<p>With the poor room temperature formability of magnesium, rare earth (RE) additions have proven a promising avenue for wrought magnesium products. However, not much is known regarding the effect of these elements on strength and ductility. Stanford et al. (2010b) summarized it best: “Although the addition of rare earth elements offers the possibility of greatly improved mechanical properties, we still lack fairly basic knowledge about the behaviour of these alloying elements”[p.6773]. Through a systematic study across three Mg-RE binary systems, the effect of gadolinium, samarium and scandium on solution strengthening, work hardening behaviour and strain rate sensitivity of Mg-RE binary alloys have been characterized.</p> <p>The results suggest that samarium offers the greatest solid solution strengthening in both tension and compression relative to the other two binary systems. For the binary alloys explored, only gadolinium and samarium in compression followed the Labusch theory of solution strengthening; in which the yield strength scales with c^2/3 . Gadolinium additions provide the largest strength and ductility in tension and compression. Increasing solute content in the binary systems leads to a decrease of the strain rate sensitivity of the alloys. At the highest level of solute, both Mg-Gd and Mg-Sm exhibit negative strain rate sensitivity under tension. In compression, Mg-Gd also exhibits a negative strain rate sensitivity at the highest level solute, whereas Mg-Sm has a low, but positive value. The asymmetry in work hardening behaviour and the form of the flow curves between tension and compression is the result of the difference in the dominating modes of deformation at a given stage of the plastic flow. The extent of the work performed established the hardening levels and thermodynamic deformation parameters which control the flow stress and work hardening behaviour, that can be applied in future work.</p> / Master of Applied Science (MASc)

Concentrations of rare earth (REE), U, Th, and other trace elements (TE) were measured using LA-ICP-MS along transects across five Late Eocene brontothere bones from the terrestrial Late Eocene Chadron Formation of Nebraska and four Miocene marine mammals from the Atlantic Coastal Plain. Samples were analyzed to determine REE diffusion periods, and to determine if histological factors affect post mortem uptake of REE/TE. In terrestrial fossil bones, concentrations of REE are highest at the bone surface and decrease with depth into the trabecular bone, consistent with diffusion-limited models. Histology may affect REE incorporation. An outer circumferential layer (OCL) is preserved along the outer 1 mm of the brontothere rib (F08-10) and femur (F08-09). REE concentrations in the OCL are much lower than in the underlying bone, indicating either lower incorporation or post fossilization leaching. REE concentrations are sometimes elevated in trabecular bone and Haversian systems, which may act as secondary diffusion pathways. REE concentration gradients are generally steeper in marine fossils than in terrestrial fossil bones, indicating longer periods of REE uptake in terrestrial fossils. Calculated periods of diffusion in terrestrial environments are 2.2 +/- 0.5 to 54.8 +/- 1.5 ka (based on a wetness factor of 0.5 +/- 0.1). Periods of diffusion for marine environments range from ca. 0.9 +/- 0.2 to 2.8 +/- 0.6 ka. However, within some terrestrial samples U is introduced into the bone over a much longer time span, possibly as a function of fluctuating redox conditions. If these values are representative, diffusion-fossilization periods are shorter in marine/lacustrine/spring/channel environments due to constant water saturation. Saturation of a bone during diffusion may also affect the morphology of REE signatures within the bone. In terrestrial bones, REE are strongly fractionated with depth, producing signatures varying from light-REE enriched at the surface to middle-REE depleted at depth. However, depth fractionation of REE is much less pronounced in marine bones, which may result from the introduction of fluid unreactive. These differences in REE fractionation are consistent with a greater influence of multiple secondary REE/TE diffusion paths in marine samples. Periods of diffusion for terrestrial samples differed within a single bonebed accumulation (2.2 +/- 0.5 to 54.8 +/- 1.5 ka). However, REE signatures are internally consistent with one another within the bonebed indicating that groundwater chemistry did vary during fossilization. If groundwater chemistry changes during diffusion, bone could be recording different signals, which has implications for using post-mortem REE/TE/Isotopes for paleoenvironmental reconstruction. Previous studies of soft tissue preservation in fossilized bone have inferred shorter periods of diffusion and suggested that the rate of diffusion must outpace the rate of decay. Diffusion periods in bone from well drained terrestrial settings are too long to preserve soft tissue. However, periods of diffusion in marine fossil bones are much shorter, suggesting the possibility for bio-molecule preservation. / Geology

Thesis. 1975. M.S.--Massachusetts Institute of Technology. Dept. of Earth and Planetary Sciences. / Bibliography : leaves 137-144. / M.S.

