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

Soret Effect Study on High-Pressure CO2-Water Solutions Using UV-Raman Spectroscopy and a Concentric-Tube Optical Cell

Spatially resolved deep-UV Raman spectroscopy was applied to solutions of CO2 and H2O (or D2O), which were subject to a temperature gradient in a thermally regulated high-pressure concentric-tube Raman cell in an attempt to measure a Soret effect in the vicinity of the critical point of CO2. Although Raman spectra of solutions of CO2 dissolved in D2O at 10 MPa and temperatures near the critical point of CO2 had adequate signal-to-noise and spatial resolution to observe a Soret effect with a Soret coefficient with magnitude of |ST| > 0.03, no evidence for an effect of this size was obtained for applied temperature gradients up to 19oC. The presence of 1 M NaCl did not make a difference. In contrast, the concentration of CO2 dissolved in H2O was shown to vary significantly across the temperature gradient when excess CO2 was present, but the results could be explained simply by the variation in CO2 solubility over the temperature range and not to kinetic factors. For mixtures of D2O dissolved in scCO2 at 10 MPa and temperatures close to the critical point of CO2, the Raman peaks for H2O were too weak to measure with confidence even at the limit of D2O solubility

Effective Permeability Change in Wellbore Cement with Carbon Dioxide Reaction

Portland cement, a common sealing material for wellbores for geological carbon sequestration was reacted with CO{sub 2} in supercritical, gaseous, and aqueous phases at various pressure and temperature conditions to simulate cement-CO{sub 2} reaction along the wellbore from carbon injection depth to the near-surface. Hydrated Portland cement columns (14 mm diameter x 90 mm length; water-to-cement ratio = 0.33) including additives such as steel coupons and Wallula basalt fragments were reacted with CO{sub 2} in the wet supercritical (the top half) and dissolved (the bottom half) phases under carbon sequestration condition with high pressure (10 MPa) and temperature (50 C) for 5 months, while small-sized hydrated Portland cement columns (7 mm diameter x 20 mm length; water-to-cement ratio = 0.38) were reacted with CO{sub 2} in dissolved phase at high pressure (10 MPa) and temperature (50 C) for 1 month or with wet CO{sub 2} in gaseous phase at low pressure (0.2 MPa) and temperature (20 C) for 3 months. XMT images reveal that the cement reacted with CO{sub 2} saturated groundwater had degradation depth of {approx}1 mm for 1 month and {approx}3.5 mm for 5 month, whereas the degradation was minor with cement exposure to supercritical CO{sub 2}. SEM-EDS analysis showed that the carbonated cement was comprised of three distinct zones; the innermost less degraded zone with Ca atom % > C atom %, the inner degraded zone with Ca atom % {approx} C atom % due to precipitation of calcite, the outer degraded zone with C atom % > Ca atom % due to dissolution of calcite and C-S-H, as well as adsorption of carbon to cement matrix. The outer degraded zone of carbonated cement was porous and fractured because of dissolution-dominated reaction by carbonic acid exposure, which resulted in the increase in BJH pore volume and BET surface area. In contrast, cement-wet CO{sub 2}(g) reaction at low P (0.2 MPa)-T (20 C) conditions for 1 to 3 months was dominated by precipitation of micron-sized calcite on the outside surface of cement, which resulted in the decrease in BJH pore volume and BET surface area. Cement carbonation and pore structure change are significantly dependent on pressure and temperature conditions as well as the phase of CO{sub 2}, which controls the balance between precipitation and dissolution in cement matrix. Geochemical modeling result suggests that ratio of solid (cement)-to-solution (carbonated water) has a significant effect on cement carbonation, thus the cement-CO{sub 2} reaction experiment needs to be conducted under realistic conditions representing the in-situ wellbore environment of carbon sequestration field site. Total porosity and air permeability for a duplicate cement column with water-to-cement ratio of 0.38 measured after oven-drying by Core Laboratories using Boyle's Law technique and steady-state method were 31% and 0.576 mD. A novel method to measure the effective liquid permeability of a cement column using X-ray micro-tomography images after injection of pressurized KI (potassium iodide) is under development by PNNL. Preliminary results indicate the permeability of a cement column with water-to-cement ratio of 0.38 is 4-8 mD. PNNL will apply the method to understand the effective permeability change of Portland cement by CO{sub 2}(g) reaction under a variety of pressure and temperature conditions to develop a more reliable well-bore leakage risk model

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

STOMP Subsurface Transport Over Multiple Phases: STOMP-CO2 and STOMP-CO2e Guide: Version 1.0

This STOMP (Subsurface Transport Over Multiple Phases) guide document describes the theory, use, and application of the STOMP-CO2 and STOMP-CO2e operational modes. These operational modes of the STOMP simulator are configured to solve problems involving the sequestration of CO2 in geologic saline reservoirs. STOMP-CO2 is the isothermal version and STOMP-CO2e is the nonisothermal version. These core operational modes solve the governing conservation equations for component flow and transport through geologic media; where, the STOMP-CO2 components are water, CO2 and salt and the STOMP-CO2e operational mode also includes an energy conservation equation. Geochemistry can be included in the problem solution via the ECKEChem (Equilibrium-Conservation-Kinetic-Equation Chemistry) module, and geomechanics via the EPRMech (Elastic-Plastic-Rock Mechanics) module. This addendum is designed to provide the new user with a full guide for the core capabilities of the STOMP-CO2 and -CO2e simulators, and to provide the experienced user with a quick reference on implementing features. Several benchmark problems are provided in this addendum, which serve as starting points for developing inputs for more complex problems and as demonstrations of the simulator’s capabilities

