It is accepted worldwide that the best final solution for spent nuclear fuel is to bury it in deep geological repositories. Despite the physical and chemical barriers that are supposed to isolate the nuclear waste for at least 100.000 years, some uncertainty factors may cause underground water to get in contact with the nuclear waste. Due to radioactivity and oxidation under air, dissolution experiments using UO2 pellets are difficult and frequently lead to incoherent results. Therefore, to enable a detailed study of the influence of microstructure and surface properties on the stability of spent nuclear fuel over time, it is necessary to produce analogues that closely resemble nuclear fuel in terms of crystallography and microstructure. At the same time, in-depth understanding of dissolution phenomena is crucial to geological processes such as dissolution precipitation creep and solvent mediated phase transformations. My thesis is based in two manuscripts. Paper I reports the microstructures obtained after sintering CaF2 powders at temperatures up to 1240°C. Pellets with microstructure, density and pore structure similar to that of UO2 spent nuclear fuel pellets were obtained in the temperature range between 900°C and 1000°C. Paper II reports how differences of surface chemistry and crystal symmetry, characteristics of each surface orientation, affect the topography of CaF2 pellets described in paper I during dissolution. I propose that every orientation of the fluorite structure can be decomposed in the three reference surfaces {100}, {110} and {111}. The {111} is the most stable surface with a dissolution rate of the top surface of 1,13x10-9 mol.m-2.s-1, and {112} the less stable surface with a dissolution rate 34 times faster that {111}. Surfaces that expose both Ca and F atoms in the same plan dissolve faster, possibly because the calcium is more susceptible to be solvated. The faster dissolving surfaces are replaced by the more stable {111} and {100} surfaces which causes the development of roughness on the top surface and stabilizes the surface on high energy sites; i.e. pores or grain boundaries. The main consequences of these observations are i) the increase of the total surface area; ii) the decrease of the overall surface energy. I present a dissolution model for surfaces of crystal with different surface energies. The main conclusions are: a) dissolution rates calculated from surface area are over estimated to the real dissolution rate; b) dissolution rates are faster at the beginning of dissolution and tend to diminish with time until a minimum value is reached.

<p>Istraživanja iz okvira ove doktorske disertacije obuhvatila su optimizaciju, kinetičko modelovanje i simulaciju dobijanja etanola fermentacijom izluženih repinih rezanaca ili ekstrakcionog, retkog i gustog soka primenom metode odzivne povr&scaron;ine, različitih kinetičkih modela i programa SuperPro Designer, redosledom.<br />Optimizacijom bioprocea doprineto je razumevanju različitih operativnih uslova, kao i međusobnih interakcija ispitanih varijabli na predtretman, hirolizu i fermentaciju date biomase. Izvođenjem procesa pod optimalnim uslovima definisana kinetika proizvodnog procesa, a dobijeni kinetički modeli su omogućili projektovanje čitavog bioprocesa kroz simulaciju. Krajnji model bioprocesa može olak&scaron;ati definisanje materijalnih i energetskih bilansa, dimenzionisanje opreme, pravljenje plana proizvodnje, analizu produktivnosti i uklanjanje &bdquo;uskih grla&ldquo;, analizu tro&scaron;kova, ekonomske isplativosti i kapaciteta proizvodnje, sprečavanje zagađenja i njenu kontrolu, itd.<br />Na osnovu toga se mogu dobiti konkretni podaci koji olak&scaron;avaju dono&scaron;enje odluka o ulaganju, odnosno realizaciji projekta datog bioprocesa.</p> / <p>Research from this framework of this study included optimization, kinetic modeling and simulation of obtaining ethanol by fermentation of spent sugar beet pulp or raw, thin and thick juice by using RSM (Response Sruface Methodology), different kinetic equations and software SuperPro Designer, respctively.<br />Bioprocess optimization contrbuted to better understanding of different operating conditions, as well as the interactions of examined parameters on pretreatment, hydrolysis and fermentation of lignocellulosic feedstock. Running the process under optimal conditions made it possible to define the kinetics of the production process, and tha obtained kinetic models were used to design the entire process through simulations. The obtained final model of the bioprocess can faciliatate defining the material and energy balances, equipment sizing, production planing, productivity analysis, debottlenecking, cost analysis, economic feasibility and production capacity, pollution prevention and control, etc.<br />Based on that, concrete data could be obtained which facilitate decision making about investing, i.e. this bioproces project realisation.</p>

