¡@¡@¡@¡@¡@¡@¡@­^¡@¤å¡@ºK¡@­n¡@¡@¡@¡@¡@¡@¡@ Heat transfer of a molten splat to a thin layer rapidly solidified on a cold substrate and the heat transfer coefficient at the bottom surface of a splat is extensively and self-consistently investigated. Rapid freezing in the splat is governed by a nonequilibrium kinetics at the solidification front in contrast to the melting in the substrate simulated by the traditional phase change problem. Solving one-dimensional unsteady heat conduction equations and accounting for distinct properties between phases and splat and substrate, the results show the effects of dimensionless parameters such as the dimensionless kinetic coefficient, stefan number, latent heat ratio, initial, equilibrium melting, and nucleation temperature, and conductivity, density, and specific heat ratios between solid and liquid and splat and substrate on unsteady temperature fields and freezing and melting rates in the splat and substrate and on unsteady variation of Biot number are presented. The unsteady variation of the heat coefficient or Biot number can be divided by five regimes: liquid splat-solid substrate, liquid splat-liquid substrate, solid splat-solid substrate, solid splat-liquid substrate, and the nucleation of the splat. Appropriate choices of dimensionless parameters to control the time for freezing and melting of the splat and substrate and an understanding and estimation of the heat coefficient at the bottom surface of the splat therefore are presented. The velocity distribution function and transport variables of the positive ions and electrons in the collisionless presheath and sheath of a plasma near a wall partially reflecting ions and electrons are determined from a kinetic analysis. Since velocities of the ions and electrons near the wall are highly non-Maxwell-Boltzmann distributions, accurate predictions of transport variables such as density, fluid velocity, mean pressure, fluidlike viscous stress and conduction require kinetic analysis. The result find that dimensionless transport variables of ions and electrons in the presheath and sheath can be exactly expressed in terms of transcendental functions determined by dimensionless independent parameters of ions and electrons reflectivities of the wall, ion-to-electron mass ratio, charge number and electron-to-ion temperature ratio at the presheath edge. The effects of the parameters on transport variables at the wall are also obtained. The computed transport variables in the presheath and sheath show agreement with available theoretical data for a completely absorbing wall.

These developmental grade samples were supplied by the Union Chemical Laboratories of Industrial Technology Research Institute(ITRI). The compositions of a series of copolyesters were identified by C1-NMR and H1-NMR. The ethylene terephthalate(ET) units are 8.9¡B33.7¡B37.9% and trimethylene terephthalate(PT) units are 91.1¡B66.3¡B62.1% in the copolyesters with sample codes of C2¡BC3¡BC4. Differential scanning calorimeter(DSC) was used to study the isothermal crystallization kinetics and melting behaviors and Polarizing Microscope(PLM) was used to study the spherulite growth rates and spherulite patterns. The Hoffman-Weeks linear plot and M-X nonlinear plot gave an equilibrium meiting temperature(Tmo ) oC of C2¡BC3¡BC4 are (240.6¡B275.5)¡B(208.8¡B247.0)¡B(194.3¡B229.4). The growth rates (£gm/s )of different samples in the different crystallination temperature(Tc) oC are C2(0.614~0.061, 180~207)¡BC3(0.112~0.021, 130~166)¡BC4(0.0213~0.003, 120~160). From the different equilibrium meiting temperature(Tmo ) and different T¡Û = ( Tg-30, Tg-51.6 oC) to analysis the regime transition temperature (T¢º¡÷¢») in units of oC are C2(234.0¡B237.1¡B240.6¡B275.5¡A195.9¡Ó0.3, 196.2¡Ó0.4)¡BC3(193.1¡B198.9¡B208.8¡B247.0¡A147.5¡Ó0.2, 147.5¡Ó0.1)¡BC4(184.1¡B187.9¡B194.3¡B229.4¡A133.3¡Ó0.4, 133.6¡Ó0.2). Compare the results with the results that using the half-time of crystallization(t1/2) from DSC (C2(193.6 oC)¡BC3(147.3 oC)¡BC4(1140.4 oC)). It can find that C2 is over 2.3 and 2.6 oC and C3 is the same and C4 is under 6.8 and 7.1 oC. From the morphology of spherulite patterns and regime transition temperature (T¢º¡÷¢») oC, the results indicated that the change from the morphology is closed to regime transition temperature. Regular spherlites were exhibited at temperature(Tc) between 180 and 196 oC and banded spherulites were observed between 197 and 208 oC in the C2. The band spacing increase with increasing crystallization temperature. Regular spherlites were exhibited at temperature(Tc) between 130 and 147 oC and banded spherulites were observed between 148 and 172 oC in the C3. The band spacing increase with increasing crystallization temperature. Regular spherlites were exhibited at temperature(Tc) between 120 and 134 oC and banded spherulites were observed between 135 and 160 oC in the C4. The band spacing increase with increasing crystallization temperature. Combine the results of M-X plot and spherulites pattern and melting behaviors at a heating rate of 80 oC/min . It indicated that the regime transition temperature (T¢¹¡÷¢º) oC are in the range of crystallization temperature of C2¡BC3¡BC4 are (210~213¡B174~178¡B160~164 oC). The heat of fusion (¡µHu) of C3 is 4.88¡Ó0.06 kcal/mol and B is 1.47¡Ó0.05 cal/c.c from the experimental. The heat of fusion(¡µHu) of C4 is 2.56¡Ó0.22 kcal/mol and B is 4.45¡Ó0.36 cal/c.c from the experimental. Compare the results with PET(¡µHu = 5.6 kcal/mol) and PTT(¡µHu = 7.2 kcal/mol). It indicated that PTT > PET > C3 > C4.