Yes / As a global strategic reserve resource, rare earth has been widely used in important industries, such as military equipment and biomedicine. However, through existing analyses based on the total volume of rare earth trade, the competition and dependency behind the trade cannot be revealed. In this paper, based on the principle of trade preference and import similarity, we construct dependency and competition networks and use complex network analysis to study the evolution of the global rare earth trade network from 2002 to 2018. The main conclusions are as follows: the global rare earth trade follows the Pareto principle, and the trade network shows a scale-free distribution. China has become the largest country in both import and export of rare earth trade in the world since 2017. In the dependency network, China has become the most dependent country since 2006. The result of community division shows that China has separated from the American community and formed new communities with the Association of Southeast Asian Nations (ASEAN) countries. The United States of America has formed a super-strong community with European and Asian countries. In the competition network, the distribution of competition intensity follows a scale-free distribution. Most countries are faced with low-intensity competition, but competing countries are relatively numerous. The competition related to China has increased significantly. The competition source of the United States of America has shifted from Mexico to China. China, the USA, and Japan have been the cores of the competition network. / This work was supported by the Ministry of Education of the People’s Republic of China Humanities and Social Sciences Youth Foundation (Grant No. 22YJC910014), the Social Sciences Planning Youth Project of Anhui Province (Grant No. AHSKQ2022D138), and the Innovation Development Research Project of Anhui Province (Grant No. 2021CX053).

The flavor changing neutral current process b → dγ is a sensitive probe to the Standard Model of elementary particle physics. Using a sample of 386 × 10⁶ B meson pairs accumulated by the Belle detector at the KEKB e⁺e⁻ collider, we measure the branching fractions for the exclusive modes B⁻ → ρ⁻γ, B̅⁰ → ρ⁰γ and B̅⁰ → ωγ as follows: B(B⁻ → ρ⁻γ) = 0.55 _−0.36^+0.42_−0.08^+0.09 B(B̅⁰ → ρ⁰γ) = 1.25 _−0.33^+0.37_−0.06^+0.07 B(B̅⁰ → ωγ) = 0.56 _−0.27^+0.34_−0.10^+0.05 where the first error on each value is statistical and the second is systematic. Assuming that these three modes are related by isospin conservation rules, we find the combined branching fraction B(B̅ → (ρ,ω)γ) = 1.32 _−0.31^+0.34_−0.09^0.10. This result is used to determine the ratio of CKM matrix elements, |V_td/V_ts| = 0.199 _−0.025^+0.026_−0.015^0.018. / Ph. D.

Rare Earth Elements (REEs: La–Lu, Y, and Sc) are critical components for technological innovations, therefore more effective methods for the domestic extraction and purification of REEs are in ever-increasing demand. Metal-chelating polymers have great potential in these applications due to their relatively low cost and high affinity for target elements. However, while much research has focused on specific ligands attached to polymers, little is known about the effect of polymer architecture itself on metal chelation. This dissertation reports recent progress in the design, synthesis, and application of polymers for the chelation of various REEs. In addition to synthesizing a series of metal-chelating polymers, we elucidated the thermodynamics of binding using isothermal titration calorimetry (ITC) to gain insight into the specific relationship between polymer structure and metal binding. ITC enables the direct measurement of the binding affinity (Ka), enthalpy changes (ΔH), and stoichiometry of the interactions between macromolecules and metal ions in solution. The thermodynamics of metal chelation underpins many technologies for REE extraction. Consequently, elucidating these parameters enables the rational design of future materials. / Doctor of Philosophy / Rare-Earth Elements (REEs) are critical metals used in many modern technologies, therefore more effective methods for the recovery and purification of REEs are in ever-increasing demand. Metal-chelating polymers—materials that can bind metals—have great potential in these applications due to their relatively low cost and high affinity for target elements. However, while much research has focused on the specific metal-binding group attached to the polymer, little is known about the effect of polymer architecture itself on metal chelation. This dissertation reports recent progress in the design, synthesis, and application of materials that bind to various REEs. In addition to synthesizing a series of metal-binding polymers, we measured the heat absorbed or produced during metal-binding interactions. These experiments produced fundamental insights into the interactions between the polymers, metals ions, and water molecules in solution. Overall, this work produces a depiction of the polymer–metal binding process, which enables insight into each polymer's properties as a metal-binding material. Future researchers can use these guidelines to develop the next generation of materials for the extraction of these critical metals.

