The effect of dissolved magnesium on creep of calcite II: transition from diffusion creep to dislocation creep

We extended a previous study on the influence of Mg solute impurity on diffusion creep in calcite to include deformation under a broader range of stress conditions and over a wider range of Mg contents. Synthetic marbles were produced by hot isostatic pressing (HIP) mixtures of calcite and dolomite powders for different intervals (2–30 h) at 850°C and 300 MPa confining pressure. The HIP treatment resulted in high-magnesian calcite aggregates with Mg content ranging from 0.5 to 17 mol%. Both back-scattered electron images and chemical analysis suggested that the dolomite phase was completely dissolved, and that Mg distribution was homogeneous throughout the samples at the scale of about two micrometers. The grain size after HIP varied from 8 to 31 μm, increased with time at temperature, and decreased with increasing Mg content (>3.0 mol%). Grain size and time were consistent with a normal grain growth equation, with exponents from 2.4 to 4.7, for samples containing 0.5–17.0 mol% Mg, respectively. We deformed samples after HIP at the same confining pressure with differential stresses between 20 and 200 MPa using either constant strain rate or stepping intervals of loading at constant stresses in a Paterson gas-medium deformation apparatus. The deformation tests took place at between 700 and 800°C and at strain rates between 10⁻⁶ and 10⁻³ s⁻¹. After deformation to strains of about 25%, a bimodal distribution of large protoblasts and small recrystallized neoblasts coexisted in some samples loaded at higher stresses. The deformation data indicated a transition in mechanism from diffusion creep to dislocation creep. At stresses below 40 MPa, the strength was directly proportional to grain size and decreased with increasing Mg content due to the reductions in grain size. At about 40 MPa, the sensitivity of log strain rate to log stress, (n), became greater than 1 and eventually exceeded 3 for stresses above 80 MPa. At a given strain rate and temperature, the stress at which that transition occurred was larger for samples with higher Mg content and smaller grain size. At given strain rates, constant temperature, and fixed grain size, the strength of calcite in the dislocation creep regime increased with solute content, while the strength in the diffusion creep regime was independent of Mg content. The results suggest that chemical composition will be an important element to consider when solid substitution can occur during natural deformation.     

Cr and Al diffusion in chromite spinel: experimental determination and its implication for diffusion creep

Diffusion coefficients of Cr and Al in chromite spinel have been determined at pressures ranging from 3 to 7 GPa and temperatures ranging from 1,400 to 1,700°C by using the diffusion couple of natural single crystals of MgAl₂O₄ spinel and chromite. The interdiffusion coefficient of Cr–Al as a function of Cr# (=Cr/(Cr + Al)) was determined as D _Cr–Al = D ₀ exp {−(Q′ + PV*)/RT}, where D ₀ = exp{(10.3 ± 0.08) × Cr#^0.54±0.02} + (1170 ± 31.2) cm²/s, Q′ = 520 ± 81 kJ/mol at 3 GPa, and V* = 1.36 ± 0.25 cm³/mol at 1,600°C, which is applicable up to Cr# = 0.8. The estimation of the self-diffusion coefficients of Cr and Al from Cr–Al interdiffusion shows that the diffusivity of Cr is more than one order of magnitude smaller than that of Al. These results are in agreement with patterns of multipolar Cr–Al zoning observed in natural chromite spinel samples deformed by diffusion creep.     

On the inter-relationship between grain size sensitive creep and dynamic recrystallization of olivine