Immobilization and detoxification of chromium in the vadose zone is made possible by the existence of an effective reductant, SO2, that exists in a gaseous form at room temperature. Experimental studies were designed to characterize stoichiometry and kinetics of chromium reduction both in aqueous solutions at pH values near neutrality and in soil. First, batch experiments and elemental analyses were conducted to characterize the stoichiometry and kinetics of Cr(VI) reduction in water. The stoichiometric ratio of S(IV) removed to Cr(VI) removed ranged between 1.6 and 1.8. The overall reaction is believed to be the result of a linear combination of two reactions in which dithionate is an intermediate and sulfate is the stable oxidized product. The reaction was also rapid, with the half-time of about 45 minutes at pH 6 and about 16 hours at pH 7. A two-step kinetic model was developed to describe changes in concentrations of Cr(VI), S(IV), and S(V). Nonlinear regression was applied to obtain the kinetic parameters. The rate of reaction was assumed to be second-order with respect to [Cr(VI)] and first-order with respect to [S(IV)], and [S(V)]. The values for the rate coefficient for the first reaction (k1) were found to be 4.5 (?10%), 0.25 (?9.4%) (mM-2h-1) at pH 6 and 7, respectively. The values of the rate coefficient for the second reaction (k2) were 25 (?29%), 1.1 (? 30%) (mM-2h-1) at pH 6 and 7, respectively. The reaction rate decreased as pH increased. Experiments showed that the rate at pH 7 was lower than that at pH 6 by one order of magnitude. Second, batch experiments and elemental analyses were conducted to characterize the stoichiometry and kinetics of Cr(VI) reduction in soil. The stoichiometric ratio of S(IV) removed to Cr(VI) removed was almost 2, which is slightly higher than that for the reaction in water. This higher value may be due to S(IV) oxidation by soil-derived Fe(III). The reaction was rapid, with the half-time less than 2 minutes, which is faster than in water. The rate coefficients, k1 and k2, were 22 (?41%) and 13 (?77%) (M-2h-1), respectively.