Rare earth elements (REE) exhibit particular and unique properties that render them essential to technological applications. Of particular interest is their involvement in the transition toward global sustainability and their military applications. The magnetic properties of the rare earth elements is of primordial importance to sustainable development. More specifically, terbium and dysprosium are two elements with no known substitutes in critical applications and with no domestic or allied sourcing available. These elements are currently mined by in-situ leaching of ion-absorbed clays, mostly from illegal operations in Myanmar financed by Chinese companies. The demand from both elements, and for the other magnet rare earths is projected to growth at very high rates through 2035 while the world undergoes a transition toward sustainability, and a drastic reduction in greenhouse gases emissions. Our team has been evaluating the potential of acid mine drainage (AMD) as a source of rare earth elements and critical materials (CM). Acid mine drainage is the result of in-situ generation of sulfuric acid due to the weathering of sulfide ores. It is a significant legacy environmental issue and one of the largest pollutants in many mining districts throughout the world. The objective of the present work is to provides a roadmap for the utilization of AMD as a critical material feedstock to preserve the independence of the United States of America with regards to these materials. To that effect, a fundamental economic assessment of REE/CM recovery from AMD using a network sourcing strategy in addition to a robust, flexible feedstock separations and refining facility was undertaken. A techno-economic analysis of the extraction, refining, separation and reduction to metal is presented along with a sensitivity analysis.The results of this analysis show that, with the exception of the minimum price scenario, all operational configurations have positive economic indicators with rates of return varying from 25% to 32% for the contemporary price scenario. This is primarily due to the very high enrichment in terbium and dysprosium of AMD. The optimal configuration was determined to be production of Co, Mn, and all REEs except for mischmetal, which is not recovered. Sensitivity analysis and Monte Carlo Simulation show that capital cost and HCl consumption are the two major factors influencing rate of return, thus indicating opportunities for future technology development and cost optimization. In order to reduce both the capital and operation cost of the facility, alternative ionic liquids extractants based on conventional acidic extractants where synthesized and investigated. The results show that the ionic liquids varied in performance, with [c101][D2EHP] and [c101][EHEHP] performing poorer than their conventional counterparts and [c101][c572] performing better. The performance of [c101][c572] was 13% superior to Cyanex 572, 20% superior to EHEHPA and 27% superior to D2EHPA the current commercially used extractants. Recommendations for further study on [c101][c572] include stripping tests, continuous pilot testing, and techno-economic analysis. The test work revealed that zinc and to a lesser extent calcium were significant deleterious elements in the solvent extraction circuit, and that selective removal would significantly reduce the acid-base consumption of the separation circuit. A process was developed to selectively remove calcium and zinc from AMD-derived feedstock and from REE products. The ammonium chloride leach process offer many advantages, including the possibility of closing the cycle by using carbon dioxide sequestration as a step to regenerate the ammonium chloride in a zero-discharge process. / Doctor of Philosophy / A younger me: - What are these elements in the bottom of the periodic table? My high school chemistry teacher: - "Don't waste time there, these are of no concern." Twenty years later, technological developments and the imperative to transition away from fossil energy to mitigate climate change have brought the rare earth elements, a series of 17 elements with unique properties to the forefront of the conversation. In addition to an organic increase in demand, the recent supply chain consolidation by China is adding a geopolitical risk to the equation. The magnetic properties of the rare earth elements is of primordial importance to sustainable development and to our military technology. More specifically, terbium and dysprosium are two elements with no known substitutes in critical applications and with no domestic or allied sourcing available. These elements are currently mined from illegal operations in Myanmar, with the support of Chinese companies. The demand from both elements, and for the other magnet rare earths is projected to growth at very high rates through 2035 while the world undergoes a transition toward sustainability, and a drastic reduction in greenhouse gases emissions. Given the important of the rare earth elements, and the absence of significant deposits in the united states, with the exception of the Bear Lodge and Elk Creek deposits, the Department of Energy has mandated academic institution of evaluating alternative sources of rare earth elements. Our team has been evaluating the potential of acid mine drainage as a source of rare earth elements and critical materials. Our team has surveyed many acid mine drainage sources and determined that many sites are highly enriched in terbium and dysprosium. Acid mine drainage is a legacy environmental issue related to past problematic mine development techniques. In the problematic mines. these acidic mine waters are permanently generated and if not treated can have severe impacts on water streams in which they flow. The toxicity of the acid mine drainage on the environment is due to its high acidity and significant levels of toxic metals. Acid mine drainage can be recognized by their yellow to red tint. It is treated by reacting it with a neutralization agent, which results in treated water and a sludge. The sludge is dewatered and stored in tailing impoundments. I have designed a process for the economical recovery of rare earth elements and critical materials from acid mine drainage. The cost to build and operate the facility was derived and it was determined that the project could be further enhanced by reducing the plant chemical reagent consumption. One specific category of chemical referred to as extractant, is central to the rare earth separation process. A novel variation on the standard extractants has been evaluated and promises to provide significant savings. While the extractants were investigated, it was noticed that some impurities such as zinc and calcium created issues in the circuit. I then developed a process for their selective removal. The process also provide a net carbon dioxide sequestration potential.

