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At least 37 records · Page 2

Enhanced Ion Conductivity through Hydrated, Polyelectrolyte-Grafted Cellulose Nanocrystal Films

Here,iIonically conductive, hydrated polyelectrolyte nanocomposites are prepared from iodomethane-treated poly(2-vinylpyridine) (mPV)-grafted cellulose nanocrystals (MxG-CNC-g-mPV). These polyelectrolyte-grafted nanoparticle (PEGN) films exhibit an order-of-magnitude higher iodide ion conductivity relative to mPV films and a high in-plane/through-plane anisotropy. The PEGN architecture prevents CNC aggregation, maximizing the CNC/polyelectrolyte interface. PEGN films were prepared with varying polymer graft density (0.03-0.12 chains/nm 2 ) and molecular weight (7k-30k g/mol). The greatest ion conductivity enhancement is observed with lower molecular weight, higher density grafts: ca. 89 ± 6 mS/cm (140 ±10 mS/cm accounting for the volume of the CNC) versus 3.3 ± 0.4 mS/cm for ungrafted mPV. Poly(styrene-block-2-vinylpyridine)-grafted CNCs were prepared in which the insulating polystyrene block or the conducting mPV block was directly attached to the CNCs; only the films with the mPV block closest to the CNCs exhibited an enhancement in conductivity relative to mPV. Together, these data point to beneficial CNC/polyelectrolyte interfacial effects, resulting in significant ionic conductivity enhancement along the length of the CNCs in these films.

74 ATOMIC AND MOLECULAR PHYSICS↗

Timescales and Processes of Methane Hydrate Formation and Breakdown, With Application to Geologic Systems

Abstract Gas hydrate is an ice‐like form of water and low molecular weight gas stable at temperatures of roughly −10°C to 25°C and pressures of ~3 to 30 MPa in geologic systems. Natural gas hydrates sequester an estimated one sixth of Earth's methane and are found primarily in deepwater marine sediments on continental margins, but also in permafrost areas and under continental ice sheets. When gas hydrate is removed from its stability field, its breakdown has implications for the global carbon cycle, ocean chemistry, marine geohazards, and interactions between the geosphere and the ocean‐atmosphere system. Gas hydrate breakdown can also be artificially driven as a component of studies assessing the resource potential of these deposits. Furthermore, geologic processes and perturbations to the ocean‐atmosphere system (e.g., warming temperatures) can cause not only dissociation, but also more widespread dissolution of hydrate or even formation of new hydrate in reservoirs. Linkages between gas hydrate and disparate aspects of Earth's near‐surface physical, chemical, and biological systems render an assessment of the rates and processes affecting the persistence of gas hydrate an appropriate Centennial Grand Challenge. This paper reviews the thermodynamic controls on methane hydrate stability and then describes the relative importance of kinetic, mass transfer, and heat transfer processes in the formation and breakdown (dissociation and dissolution) of gas hydrate. Results from numerical modeling, laboratory, and some field studies are used to summarize the rates of hydrate formation and breakdown, followed by an extensive treatment of hydrate dynamics in marine and cryospheric gas hydrate systems.

58 GEOSCIENCES↗

Pore-scale observations of natural hydrate-bearing sediments via pressure core sub-coring and micro-CT scanning

Abstract Both intra-pore hydrate morphology and inter-pore hydrate distribution influence the physical properties of hydrate-bearing sediments, yet there has been no pore-scale observations of hydrate habit under pressure in preserved pressure core samples so far. We present for the first time a pore-scale micro-CT study of natural hydrate-bearing cores that were acquired from Green Canyon Block 955 in UT-GOM2-1 Expedition and preserved within hydrate pressure–temperature stability conditions throughout sub-sampling and imaging processes. Measured hydrate saturation in the sub-samples, taken from units expected to have in-situ saturation of 80% or more, ranges from 3 ± 1% to 56 ± 11% as interpreted from micro-CT images. Pore-scale observations of gas hydrate in the sub-samples suggest that hydrate in silty sediments at the Gulf of Mexico is pore-invasive rather than particle displacive, and hydrate particles in these natural water-saturated samples are pore-filling with no evidence of grain-coating. Hydrate can form a connected 3D network and provide mechanical support for the sediments even without cementation. The technical breakthrough to directly visualize particle-level hydrate pore habits in natural sediments reported here sheds light on future investigations of pressure- and temperature-sensitive processes including hydrate-bearing sediments, dissolved gases, and other biochemical processes in the deep-sea environment.

58 GEOSCIENCES↗

Three-Dimensional Free Gas Flow Focuses Basin-Wide Microbial Methane to Concentrated Methane Hydrate Reservoirs in Geological System

Here, we present a systematic model that links the generation, migration, phase partitioning, and accumulation of methane into a closed loop as the sediment is deposited from the seafloor and buried through the base of hydrate stability zone (BHSZ). In our model, methane is generated by biodegradation of organic carbon in muds. Hydrate does not form and methane is not trapped until a coarse-grained layer is deposited, because the small pores prevent hydrate formation in muds. Instead, methane diffuses into sands/silts where methane solidifies into hydrate. As hydrate-bearing sands/silts pass through the BHSZ during sediment burial, methane hydrate dissociates, and releases free gas. The released and the newly generated free gas below the BHSZ concentrates into a vertical/dipping zone with low capillary entry pressure and high permeability and flows upward driven its buoyancy. When free gas reaches the hydrate stability zone (HSZ), capillary forces drive free gas to flow laterally, preferentially enter sands/silts, feed hydrate growth, and elevate hydrate saturation. With three-dimensional focused free gas flow, microbial methane that is generated from a much larger fetch area of the entire basin, both above and below the BHSZ, is concentrated into coarse-grained layers at structural closures for hydrate formation. Our model illustrates how geological evolution, microbial methane generation, and gas flow by buoyancy couple to generate concentrated hydrate deposits in geological system. These insights can be used to explore for high-concentration methane hydrate and are important for understanding the methane budget and carbon cycle under the seafloor.

58 GEOSCIENCES↗

Current challenges in hydrate‐based desalination: Kinetic and thermodynamic perspective

Abstract Water scarcity is becoming a severe problem worldwide due to inadequate freshwater resources and swift population growth. Seawater desalination is one of the vital approaches to meet the demand for freshwater. However, energy and associated costs with conventional seawater desalination techniques are incentivizing non‐conventional water desalination processes. Water desalination using gas hydrates formation is one of the emerging non‐conventional processes. In this perspective article, recent advances in hydrate‐based seawater desalination (HBSD) have been critically analyzed to outline a future path towards a clean and efficient hydrate‐based desalination process. It provides a detailed comparison of various processes developed over decades, and measured desalination efficiencies with their process details. Moreover, the current challenges, limitations, and future perspectives of hydrate‐based desalination are also discussed. The study also recapitulates the thermodynamics and kinetics aspects of the hydrate‐based desalination process. In addition, various factors controlling the desalination efficiencies, such as control of the separation of hydrate crystals, salt deposition on hydrate particles, and hydrate morphology, were thoroughly investigated with their proposed process designs. The kinetics of hydrate formation is also assessed, with the possibility of a zero‐induction regime and its consequent impact on hydrate morphology. The current capabilities of the thermodynamics models (Gibbs energy minimization + electrolyte equation of state) were discussed using various commercially available software. Additionally, the role of hydrate promotors is also discussed, which can reduce the higher cost associated with the hydrate‐based desalination process.

Khan, Muhammad Naveed↗