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My research has focused on the precipitation of iron minerals, mostly oxides and hydroxides, in aqueous systems across steep pH and Eh gradients. Unlike most work in this area, which involves loose precipitates filtered out of solutions, I have focused on precipitated aggregates and, more specifically, on those that are self-organized into dis-crete structures or patterns. This topic is actually quite narrow because such types of natu-ral material organization are rare within the geochemical realm compared with the mor-phological richness of crystals, not to mention the phantasmagoria of life.My investigation of iron-based examples has included three types of physical sys-tems: 1) growth of tubular structures around bubbles coming off a charged cathode in a free solution where convection dominates; 2) development of Liesegang patterns within gelled solutions due to reactions dominated by diffusion; and 3) formation of a cement-ing matrix within the aqueous interface between particles of silica. The third case in-volves physical characteristics of the first two in that it is primarily a tightly packed, dif-fusion-limited process, but at least initially the generation of gases can create mechani-cally driven flows through the interstitial spaces.All three systems and studies are inextricably related for both tubular ('vermi-form') structures and Liesegang patterns are commonly found in natural iron-cemented sediments such as massive laterite, ironstone deposits, and banded iron formations. They are also found on a much smaller scale within discrete 'concretions' and represent the two poles of the gradient between convection-based and diffusion-based systems. As Seilacher (2001) states concerning concretions, "the distribution and precipitation of dis-solved constituents, such iron and manganese, proceeds in two radically different mor-phospaces, which are typified by dendrites [and I would include tubes and other linear growth] on the one hand and Liesegang rings on the other." Both have been observed in my lab creations with surprising frequency and tenacity even in systems thought to be in-hibitory.

The main objective of this research was to better understand, predict and control of the periodic precipitation process and to apply such programmed periodic precipitation to the design of a pulsatile delivery system. In the first part of this study, a generalized model taking into account both nucleation, particle growth, and ripening process was refined and solved under various new concentration boundary conditions not previously investigated. The results clearly delineate the key differences between boundary conditions of infinite versus finite supply of inner electrolyte. When the inner electrolyte boundary concentration was allowed to increase exponentially with time, equidistant periodic precipitation was predicted and subsequently confirmed experimentally. In addition, the effects of product solubility and reaction rate constant were also shown to be important in determining the band number and band spacing. In the second part of this study, the effects of gel crosslinking and gel charge density on the periodic precipitation were investigated. The results indicate that by increasing either the gel crosslinking or decreasing the gel charge density will reduce the diffusion rate of the reactants resulting in closely spaced bands. In addition, a new and improved rotating disk method for characterizing polyelectrolyte gels with ion-penetrable soft surfaces has been established by taking into account the effect of surface conductivity which is usually ignored for ion-impenetrable hard surfaces. In the third part of this work, periodic precipitation formed in multi-component systems has been shown to be governed by a heterogeneous nucleation mechanism. Using this approach, periodic precipitation of an insulin mimetic compound VO2+ in gelatin gel, which cannot form alone in a single reaction system, was induced by the periodic precipitation of Mg(OH)2 in a multi-component system. Pulsatile release of VO2+ from the resulting multi-layered structure of VO(OH)2 via a surface erosion mechanism was subsequently demonstrated.

The main objective of this research was to better understand, predict and control of the periodic precipitation process and to apply such programmed periodic precipitation to the design of a pulsatile delivery system. In the first part of this study, a generalized model taking into account both nucleation, particle growth, and ripening process was refined and solved under various new concentration boundary conditions not previously investigated. The results clearly delineate the key differences between boundary conditions of infinite versus finite supply of inner electrolyte. When the inner electrolyte boundary concentration was allowed to increase exponentially with time, equidistant periodic precipitation was predicted and subsequently confirmed experimentally. In addition, the effects of product solubility and reaction rate constant were also shown to be important in determining the band number and band spacing. In the second part of this study, the effects of gel crosslinking and gel charge density on the periodic precipitation were investigated. The results indicate that by increasing either the gel crosslinking or decreasing the gel charge density will reduce the diffusion rate of the reactants resulting in closely spaced bands. In addition, a new and improved rotating disk method for characterizing polyelectrolyte gels with ion-penetrable soft surfaces has been established by taking into account the effect of surface conductivity which is usually ignored for ion-impenetrable hard surfaces. In the third part of this work, periodic precipitation formed in multi-component systems has been shown to be governed by a heterogeneous nucleation mechanism. Using this approach, periodic precipitation of an insulin mimetic compound VO2+ in gelatin gel, which cannot form alone in a single reaction system, was induced by the periodic precipitation of Mg(OH)2 in a multi-component system. Pulsatile release of VO2+ from the resulting multi-layered structure of VO(OH)2 via a surface erosion mechanism was subsequently demonstrated.

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Iron precipitation during matrix acidizing treatments is a well-known problem. During matrix acidizing, successful iron control can be critical to the success of the treatment. Extensive literature review highlighted that no systematic study was conducted to determine where this iron precipitates, the factors that affect this precipitation, and the magnitude of the resulting damage. Iron (III) precipitation occurs when acids are spent and the pH rises above 1, which can cause severe formation damage. Chelating agents are used during these treatments to minimize iron precipitation. Disadvantages of currently used chelating agents include limited solubility in strong acids, low thermal stability, and/or poor biodegradability. In this study, different factors affecting iron precipitation in Indiana limestone rocks were examined. Two chelating agents, GLDA and HEDTA, were tested at different conditions to assess their iron control ability. Results show that a significant amount of iron precipitated, producing a minimal or no gain in the final permeability, this indicated severe formation damage. The damage increased with the increase of the amount of iron in solution. When chelating agents were used, the amount of iron recovered depended on both chelate-to-iron mole ratio and the initial permeability of the cores. Calcium is chelated along with iron, which limits the effectiveness of chelating agents to control iron (III) precipitation. Acid solutions should be designed considering this important finding for more successful treatments.

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