Waste Form Release Data Package for the 2001 Immobilized Low-Activity Waste Performance Assessment

This data package documents the experimentally derived input data on the representative waste glasses LAWABP1 and HLP-31 that will be used for simulations of the immobilized lowactivity waste disposal system with the Subsurface Transport Over Reactive Multiphases (STORM) code. The STORM code will be used to provide the near-field radionuclide release source term for a performance assessment to be issued in March of 2001. Documented in this data package are data related to 1) kinetic rate law parameters for glass dissolution, 2) alkali-H ion exchange rate, 3) chemical reaction network of secondary phases that form in accelerated weathering tests, and 4) thermodynamic equilibrium constants assigned to these secondary phases. The kinetic rate law and Na+-H+ ion exchange rate were determined from single-pass flow-through experiments. Pressurized unsaturated flow and vapor hydration experiments were used for accelerated weathering or aging of the glasses. The majority of the thermodynamic data were extracted from the thermodynamic database package shipped with the geochemical code EQ3/6. However, several secondary reaction products identified from laboratory tests with prototypical LAW glasses were not included in this database, nor are the thermodynamic data available in the open literature. One of these phases, herschelite, was determined to have a potentially significant impact on the release calculations and so a solubility product was estimated using a polymer structure model developed for zeolites. Although this data package is relatively complete, final selection of ILAW glass compositions has not been done by the waste treatment plant contractor. Consequently, revisions to this data package to address new ILAW glass formulations are to be regularly expected

Gas-liquid segmented flow microwave-assisted synthesis of MOF-74(Ni) under moderate pressures

The metal organic framework, MOF-74(Ni), was synthesized in a continuous flow microwave-assisted reactor obtaining a high space-time yield (~90 g h⁻¹ L⁻¹) and 96.5% conversion of reagents. Separation of the nucleation and growth steps was performed by using uniform and rapid microwave heating to induce nucleation, which allowed a substantial increase in conversion for shorter reaction times under mild pressure. High yields were achieved in minutes, as opposed to days for typical batch syntheses, with excellent control over the material's properties due to more uniform nucleation, and the separation of the nucleation and growth steps. Optimization of the microwave reactor parameters led to improvements in MOF-74(Ni) crystallinity, reagent conversion, and production rates. Differences in MOF-74(Ni) crystallinity were observed as smaller grains were formed when higher microwave zone temperatures were used. Crystallinity differences led to different final adsorption properties and surface areas. Herein we show that a continuous high space-time yield synthesis of MOF-74(Ni) allows control over nucleation using microwave heating

Using Carbon Dioxide to Enhance Recovery of Methane from Gas Hydrate Reservoirs: Final Summary Report

Carbon dioxide sequestration coupled with hydrocarbon resource recovery is often economically attractive. Use of CO2 for enhanced recovery of oil, conventional natural gas, and coal-bed methane are in various stages of common practice. In this report, we discuss a new technique utilizing CO2 for enhanced recovery of an unconventional but potentially very important source of natural gas, gas hydrate. We have focused our attention on the Alaska North Slope where approximately 640 Tcf of natural gas reserves in the form of gas hydrate have been identified. Alaska is also unique in that potential future CO2 sources are nearby, and petroleum infrastructure exists or is being planned that could bring the produced gas to market or for use locally. The EGHR (Enhanced Gas Hydrate Recovery) concept takes advantage of the physical and thermodynamic properties of mixtures in the H2O-CO2 system combined with controlled multiphase flow, heat, and mass transport processes in hydrate-bearing porous media. A chemical-free method is used to deliver a LCO2-Lw microemulsion into the gas hydrate bearing porous medium. The microemulsion is injected at a temperature higher than the stability point of methane hydrate, which upon contacting the methane hydrate decomposes its crystalline lattice and releases the enclathrated gas. Small scale column experiments show injection of the emulsion into a CH4 hydrate rich sand results in the release of CH4 gas and the formation of CO2 hydrat

Final Report for the ZERT Project: Basic Science of Retention Issues, Risk Assessment & Measurement, Monitoring and Verification for Geologic Sequestration

ZERT has made major contributions to five main areas of sequestration science: improvement of computational tools; measurement and monitoring techniques to verify storage and track migration of CO{sub 2}; development of a comprehensive performance and risk assessment framework; fundamental geophysical, geochemical and hydrological investigations of CO{sub 2} storage; and investigate innovative, bio-based mitigation strategies

Laboratory Testing of Bulk Vitrified Low-Activity Waste Forms to Support the 2005 Integrated Disposal Facility Performance Assessment

The purpose of this report is to document the results from laboratory testing of the bulk vitri-fied (BV) waste form that was conducted in support of the 2005 integrated disposal facility (IDF) performance assessment (PA). Laboratory testing provides a majority of the key input data re-quired to assess the long-term performance of the BV waste package with the STORM code. Test data from three principal methods, as described by McGrail et al. (2000a; 2003a), are dis-cussed in this testing report including the single-pass flow-through test (SPFT) and product con-sistency test (PCT). Each of these test methods focuses on different aspects of the glass corrosion process. See McGrail et al. (2000a; 2003a) for additional details regarding these test methods and their use in evaluating long-term glass performance. In addition to evaluating the long-term glass performance, this report discusses the results and methods used to provided a recommended best estimate of the soluble fraction of 99Tc that can be leached from the engineer-ing-scale BV waste package. These laboratory tests are part of a continuum of testing that is aimed at improving the performance of the BV waste package