The recent theoretical results of Twiss (1976) and Goetze (1978) suggest that at high temperatures and sufficiently high stresses the creep behavior of dry olivine should be dominated by either nonlinear diffusion accommodated grain-boundary sliding or nonlinear Coble creep mechanisms. This would result following the production of a fine grain-size by dynamic recrystallization. For the high-temperature experimental work performed by Karato et al. (1982) dry single crystals of olivine were almost totally recrystallized during creep, and temperature changing experiments were performed on the resulting dynamically recrystallizing polycrystalline aggregates. However, the activation energy for creep determined by Karato et al. (1982) was far higher than that predicted by the models of Twiss (1976) or Goetze (1978), although the conditions required for operation of at least the model of Twiss (1976) apparently were satisfied. The data for the highly recrystallized specimens from the higher stress, lower temperature experiments of Zeuch and Green (1979) and Zeuch (1980) are in good agreement with the results of Karato et al. (1982). These latter experiments were conducted under conditions where either the model of Twiss (1976) or Goetze (1978) should have been applicable. I tentatively conclude that although fine grain sizes were produced in the experiments of Karato et al. (1982), Zeuch and Green (1979) and Zeuch (1980) by dynamic recrystallization, there is no evidence for a transition to grain-boundary diffusional creep mechanisms at high or low stresses despite the predictions of Twiss (1976) or Goetze (1978). Instead, deformation is dominated by dislocation movement with recovery by dynamic recrystallization.     

An experimental study of Ostwald ripening of olivine and plagioclase in silicate melts: implications for the growth and size of crystals in magmas

We carried out an experimental study to characterize the kinetics of Ostwald ripening in the forsterite-basalt system and in the plagioclase (An₆₅)-andesite system. Eight experiments were done in each system to monitor the evolution of mean grain size and crystal size distribution (CSD) with time t; the experiments were performed in a 1-atmosphere quench furnace, at 1,250°C for plagioclase and 1,300°C for olivine. Very contrasted coarsening kinetics were observed in the two series. In the plagioclase series, the mean grain size increased as log(t), from ≈3 μm to only 8.7 μm in 336 h. The kinetic law in log(t) means that Ostwald ripening was rate-limited by surface nucleation at plagioclase-liquid interfaces. In the olivine series, the mean grain size increased as t ^1/3, from ≈3 μm to 23.2 μm in 496 h. A kinetic law in t ^1/3 is expected when Ostwald ripening is rate-limited either by diffusion in the liquid or by grain growth/dissolution controlled by a screw dislocation mechanism. The shape of olivine CSDs, in particular their positive skewness, indicates that grain coarsening in the olivine experiments was controlled by a screw dislocation mechanism, not by diffusion. As the degrees of undercooling ΔT (or supersaturation) involved in Ostwald ripening are essentially <1°C, the mechanisms of crystal growth identified in our experiments are expected to be those prevailing during the slow crystallisation of large magma chambers. We extrapolated our experimental data to geological time scales to estimate the effect of Ostwald ripening on the size of crystals in magmas. In the case of plagioclase, Ostwald ripening is only efficient for mean grain sizes of a few microns to 20 μm, even for a time scale of 10⁵ years. It can, however, result in a significant decrease of the number of small crystals per unit volume, and contribute to the development of convex upwards CSDs. For olivine, the mean grain size increases from 2–3 μm to ≈70 μm in 1 year and 700 μm in 10³ years; a mean grain size of 3 mm is reached in 10⁵ years. Accordingly, the rate of grain size-dependent processes, such as compaction of olivine-rich cumulates or melt extraction from partially molten peridotites, may significantly be enhanced by textural coarsening.     

含水对富铁橄榄石流变性的影响

橄榄石是下地壳上地幔最丰富的造岩矿物,橄榄石集合体的高温高压流变性对地幔动力学过程有着很大的影响。以往对橄榄石单晶和集合体进行过的流变性实验研究,涉及了温度、压力、氧逸度、含铁量以及含水等因素的影响,本文研究了含水对富铁橄榄石集合体流变性能的影响,首先,利用高精度 Paterson 气体介质变形装置对含水富铁橄榄石集合体(Mg_(0.9),Fe_(0.1))_2SiO_4、(Mg_(0.7),Fe_(0.3))_2SiO_4和(Mg_(0.5),Fe_(0.5))_2SiO_4进行了高温三轴压缩蠕变试验,变形试验条件为:温度1323～1473K,围压300MPa,差应力10～300MPa,应变率10~(-7)～10~(-4)s~(-1),每个试件的最大变形量为20%。利用三维非线性拟合方法对蠕变试验数据进行分析,结果表明,含水富铁橄榄石集合体的微观变形机制为扩散域和位错域,对三种铁含量,扩散域的应力指数为1。位错蠕变域中,Fo_(50)应力指教为3.8,活化能为444kJ/mol;Fo_(70)应力指数为3.7,活化能为479kJ/mol,Fo_(90)应力指数为3.6,活化能为514kJ/mol。将实验结果与不含水富铁橄榄石集合体的强度进行对比,发现含水使富铁橄榄石的强度明显下降,舍铁量相同时,含水橄榄石集合体的流变强度比干燥时小至少一个数量级。从而得到了含水对含铁量不同的橄榄石集合体粘性(强度)影响的初步试验结果。     