The purpose of this study was to analyze the amount of time spent shopping by family members. The researcher also intended to identify factors that influence the amount of time devoted to shopping. Data for the study came from the Utah portion of the "Interstate Comparison of Urban/Rural Families' Time Use" which involved 210 two - parent / two -child families in Utah. Data were collected through interviews with the homemakers in each family using diaries and an information questionnaire . Shopping time of the homemaker, spouse, and children were analyzed. The factors considered included employment status of the homemaker, place of residence, family income level, age of younger child, and the number of family members 16 and elder. Statistical analysis W3S done using a Pearson product moment correlation, a t test, and analysis of variance. Findings revealed that shopping is an activity that consumes approximately 10% of total housework time of all family members. The homemaker spends more minutes per day shopping than any other family member. Time spent in paid employment by the homemaker seems to be the major factor influencing her time spent shopping. The more time spent in paid employment, the less time the homemaker spent shopping. The factors influencing the shopping time of children are level of family income and age of child. As level of family income increases, the amount of time spent shopping by the child increases. It was found that as children get older, they spend less time shopping. The shopping time of the wife was the only factor related to the shopping time of the husband. As the wives' shopping time increased, the amount of time spent shopping by husbands also increased.

No description available.

This research study was designed to help illuminate if there is a relationship between the quality of career and technical education programs from centralized and decentralized-controlled systems in relation to the level of authority exerted by state governing/coordinating boards over the community college system. This study included data from the 50 states that are part of the United States of America. This study used a quasi-experimental, nonequivalent design. This study did not include randomly selected groups and was a nonequivalent control group design. The independent variables included: centralized or decentralized governance, median household income, the percent of community colleges that are rural, unemployment rate, and amount spent per full time enrolled community college student. The independent variable data that was collected came from the Bureau of Labor and Statistics, the United States Census Bureau, and the Integrated Post-Secondary Education Data System (IPEDS). The dependent variable was the mean score of Carl Perkins Act reporting data that each state is required to report to federal authorities every year. The states were divided in two separate groups, centralized or decentralized form of governance. A regression analysis was performed in order to analyze if a relationship exists between the independent and dependent variables for each group. The research indicated that the form of governance does impact Carl Perkins Act reporting scores in a decentralized form of governance in relation to median income, but overall the model is not a good predictor of overall scores. A significant difference was found in states that have a decentralized form of governance and median household income in relation to Carl Perkins Act reporting data. However, the model, as a whole, did not produce significant results in relation to the independent and dependent variables. Considerations for future research are discussed.

