Review of foundational concepts and emerging directions in metamaterial research: Design, phenomena, and applications

In the past two decades, artificial structures known as metamaterials have been found to exhibit extraordinary material properties that enable the unprecedented manipulation of electromagnetic waves, elastic waves, molecules, and particles. Phenomena such as negative refraction, bandgaps, near perfect wave absorption, wave focusing, negative Poissons ratio, negative thermal conductivity, etc., all are possible with these materials. Metamaterials were originally theorized and fabricated in electrodynamics, but research into their applications has expanded into acoustics, thermodynamics, seismology, classical mechanics, and mass transport. In this Research Update we summarize the history, current state of progress, and emerging directions of metamaterials by field, focusing the unifying principles at the foundation of each discipline. We discuss the different designs and mechanisms behind metamaterials as well as the governing equations and effective material parameters for each field. Also, current and potential applications for metamaterials are discussed. Finally, we provide an outlook on future progress in the emerging field of metamaterials.Comment: 22 pages, 3 figures, 1 tabl

Selective Thermal Emission Coatings for Improved Turbine Efficiency

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Fluorocarbon adsorption in hierarchical porous frameworks

Metal-organic frameworks comprise an important class of solid-state materials and have potential for many emerging applications such as energy storage, separation, catalysis and bio-medical. Here we report the adsorption behaviour of a series of fluorocarbon derivatives on a set of microporous and hierarchical mesoporous frameworks. The microporous frameworks show a saturation uptake capacity for dichlorodifluoromethane of >4 mmol g-1 at a very low relative saturation pressure (P/Po) of 0.02. In contrast, the mesoporous framework shows an exceptionally high uptake capacity reaching >14 mmol g-1 at P/Poof 0.4. Adsorption affinity in terms of mass loading and isosteric heats of adsorption is found to generally correlate with the polarizability and boiling point of the refrigerant, with dichlorodifluoromethane > chlorodifluoromethane > chlorotrifluoromethane > tetrafluoromethane > methane. These results suggest the possibility of exploiting these sorbents for separation of azeotropic mixtures of fluorocarbons and use in eco-friendly fluorocarbon-based adsorption cooling

CO2 Utilization and Storage in Shale Gas Reservoirs: Experimental Results and Economic Impacts

AbstractNatural gas is considered a cleaner and lower-emission fuel than coal, and its high abundance from advanced drilling techniques has positioned natural gas as a major alternative energy source for the U.S. However, each ton of CO2 emitted from any type of fossil fuel combustion will continue to increase global atmospheric concentrations. One unique approach to reducing anthropogenic CO2 emissions involves coupling CO2 based enhanced gas recovery (EGR) operations in depleted shale gas reservoirs with long-term CO2 storage operations. In this paper, we report unique findings about the interactions between important shale minerals and sorbing gases (CH4 and CO2) and associated economic consequences. Where enhanced condensation of CO2 followed by desorption on clay surface is observed under supercritical conditions, a linear sorption profile emerges for CH4. Volumetric changes to montmorillonites occur during exposure to CO2. Theory-based simulations identify interactions with interlayer cations as energetically favorable for CO2 intercalation. In contrast, experimental evidence suggests CH4 does not occupy the interlayer and has only the propensity for surface adsorption. Mixed CH4:CO2 gas systems, where CH4 concentrations prevail, indicate preferential CO2 sorption as determined by in situ infrared spectroscopy and X-ray diffraction techniques. Collectively, these laboratory studies combined with a cost-based economic analysis provide a basis for identifying favorable CO2-EOR opportunities in previously fractured shale gas reservoirs approaching final stages of primary gas production. Moreover, utilization of site-specific laboratory measurements in reservoir simulators provides insight into optimum injection strategies for maximizing CH4/CO2 exchange rates to obtain peak natural gas production

Anomalous porosity preservation and preferential accumulation of gas hydrate in the Andaman accretionary wedge, NGHP-01 site 17A