Dislocation recovery in fine-grained polycrystalline olivine

The rate of static dislocation recovery in Fo₉₀ olivine has been studied under conditions of high temperature and controlled atmosphere in compressively deformed polycrystals hot-pressed from synthetic (sol–gel) and natural (San Carlos) precursor powders. The sol–gel olivine, containing a small fraction of orthopyroxene, was deformed to a final strain of 19% with a maximum differential stress of 266 MPa whereas the San Carlos specimen was deformed to 15% strain and 260 MPa differential stress. Small samples cut from these deformed materials were annealed under high-temperature, controlled atmosphere conditions, for different durations to allow partial recovery of the dislocation sub-structures. Oxidative-decoration of the microstructural features, followed by backscattered electron imaging at 5 kV and image analysis, was used to determine dislocation density. The variation of dislocation density ρ with time t at absolute temperature T was fitted to a second-order rate equation, in integral form, 1/ρ(t) − 1/ρ(0) = kt with k = k ₀ exp(−E _a/RT). The activation energy E _a of the recovery process is 240 ± 43 and 355 ± 81 kJ mol⁻¹ for sol–gel and San Carlos olivine polycrystals, respectively. The measured rates are one to two orders of magnitude lower than those reported in previous studies on natural single crystal olivine. The difference may be explained by several factors such as high dislocation densities measurable from large areas at high magnification for the SEM and the technique used to estimate dislocation densities. Comparison between fine-grained sol–gel olivine and the coarser-grained San Carlos olivine aggregate did not indicate that grain boundaries play an important role in dislocation recovery, but the absence of grain boundaries might also have contributed to the high dislocation recovery rates previously measured for single crystals.     

The rheology of olivine and spinel magnesium germanate (Mg2GeO4): TEM study of the defect microstructures

Synthetic polycrystals of α-Mg₂GeO₄ (with the olivine structure) and γ-Mg₂GeO₄ (with the spinel structure) deformed at high temperature and pressure in their respective stability fields were investigated by analytical transmission electron microscopy. Specimens with a mean grain size of 20–30 µm deform by dislocation glide and/or climb. The predominance of glide versus climb depends on stress and grain orientation. The defect microstructures of both polymorphs are very similar to those observed in their respective silicate analogues, α- and γ-(Mg,Fe)₂SiO₄, and, in the case of the spinel phase, very similar to those observed in magnesium aluminate spinels. These observations suggest that Mg₂GeO₄ is a good rheological analogue for the Earth’s upper mantle. A spinel specimen deformed under the same conditions of temperature and strain rate as an olivine specimen was approximately three times stronger than olivine. In specimens of both phases deformed at or above 1400 K, a thin amorphous film composed of Mg, Ge, and O was detected along some grain boundaries. Grains ≤10 µm diameter surrounded by a film of amorphous phase (>10 nm thick) exhibited low dislocation densities, and deformation appeared to have occurred by grain boundary sliding.     

