THERMORESPONSIVE PROPERTIES OF GOLD HYBRID NANOPARTICLES OF POLY(DI(ETHYLENE GLYCOL) METHYL ETHER METHACRYLATE) (PDEGMA) AND ITS BLOCK COPOLYMERS WITH DIFFERENT ANCHORING REGIMES

Thermo-responsive materials have been of interest for many years, and have been studied mostly as thermally stimulated drug delivery vehicles. Recently acrylate and methacrylates with pendant ethylene glycol methyl ethers been studied as thermo responsive materials. This work explores thermo response properties of hybrid nanoparticles of one of these methacrylates (DEGMA) and a block copolymer with one of the acrylates (OEGA), with gold nanoparticle cores of different sizes. We were interested in the effects of gold core size, number and type of end groups that anchored the chains to the gold cores, and location of bonding sites on the thermo-response of the polymer. To control the number and location of anchoring groups we using a type of controlled radical polymerization called Reversible Addition Fragmentation Transfer (RAFT) Polymerization. Smaller gold cores did not show the thermo responsive behavior of the polymer but the gold cores did seem to self-assemble. Polymer anchored to larger gold cores did show thermo responsivity. The anchoring end group did not alter the thermoresponsivity but thiol-modified polymers stabilized gold cores less well than chains anchored by dithioester groups, allowing gold cores to grow larger. Use of multiple bonding groups stabilized the gold core. Using block copolymers we tested the effects of number of thiol groups and the distance between them. We observed that the use of multiple anchoring groups on the block copolymer with a sufficiently large gold core did not prevent thermo responsive behavior of the polymer to be detected which allows a new type of thermo-responsive hybrid nanoparticle to be used and studied for new applications.

Impact of copper mine tailings (stamp sand) on survival and development of aquatic organisms near Gay, Michigan

Heavy metal-rich copper mine tailings, called stamp sands, were dumped by mining companies directly into streams and along the Lake Superior shoreline, degrading Keweenaw Peninsula waterways. One of the largest disposal sites is near Gay, Michigan, where tailings have been moved along the shoreline by currents since mining ceased. As a result, the smallest sand particles have been washed into deeper water and are filling the interstitial spaces of Buffalo Reef, a critical lake trout spawning site. This research is the first to investigate if stamp sand is detrimental to survival and early development of eggs and larvae of lake sturgeon, lake trout, and Northern leopard frogs, and also examines if the presence of stamp sands influences substrate selection of earthworms. This study found that stamp sand had significantly larger mean particle sizes and irregular shapes compared to natural sand, and earthworms show a strong preference for natural substrate over any combination that included stamp sand. Additionally, copper analysis (Cu2+) of surface water over stamp sand and natural sand showed concentrations were significantly higher in stamp sand surface water (100 μg/L) compared to natural sand surface water (10 μg/L). Frog embryos had similar hatch success over both types of sand, but tadpoles reared over natural sand grew faster and had higher survival rates. Eggs of lake sturgeon showed similar hatch success and development over natural vs. stamp sand over 17 days, while lake trout eggs hatched earlier and developed faster when incubated over stamp sand, yet showed similar development over a 163 day period. Copper from stamp sand appears to impact amphibians more than fish species in this study. These results will help determine what impact stamp sand has on organisms found throughout the Keweenaw Peninsula which encounter the material at some point in their life history.

Economic sustainability of the Flambeau Mine Ladysmith, Wisconsin

Today sustainable development is a very pertinent issue. Communities do not want companies, specifically mining companies, to deplete a natural resource and leave. The goal is to minimize the negative impacts of mining and the boom/bust cycles of natural resource extraction. In this study a three part framework was developed to analyze the sustainability of the Flambeau Mine in Ladysmith, Wisconsin. The first and second part dealt with an in-depth local and regional analysis and whether the community was developing within its own vision. The third part used nine sustainability measures including: 1. Need Present Generation 2. Future Need 3. Acceptable Legacy 4. Full-Cost 5. Contribution to Economic Development 6. Equity 7. Consent 8. Respect for Ecological Limits, Maintenance of Ecological Integrity and Landscape Requirements 9. Offsetting Restoration This study concluded that the Flambeau Mine was sustainable relative to the first two criteria and that it can be considered mostly sustainable relative to the nine criteria. Overall it can be stated that the Flambeau Mine was a beneficial project to the Ladysmith Wisconsin area. Additionally it appeared to decrease the public’s negative perception of mining. Recommendations for future analytical work are made. Suggestions are made as to how mining companies could increase the potential for the attainment of sustainability in projects. It is recommended that this framework be used by other industries.

