A laboratory test program was conducted to determine the moisture-suction relationships of geosynthetic clay liners (GCLs). Moisture-suction relationships were determined by combining suction data from pressure plate tests, contact filter paper tests, and relative humidity tests, then fitting water retention curves (WRCs) to the data. WRCs were determined for wetting processes and drying processes in terms of gravimetric moisture content and volumetric moisture content. The effects of GCL type, hydration solution, wet-dry cycles, and temperature on the moisture-suction relationships were analyzed. The three GCLs of the test program consisted of configurations of woven and nonwoven geotextiles reinforced with needlepunched fibers. A geofilm was adhesively bonded to the nonwoven side of one of the GCL products. The hydration solution tests involved hydrating GCLs with deionized water, tap water, 0.1 M CaCl2, or soil water from a landfill cover test plot for a 30-day conditioning period prior to testing. Cyclic wet-dry tests were conducted on the GCL specimens subjected to 20 wet-dry cycles from 50% to 0% gravimetric moisture content prior to testing. Temperature tests were conducted at 2°C, 20°C, and 40°C. GCL type affected moisture-suction relationships. The GCLs with an adhesively-bonded geofilm exhibited lower air-entry suction and higher residual suction than GCLs without a geofilm. The degree of needlepunched fiber pullout during hydration contributed to hysteresis between wetting WRCs and drying WRCs. Hysteresis was high for suction values below air-entry suction and was low for suction values greater than air-entry suction. Cation exchange reduced the water retention capacity for all three GCL types. The saturated gravimetric moisture contents were reduced from approximately 140% to 70% for wetting WRCs and 210% to 90% for drying WRCs for GCLs hydrated in deionized water compared to CaCl2 solution. Hysteresis of the nonwoven product decreased from 71%, to 62%, to 28% with respect to deionized water, tap water, and CaCl2 solution. Hysteresis of the woven product exposed to soil water was 24% and 0%, in terms of saturated gravimetric moisture content and saturated volumetric moisture content, respectively. The swell index, Atterberg Limits, mole fraction of bound sodium, and scanning electron microscopy images that were determined of bentonite from the conditioned GCLs indicated that changes in water retention capacity corresponded with cation exchange. Wet-dry cycles and temperature affected the moisture-suction behavior for GCLs. Wet-dry cycles reduced hysteresis and increased the swelling capacity of GCL specimens. Microscopy images indicated that wet-dry cycles caused weak orientation of the clay particles. Increasing temperature resulted in a small decrease in water retention capacity. Results of the test program provided a means for predicting unsaturated behavior for GCLs.

No description available.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23598号 / 理博第4760号 / 新制||理||1682(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 寺西 利治, 教授 若宮 淳志, 教授 倉田 博基 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Mesoporous silica gel containing embedded phosphotungstic acid (PTA) was synthesized by sol-gel co-condensation of tetraethoxysilane with PTA in acidic media. The obtained material had high BET surface area and pore volume. A characteristic band of the Keggin structure of PTA was present in its FT-IR spectrum while its XRD patterns were absent. This proved the embedding of PTA on a sub-molecular level. The material demonstrated high adsorption capacity of Cs. Unexpectedly, porosity of the adsorbent increased after substitution of most protons by cesium cations. Cation exchange also favored agglomeration of the material particles. Kinetic studies showed that the adsorption data correlates strongly with the pseudo-second order model. The adsorbent had two types of adsorption sites: heteropolyacid anions and silanol groups. However, adsorption on silanol groups was very sensitive to the temperature. At the increased temperature, the nature of adsorption fit the Langmuir model extremely well. The obtained results can be used in the development of an effective adsorbent for clean-up of water contaminated by radioactive cesium-137.