Deformation mechanism maps for feldspar rocks

Deformation mechanism maps for feldspar rocks were constructed based on recently published constitutive laws for dislocation and grain boundary diffusion creep of wet and dry plagioclase aggregates. The maps display constant temperature contours in stress-grain size space for strain rates ranging from 10⁻¹⁶ to 10⁻¹² s⁻¹.Two fields of dominance of grain boundary diffusion-controlled creep and dislocation creep are separated by a strongly grain size-sensitive transition zone. For wet rocks, diffusion-controlled creep dominates below a grain size of about 0.1–1 mm, depending on temperature, stress, strain rate and feldspar composition. Plagioclase aggregates containing up to 0.3 wt.% water as often found in natural feldspars are more than 2 orders of magnitude weaker than dry rocks. The strength of water-bearing feldspar rocks is moderately dependent on composition and water fugacity.For a grain size range of about 10–50 μm commonly observed in natural ultramylonites, the deformation maps predict that diffusion-controlled creep is dominant at greenschist to granulite facies conditions. Low viscosity estimates of 10¹⁸–10¹⁹ Pa·s from modeling postseismic stress relaxation and channel flow of the continental lower crust can only be reconciled with laboratory experiments assuming dislocation creep at high temperatures >900 °C or, at lower temperatures, diffusion creep of fine-grained rocks possibly localized in abundant high strain shear zones. For similar thermodynamic conditions and grain size, lower crustal rocks are predicted to be less than order of magnitude weaker than upper mantle rocks.     

Large-strain deformation and strain partitioning in polyphase rocks: Dislocation creep of olivine–magnesiowüstite aggregates

Aggregates composed of olivine and magnesiowüstite have been deformed to large strains at high pressure and temperature to investigate stress and strain partitioning, phase segregation and possible localization of deformation in a polyphase material. Samples with 20 vol.% of natural olivine and 80 vol.% of (Mg_0.7Fe_0.3)O were synthesized and deformed in a gas-medium torsion apparatus at temperatures of 1127 °C and 1250 °C, a confining pressure of 300 MPa and constant angular displacement rates equivalent to constant shear strain rates of 1–3.3 × 10^− 4 s^− 1. The samples deformed homogeneously to total shear strains of up to γ  15. During constant strain rate measurements the flow stress remained approximately stable at 1250 °C while it progressively decreased after the initial yield stress at the lower temperature. Mechanical data, microstructures and textures indicate that both phases were deforming in the dislocation creep regime. The weaker component, magnesiowüstite, controlled the rheological behavior of the bulk material and accommodated most of the strain. Deformation and dynamic recrystallization lead to grain refinement and to textures that were not previously observed in pure magnesiowüstite and may have developed due to the presence of the second phase. At 1127 °C, olivine grains behaved as semi-rigid inclusions rotating in a viscous matrix. At 1250 °C, some olivine grains remained largely undeformed while deformation and recrystallization of other grains oriented for a-slip on (010) resulted in a weak foliation and a texture typical for pure dry olivine aggregates. Both a-slip and c-slip on (010) were activated in olivine even though the nominal stresses were up to 2 orders of magnitude lower than those needed to activate these slip systems in pure olivine at the same conditions.     

Superplastic flow in finegrained limestone

Creep of Solnhofen limestone at temperatures between 600° and 900° C was found to fall into three different flow regimes: regime 1 with an exponential stress-dependence of strain rate, regime 2 with power-law creep and n ~ 4.7 and finally a superplastic regime 3 with n ~ 1.7. Within the superplastic regime the creep behaviour is strongly grain-size dependent, the strain rate increasing markedly with decrease in grain size at a given stress. Microstructural observations indicate that in regimes 1 and 2 intracrystalline plasticity is dominant whereas the superplastic regime is characterized by grain-boundary sliding. The crystallographic preferred orientation within the superplastic regime is weaker and of different geometry when compared with that in flow regimes 1 and 2. In a discussion on the deformation mechanisms it is suggested that flow regimes 1 and 2 are regimes of dis location creep in which the rate controlling step is diffusion assisted; for the superplastic regime existing models of grain-boundary sliding are compared with the observations Finally, the tectonophysical importance of superplasticity is discussed and by extra polating the observed creep behaviour to geological strain rates it is found that super plasticity in rocks is to be expected under a wide range of conditions, particularly at smal grain sizes.     