The kinetics for radiation induced dissolution of spent nuclear fuel is a key issue in the safety assessment of a future deep repository. Spent nuclear fuel mainly consists of UO2 and therefore the release of radionuclides (fission products and actinides) is assumed to be governed by the oxidation and subsequent dissolution of the UO2 matrix. The process is influenced by the dose rate in the surrounding groundwater (a function of fuel age and burn up) and on the groundwater composition. In this licentiate thesis the effects of HCO3- (a strong complexing agent for UO22+) and ionic strength on the kinetics of UO2 oxidation and dissolution of oxidized UO2 have been studied experimentally. The experiments were performed using aqueous UO2 particle suspensions where the oxidant concentration was monitored as a function of reaction time. These reaction systems frequently display first order kinetics. Second order rate constants were obtained by varying the solid UO2 surface area to solution volume ratio and plotting the resulting pseudo first order rate constants against the surface area to solution volume ratio. The oxidants used were H2O2 (the most important oxidant under deep repository conditions), MnO4- and IrCl62-. The kinetics was studied as a function of HCO3- concentration and ionic strength (using NaCl and Na2SO4 as electrolytes). The rate constant for the reaction between H2O2 and UO2 was found to increase linearly with the HCO3- concentration in the range 0-1 mM. Above 1 mM the rate constant is independent of the HCO3- concentration. The HCO3- concentration independent rate constant is interpreted as being the true rate constant for oxidation of UO2 by H2O2 [(4.4 ± 0.3) x 10-6 m min-1] while the HCO3- concentration dependent rate constant is used to estimate the rate constant for HCO3- facilitated dissolution of UO22+ (oxidized UO2) [(8.8 ± 0.5) x 10-3 m min-1]. From experiments performed in suspensions free from HCO3- the rate constant for dissolution of UO22+ was also determined [(7 ± 1) x 10-8 mol m-2 s-1]. These rate constants are of significant importance for simulation of spent nuclear fuel dissolution. The rate constant for the oxidation of UO2 by H2O2 (the HCO3- concentration independent rate constant) was found to be independent of ionic strength. However, the rate constant for dissolution of oxidized UO2 displayed ionic strength dependence, namely it increases with increasing ionic strength. The HCO3- concentration and ionic strength dependence for the anionic oxidants is more complex since also the electron transfer process is expected to be ionic strength dependent. Furthermore, the kinetics for the anionic oxidants is more pH sensitive. For both MnO4- and IrCl62- the rate constant for the reaction with UO2 was found to be diffusion controlled at higher HCO3- concentrations (~0.2 M). Both oxidants also displayed ionic strength dependence even though the HCO3- independent reaction could not be studied exclusively. Based on changes in reaction order from first to zeroth order kinetics (which occurs when the UO2 surface is completely oxidized) in HCO3- deficient systems the oxidation site density of the UO2 powder was determined. H2O2 and IrCl62- were used in these experiments giving similar results [(2.1 ± 0.1) x 10-4 and (2.7 ± 0.5) x 10-4 mol m-2, respectively]. / QC 20101116

No description available.

No description available.

