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S. H. Kirby

Publications and source records attributed to S. H. Kirby.

48 records · Page 3Linked to original sources

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 In addition, there are unpublished data from ongoing research that also amend the constitutive laws.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

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

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

Metastable mantle phase transformations and deep earthquakes in subducting oceanic lithosphere

Earth's deepest earthquakes occur as a population in subducting or previously subducted lithosphere at depths ranging from about 325 to 690 km. This depth interval closely brackets the mantle transition zone, characterized by rapid seismic velocity increases resulting from the transformation of upper mantle minerals to higher-pressure phases. Deep earthquakes thus provide the primary direct evidence for subduction of the lithosphere to these depths and allow us to investigate the deep thermal, thermodynamic, and mechanical ferment inside slabs. Numerical simulations of reaction rates show that the olivine → spinel transformation should be kinetically hindered in old, cold slabs descending into the transition zone. Thus wedge-shaped zones of metastable peridotite probably persist to depths of more than 600 km. Laboratory deformation experiments on some metastable minerals display a shear instability called transformational faulting. This instability involves sudden failure by localized superplasticity in thin shear zones where the metastable host mineral transforms to a denser, finer-grained phase. Hence in cold slabs, such faulting is expected for the polymorphic reactions in which olivine transforms to the spinel structure and clinoenstatite transforms to ilmenite. It is thus natural to hypothesize that deep earthquakes result from transformational faulting in metastable peridotite wedges within cold slabs. This consideration of the mineralogical states of slabs augments the traditional largely thermal view of slab processes and explains some previously enigmatic slab features. It explains why deep seismicity occurs only in the approximate depth range of the mantle transition zone, where minerals in downgoing slabs should transform to spinel and ilmenite structures. The onset of deep shocks at about 325 km is consistent with the onset of metastability near the equilibrium phase boundary in the slab. Even if a slab penetrates into the lower mantle, earthquakes should cease at depths near 700 km, because the seismogenic phase transformations in the slab are completed or can no longer occur. Substantial metastability is expected only in old, cold slabs, consistent with the observed restriction of deep earthquakes to those settings. Earthquakes should be restricted to the cold cores of slabs, as in any model in which the seismicity is temperature controlled, via the distribution of metastability. However, the geometries of recent large deep earthquakes pose a challenge for any such models. Transformational faulting may give insight into why deep shocks lack appreciable aftershocks and why their source characteristics, including focal mechanisms indicating localized shear failure rather than implosive deformation, are so similar to those of shallow earthquakes. Finally, metastable phase changes in slabs would produce an internal source of stress in addition to those due to the weight of the sinking slab. Such internal stresses may explain the occurrence of earthquakes in portions of lithosphere which have foundered to the bottom of the transition zone and/or are detached from subducting slabs. Metastability in downgoing slabs could have considerable geodynamic significance. Metastable wedges would reduce the negative buoyancy of slabs, decrease the driving force for subduction, and influence the state of stress in slabs. Heat released by metastable phase changes would raise temperatures within slabs and facilitate the transformation of spinel to the lower mantle mineral assemblage, causing slabs to equilibrate more rapidly with the ambient mantle and thus contribute to the cessation of deep seismicity. Because wedge formation should occur only for fast subducting slabs, it may act as a “parachute” and contribute to regulating plate speeds. Wedge formation would also have consequences for mantle evolution because the density of a slab stagnated near the bottom of the transition zone would increase as it heats up and the wedge transforms to denser spinel, favoring the subsequent sinking of the slab into the lower mantle.