Microstructural and experimental constraints on the rheology of partially molten gabbro beneath oceanic spreading centers

Flow laws for high-temperature creep of olivine, plagioclase, and diabase are used to place constraints on the rheology of partially molten lower oceanic crust. This analysis is motivated by the observation of olivine lattice preferred orientations and subgrain microstructures in oceanic gabbros that lack evidence for dislocation creep in coexisting plagioclase and pyroxene. Extrapolation of experimental flow laws indicates that at temperatures above 1100°C and stresses less than 10 MPa, olivine may be the weakest phase in rocks with gabbroic composition. By accounting for variations in the melt fraction (0–10%) and grain size of partially molten plagioclase aggregates we can constrain the rheological conditions where olivine deforms by dislocation creep while plagioclase deforms by diffusion creep. Calculated effective viscosities range from 10¹⁵ to 10¹⁹ Pa s; based on observations of the geometry of the partially molten zone beneath the East Pacific Rise and the microstructural and experimental constraints we favor a value of ∼10¹⁸ Pa s. This value approaches estimates for the viscosity of the upper mantle beneath ridge axes, but is significantly higher than previously suggested for the partially molten lower crust. Such high viscosities are inconsistent with ridge evolution models that require large amounts of lower crustal flow to accommodate melt redistribution. However, the results are compatible with recent models that favor local magma replenishment from the mantle at closely spaced intervals along the spreading center axis in a 2D, ‘sheet-like’ fashion.     

A close look at dihedral angles and melt geometry in olivine-basalt aggregates: a TEM study

Olivine-basalt aggregates sintered at high P/T have been used as a simplest approximation of partially molten upper mantle peridotite. In the past, geometry of partial melt in polycrystalline olivine (and other materials) has been characterised by dihedral (wetting) angles which depend upon surface free energy. However, since olivine (like most other crystalline materials) is distinctively anisotropic, the simple surface energy balance defining the dihedral angles cos(Θ/2)=_gb/2_sl is not valid and melt geometry is more complicated than can be expressed by a single dihedral angle value. We examine in detail melt geometry in aggregates held at high temperature and pressure for very long times (240–612 h). We show the simple dihedral angle concept to be invalid via transmission electron microscope images. Olivine-basalt interfaces are frequently planar crystal faces (F-faces) which are controlled by the crystal structure rather than the surface area minimisation used in the simple dihedral angle concept. Nevertheless, the dihedral angles may provide useful insights in some situations. They may give a rough estimation of the wetting behaviour of a system, or be used to approximate the melt distribution if F-faces are not present (possibly at large grain size and very low melt fraction). Our measurements, excluding F-faces, give a range of dihedral angle values from 0 to 10° which is significantly lower than reported previously (20–50°). The nature of 0° angles (films and layers up to 1 μm in thickness) is unclear but their frequency compared to dry grain boundaries depends on grain size and melt fraction (e.g. 70% for grain size 43 μm and melt fraction 2%). Received: 13 April 1997 / Accepted: 2 October 1997     

Spinel inclusions in olivine of peridotite xenoliths from TUBAF seamount (Bismarck Archipelago/Papua New Guinea): evidence for the thermal and tectonic evolution of the oceanic lithosphere

Olivine in spinel peridotite xenoliths from the Bismarck Archipelago northeast of Papua New Guinea, which were transported to the surface by Quaternary basalts, shows spinel inclusions up to 25 μm long and 200 nm wide. These inclusions mainly occur as inhomogeneously distributed needles and subordinately as octahedral grains in olivine of veined metasomatic peridotites as well as peridotites without obvious metasomatism. The needles very often occur in swarms with irregular spacing in between them. Similar spinel inclusions in olivine have only previously been reported from ultramafites of meteoritic origin. Composition and orientation of the spinel inclusions were determined by transmission electron microscopy (TEM) and analytical electron microscopy (AEM). Both the needles and the grains display a uniform crystallographic orientation in the host olivine with [001]^O1//[1ˉ10]_Spl and (100)_Ol// (111)_Spl. The needles eare elongated parallel [010] in olivine, which is the same in all olivine grains. As these needles have no relation to the metasomatic sections in the peridotite, it is concluded that they are primary features of the rock. Although the composition of the spinel needles is often very similar to the large chromian spinel octahedra in the matrix, the small octahedral spinel inclusions in olivine are in part Mg-rich aluminous spinel and sometimes almost pure magnetite. The spinel needles are suggested to have formed by exsolution processes during cooling of Al- and Cr-rich, high-temperature olivine during the initial formation of the lithospheric mantle at the mid-ocean ridge. The Al-rich spinel octahedra probably formed by the breakdown of an Al-rich phase such as phlogopite or by metasomatism, whereas the magnetite was generated by oxidizing fluids. These oxidizing fluids may either have been set free by dehydration of the underlying, subducted plate or by the Quaternary magmatism responsible for the transport of the xenoliths to the seafloor. Received: 25 May 2000 / Accepted: 12 July 2000     