Unwanted uranium released in the aquatic environment from uranium mining and nuclear fuel industry has become a growing threat to human health and environment safety due to its radiological and chemical toxicity. Biosorbents from agro-industrial waste are the most preferred materials for the removal of uranium from the wastewater due to their good cost-to-performance ratio. Brewer’s spent grain (BSG), a widely produced by-product from the beer brewery industry, is an inexpensive and readily available feedstock for the production of uranium biosorbents. In the current work, the use of BSG as a promising starting feedstock for low-cost and efficient adsorbents with high adsorption capacity, fast kinetics, selectivity, and reusability, is investigated. Functionalization methods such as thermal treatment, chemical modification (oxidation), and polymer grafting were explored, and the selectivity was tuned using surface ion-imprinting technology. The adsorption performance of adsorbents prepared from BSG was tested under various conditions for practical application, and structure affinity principles were derived from the characterization, data modeling and experimental results (Fig. 1). In the first part of this work, BSG is successfully converted into altered BSG (ABSG), an effective biosorbent, by mild hydrothermal treatment approach (150 ℃, 16 h). Compared with the conventional hydrothermal carbonation method (up to 250 ℃), the current method is carried out at a significantly lower temperature without any additional activation process, which minimizes the energy consumption and environmental impact during the treatment. Maillard reaction plays an important role in increasing the adsorption capacity by forming various Maillard reaction products (methylglyoxal-derived hydroimidazolone-1 with the highest content) and melanoidins with a large number of functional groups. In addition, other pathways such as dehydration, decarboxylation, aromatization and oxidation also contribute to the increased adsorption capacity. Therefore, the content of carboxyl groups in ABSG increases up to 1.46 mmol/g with maximum adsorption capacities for La(Ⅲ), Eu(Ⅲ), Yb(Ⅲ) (pH = 5.7), and U(Ⅵ) (pH = 4.7) of 38, 68, 46 and 221 mg/g, respectively (estimated by the Langmuir model). Moreover, FT-IR spectra show that both O- and N-containing functional groups are involved in the adsorption of studied ions. The second part of this work demonstrates for the first time the successful oxidization of BSG using 85 wt% H3PO4 and NaNO2, increasing the carboxyl groups content from 0.15 mmol/g for BSG to 1.3 mmol/g for oxidized BSG (OBSG). OBSG exhibits fast adsorption kinetics in 1 h and an adsorption capacity for U(Ⅵ) of 297.3 mg/g (c0(U) = 900 mg/L, pH = 4.7), which is superior to other biosorbents reported in the literature. Possible adsorption mechanisms are based on ion-exchange between UO22+ and H+ released from carboxyl groups, and the complexation of UO22+ with the two oxygen atoms of carboxyl groups. For practical application, adsorption/desorption studies show that OBSG retains 60% of original adsorption capacity (167 mg/g) with a desorption ratio of 89% after 5 adsorption/desorption cycles. Evaluation of OBSG performance in simulated seawater (10.8 mg/g, c0(U) = 10 mg/L, 193 mg/L NaHCO3 and 25.6 g/L NaCl, pH0 = 7.7) indicates a potential usage at low concentration, high salinity, and in the presence of carbonate. In the third part of this work, brewer’s spent grain supported superabsorbent polymers (BSG-SAP) with various cross-linking density are prepared for the first time via one-pot swelling and graft polymerization of acrylic acid (AA) and acrylamide as low-cost and environmentally friendly adsorbents. A 7 wt% NaOH solution was used as a swelling agent for BSG and as a neutralization agent for AA without generating alkaline effluents. The use of BSG and graft polymerization can significantly increase the available hydroxyl, carboxyl and amide groups, resulting in a highly cross-linked and highly hydrophilic three-dimensional polymer network of BSG-SAP. The BSG-SAP (BSG-SAP-H) prepared with high cross-linking density exhibits better properties with exceptional adsorption capacity for U(VI) of 1465 mg/g (estimated by the Toth model) at pH0 = 4.6 within 45 min. It also shows good selectivity for U(VI) in the presence of several metal ions (V(V), K(I), Na(I), Mg(II), Zn(II), Co(II), Ni(II), and Cu(II)) with selectivity coefficients (SU) higher than 72%. In simulated seawater, BSG-SAP-H showed higher adsorption capacity (17.6 mg/g for c0(U) = 8 mg/L, pH0 = 8) compared to the currently reported adsorbents based on natural polymers. In the experiments with the fixed bed column (c0(U) = 30 mg/L), the uranyl ions could be concentrated up to 15 folders in U(VI)-spiked water and up to 13 folds in simulated seawater. Moreover, after four cycles, BSG-SAP-H was able to maintain 80% of adsorption capacity in U(VI)-spiked water (254.4 mg/g) and 90% in simulated seawater (37.4 mg/g). FT-IR and 13C solid-state NMR spectra show the function of amide groups for U(VI) adsorption, the bidentate binding structure between UO22+ and the carboxyl groups, and the cation exchange between Na+ in BSG-SAP and UO22+. The fourth part of this work describes a new strategy for the preparation of surface ion imprinted brewer’s spent grain (IIP-BSG) using binary functional monomers (2-hydroxyethyl methacrylate and diethyl vinylphosphonate) for selective removal of U(VI). A high monomer/template molar ratio of 500:1 is used to ensure high site accessibility and easy template removal. IIP-BSG exhibits a maximum U(VI) adsorption capacity of 165.7 mg/g (pH0 = 4.6, estimated by the Sips model), a high selectivity (SU > 80%) for U(VI) in the presence of an excess amount of Eu(III) (Eu/U molar ratio = 20), and good tolerance to salinity (47.4 mg/g for U(VI) at ionic strength = 1 mol/L and c0(U) = 0.5 mM = 120 mg/L). After 5 adsorption and desorption cycles, IIP-BSG retains 90% of its adsorption capacity (36.9 mg/g) and high selectivity (SU > 92%) in binary U(VI)/Eu(III) solution (c0 = 0.5 mM = 120 mg/L). In addition, FT-IR spectra show the electrostatic interaction and a coordination of uranyl ions by carboxyl and phosphoryl groups, the site energy distribution theory shows the predominant contribution of high-energy (specific) sites during selective adsorption, and the kinetic model shows that the internal mass transfer is the rate-determining step of U(VI) adsorption. In the last part of this work, the additional tests were performed for BSG and its derived adsorbents to evaluate their potential for practical application. BSG and most of its derived adsorbents retain 90% of their adsorption capacity after aging in water for 6 days, except for ABSG (60% decrease in adsorption capacity). IIP-BSG shows efficient separation of U(VI)/Ln(Ⅲ) (e.g. La(III), and Nd(III), Sm(III)) in weakly acidic nuclear wastewater (pH0 = 3.5) and U(VI) concentration in carbonate-rich-mine water (e.g. Schlema mine water, pH0 = 7.1) and tailings water (e.g. Helmsdorf tailings water, pH0 = 9.8), demonstrating a high potential for practical use. Selectivity of IIP-BSG is also given for acidic mine water (e.g. Königstein mine water, pH0 = 2.6). In addition, the unmodified BSG and BSG-SAP-H could effectively remove uranyl ions from acidic mine water with high selectivity. In particular, the cost efficiency and the availability of unmodified BSG make it of great interests for the remediation of uranium containing acidic mine water (Table 1).