Microfluidics has found numerous applications ranging from the life sciences industries for pharmaceuticals and biomedicine (drug design, delivery and detection, diagnostic devices) to industrial applications of combinational synthesis (such as rapid analysis and high throughput screening). Among all these, one of the intriguing exploitation of microfluidics or micro total analysis systems (µTAS) is the separation of circulating tumor cells (CTCs) from body fluids. Cancer cells spread from the initial site of a tumor by first invading the surrounding tissue, then by entering the blood or lymph vessels, and finally by crossing the vessel wall to exit the vasculature into distal organs. The September 2006 issue of the Journal of the National Cancer Institute (NCI) states: "The war on cancer was declared 40 years ago and cancer is still here," and "Technologies that capture enemy CTCs for further interrogation might prove useful in the war on cancer." CTCs cannot only become a new marker for cancer prognosis, but their detection can also be a valid new parameter for diagnosing cancer early, for monitoring disease progression and relapse, and for optimizing therapy. This research established a new method to manipulate rare cell types based on their electrical signatures using dielectrophoresis (DEP) without having direct contact between the electrodes and the sample, known as contactless dielectrophoresis (cDEP). DEP is the motion of a particle in a suspending medium due to its polarization in the presence of a non-uniform electric field. cDEP relies upon reservoirs filled with highly conductive fluid to act as electrodes and provide the necessary electric field. These reservoirs are placed adjacent to the main microfluidic channel and are separated from the sample by a thin barrier of a dielectric material as is shown in Figure 1h. The application of a high-frequency electric field to the electrode reservoirs causes their capacitive coupling to the main channel and an electric field is induced across the sample fluid. Similar to traditional DEP, cDEP exploits the varying geometry of the electrodes to create spatial non-uniformities in the electric field. However, by utilizing reservoirs filled with a highly conductive solution, rather than a separate thin film array, the electrode structures employed by cDEP can be fabricated in the same step as the rest of the device; hence the process is conducive to mass production. We demonstrated the ability to isolate human leukemia cancer cells (THP-1) cells from a heterogeneous mixture of live and dead cells using cDEP with more than 99% selectivity and 95% removal efficiency. Through numerical and experimental investigations, new generation of cDEP devices have been designed and tested to detect and isolate THP-1 cells from spiked blood samples with high selectivity and cell capture efficiency. Our experimental observations, using prototype devices, indicate that breast cancer cell lines at their different stages (MCF-7, MCF-10, and MDA-MB231) have unique electrical. Furthermore, through collaborations at the Wake Forest Comprehensive Center, we demonstrated that prostate tumor initiating cells (TICs) exhibit unique electrical signatures and DEP responses and cDEP technology can be exploited to isolate and enrich TICs for further genetic pathways investigations. / Ph. D.