Genesis and evolution of low-Al orthopyroxene in spinel peridotite xenoliths, Grand Canyon field, Arizona, USA

Orthopyroxene porphyroblasts zoned to interiors abnormally low in Al and Cr and containing numerous inclusions of olivine occur in some spinel peridotite xenoliths from the Colorado Plateau. Rims of these orthopyroxene grains contain 2.5–3.0 wt% Al₂O₃, consistent with equilibration in spinel peridotite at temperatures near 850 °C, but interiors contain as little as 0.20 wt% Al₂O₃ and 0.04 wt% Cr₂O₃. The Al-poor compositions are inferred to have equilibrated in chlorite peridotite, before porphyroblast growth during heating and consequent reactions that eliminated talc, tremolite, and chlorite. The distinctive orthopyroxene textures are inferred to have formed during reaction of talc and olivine. Rare intergrowths of orthopyroxene plus diopside are attributed to olivine-tremolite reaction. Al and Cr have gradients at grain rims that appear little modified by diffusion, but divalent elements are almost homogeneous throughout the porphyroblasts. Judging from the relative gradients, diffusion of Ca was at least 100 times faster than that of Al and Cr at the temperatures near and below 850 °C. Diffusion of Al and Cr was most effective along subgrain boundaries, and along these boundaries it appears to have been at least ten times faster than within the lattice: diffusion along such boundaries may be a dominant mechanism for re-equilibration of orthopyroxene at low mantle temperatures. Orthopyroxene with similar low Al and Cr occurs in chlorite peridotite xenoliths from the Navajo field, 300 km east of the Grand Canyon localities, and in spinel peridotite xenoliths from the Sierra Nevada, 500 km west across the extended Basin and Range province. Chlorite peridotite may therefore have been a significant minor component in much of the mantle lithosphere of western North America, although evidence for it would be erased at the higher temperatures recorded by xenoliths from the Basin and Range. Chemical changes during hydration may have been important in the evolution of these mantle volumes, and the case for addition of Sr is particularly strong. Dehydration reactions during heating could have influenced patterns of extension and crustal magmatism. Received: 1 July 1996 / Accepted: 2 December 1996     

Recrystallisation,phase mixing and strain localisation in peridotite during rapid extrusion of sub-arc mantle lithosphere

The Anita Peridotite, in southwestern New Zealand, is a ∼1 × 20 km ultramafic massif that was rapidly extruded from beneath a Cretaceous arc within the 4 km wide mylonitic Anita Shear Zone. The peridotitic body contains a spectacular array of textures that preserve evidence for changing temperature, stress, and deformation mechanisms during the exhumation process. Olivine and orthopyroxene microstructures and lattice-preferred orientations (LPO) record a three-phase deformation history. Dislocation glide on the C- and E-type slip systems is recorded by coarse pre-mylonitised olivine grains, and occurred under hydrous conditions at T ∼650 °C, stress ∼200–700 MPa and strain rate ∼10⁻¹⁵ s⁻¹, probably within hydrated sub-arc mantle lithosphere. Rare protomylonite pods record deformation by dislocation creep in porphyroclasts and dislocation-accommodated grain boundary sliding in the matrix on {0kl}[100] in olivine and (100)[001] in orthopyroxene, under conditions of T ∼730–770 °C, stress ∼52–700 MPa and strain rate ∼10⁻¹⁵ s⁻¹. The massif, however, is dominated by mylonite and ultramylonite that wrap the protomylonite pods, comprising mostly fine-grained olivine neoblasts that lack internal distortions and have uniform LPOs. These textures indicate deformation occurred by grain-size sensitive (GSS) creep at T ∼650 °C, stress ∼69–137 MPa and strain rate ∼10⁻¹⁵ s⁻¹, and thus during conditions of cooling and decreasing stress. GSS creep became more dominant with time, as the proportion of randomly-oriented neoblasts increased and formed interlinked networks that accommodated much of the strain. Grain boundary pinning allowed GSS creep to be maintained in polyphase regions, following mixing of olivine and orthopyroxene, which may have occurred by grain boundary transport in a fluid phase during a “creep cavitation” process. The results indicate that the Anita Peridotite recrystallised and underwent rheological weakening at a constant strain rate, with strain distributed across the entire section. This widespread deformation caused rapid exhumation of the peridotite from the lithospheric mantle into the overlying arc crust. The massif therefore records multiple overprinting phases of deformation under mantle and crustal conditions associated with the rapid exhumation of a large orogenic peridotite.     

