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L.A. Stern

Publications and source records attributed to L.A. Stern.

29 records · Page 2Linked to original sources
USGS2001

Diamond-anvil cell observations of a new methane hydrate phase in the 100-MPa pressure range

A new high-pressure phase of methane hydrate has been identified based on its high optical relief, distinct pressure-temperature phase relations, and Raman spectra. In-situ optical observations were made in a hydrothermal diamond-anvil cell at temperatures between -40?? and 60 ??C and at pressures up to 900 MPa. Two new invariant points were located at -8.7 ??C and 99 MPa for the assemblage consisting of the new phase, structure I methane hydrate, ice Ih, and water, and at 35.3 ??C and 137 MPa for the new phase-structure I methane hydrate-water-methane vapor. Existence of the new phase is critical for understanding the phase relations among the hydrates at low to moderate pressures, and may also have important implications for understanding the hydrogen bonding in H2O and the behavior of water in the planetary bodies, such as Europa, of the outer solar system.

Journal of Physical Chemistry A↗
USGS2001

Preservation of methane hydrate at 1 atm

A "pressure-release" method that enables reproducible bulk preservation of pure, porous, methane hydrate at conditions 50 to 75 K above its equilibrium T (193 K) at 1 atm is refined. The amount of hydrate preserved by this method appears to be greatly in excess of that reported in the previous citations, and is likely the result of a mechanism different from ice shielding.

Energy and Fuels↗
USGS2001

Measurement of gas yields and flow rates using a custom flowmeter

A simple gas collection apparatus based on the principles of a Torricelli tube has been designed and built to measure gas volume yields and flow rates. This instrument is routinely used to monitor and collect methane gas released during methane hydrate dissociation experiments. It is easily and inexpensively built, operates at ambient pressures and temperatures, and measures gas volumes of up to 7 L to a precision of about 15 ml (about 0.0025 mol). It is capable of measuring gas flow rates varying from more than 103 to less than 10-1 ml/min during gas evolution events that span minutes to several days. We have obtained a highly reproducible hydrate number of n=5.891 with a propagated uncertainty of ??0.020 for synthetic methane hydrate. ?? 2001 American Institute of Physics.

Review of Scientific Instruments↗
USGS2000

Transformations in methane hydrates

Detailed study of pure methane hydrate in a diamond cell with in situ optical, Raman, and x-ray microprobe techniques reveals two previously unknown structures, structure II and structure H, at high pressures. The structure II methane hydrate at 250 MPa has a cubic unit cell of a = 17.158(2) A?? and volume V = 5051.3(13) A??3; structure H at 600 MPa has a hexagonal unit cell of a = 11.980(2) A??, c = 9.992(3) A??, and V = 1241.9(5) A??3. The compositions of these two investigated phases are still not known. With the effects of pressure and the presence of other gases in the structure, the structure II phase is likely to dominate over the known structure I methane hydrate within deep hydrate-bearing sediments underlying continental margins.

Proceedings of the National Academy of Sciences of↗
USGS2000

Methane hydrate dissociation rates at 0.1 MPa and temperatures above 272 K

We performed rapid depressurization experiments on methane hydrate under isothermal conditions above 272 K to determine the amount and rate of methane evolution. Sample temperatures rapidly drop below 273 K and stabilize near 272.5 K during dissociation. This thermal anomaly and the persistence of methane hydrate are consistent with the reported recovery of partially dissociated methane hydrate from ocean drilling cores.

Conference Paper↗
USGS1998

Optical-cell evidence for superheated ice under gas-hydrate-forming conditions

We previously reported indirect but compelling evidence that fine-grained H 2 O ice under elevated CH 4 gas pressure can persist to temperatures well above its ordinary melting point while slowly reacting to form methane clathrate hydrate. This phenomenon has now been visually verified by duplicating these experiments in an optical cell while observing the very slow hydrate-forming process as the reactants were warmed from 250 to 290 K at methane pressures of 23 to 30 MPa. Limited hydrate growth occurred rapidly after initial exposure of the methane gas to the ice grains at temperatures well within the ice subsolidus region. No evidence for continued growth of the hydrate phase was observed until samples were warmed above the equilibrium H 2 O melting curve. With continued heating, no bulk melting of the ice grains or free liquid water was detected anywhere within the optical cell until hydrate dissociation conditions were reached (292 K at 30 MPa), even though full conversion of the ice grains to hydrate requires 6−8 h at temperatures approaching 290 K. In a separate experimental sequence, unreacted portions of H 2 O ice grains that had persisted to temperatures above their ordinary melting point were successfully induced to melt, without dissociating the coexisting hydrate in the sample tube, by reducing the pressure overstep of the equilibrium phase boundary and thereby reducing the rate of hydrate growth at the ice−hydrate interface. Results from similar tests using CO 2 as the hydrate-forming species demonstrated that this superheating effect is not unique to the CH 4 −H 2 O system.