>Magister Scientiae - MSc / Studies involving the use of natural clays such as bentonite, montmorillonite and natural zeolite clinoptilolite in water treatment have been reported. Researchers suggested cost effective processes, such as ion-exchange and adsorption for the removal of heavy metals from waste waters by using naturally occurring and synthetic materials. The current study investigated application of natural adsorbents in brine treatment. Brines are hypersaline waters generated in power stations and mining industries rich in Mg2+, K+, Ca2+,Na+, so,': cr and traces of heavy metals, thus there is a need for these brines to be treated to recover potable water and remove problematic elements. Natural adsorbents have been successfully used in waste water treatment because of their high surface area and high adsorptive properties when they are conditioned with acid or base. The natural adsorbents used in this study were obtained from Ecca Holdings company (Cape bentonite mine) Western Cape in South Africa, comprising bentonite clay and natural zeolite (clinoptilolite) and another clinoptilolite sample was obtained from Turkey. These adsorbents were investigated in their natural and pretreated form for removal of toxic elements in brine water. The pretreatment was aimed at removing Na+, K+, Ca2+, Mg2+ from the clinoptilolite as well as the bentonite and replacing these cations with the H+ cation to activate the materials. The cation exchange capacity (CEC) of natural zeolite from South Africa was found to be 2.14 meq/ g, Turkish Clinoptilolite was 2.98 meq/ g while South African bentonite was 1.73 meq/g. at 25°C using ammonium acetate (pH 8.2) method. Characterization of these natural adsorbents was done prior to pretreatment and after the treatment. ICP-AES analysis was used for determination of toxic elements in brines before and after sorption. The morphology of clays was characterized by X-ray diffraction (XRD), Brunauer Emmett Teller (N2-BET) and Scanning electron microscopy (SEM) for confirmatory purposes and X-ray Fluorescent spectroscopy (XRF) was used for the composition analysis of the natural adsorbent. The results from batch experiments prior to pretreatment of the natural adsorbents showed that these natural adsorbents contained Mg2+, K+, Ca2+, Na+ in their structures as charge balancing cations, thus needed pretreatment to remove the cations. The natural adsorbents were pre-treated with 0.02M HCI. After the pretreatment of natural adsorbents it was possible to enhance the percentage removal of the major cations from brine, and the Na+ and Mg2+ removal achieved (86 % and 85% respectively) from brine was more than C02+ (70% ) the SC was the adsorbent one that gave highest removal of cations in the brines. Trace elements removal was high with Cu2+and Zn2+ being the highest of toxic elements in brine. The optimum contact for the toxic element removal was found to be 30 min for the Turkish clinoptilolite and 1 hr for the South African clinoptilolite and South African bentonite clay. Leaching of Ae+ and Si4+ during adsorption was also investigated and it was found that less than 1 ppm of A13+ and Si4+ were leached into the solution during adsorption experiments indicating that these materials were stable. The investigation of pH showed that natural adsorbents did not perform well at low pH of 4 and 6. The adsorbents were able to work efficiently at the natural pH of 8.52 of the brine solution. These results show that natural adsorbents hold great potential to remove cationic major components and selected heavy metal species from industrial brine wastewater. Heterogeneity of natural adsorbents samples, even when they have the same origin, could be a problem when wastewater treatment systems utilizing natural clinoptilolite and bentonite are planned to be developed. Therefore, it is very important to characterize the reserves fully in order to make them attractive in developing treatment technologies.

The aim of this study was to arrive at a fundamental understanding of kimberlite weathering and of factors which affect the rate and extent of weathering. Weathering was evaluated by measuring the change in size distribution after immersing crushed kimberlite in solutions of various compositions. Reproducibility of the measurements was found to be good, with the cumulative mass passing a given size differing by 7% or less, as tested for various weathering conditions. Kimberlite mineralogy, specifically the swelling clay content, was found to play a central role: kimberlite ores containing no swelling clay were not prone to weathering under any of the conditions tested. The cation exchange capacity (CEC) correlates well with the swelling clay content and with the weathering behaviour. The cation exchange capacity may be used in conjunction with the swelling clay content, as a predictor of possible kimberlite behaviour; however, given the relative complexity and cost of measuring swelling clay content (by X-ray diffraction), the CEC is the preferred parameter for practical use. Cations in the weathering solution have a strong effect on kimberlite weathering; the strength of the effect followed the series Cu2+ > Li+ > Fe2+ > Ca2+ > Fe3+ > Mg2+, whereas K+ and NH4+ stabilised the kimberlite somewhat against weathering. This sequence was in reasonable correlation with the ionic potential (ratio of valency to ionic radius), but with exceptionally strong weathering effects of Cu2+, and (to a lesser extent) of Li+ and Fe2+. The strong effect of the latter group of cations may be related to their tendency to adsorb onto other crystal sites in addition to the interlayer – the associated change in surface energy can change the fracture behaviour of the kimberlite. Measurement of the layer spacing of the swelling clay (by X-ray diffraction) showed no correlation between the weathering effect of a cation and the associated thickness of the interlayer. For solutions of cupric ions, the identity of the anion (chloride or sulphate) has little effect on weathering. The size of the crushed kimberlite ore similarly has little effect on the relative extent of size degradation by weathering. The concentration of cupric ions affects weathering, as does the weathering time – although 85% of the weathering caused by 30 days' exposure was found to occur within the first 24 hours. Increasing the temperature to 40°C (in a magnesium chloride solution) also increased weathering strongly. The kinetics of exchange of cuprous and potassium ions was measured (for two different kimberlites); the apparent reaction order (with respect to the concentration of exchanging cations in solution) varied between 1 and 3.5, and exchange of potassium was more rapid. This work has practical implications for in-plant processing of kimberlite, possible alternative kimberlite processing routes which eliminate one or more crushing steps, and for the stability of mine tunnels which pass through kimberlite. / Thesis (PhD (Metallurgical Engineering))--University of Pretoria, 2006. / Materials Science and Metallurgical Engineering / PhD / unrestricted