The normal grain growth behaviour of nominally pure calcitic aggregates

The normal grain growth behaviour of four different, but all nominally pure, calcite powders (99%+ analytic grade calcite, 99.7% chalk, 99.97% crushed Iceland Spar, 99.95%+ chelometric grade calcite) has been investigated as a function of temperature (550, 600, 650, 700 °C) and confining pressure (100, 190 MPa) under both “dry” and hydrostatic (P _fluid = P _total) conditions. The initial particle size of both the analytic grade and chelometric grade calcite was about 5 μm, and that of the chalk was about 3 μm, while the experiments on the Iceland Spar were conducted on powders of three different initial particle sizes (3.4, 7.5, 38.5 μm). On each material, at each pressure/temperature condition 6 to 15 experiments, equally spaced in log time from 15 minutes to 50 days, were conducted. Under dry conditions all four materials recrystallized to aggregates which contained less than 2% porosity and which had a grain size of between 4 and 20 μm (depending on the initial particle size). Subsequently the aggregates coarsened by normal grain growth, with the kinetics of the growth process being controlled by the rate at which the grain boundaries could drag the residual pores with them as they migrated. Under nominally identical conditions both the mechanism and rates of pore drag differed greatly for the different materials, implying that this process is highly sensitive to trace solute impurity concentrations. This sensitivity renders the task of providing a systematic account of dry calcite grain growth kinetics highly problematic. Under hydrostatic conditions all the powders followed the same normal grain growth kinetics in which the growth process was rate-controlled by diffusion through the pore fluid on the grain boundaries. An activation enthalpy of 162.6 kJ mol⁻¹ and an activation volume of 34.35 cm³ mol⁻¹ was obtained for this process. Received: 23 May 1996 / Accepted: 8 July 1997     

The transition between deformation regimes dominated by intercrystalline diffusion and intracrystalline creep evaluated by oxygen isotope thermometry

The dominant flow mechanism in tectonic processes depends on the rheological properties of geological materials and the physical conditions prevailing during deformation. We have evaluated the relative importance of intercrystalline diffusion and intracrystalline creep in crustal deformation in terms of temperature and grain size.Oxygen isotope thermometry has been used to elucidate the thermal environment obtaining during deformation and contemporaneous metamorphism of Dalradian rocks from Southwest Scotland. The temperature and grain size data, applied in conjunction with microstructural criteria for evaluating independent mechanisms of steady-state flow, allow recognition of a low-temperature deformation regime dominated by intercrystalline diffusion, and a high-temperature regime dominated by dislocation processes.The transition between the fields of intercrystalline diffusion and dislocation creep for quartz and calcite of 100 Mm grain size occurs at about 450° C and about 300° C, respectively. These empirically derived results are consistent with the temperature intervals over which intercrystalline diffusion and dislocation creep, respectively, are predicted to be dominant at geologically reasonable strain rates, as derived from theoretically formulated deformation mechanism maps for quartz and calcite.Grain growth may play an important role in delimiting the higher-temperature boundary of the intercrystalline diffusion field. Intercrystalline diffusion is the only deformation mechanism that involves mass transfer over distances that are large in relation to the grain size. This result has important consequences for geochemical transport phenomena.     

