Browsing by Subject "Lead"

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Alkali impurities on quantum thin films : adsorption, electron scattering, and impurity-induced nano-structure formation in the quantum regime
(2008-12) Khajetoorians, Alexander Ako, 1980-; Shih, Chih-kang
For thin epitaxial metal films, when the thickness is on the order of the Fermi wavelength, [lambda subscript F], quantum confinement can dramatically alter the physical properties of the film. These so-called Quantum Size Effects (QSE) can dramatically alter the morphology of thin films by an intricate interplay between kinetics and surface energy driven thermodynamics. These effects lead to rich growth-related phenomena in Pb(111) films grown on semiconductor substrates such as Si(111). For example, QSE can drive flat film formation when growth is dominated by surface energy oscillations. This is rather surprising for Pb/Si systems because of a rather high lattice mismatch. However, these films are not defect free, but rather show common occurrences of three defect types. Low Temperature Scanning Tunneling Microscopy (LT-STM) was utilized to characterize these defects on the atomic scale. Furthermore, these defects create modulations in the electron density resulting in fluctuations in QWS near defect sites. Another topic of recent interest is how QSE affect adsorption of as well as how adsorbates modify QSE for these Pb films. In this thesis, LT-STM and first principles calculations were utilized to study Cs adsorbates on Pb film surfaces, defects, and step edges. Cs adsorption is intricately related to the electronic structure of the surface, especially the defect sites which can act as surface traps. These Cs adsorbates, which are assumed to be ionized, enhance elastic surface scattering of empty-state electrons. This results in observable wave interference patterns near Cs impurities. Furthermore, Cs adsorbates, by an overall step energy reduction, can promote QSE-related nanostructures, which are otherwise too weak when kinetic effects cannot be ignored. This enhancement of "quantum stability" is driven by favorable Cs step binding and can be explained within the contexts of Density Functional Theory (DFT).
Controlled prelithiation of PbS to Pb/Li₂S for high initial Coulombic efficiency in lithium ion batteries
(2018-12) Guo, Yong, M.A.; Mullins, C. B.
PbS nanoparticle aggregates were synthesized in a simple aqueous reaction at room temperature, and were tested as a lithium ion anode material, with a gravimetric capacity of 374 mAh/g at C/2, and a 0.15% capacity loss per cycle. However, its half cell initial Coulombic efficiency (ICE) was only 40%, due to a combination of irreversible Li₂S and solid electrolyte interface (SEI) formations. A custom controlled prelithiation technique was then applied to the PbS electrodes, converting the active material to Pb/Li₂S, and consolidating the SEI prior to coin cell assembly. This brought the ICE from 40% to >97%, and allowed for immediate cycling of the electrode at high Coulombic efficiency, without further formation cycles. Upon construction of prelithiated Pb/Li₂S vs NCM full cells, an 82% ICE was observed, with the majority of the lithium loss from the NCM. The full cells had a combined electrode capacity of 100 mAh/g at C/2
Impact of prechlorination pH on Pb(II)-NOM complexation and lead release in drinking water distribution systems
(2023-08) Goodman, Jacob (Ph. D. in environmental and water resources engineering); Katz, Lynn Ellen
The presence of Pb in drinking water resulting from corrosion of lead pipes, solder and fixtures poses a significant threat to public health and safety. Pb is a potent neurotoxin that can impair the cognitive development of children at low concentrations in the bloodstream. During the corrosion of distribution system components containing Pb, precipitate scales form on the interior surfaces of pipes in the distribution system providing a protective barrier between the bulk solution and the pipe surface; the amount of dissolved Pb²⁺ is controlled by the thermodynamics and kinetics of precipitation/dissolution of the particular Pb scales in the system. The solubility and composition of Pb scales phases residing on the pipe surfaces are a function of the background water chemistry (including pH, redox potential and ligand types and concentration). Therefore, considering the conditional stability of lead scales is crucial when making changes to water treatment processes, as alterations in water quality can significantly disrupt the stability of scales in the DWDS, leading to elevated lead concentrations. In distribution systems that employ monochloramine to provide residual disinfection, the formation of Pb(II) scales such as cerussite (PbCO₃) and hydroxyapatite are favored depending on the background water composition (e.g., phosphates added for corrosion protection or carbonate present). Utilities that chloraminate typically implement a prechlorination step in which free chlorine reacts for a specified time prior to ammonia addition to meet disinfection requirements. During the prechlorination step, free chlorine can react with natural organic matter (NOM) to promote Pb release. The formation of NOM-Pb complexes increases the total soluble Pb in distribution systems containing Pb scales. However, before NOM enters the drinking water distribution system (DWDS) oxidation or nucleophilic substitution of NOM functional groups during prechlorination can decrease the extent of Pb(II)-NOM complexation. The relative impact of these processes on Pb(II) concentrations in drinking water distribution systems must be understood for effective Pb control in DWDS’s containing NOM. In this study, the impact of Pb-NOM complexation on Pb(II) release from cerussite (PbCO₃), a Pb scale phase that can form in the DWDS, is studied in batch dissolution experiments with and without prechlorination. Prechorination of the water containing NOM for a 30-minute contact time decreased the amount of Pb released in the presence of NOM with greater reduction at lower pH. The trends in pH were consistent with the greater reactivity between free chlorine and NOM at lower pH. Additionally, excitation emission matrices (EEMs) and near edge x-ray fine structures (NEXAFS) spectroscopy confirmed that chlorination of the NOM led to destruction of electron rich aromatic moieties that function as prominent ligands in Pb(II)-NOM complexation Further, it was found that fewer in number of disinfection byproducts (DBPs) precursors were generated upon reaction of chlorine and NOM at lower pH conditions. These results demonstrate the potential for chlorination to reduce Pb(II)-NOM complexation. The concentrations of total soluble Pb observed in the batch dissolution experiments ranging from 40 ppb to 600 ppb are not representative of dissolved Pb concentrations in the water distribution system as a Pb concentration of 15 ppb necessitates the implementation of corrosion control measures. Further studies are needed to assess the relative impact of Pb(II)-NOM complexation under continuous flow conditions that more closely mimic pipe flow through conditions representative of water distribution system conditions.