Chloride-induced stress corrosion cracking (CISCC) has been identified as the main degradation mechanism for spent nuclear fuel dry storage canisters. This type of induced cracking is complex and depends on several factors, such as material composition, exposure temperature, relative humidity, applied tensile stress, and atmospheric salt concentration. An accelerated experiment was designed to simulate marine environments in a controlled fogging chamber to examine 304 and 304L stainless steel U-bend and welded U-bend samples. The samples were exposed to chloride rich and humid fogging in a corrosion chamber at 35℃ continuously for 4 weeks, 8 weeks, and 12 weeks. The same experiment was repeated at 50℃ for 4 weeks, 8 weeks, and 14 weeks to study the sensitivity of CISCC to temperature changes. A qualitative evaluation of optical micrographs from a 3D Surface Profiler was performed for 16 corroded samples and compared with 2 reference samples. Cracking was observed on 12 out of 16 samples exposed to 35℃ and 50℃ for durations ranging from 8 to 14 weeks. Likely cracking observations were noted on 4 out of 16 samples. A quantitative statistical analysis was also performed using surface profile depth (valley) data from corroded and reference samples. The quantitative analysis examined the effect of temperature, welding, exposure duration, and material composition. The quantitative results were compared with the qualitative results and literature published in CISCC. / Master of Science / Most nuclear power plants are currently using dry storage canisters (DSCs) which are made of a concrete vault and a stainless steel canister that houses the spent nuclear fuel (SNF) assemblies. Multiple conditions must be present simultaneously for chloride-induced stress corrosion cracking (CISCC) to develop, such as the presence of a susceptible alloy, high relative humidity, high temperature, high atmospheric salt concentrations, and applied tensile stresses. DSCs are typically made from 300-series austenitic stainless steels which are susceptible to this type of corrosion during long-term storage near marine environments. Therefore, understanding of the factors leading to CISCC is critically important for proper management and mitigation and to estimate the service life of DSCs for the safe long-term storage of SNF. An accelerated experiment was designed to examine the effects of temperature, exposure duration, and welding on pitting and cracking for 304 and 304L U-bend samples. The experimental results concluded that stainless-steel grades 304 and 304L are susceptible to CISCC when exposed for 8 weeks or longer to fogging at temperatures between 35℃ and 50℃, 95% relative humidity, and 5% salt concentration. This study also concluded that increasing exposure duration from 8 to 12 weeks or the temperature from 35℃ to 50℃ had no significant effect on the acceleration of CISCC. Also, unwelded samples were deemed more susceptible to CISCC than welded samples and the susceptibility of 304 and 304L grades were relatively similar.