High-temperature viscoelasticity of fine-grained polycrystalline olivine

 Torsional forced-oscillation and microcreep methods have been employed in a study of the viscoelastic behaviour of fine-grained polycrystalline olivine at high temperatures (to 1300 °C), seismic frequencies and low strain amplitudes. The Fo₉₀ specimens are of low porosity and low dislocation density. They vary in mean grain size from 8 to 150 μm and contain only trace amounts (≪0.1 vol%) of quenched melt glass. For T ≤ 900 °C, their behaviour is essentially elastic and the shear modulus G closely approaches that expected for a dense polycrystal from single-crystal elasticity data – confirming the suppression of thermal microcracking in␣this study. At higher temperatures, pronounced absorption-band dissipation and associated dispersion␣of the shear modulus provide evidence of linear viscoelastic behaviour. Both recoverable (anelastic) and permanent (viscous) strains are involved and the proportion of the latter increases with increasing temperature and decreasing frequency. Comparison of the results for the three specimens provides a clear indication that the viscoelastic behaviour, attributed to diffusional processes, is grain-size-sensitive with the dissipation and associated dispersion increasing with decreasing grain size. Both elastically accommodated and diffusionally accommodated grain-boundary sliding appear to be implicated. Received: 29 September 2000 / Accepted: 7 May 2001     

Spinel minerals in transitional and alkali basaltic glasses from Iceland

Crystallization of spinel minerals in transitional and alkali basalts from Iceland can be related to the FeO, MgO, TiO₂ and Cr contents of the coexisting melt. Chromian spinel occurs in glasses in which TiO₂ is less than 2.8 wt.% and the weight ratio FeO/MgO is less than 2.0, whereas titanomagnetite occurs when the same parameters are greater than 4 wt.% and 2.7, respectively. In addition, chromian spinel only occurs in basalts with Cr greater than 200 ppm. It is suggested that chromian spinel crystallizes, together with olivine, from liquids with olivine liquidus temperatures ranging from above 1,200° C to approximately 1,150° C. A discontinuity in spinel crystallization follows until below 1,100° C, where titanomagnetite starts to crystallize. Compositional variations in chromian spinel attached to, or included, in homogeneous olivine phenocrysts, however, cannot be related to equilibrium relations. Textural relations suggest homogeneous nucleation for titanomagnetite, whereas chromian spinel nucleates heterogeneously, dependent on growth of olivine phenocrysts. The composition of chromian spinels cannot in detail be related to physical and compositional parameters of the average melt, but may be related to local compositional relations in the melt adjacent to growing crystals. Such compositional variation around growing olivine crystals may be the prime reason for the non-equilibrium precipitation of included chromian spinels.     

Compositional changes of minerals associated with dynamic recrystallizatin

The rate of compositional and isotopic exchange between minerals may be enhanced significantly if the rock is deformed simultaneously. The enhanced exchange rate may result from a reduction in grain size (shorter distance for volume diffusion), dissolution and growth of grains by diffusion creep (pressure solution), or the movement of high-angle grain boundaries through strained grains during recrystallization in the dislocation creep regime. The migration of high-angle grain boundaries provides high diffusivity paths for the rapid exchange of components during recrystallization. The operation of the latter process has been demonstrated by deforming aggregates consisting of two plagioclases (An₁ and An₇₉) at 900°C, 1 GPa confining pressure, and a strain rate of ∼2x10^-6s^-1. The polygonal, recrystallized grains were analyzed using an analytical transmission electron microscope and have a variable but often intermediate composition. At the conditions of these experiments, the volume interdiffusion rate of NaSi/CaAl is too slow to produce any observable chemical change, and microstructural-chemical relations indicate that the contribution from diffusion creep was insignificant except for initially fine-grained (2–10 μm) aggregates. These results indicate that strain-induced recrystallization can be an effective mechanism for enhancing the kinetics of metamorphic reactions and for resetting the isotope systematics of minerals such as feldspars, pyroxenes, and amphiboles.