Reviews of Geophysics

High-pressure deformation of calcite marble and its transformation to aragonite under non-hydrostatic conditions

We conducted deformation experiments on Carrara marble in the aragonite and calcite stability fields to observe the synkinematic transformation of calcite to aragonite, and to identify any relationships between transformation and deformation or sample strength. Deformation-induced microstructures in calcite crystals varied most significantly with temperature, ranging from limited slip and twinning at 400°C, limited recrystallization at 500°C, widespread recrystallization at 600 and 700°C, to grain growth at 800–900°C. Variations in confining pressure from 0.3 to 2.0 GPa have no apparent effect on calcite deformation microstructures. Aragonite grew in 10 −6 -10 −7 s −1 strain rate tests conducted for 18–524 h at confining pressures of 1.7–2.0 GPa and temperatures of 500–600°C. As in our previously reported hydrostatic experiments on this same transformation, the aragonite nucleated on calcite grain boundaries. The extent of transformation varied from a few percent conversion near pistons at 400°C, 2.0 GPa and 10 −4 s −1 strain rate in a 0.8 h long experiment, to 98% transformation in a 21-day test at a strain rate of 10 −7 s −7 , a temperature of 600°C and a pressure of 2.0 GPa. At 500°C, porphyroblastic 100–200 μm aragonite crystals grew at a rate faster than 8 × 10 −1 m s −1 . At 600°C, the growth of aragonite neoblasts was slower, ≈6 × 10 −1 m s −1 , and formed ‘glove-and-finger’ cellularprecipitation-like textures identical to those observed in hydrostatic experiments. The transformation to aragonite is not accompanied by a shear instability or anisotropic aragonite growth, consistent with its relatively small volume change and latent heat in comparison with compounds that do display those features.

Journal of Structural Geology

Time and metamorphic petrology: Calcite to aragonite experiments

Although the equilibrium phase relations of many mineral systems are generally well established, the rates of transformations, particularly in polycrystalline rocks, are not. The results of experiments on the calcite to aragonite transformation in polycrystalline marble are different from those for earlier experiments on powdered and single-crystal calcite. The transformation in the polycrystalline samples occurs by different mechanisms, with a different temperature dependence, and at a markedly slower rate. This work demonstrates the importance of kinetic studies on fully dense polycrystalline aggregates for understanding mineralogic phase changes in nature. Extrapolation of these results to geological time scales suggests that transformation of calcite to aragonite does not occur in the absence of volatiles at temperatures below 200°C. Kinetic hindrance is likely to extend to higher temperatures in more complex transformations.

Science

Dikes, joints, and faults in the upper mantle

Three different types of macroscopic fractures are recognized in upper-mantle and lower-crustal xenoliths in volcanic rocks from around the world: 1. (1) joints that are tensile fractures not occupied by crystallized magma products 2. (2) dikes that are tensile fractures occupied by mafic magmas crystallized to pyroxenites, gabbros or hydrous-mineral-rich rocks, 3. (3) faults that are unfilled shear fractures with surface markings indicative of shear displacement. In addition to intra-xenolith fractures, xenoliths commonly have polygonal or faceted shapes that represent fractures exploited during incorporation of the xenoliths into the host magma that brought them to the surface. The various types of fractures are considered to have formed in response to the pressures associated with magmatic fluids and to the ambient tectonic stress field. The presence of fracture sets and crosscutting relations indicate that both magma-filled and unfilled fractures can be contemporaneous and that the local stress field can change with time, leading to repeated episodes of fracture. These observations give insight into the nature of deep fracture processes and the importance of fluid-peridotite interactions in the mantle. We suggest that unfilled fractures were opened by volatile fluids exsolved from ascending magmas to the tops of growing dikes. These volatile fluids are important because they are of low viscosity and can rapidly transmit fluid pressure to dike and fault tips and because they lower the energy and tectonic stresses required to extend macroscopic cracks and to allow sliding on pre-existing fractures. Mantle seismicity at depths of 20-65 km beneath active volcanic centers in Hawaii corresponds to the depth interval where CO2-rich fluids are expected to be liberated from ascending basaltic magmas, suggesting that such fluids play an important role in facilitating earthquake instabilities in the presence of tectonic stresses. Other phenomena related to the fractures include permeation of peridotite by fluid inclusions derived by degassing of magmas, partial melting of peridotite and dike rocks, and metasomatic alteration of peridotite host rock by magmas emplaced in fractures. These effects of magmatism generally reduce the bulk density of peridotite and might also reduce seismic velocities. The velocity contrasts between fractured and unfractured peridotite might be detected by seismic-velocity profiling techniques.