Journal of Physical Chemistry B↗
USGS1997

Creep of water ices at planetary conditions: A compilation

Many constitutive laws for the flow of ice have been published since the advent of the Voyager explorations of the outer solar system. Conflicting data have occasionally come from different laboratories, and refinement of experimental techniques has led to the publication of laws that supersede earlier ones. In addition, there are unpublished data from ongoing research that also amend the constitutive laws. Here we compile the most current laboratory-derived flow laws for water ice phases I, II, III, V, and VI, and ice I mixtures with hard particulates. The rheology of interest is mainly that of steady state, and the conditions reviewed are the pressures and temperatures applicable to the surfaces and interiors of icy moons of the outer solar system. Advances in grain-size-dependent creep in ices I and II as well as in phase transformations and metastability under differential stress are also included in this compilation. At laboratory strain rates the several ice polymorphs are rheologically distinct in terms of their stress, temperature, and pressure dependencies but, with the exception of ice III, have fairly similar strengths. Hard particulates strengthen ice I significantly only at high particulate volume fractions. Ice III has the potential for significantly affecting mantle dynamics because it is much weaker than the other polymorphs and its region of stability, which may extend metastably well into what is nominally the ice II field, is located near likely geotherms of large icy moons.

Journal of Geophysical Research E: Planets↗
USGS1997

Synthesis of polycrystalline methane hydrate, and its phase stability and mechanical properties at elevated pressure

Test specimens of methane hydrate were grown under static conditions by combining cold, pressurized CH4 gas with H2O ice grains, then warming the system to promote the reaction CH4 (g) + 6H2O (s???l) ??? CH4??6H2O. Hydrate formation evidently occurs at the nascent ice/liquid water interface, and complete reaction was achieved by warming the system above 271.5 K and up to 289 K, at 25-30 MPa, for approximately 8 hours. The resulting material is pure methane hydrate with controlled grain size and random texture. Fabrication conditions placed the H2O ice well above its melting temperature before reaction completed, yet samples and run records showed no evidence for bulk melting of the ice grains. Control experiments using Ne, a non-hydrate-forming gas, verified that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting is easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably at temperatures well above its melting point. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T= 140-200 K, Pc= 50-100 MPa, and ????= 10-4-10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to a higher degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; x-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

ACS Division of Fuel Chemistry, Preprints↗
USGS1996

Rheology of water ices V and VI

We have measured the mechanical strength (σ) of pure water ices V and VI under steady state deformation conditions. Constant displacement rate compressional tests were conducted in a gas apparatus at confining pressures from 400 < P < 800 MPa, temperatures from 209 < T < 270 K, and strain rates 7 × 10 −7 < < 7 × 10 −4 s −1 . Most of the results fit to an empirical flow law of the form = A σ n exp {−( E * + PV *)/ RT }, where the four material constants A , n , E *, and V * are (for in inverse seconds and P and σ in megapascals) 10 23.0 , 6.0, 136 kJ/mol, and 29 cm 3 /mol, respectively, for ice V; and 10 6.7 , 4.5, 66 kJ/mol, and 11 cm 3 /mol, respectively, for ice VI. Ice VI may weaken to a mechanism of higher E * at T > 250 K. Ices V and VI are thus rheologically distinct but by coincidence have approximately the same strength under the conditions chosen for these experiments. To avoid misidentification, these tests are therefore accompanied by careful observations of the occurrences and characteristics of phase changes. One sample each of ice V and VI was quenched at pressure to metastably retain the high-pressure phase and the acquired deformation microstructures; X ray diffraction analysis of these samples confirmed the phase identification. Surface replicas of the deformed and quenched samples suggest that ice V probably deforms largely by dislocation creep, while ice VI deforms by a more complicated process involving substantial grain size reduction through recrystallization.

Journal of Geophysical Research B: Solid Earth↗
USGS1991

Mantle phase changes and deep-earthquake faulting in subducting lithosphere

Inclined zones of earthquakes are the primary expression of lithosphere subduction. A distinct deep population of subduction-zone earthquakes occurs at depths of 350 to 690 kilometers. At those depths ordinary brittle fracture and frictional sliding, the faulting processes of shallow earthquakes, are not expected. A fresh understanding of these deep earthquakes comes from developments in several areas of experimental and theoretical geophysics, including the discovery and characterization of transformational faulting, a shear instability connected with localized phase transformations under nonhydrostatic stress. These developments support the hypothesis that deep earthquakes represent transformational faulting in a wedge of olivine-rich peridotite that is likely to persist metastably in coldest plate interiors to depths as great as 690 km. Predictions based on this deep structure of mantle phase changes are consistent with the global depth distribution of deep earthquakes, the maximum depths of earthquakes in individual subductions zones, and key source characteristics of deep events.

Science↗