Peripheral capture locations have been used traditionally for predicting biological range limits. Maps based on these data may be inaccurate and may not provide useful information regarding the ranges of endangered species. A method was presented for predicting probable ranges of mammals based on the distribution of environmental factors associated with areas where animals have been known to occur. These factors were determined primarily from the literature. They were assigned relative weights based on frequency of occurrence in the literature. Computer technology was used to analyze an existing database stored at a cellular level to describe the probable distribution of the factors over large areas. Geomorphological, topographic, land-use, and physiographic data were included in the analyses. The method was applied to three mammals endangered in Virginia -- water shrew (Sorex palustris), northern flying squirrel (Glaucomys sabrinus), and Indiana bat (Myotis sodalis). Computer maps were produced showing the distribution of areas potentially favorable to each species in one of two study areas in Virginia. Maps produced by this method provide more information about ranges and range dynamics than tbos€ produced by traditional methods. Specifically, areas least likely to be favorable are shown as are those more likely to provide conditions suitable to the continued existence of the animal. Maps produced by this method may be useful for initial identification of critical areas, preliminary planning activities, endangered species management generally, and multiple range analyses. The method may be useful for range analyses of non-endangered species whenever information about range dynamics is needed. / Master of Science

Several recent studies have shown that acid mine drainage (AMD) may be a promising source of rare earth elements (REEs), which are essential feedstocks for many high tech applications and defense products. AMD is a longstanding environmental challenge and is currently the primary pollutant of water in the Appalachian coal mining region. Acid generated during the coal mining process tends to leach several transition metals from the surrounding rock strata. While iron, aluminum, and manganese have traditionally been noted as the predominant metals in AMD, recent studies have also shown that REEs are also present, albeit in trace concentrations, often less than 5 μg/L. The recovery of REEs from AMD can be both an economic and environmental advantage; however, the low REE concentrations and high contamination from other metals makes the concentration and purification of REEs quite difficult. This research seeks to develop and optimize a process capable of producing mixed rare earth concentrates with purities exceeding 90% from an AMD feedstock. Parallel efforts by other members of the research team showed that a solid preconcentrate, nominally 0.1 to 2% REE, can be readily produced from AMD; however, that pre-concentration process cannot provide the further enrichment needed to generate high purity oxides suitable for downstream markets. In this project, solvent extraction was investigated as secondary process used to further enrich the low grade preconcentrate to a purity exceeding 90%. Initially, laboratory-scale batch solvent extraction tests were performed on synthetic REE solutions to determine the influence of various process parameters (e.g. pH, extractant dosage, diluent type, and feedstock concentration). Next, the separation of REEs from major AMD gangue elements was investigated using synthetic leachate solutions with concentrations similar to those expected from the pre-concentrate samples. This process showed that the grade targets could easily be met when combining optimal parameters from each step. From this preliminary work with synthetic solutions, an optimal SX process was developed and validated using a real leachate generated from a pre-concentrate sample. By integrating leachate preparation, solvent extraction, scrubbing, stripping, and oxalic acid precipitation, an oxide containing 90.5% rare earth oxides was generated. Details on the process development, experimental optimization, and opportunities for process improvement are described. / Master of Science / Rare earth elements (REEs) are essential for many modern industries, high-tech applications, and defense products. The U.S. consumes approximately 11% of the global REE demand; however, the US supply chain is heavily reliant on imported Chinese feedstocks. This lack of a domestic supply chain exposes the US to both price and supply volatility, which are prevalent in the international markets. This supply issue is further compounded by a lack of suitable domestic feedstocks. REEs are rarely concentrated into mineable ore deposits, and in some cases the extraction and processing of conventional REEs deposits entails considerable environmental risk. As a result of these challenges, numerous federal agencies and private companies have recently sought to identify promising alternative resources. One potential alternative resource is acid mine drainage (AMD), which is a common environmental challenge associated with coal and hard rock mining. Prior studies have shown that acid mine drainage contains REEs; however, other metals, such as iron, aluminum, and manganese, preclude REE recovery using conventional processing techniques. As such, the goal of this research is to develop and optimize a process capable of recovering and concentrating REEs from an AMD feedstock. The research conducted in this thesis predominantly included laboratory testing using synthetic AMD samples. The complexity of the synthetic AMD progressively increased from very simple, single element solutions to complex multi-component mixtures. Through this research, data and information from these controlled experiments was used to design a multi-step solvent extraction process capable of producing final REE products exceeding 90% purity. In the last stage of the research, the final process was validated using actual AMD recovered from an operating mine site. The validation test showed that the process was effective in meeting its initial objectives: the grade of the final rare earth oxide was determined to be 90.5%. This laboratory-scale experimental work represents the first step of process needed to develop and deploy a commercial technology capable of producing REE products from AMD feedstocks.