods have been selected according to certain criteria. These Criteria are that the method should be simple, use easily available materials and have been reported as having good results in terms of their dielectric properties and structural composition. It is also important that the syntheses are easy to control, to enable the extension of the work to synthesise other perovskites, poly titanates and doped barium titanate.

The theory of ferroelectricity, and in particular the ferroelectric behavior of barium titanate, are discussed and qualitative agreement is obtained with experimental results. Limitations of the theory are pointed out. Experimental procedure used to manufacture samples of polycrystaline barium titanate ceramic, and to investigate their ferroelectric properties is outlined. The phenomena of permanent polarization and hysteresis are investigated in the ferroelectric temperature range, and are discussed. An electric equivalent of the Barkhausen effect is observed. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

Hepatocyte transmembrane potential (V(m)) during osmotic stress responds as an osmometer, in part because of changes in membrane K+ conductance. This may contribute to the electromotive force that drives transmembrane Cl- fluxes. To test this, double-barreled ion-sensitive microelectrodes were used to measure changes in steady-state intracellular Cl- activity (a(Cl)/(i)) during osmotic stress applied to mouse liver slices. Hyperosmotic and hyposmotic conditions were created by rapidly switching to a solution in which sucrose concentrations were increased or reduced, respectively. Hyperosmotic stress [1.4 x control osmolality (280 mosmol/kgH2O)] decreased hepatocyte V(m) 46% from -39 ± 1 to -21 ± 1 mV (SE; n = 16 animals). Corresponding a(Cl)/(i) increased twofold from 19 ± 2 to 38 ± 3 mM. This shifted the Cl- equilibrium potential (E(Cl)) 19 mV, from -38 ± 0.3 to -19 ± 2 mV. Hyposmotic stress [0.71 x control osmolality (290 mosmol/kgH2O)] increased hepatocyte V(m) 64% from -28 ± 1 to -46 ± 1 mV (SE; n = 13 animals). Corresponding a(Cl)/(i) decreased 0.53-fold from 17 ± 1 to 8 ± 1 mM. This shifted the E(Cl) 20 mV from -26 ± 2 to -46 ± 3 mV. Thus hepatocyte a(Cl)/(i) is in electrochemical equilibrium with V(m). The paired measurements above were repeated after addition of K+-channel blockers quinine or Ba2+. Ba2+ (2 mM) had no effect on either V(m) or a(Cl)/(i) during hyperosmotic stress; however, Ba2+ significantly inhibited changes in V(m) and a(Cl)/(i) during hyposmotic stress. Effects of quinine (0.5 mM) on V(m) and a(Cl)/(i) during both hyperosmotic stress and hyposmotic stress were similar to those of Ba2+. A previous report shows that inhibition of hyposmotic stress-induced V(m) changes results in loss of hepatocyte volume regulation and greater swelling. Thus osmotic stress-induced changes in a(Cl)/(i) are nowhere near those predicted by cell water volume changes based on transmembrane osmotic pressure differences. We conclude that these larger changes in a(Cl)/(i) resulted from voltage-driven transmembrane Cl- fluxes.