Origin of silver-copper-lead deposits in red-bed sequences of Trans-Pecos Texas : tertiary mineralization in precambrian, permian, and cretaceous sandstones
(University of Texas at Austin. Bureau of Economic Geology, 1985) Price, Jonathan G.
Silver deposits occur in Precambrian, Permian, and Cretaceous red-bed sequences near Van Horn, Texas. These deposits are geochemically similar and contain economically important quantities of silver, copper, and lead, as well as anomalously high amounts of arsenic, zinc, cadmium, and molybdenum. Gold is not enriched. Primary minerals include chalcopyrite, tennantite-tetrahedrite, bornite, galena, sphalerite, acanthite, pyrite, marcasite, barite, and calcite. The deposits are dominantly steeply dipping veins. Strata-bound occurrences are near veins or closely spaced fractures. Structural evidence, including orientations of veins, relative ages of fractures, and relationships to major tectonic events in the region, suggests that the most likely time of mineralization was during late Basin and Range extensional deformation. Ore deposition probably occurred at least 18 m.y. after the period of voluminous silicic volcanism (38 to 28 m.y.a.) in the Trans-Pecos region. Other features indicate that, in contradiction to a hypothesis suggested by previous workers, the deposits did not form as a result of middle Tertiary magmatism. (1) Centers of igneous activity were distant from the sites of mineralization. (2) Potentially reactive limestones above and below the ore zones in red beds are generally unmineralized. (3) Zones of argillic, phyllic, and propylitic alteration typical of igneous-hydrothermal veins are absent. (4) Characteristic igneous hydrothermal gangue minerals such as quartz and fluorite are rare or absent. (5) Homogenization temperatures of fluid inclusions in barite and calcite suggest formation temperatures in the range of 120C to 170C, that is, lower than temperatures typical in copper-lead-zinc-bearing igneous-hydrothermal veins. These temperatures are higher than those usually attributed to strata-bound, red-bed copper deposits. The elevated formation temperatures are the result of high heat flow in the Basin and Range province of Texas at the time of mineralization; they are not the result of igneous activity. The hypothesis developed in this study on the origin of the veins involves a rise of moderate-temperature, moderately saline hydrothermal fluids along Basin and Range fractures and precipitation of metal sulfides in response to mixing with shallow ground water. This hypothesis has implications for exploration of additional deposits in Trans-Pecos Texas and elsewhere.
Predicting ion adsorption onto the iron hydroxide goethite in single and multi-solute systems
(2013-12) Mangold, Jeremiah Edward; Katz, Lynn Ellen
Surface complexation models (SCMs) have proven to be a useful tool in predicting ion adsorption at the mineral – water interface. In particular, previous research has shown that the Diffuse Layer Model (DLM), Constant Capacitance Model (CCM), and Triple Layer Model (TLM), are all capable of predicting ion adsorption in relatively simple single solute systems. To better simulate the environmental conditions experienced by groundwater sources present in the Earth’s subsurface, experimental adsorption studies have been conducted for more complex multi-solute systems. Under these conditions, SCMs have not proven to be reliable in consistently predicting ion adsorption behavior for the adsorbates of interest. This inability of these SCMs to predict ion adsorption for more complex, multi-solute systems is thought to stem from the variable site density (NS) values utilized in these models. In this research, a methodology was developed for characterizing mineral surface heterogeneity that allows for the different site density values predicted from crystallography, microscopic imaging, tritium exchange, surface saturation data, and surface charging data to all be explained using a single unified theory. This methodology was applied to a goethite mineral sample used in performing batch adsorption studies in single and bi-solute systems with Cd(II), Pb(II), and Se(IV). The adsorption behavior of these adsorbates onto the goethite sample was successfully predicted using the Charge Distribution Multi-Site Complexation (CD-MUSIC) Model and surface complexes consistent with spectroscopic data and computational molecular modeling simulations. A second, separate modeling study was performed using CD-MUSIC to predict Hg(II) adsorption onto different goethite samples of varying size and crystal morphology in single and multi-solute systems. In this study, site density values were predicted for the mineral samples studied utilizing a linear relationship observed for goethite between specific surface area and proton reactive site density. The CD-MUSIC model proved successful in predicting Hg(II) adsorption over all conditions studied while employing only surface complexes consistent with molecular scale analyses. In addition, a novel method for quantifying carbonate’s presence in experimental systems was developed.