Agricultural soil properties exhibit variation over field plot scales that can ultimately effect the yield. This study performs multiple spatial pattern analyses in order to design spatially dependent regression models to better understand the interaction between these soil properties. The Cation Exchange Capacity (CEC) and Calcium-Magnesium Ratio (CaMgR) are analyzed with respect to Calcium, Magnesium, and soil moisture values. The CEC and CaMgR are then used to determine impact on the yield values present for the field. Results of this study show a significant measure of model parsimony (0.979) for the Geographically Weighted Regression (GWR) model of the CEC with free Ca, Mg, and soil moisture as explanatory variables. The model for CaMgR using the same explanatory variables has a much lower measure of model fit. The yield model using the CEC and CaMgR as explanatory variables is also low, which is representative of the underlying processes also impacting yield.

Semiconductor nanocrystals (NCs) have emerged as promising fluorophores in a plethora of applications including lighting and display technologies. Cd/Pb-chalcogenide-based NCs are by far the most studied classes of semiconductor NCs due to their exemplary luminescence properties. However, their toxicity poses a limit to their widespread application and use in biological systems, nanomedicine, as biomarkers, etc. Therefore, the search for alternatives that can replace Cd/Pb-chalcogenide-based NCs as fluorophores in various applications is a topic of rigorous research. This PhD thesis delves into the development of synthetic strategies for one such class of materials that can potentially replace Cd/Pb-chalcogenide-based NCs in various applications. I-III-VI semiconductor NCs, containing earth abundant metals which are comparatively less toxic than Cd and Pb have emerged as a suitable alternative. In this group, Cu-In-S/Se (CIS/Se) based NCs have gained significant interest due to their nontoxic nature and interesting optical properties. The principal aim of this thesis is to develop synthetic strategies to obtain morphologically vivid CIS/Se NCs and study their optical properties. Due to the multiple reactive species present in ternary /quaternary NCs, direct method of synthesis wherein all precursors are reacted at the same time exhibit problems of inhomogeneous size, shape, and compositions, along with binary byproducts formed in addition to the desired ternary/quaternary NCs. In view of this limitation of direct method of synthesis, a cation exchange (CE) pathway of synthesis has been developed. In this approach, a binary NC is first synthesized using a conventional direct method, which then serves as a host lattice for the incoming third or fourth cation thus leading to the synthesis of ternary or quaternary multicomponent NCs. Employing this route enables the preservation of the morphology and crystal structure of the host NC after the exchange process, leading to better control over size, shape, and composition of the desired NCs. In this thesis, 0D spherical Cu-Zn-In-Se (CZISe) NCs were synthesized using a CE approach starting with binary Cu2-xSe NCs and thereafter the composition dependence of their optical properties was studied. The synthesized quaternary CZISe NCs exhibited intensive tuneable photoluminescence (PL) in the near infrared (NIR) range and narrow PL band widths in comparison to the band widths generally observed in this class of materials. Long-chain organic ligands on the surface of colloidal NCs limit carrier mobility, and hence surface modification of the NCs becomes necessary for applications where carrier mobility is an important aspect, e.g., in solar cell fabrication. Thus, surface modification of the synthesized CZISe NCs was also explored to make the NCs compatible for prospective applications of solar energy harvesting. In addition to 0D NCs, two-dimensional (2D) NCs have gained significant interest due to their unique anisotropic optical properties. For example, extremely narrow PL band widths were exhibited for CdSe nanoplatelets (NPLs) due to the strong confinement of the NPLs in the thickness direction. These 2D NCs have also been utilized in a wide array of applications, particularly in thin film photovoltaics and optoelectronics, and therefore investigation of 2D morphologies of I-III-VI based NCs is also of utmost interest. In this thesis, 2D Cu-Zn-In-S (CZIS) NPLs were synthesized which exhibited rectangular morphology and were unstacked due to the synthetic strategy employed. CIS NPLs were synthesized using a seed-mediated approach and a subsequent CE with Zn enabled the synthesis of CZIS NPLs. Subsequently, a ZnS shell growth leading to the formation of CZIS/ZnS NPLs resulted in the enhancement of PL intensity. As compared to 2D CIS NCs the Se counterpart is less studied and very few reports of 2D CISe-based NCs are present in literature and the reported 2D CISe based NCs have not exhibited any PL. Due to the narrower band gap of CISe than CIS, it is possible to push the PL into the NIR range which unlocks new applications and therefore developing synthetic strategies for 2D CISe based NCs which exhibit PL in the NIR range was also explored in this synthesis. CISe NPLs were synthesized using a similar seed-mediated approach used for CIS NPLs, but the difference in reactivities of S and Se required significant optimization of the synthesis parameters. A subsequent CE with Zn resulted in the synthesis of CZISe NPLs with inherent PL in the NIR range with very narrow PL band widths.

