When trace quantities of an alkali element are added to a flame, its optical and electrical properties change significantly. Addition of alkali seed to both premixed and diffusion flames has been used in the development of two new techniques, one for flame temperature measurement and the other for enhanced mixing. Advantage has been taken of the spectral characteristics of alkali seeds in the development of a non-invasive optical flame temperature measurement technique. The strongest resonance line of alkalis is in fact a doublet, and the two peaks can be subjected to different optical treatment. A cesium-seeded flame was exposed to radiation which was selectively filtered to yield different apparent source temperatures at the wavelengths corresponding to the doublet resonance lines. The ratio of the emission peak heights at the two wavelengths relates directly to flame temperature. This technique allows real-time measurement of flame temperatures up to 2800 K. A second process has been investigated which takes advantage of the enhanced electrical conductivity of alkali-seeded diffusion flames. The study first required a characterization of electrical discharges through planar diffusion flames. Because of the increase in conductivity, alkali-seeded diffusion flames can carry current when a transverse electric potential is applied. The behavior of diffusion flames carrying electrical current has been investigated. The dependence on electrode position and gap is reported and the behavior is contrasted with that described in the literature for premixed flames. A planar diffusion flame was subjected to a steady magnetic field parallel to the flow direction while an orthogonal, oscillating current passed through the flame sheet. A Lorentz body force was induced on the flame sheet which acted to move it alternately toward the fuel and oxidizer streams, improving bulk mixing in the flame. High-speed video images of the oscillating flame were analyzed to obtain its maximum lateral velocity. The results compared well with predictions from a simple theoretical model. / Graduation date: 1992

Alkali silica reaction (ASR), a reaction which occurs between reactive siliceous mineral components in the aggregate and the alkaline pore solution in concrete, is responsible for substantial damage to concrete structures in the U. S. and across the world. Lithium admixtures, including lithium nitrate (LiNO3), have been demonstrated to mitigate ASR damage, and are of particular interest for use in concrete airfield pavement construction, where ASR damage has been recently linked to the use of certain de-icing chemicals. Although the effectiveness of lithium admixtures at ASR-mitigation is well-researched, relatively less is known regarding the potential effects, including negative effects, on overall concrete behavior. The goal of this research is to better understand the influence of LiNO3 admixture on early age concrete behavior, and to determine if a maximum dosage rate for its use exists. Isothermal calorimetry, rheology and bleed water testing, time of setting, chemical shrinkage, autogenous shrinkage, free and restrained concrete shrinkage, and compressive and flexural strength were measured for pastes and concretes prepared with a range of LiNO3 dosages (i.e., 0, 50, 100, 200, and 400% of the recommended dosage). In addition, the interaction of LiNO3 with cement was evaluated by comparing results obtained with six cements of varying alkali and tricalcium aluminate (C3A) contents. Additionally, one of these cements, was examined alone and with 20% by weight Class F fly ash replacement. Results indicate that the hydration of the tricalcium silicate and tricalcium aluminate components of cement are accelerated by the use of LiNO3, and that low alkali cements (typically specified to avoid damage by ASR) may be particularly susceptible to this acceleration. However, inclusion of Class F fly ash at 20% by weight replacement of cement (also common in applications where ASR is a concern) appears to diminish these possibly negative effects of LiNO3 on early age hydration acceleration and heat generation. Dosages higher than the current standard dosage of LiNO3 may have minor effects on fresh concrete workability, causing slight decreases in Bingham yield stress, corresponding to slightly higher slump. Fresh concrete viscosity may also be affected, though more research is necessary to confirm this effect. LiNO3 had no effect on quantity of bleed water in the mixes tested. Generally, LiNO3 had no effect on initial and final setting times, although increasing dosages caused faster set times in the lowest alkali (Na2Oeq = 0.295%) cement examined. In shrinkage testing, higher LiNO3 dosages appeared to cause initial expansion in some sealed paste specimens, but in all cases the highest dosage led to greater autogenous shrinkage after 40 days. In concrete specimens, however, the restraining effect of aggregates diminished shrinkage, and no effect of the LiNO3 was apparent. In no cases, with any dosage of lithium tested, with or without fly ash replacement, did restrained shrinkage specimens show any cracking. Strength testing produced mixed results, with laboratory specimens increasing in 28-day compressive strength, but companion specimens cast in the field and tested by an outside laboratory, exhibited lower 28-day compressive strength, with increasing lithium dosages. Flexural specimens, also cast in the field and tested by an outside laboratory, appeared to show an increase in 28-day flexural strength with increasing lithium dosages. However, because of the conflicting results when comparing the various strength data, further research is necessary for conclusive evidence of LiNO3 effects on concrete strength.

The undesirable expansion of concrete because of a reaction between alkalis and certain type of reactive siliceous aggregates, known as alkali-silica reactivity (ASR), continues to be a major problem across the entire world. The renewed interest to minimize distress resulting from ASR has emphasized the need to develop predictable modeling of concrete ASR behavior under field conditions. Current test methods are either incapable or need long testing periods in which to only offer rather limited predictive estimates of ASR behavior in a narrow and impractical band of field conditions. Therefore, an attempt has been made to formulate a robust performance approach based upon basic properties of aggregate and concrete ASR materials derived from dilatometry and a kinetic-based mathematical expressions for ASR behavior. Because ASR is largely an alkali as well as a thermally activated process, the use of rate theory (an Arrhenius relationship between temperature and the alkali solution concentration) on the dilatometer time-expansion relationship, provides a fundamental aggregate ASR material property known as “activation energy.” Activation energy is an indicator of aggregate reactivity which is a function of alkalinity, particle size, crystallinity, calcium concentration, and others. The studied concrete ASR material properties represent a combined effects of mixture related properties (e.g., water-cementitious ratio, porosity, presence of supplementary cementitious materials, etc.) and maturity. Therefore, the proposed performance-based approach provides a direct accountability for a variety of factors that affect ASR, such as aggregate reactivity (activation energy), temperature, moisture, calcium concentration, solution alkalinity, and water-cementitious material ratio. Based on the experimental results, the following conclusion can be drawn concerning the performance-based approach to evaluate ASR potential of aggregate and concrete using dilatometer method; (i) the concept of activation energy can be used to represent the reactivity of aggregate subjected to ASR, (ii) the activation energy depends on the reactivity of aggregate and phenomenological alkalinity of test solution, and (iii) The proposed performance-based model provides a means to predict ASR expansion development in concrete.

Thesis (Ph. D.)--University of Texas at Austin, 2000. / Vita. Includes bibliographical references (leaves 506-525). Available also in a digital version from Dissertation Abstracts.

Thesis (Ph. D.)--Florida State University, 2002. / Advisor: Dr. James G. Skofronick, Florida State University, College of Arts and Sciences, Dept. of Physics. Title and description from dissertation home page (viewed Oct. 3, 2003). Includes bibliographical references.

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