Scanning tunneling microscope studies of 2D superconductor and 3D intrinsic topological insulator
(2015-05) Nam, Hyoungdo; Shih, Chih-Kang; de Lozanne, Alex; Markert, John T; Fiete, Gregory A; Shi, Li
Electrons show unusual and interesting behaviors both in low dimensions and on material surfaces, distinct from what they display in bulk materials. These intriguing properties have been studied in order to understand their origins. One area where this can be seen is in the case of superconductivity, where superconducting phase fluctuation in a thin superconductor is supposed to substantially suppress the superconductivity of the material as the film thickness decreases. To test this, we prepared epitaxially grown and globally flat lead (Pb) films; here, the thinnest film was 1.4 nm thick. Four different length scale measurements, ranging from the nm to the mm scale, gave consistent superconducting transition temperatures. Our results proved that the film of 1.4 nm still has strong superconducting phase stiffness; namely, the superfluid phase is rigid even in 1.4 nm thin superconductor film. Moreover, the parallel critical magnetic field is remarkably strong so that superconductivity is still observed in Zeeman fields, exceeding the Pauli limit. In addition, the surface of 3D topological insulator has a novel quantum state induced by strong spin-orbit interaction. A number of material studies were conducted to find a surface dominated conduction topological insulator that has a large energy gap and a single Dirac cone. Moreover, it is necessary for the material to be stable against aging unlike most 3D topological insulators, such as Bi₂Se₃. Here, Bi₂Te₂Se and BiSbTeSe₂ were studied in terms of their structures, electronic properties, and aging effects on them. Scanning tunneling microscopy analysis attested that Bi₂Te₂Se is an order alloy, which has a slight randomness of 15 %, whereas BiSbTeSe₂ is a random alloy. Scanning tunneling spectroscopy on BiSbTeSe₂ confirmed that the Dirac point tends to stay around the Fermi level under the strong band structure change, induced by random structure. The most surprising observation was that BiSbTeSe₂ showed remarkable stability despite the rich composition of selenium (Se). Even after aging for seven days, the Fermi level and the Dirac point remained at almost the same level in bulk band gap. Both observations are very important for applications to utilize the exotic topological surface state.
Study of quantum thin films : phase relationship, surface reactivity, and coherent coupling
(2011-08) Kim, Jisun, Ph. D.; Shih, Chih-Kang; de Lozanne, Alegandro; Tsoi, Maxim; Fiete, Gregory A.; Chelikowsky, James R.
When an electronic system is confined in one or more dimensions to a length scale comparable to the de Broglie wavelength, quantum confinement occurs. In metallic quantum thin films grown on semiconductor substrates, such confinement occurs between the vacuum-solid and the solid-solid interfaces, which results in the formation of distinctive quantum well states (QWS). Due to this confinement, many physical phenomena occurring in the thin metal system are totally different from the bulk system, which makes the study of quantum thin films interesting and important. In this thesis, quantum thin film studies, mainly based on the Pb/Si(111) system, were performed utilizing low-temperature scanning tunneling microscopy/spectroscopy (STM/STS) with a focus on three main aspects: phase relationship, surface reactivity, and coherent coupling. The Pb/Si(111) system is chosen due to its unique phase matching between the Fermi wavelength and the lattice spacing along [111], leading to a bi-layer quantum oscillation in many physical properties, including the surface energy and the work function. Surprisingly, STM/STS measurement revealed that quantum oscillations of work function and surface energy have identical phase, in contrast to a theoretically predicted 1/4 wavelength phase shift in the phase relationship. Here, a new solution to this puzzle is provided. Furthermore, it is found out that the oxidation rate of Pb/Si(111) system is greatly enhanced in the presence of atomic scale catalyst -- Cs substitutional atoms, while the reactivity to CO is saturated after the initial enhanced nucleation. Finally, by inserting thin Ag layers in between Pb/Si(111) system, the coherent coupling of double quantum wells (a Pb quantum well and a Ag quantum well) are probed, where combined QWS features are observed by STS measurement. The growth mechanism of these heterostructures -- Pb/Ag/Si(111) -- is also investigated.