Tectonophysics

Inelastic properties of ice Ih at low temperatures and high pressures

The aim of our research programme is to explore the rheological behavior of H 2 O ices under conditions appropriate to the interiors of the icy satellites of the outer planets in order to give insight into their deformation. To this end, we have performed over 100 constant-strain-rate compression tests at pressures to 500 MPa and temperatures as low as 77 K. At P > 30 MPa, ice I h fails by a shear instability producing faults in the maximum shear stress orientation and failure strength typically is independent of pressure. This unusual faulting behavior is thought to be connected with phase transformations localized in the shear zones. The steady-state strength follows rheological laws of the thermally-activated power-law type, with different flow law parameters depending on the range of test temperatures. The flow laws will be discussed with reference to the operating deformation mechanisms as deduced from optical-scale microstructures and comparison with other work.

Journal de Physique Colloques

Hydrogen speciation in synthetic quartz

The dominant hydrogen impurity in synthetic quartz is molecular H2O. H-OH groups also occur, but there is no direct evidence for the hydrolysis of Si-O-Si bonds to yield Si-OH HO-Si groups. Molecular H2O concentrations in the synthetic quartz crystals studied range from less than 10 to 3,300 ppm (H/Si), and decrease smoothly by up to an order of magnitude with distance away from the seed. OH- concentrations range from 96 to 715 ppm, and rise smoothly with distance away from the seed by up to a factor of three. The observed OH- is probably all associated with cationic impurities, as in natural quartz. Molecular H2O is the dominant initial hydrogen impurity in weak quartz. The hydrolytic weakening of quartz may be caused by the transformation H2O + Si-O-Si ??? 2SiOH, but this may be a transitory change with the SiOH groups recombining to form H2O, and the average SiOH concentration remaining very low. Synthetic quartz is strengthened when the H2O is accumulated into fluid inclusions and cannot react with the quartz framework. ?? 1984 Springer-Verlag.

Physics and Chemistry of Minerals

Exsolution of Ca-clinopyroxene from orthopyroxene aided by deformation

Monoclinic calcium-poor shear-transformation lamellae and calcium-rich exsolution lamellae occur parallel to (100) in orthopyroxene. The formation of both structures from an orthopyroxene host involves a shear on (100) parallel to [001], with additional cation exchange in the exsolution case. The shear transformation involves a macroscopic simple shear angle of 13.3?? (shear strain of 0.236) and produces a specific a-axis orientation with respect to the sense of shear; we have found that this orientation dominates in exsolution lamellae in kinked orthopyroxene, where the sense of shear is known. In undeformed orthopyroxene, there is generally no preferred sense of orientation of the monoclinic a axes. We advance a specific model for exsolution involving nucleation and growth by shear transformation combined with cation exchange, thus circumventing the classical nucleation barrier and permitting exsolution at lower solute supersaturations. ?? 1981 Springer-Verlag.

Physics and Chemistry of Minerals

State of stress in the lithosphere: Inferences from the flow laws of olivine

The experimental flow data for rocks and minerals are reviewed and found to fit a law of the form {Mathematical expression} where {Mathematical expression} This law reduces to the familiar power-law stress dependency at low stress and to an exponential stress dependency at high stress. Using the material flow law parameters for olivine, stress profiles with depth and strain rate are computed for a representative range of temperature distributions in the lithosphere. The results show that the upper 15 to 25 km of the oceanic lithosphere must behave elastically or fail by fracture and that the remainder deforms by exponential law flow at intermediate depths and by power-law flow in the rest. A model computation of the gravitational sliding of a lithospheric plate using olivine rheology exhibits a very sharp decoupling zone which is a consequence of the combined effects of increasing stress and temperature on the flow law, which is a very sensitive function of both. ?? 1977 Birkha??user Verlag.

Pure and Applied Geophysics PAGEOPH