A laboratory test program was conducted to investigate the effects of temperature, solution strength, and applied stress over increasing conditioning durations on cation exchange processes in sodium bentonite (Na-B) geosynthetic clay liners (GCLs). The test program was intended to determine if the variables of temperature, solution strength, and applied stress had beneficial or detrimental effects on the engineering behavior of Na-B GCLs in municipal solid waste (MSW) landfills and laboratory testing applications. Needlepunched-reinforced, double non-woven Na-B GCL specimens were conditioned in fluids of increasing ionic strength (DI water, 2 mM CaCl2, 50 mM CaCl2, and 200 mM CaCl2 representing control, pore water, mild MSW leachate, and harsh MSW leachate, respectively), temperatures of 5 degrees C, 20 degrees C, 40 degrees C, and 60 degrees C, and overburden stresses (30 kPa and 500 kPa representing stresses experienced by cover and bottom liner systems, respectively) which are all representative of geoenvironmental conditions observed in MSW landfill barrier systems. Cation exchange in the bentonite component of all conditioned Na-B GCL specimens was quantified by measuring the bound cation (BC) complexes and cation exchange capacities (CEC) of the specimens using inductively coupled plasma-optical emission spectroscopy (ICP-OES) analysis and by conducting index tests to determine the dimensional characteristics, swell index, and gravimetric moisture content of the specimens. For zero stress conditions, periodic measurements of electrical conductivity, total dissolved solids, sodium and calcium cation concentration, and temperature of the conditioning fluids were recorded to supplement bound cation complex data. For applied stress conditions, electrical conductivity, total dissolved solids, and temperature of the conditioning fluid were recorded. For zero stress conditions, 152 mm x 152 mm Na-B GCL specimens were conditioned in all conditioning fluids and temperatures over increasing time durations ranging from 4 hours to 32 days. For applied stress conditions, 60-mm-diameter Na-B GCL specimens were conditioned in 50 mM CaCl2 conditioning fluid at all temperatures for 4 to 16 days under the applied overburden stresses of 30 kPa and 500 kPa. Temperature, solution strength, and applied stress were all observed to affect cation exchange in the bentonite component of Na-B GCLs. Cation exchange processes were observed to increase with increasing temperature, increasing solution strength, and decreasing applied overburden stress. The majority of cation exchange processes were observed to occur within 8 to 10 days for specimens conditioned under zero stress. Cation exchange processes were observed to have a higher sensitivity to changes in solution strength (up to 625% increase in the change of Na+ BC from DI water to 200 mM CaCl2) compared to changes in temperature (up to 52% increase in the change of Na+ BC from 5 degrees C to 60 degrees C) in zero stress conditions. Changes in the bound cations of the Na-B GCL specimens over time were not reflected in the periodic electrical conductivity measurements taken of the high strength conditioning fluids. The results of this study can be used for quality assurance evaluations of in-service GCLs using thresholds developed for index properties. From the numerical thresholds determined in this study, hydrated Na-B GCL specimens sampled from the field conditioned under zero stress that exhibit swell indices greater than or equal to approximately 70% of the swell index reported by the manufacturer and gravimetric moisture contents of greater than or equal to approximately 200% will likely exhibit adequate hydraulic barrier performance. Hydrated Na-B GCL specimens sampled from the field conditioned under zero stress that exhibit swell indices of less than or equal to approximately 20% of the swell index reported by the manufacturer and gravimetric moisture contents of less than or equal to approximately 100% will likely exhibit inadequate hydraulic barrier performance. The Na-B GCL component of cover liner systems may be susceptible to high rates of cation exchange due to experiencing low overburden stress and elevated temperatures compared to typical earth temperatures. The Na-B GCL component of bottom liner systems may exhibit low rates of cation exchange due to experiencing high overburden stress and cooler temperatures.

Mesoporous silica gel containing embedded phosphotungstic acid (PTA) was synthesized by sol-gel co-condensation of tetraethyl orthosilicate with PTA in acidic media. The obtained material had high Brunauer-Emmett-Teller Theory (BET) surface area and pore volume. A characteristic band of the Keggin structure of PTA was present in its FT-IR spectrum while its X-ray diffraction patterns were absent. This proved the embedding of PTA on a sub-molecular level and not as a second phase. Acidic sites were determined by neutralization with base in aprotic solvent, followed by titration of the remaining base with an acid. The material demonstrated high adsorption capacity of Cs. Kinetic studies showed that the adsorption data correlates strongly with the pseudo-second order model. At higher temperatures, the nature of adsorption fit the Langmuir model extremely well. The obtained results can be used in the development of an effective adsorbent for clean-up of water contaminated by radioactive 137Cs.