In addition to well established properties that control the presence or absence of the hydrate stability zone, such as pressure, temperature, and salinity, additional parameters appear to influence the concentration of gas hydrate in host sediments. The stratigraphic record at Site 17A in the Andaman Sea, eastern Indian Ocean, illustrates the need to better understand the role pore-scale phenomena play in the distribution and presence of marine gas hydrates in a variety of subsurface settings. In this paper we integrate field-generated datasets with newly acquired sedimentology, physical property, imaging and geochemical data with mineral saturation and ion activity products of key mineral phases such as amorphous silica and calcite, to document the presence and nature of secondary precipitates that contributed to anomalous porosity preservation at Site 17A in the Andaman Sea. This study demonstrates the importance of grain-scale subsurface heterogeneities in controlling the occurrence and distribution of concentrated gas hydrate accumulations in marine sediments, and document the importance that increased permeability and enhanced porosity play in supporting gas concentrations sufficient to support gas hydrate formation. The grain scale relationships between porosity, permeability, and gas hydrate saturation documented at Site 17A likely offer insights into what may control the occurrence and distribution of gas hydrate in other sedimentary settings.This is the publisher’s final pdf. The published article is copyrighted by Elsevier and can be found at: http://www.journals.elsevier.com/marine-and-petroleum-geologyKeywords: Indian Ocean, Porosity, Saturation, Gas hydrate, Grain size, Carbonate, Permeability, Volcanic as

Arctic Energy Technology Development Laboratory

The Arctic Energy Technology Development Laboratory was created by the University of Alaska Fairbanks in response to a congressionally mandated funding opportunity through the U.S. Department of Energy (DOE), specifically to encourage research partnerships between the university, the Alaskan energy industry, and the DOE. The enabling legislation permitted research in a broad variety of topics particularly of interest to Alaska, including providing more efficient and economical electrical power generation in rural villages, as well as research in coal, oil, and gas. The contract was managed as a cooperative research agreement, with active project monitoring and management from the DOE. In the eight years of this partnership, approximately 30 projects were funded and completed. These projects, which were selected using an industry panel of Alaskan energy industry engineers and managers, cover a wide range of topics, such as diesel engine efficiency, fuel cells, coal combustion, methane gas hydrates, heavy oil recovery, and water issues associated with ice road construction in the oil fields of the North Slope. Each project was managed as a separate DOE contract, and the final technical report for each completed project is included with this final report. The intent of this process was to address the energy research needs of Alaska and to develop research capability at the university. As such, the intent from the beginning of this process was to encourage development of partnerships and skills that would permit a transition to direct competitive funding opportunities managed from funding sources. This project has succeeded at both the individual project level and at the institutional development level, as many of the researchers at the university are currently submitting proposals to funding agencies, with some success

Chemistry and Dynamics of Supercritical Carbon Dioxide and Methane in the Slit Pores of Layered Silicates