The killing effectiveness of electron beam irradiation has not been completely characterized. The type of microorganisms and the composition of food have a direct effect on the efficiency of this technology. The objectives of this study were to select a surrogate suitable for use in electron beam irradiation studies of fruits and to evaluate the effect of sugar content on the kinetics of microbial damage and recovery. A 2.0 MeV Van de Graaff linear accelerator was used to apply irradiation (up to 5.0 kGy), using different configurations, on gelatin-based systems with the addition of sugars. The systems were inoculated with pathogenic and non-pathogenic bacteria strains (surrogates). Initial studies showed that Escherichia coli K-12 MG1655 is a suitable surrogate that represents the damage induced to common fruit pathogens by irradiation. The reduction in bacteria population can be maintained by storing samples at 4°C. An increase in temperature up to 20°C was enough for the damaged population to recover in 48 hours. Gelatin-based systems proved to be a simple and inexpensive medium to evaluate the effects of irradiation (up to 5.0 kGy) on selected bacteria. Reduction of the system dimensions and their positioning related to the beam source were key factors in increasing the killing effectiveness of irradiation. The sugar levels (up to 8 %) used to mimic the maturity of cantaloupes had no effect on the radiation D10 values and the recovery of the surrogate population quantified as Generation Times. The resistance of the surrogate to irradiation was validated in an optimum configuration and in cantaloupes. Temperature and sugar content caused significantly higher changes to the physical structure of the gel-based systems than irradiation (1.0 kGy). Plate counts and light microscopy techniques demonstrated that the structure of the gelatin-based systems allow for motility of the bacteria in a 3-D array (length, width and depth). When little information was available about the effectiveness of using a low energy linear accelerator, the inoculation of gelatin-based systems proved to be a reliable method to select a suitable surrogate and to predict the effects of irradiation on bacteria as a function of sugar content.

<p>The focus of this thesis is to explore and use the benefits of time-varying excitation in fluorescence spectroscopy for studies of biomolecular dynamics. Two new techniques taking advantage of modulated excitation are presented. Also described are the first efforts in a project where single molecule FRET and multi-parameter fluorescence detection are used for characterization of the conformational dynamics of the retinoid X receptor (RXR).</p><p>RXR is one of the most important proteins in the group of nuclear receptors. It is believed to be involved in many diseases and is hence most interesting as a potential drug target. Our study is at present at a very early stage and some sample issues are still to be resolved. However, single molecule measurements should give insights not attainable by previously applied ensemble methods and help explaining how RXR can regulate so many different processes.</p><p>Long-lived transient states of fluorescent molecules can, because of their long lifetimes, be used to detect subtle changes in the microenvironment of the molecule. A method for determining the kinetic rates for transitions to and from such states by registration of changes in the average fluorescence intensity related to different modulation of the excitation source is introduced. It combines the sensitivity of fluorescence with the environmental sensitivity of the long-lived transient states and allows the use of slow detectors such as CCD cameras, making parallelization and imaging possible developments. The approach was experimentally verified by measurements of the triplet kinetics of rhodamine 6G (Rh6G) in aqueous solution and compared with fluorescence correlation spectroscopy (FCS). It should also be applicable to any other photoinduced transient states affecting the fluorescence intensity.</p><p>A strategy to combine FCS with modulated excitation, in a way that allows extraction of correlation data for all correlation times, is presented. This enables the use of modulation to optimize the measurement conditions with respect to the photophysical properties of the dyes used. Measurements were made on Rh6G to verify the method. To illustrate its usefulness, it was applied to measurements of protonation kinetics of fluorescein at different pH. FCS with modulated excitation will most probably prove very useful in many future studies involving multiple kinetic processes occurring in overlapping time ranges.</p>

Thesis (Ph.D.)--University of Delaware, 2009. / Principal faculty advisor: Dionisios G. Vlachos, Dept. of Chemical Engineering. Includes bibliographical references.

Thesis (Ph. D.)--University of Texas at Austin, 2001. / Vita. Includes bibliographical references. Available also from UMI Company.

Thesis (Ph. D.)--University of Washington, 2001. / Vita. Includes bibliographical references (leaves 76-85).

Thesis (Ph. D.)--University of Queensland, 2002. / Includes bibliographical references.

Thesis (M. Phil.)--University of Hong Kong, 1977.