Paleomagnetic Study of the Portage Lake Volcanics exposed in the Quincy Mine

A detailed paleomagnetic and rock-magnetic investigation was conducted on thirty six basaltic flows of the ~1095 Ma Portage Lake Volcanics. The flows were sampled along the East Adit of the Quincy Mine (Hancock, MI). Thirty two flows yielded well-defined primary magnetization directions carried by magnetite. A secondary magnetization component carried by hematite was also found in twenty nine flows. After correction for serial correlation between the flows, nineteen independent mean directions were calculated. The corresponding paleomagnetic pole is located at 25.5 °N, 182.1 °W (A95 = 3.5°). The new pole overlaps with the pole from the ~1087 Ma Lake Shore Traps suggesting a standstill of the North American plate during that time period. The low angular dispersion of virtual geomagnetic poles (S = 7.9°) suggests that the flows were erupted within a short time period, or that the strength of geomagnetic secular variation was lower than that of the recent field.

Biological materials : Part A. tuning LCST of raft copolymers and gold/copolymer hybrid nanoparticles and Part B. biobased nanomaterials

The research described in this dissertation is comprised of two major parts. The first part studied the effects of asymmetric amphiphilic end groups on the thermo-response of diblock copolymers of (oligo/di(ethylene glycol) methyl ether (meth)acrylates, OEGA/DEGMA) and the hybrid nanoparticles of these copolymers with a gold nanoparticle core. Placing the more hydrophilic end group on the more hydrophilic block significantly increased the cloud point compared to a similar copolymer composition with the end group placement reversed. For a given composition, the cloud point was shifted by as much as 28 °C depending on the placement of end groups. This is a much stronger effect than either changing the hydrophilic/hydrophobic block ratio or replacing the hydrophilic acrylate monomer with the equivalent methacrylate monomer. The temperature range of the coil-globule transition was also altered. Binding these diblock copolymers to a gold core decreased the cloud point by 5-15 °C and narrowed the temperature range of the coil-globule transition. The effects were more pronounced when the gold core was bound to the less hydrophilic block. Given the limited numbers of monomers that are approved safe for in vivo use, employing amphiphilic end group placement is a useful tool to tune a thermo-response without otherwise changing the copolymer composition. The second part of the dissertation investigated the production of value-added nanomaterials from two biorefinery “wastes”: lignin and peptidoglycan. Different solvents and spinning methods (melt-, wet-, and electro-spinning) were tested to make lignin/cellulose blended and carbonized fibers. Only electro-spinning yielded fibers having a small enough diameter for efficient carbonization ( Peptidoglycan (a bacterial cell wall material) was copolymerized with poly-(3-hydroxybutyrate), a common polyhydroxyalkanoate produced by bacteria with the objective of determining if a useful material could be obtained with a less rigorous work-up on harvesting polyhydroxyalkanoates. The copolyesteramide product having 25 wt.% peptidoglycan from a highly purified peptidoglycan increased thermal stability by 100-200 °C compared to the poly-(3-hydroxybutyrate) control, while a less pure peptidoglycan, harvested from B. megaterium (ATCC 11561), gave a 25-50 °C increase in thermal stability. Both copolymers absorbed more moisture than pure poly-(3-hydroxybutyrate). The results suggest that a less rigorously harvested and purified polyhydroxyalkanoate might be useful for some applications.

Cut slope design for the access to an underground copper mine

Slope stability analysis is a major area of research in geotechnical engineering. That being said, very little is written in the geotechnical engineering literature on the design of box-cuts. The goal of this thesis will be to investigate the proper design of a boxcuts, and to design a box-cut for access to an underground copper mine. Issues that need to be considered in the box-cut design include, long term dewatering design, slope stability analysis, and erosion control. The soils at the project site were extremely low permeability, as a result a system of ejectors was designed both to improve the stability of the slopes and prevent flooding. Based on the results of limit equilibrium analysis and finite element analysis, a slope design of two horizontal on one vertical was selection, with a rock fill buttress providing reinforcement. Finally, Michigan DOT standards for seeding were used to provide erosion control

Technology, Transportation, and Scale in the Koyokuk Placer Mining District 1890s - 1930s

The Koyukuk Mining District was one of several northern, turn of the century, gold rush regions. Miners focused their efforts in this region on the Middle Fork of the Koyukuk River and on several of its tributaries. Mining in the Koyukuk began in the 1880s and the first rush occurred in 1898. Continued mining throughout the early decades of the 1900s has resulted in an historic mining landscape consisting of structures, equipment, mining shafts, waste rock, trash scatters, and prospect pits. Modern work continues in the region alongside these historic resources. An archaeological survey was completed in 2012 as part of an Abandoned Mine Lands survey undergone with the Bureau of Land Management, Michigan Technological University, and the University of Alaska Anchorage. This thesis examines the discrepancy between the size of mining operations and their respective successes in the region while also providing an historical background on the region and reports on the historical resources present.