ConspectusIn the mid 2010s, high-pressure diffraction and spectroscopic tools opened a window into the molecular-scale behavior of fluids under the conditions of many CO2 sequestration and shale/tight gas reservoirs, conditions where CO2 and CH4 are present as variably wet supercritical fluids. Integrating high-pressure spectroscopy and diffraction with molecular modeling has revealed much about the ways that supercritical CO2 and CH4 behave in reservoir components, particularly in the slit-shaped micro- and mesopores of layered silicates (phyllosilicates) abundant in caprocks and shales. This Account summarizes how supercritical CO2 and CH4 behave in the slit pores of swelling phyllosilicates as functions of the H2O activity, framework structural features, and charge-balancing cation properties at 90 bar and 323 K, conditions similar to a reservoir at ∼1 km depth. Slit pores containing cations with large radii, low hydration energy, and large polarizability readily interact with CO2, allowing CO2 and H2O to adsorb and coexist in these interlayer pores over a wide range of fluid humidities. In contrast, cations with small radii, high hydration energy, and low polarizability weakly interact with CO2, leading to reduced CO2 uptake and a tendency to exclude CO2 from interlayers when H2O is abundant. The reorientation dynamics of confined CO2 depends on the interlayer pore height, which is strongly influenced by the cation properties, framework properties, and fluid humidity. The silicate structural framework also influences CO2 uptake and behavior; for example, smectites with increasing F-for-OH substitution in the framework take up greater quantities of CO2. Reactions that trap CO2 in carbonate phases have been observed in thin H2O films near smectite surfaces, including a dissolution-reprecipitation mechanism when the edge surface area is large and an ion exchange-precipitation mechanism when the interlayer cation can form a highly insoluble carbonate. In contrast, supercritical CH4 does not readily associate with cations, does not react with smectites, and is only incorporated into interlayer slit mesopores when (i) the pore has a z-dimension large enough to accommodate CH4, (ii) the smectite has low charge, and (iii) the H2O activity is low. The adsorption and displacement of CH4 by CO2 and vice versa have been studied on the molecular scale in one shale, but opportunities remain to examine behavioral details in this more complicated, slit-pore inclusive system

Rhenium Uptake as Analogue 96Tc by Steel Corrosion Products

Static batch experiments were used to examine the sorption of dissolved perrhenate [Re(VII)], as a surrogate for pertechnetate [Tc(VII)], on corrosion products of A-516 carbon steel coupons contacted with synthetic groundwater or dilute water. After 109 days of contact time, the concentration of dissolved Re(VII) in the synthetic groundwater matrix decreased by approximately 26%; the dilute water matrix experienced a 99% decrease in dissolved Re(VII) over the same time period. Bulk x-ray diffraction (XRD) results for the corroded steel coupons showed that the corrosion products consisted primarily of maghemite, lepidocrocite, and goethite. Analyses of the coupons by scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) indicated that Re was present with the morphologically complex assemblages of Fe oxide/hydroxide corrosion products for samples spiked with the highest dissolved Re(VII) concentration (1.0 mmol/L) used for these experiments. Analyses of corroded steel coupons contacted with solutions containing 1.0 mmol/L Re(VII) by synchrotron-based methods confirmed the presence of Re sorbed with the corrosion product on the steel coupons. Analyses showed that the Re sorbed on these corroded coupons was in the +7 oxidation state, suggesting that the Re(VII) uptake mechanism did not involve reduction of Re to a lower oxidation state, such as +4. The results of our studies using Re(VII) as an analogue for {sup 99}Tc(VII) suggest that {sup 99}Tc(VII) would also be sorbed with steel corrosion products and that the inventory of {sup 99}Tc(VII) released from breached waste packages would be lower than what is now conservatively estimated

Quantification of CO2 Mineralization at the Wallula Basalt Pilot Project

In 2013, the Pacific Northwest National Laboratory led a geologic carbon sequestration field demonstration where ∼1000 tonnes of CO2 was injected into several deep Columbia River Basalt zones near Wallula, Washington. Rock core samples extracted from the injection zone two years after CO2 injection revealed nascent carbonate mineralization that was qualitatively consistent with expectations from laboratory experiments and reactive transport modeling. Here, we report on a new detailed analysis of the 2012 pre-injection and 2015 post-injection hydrologic tests that capitalizes on the difference in fluid properties between scCO2 and water to assess changes in near-field, wellbore, and reservoir conditions that are apparent approximately two years following the end of injection. This comparative hydrologic test analysis method provides a new way to quantify the amount of injected CO2 that was mineralized in the field test. Modeling results indicate that approximately 60% of the injected CO2 was sequestered via mineralization within two years, with the resulting carbonates occupying ∼4% of the available reservoir pore space. The method presented here provides a new monitoring tool to assess the fate of CO2 injected into chemically reactive basalt formations but could also be adapted for long-term monitoring and verification within more traditional subsurface carbon storage reservoirs