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1.
Phengite samples (2M 1 and 3T politypes) and a synthetic end-member muscovite specimen were studied by in situ high-temperature synchrotron radiation X-ray diffraction. The measured volume thermal expansion of 2M 1 phengite (<α V> ≈ 36.6 × 10−6 K−1) was systematically greater than <α V> of the 3T polytype (≈33.3 × 10−6 K−1). A positive linear correlation between the average thermal expansion on (001) plane and the mean tetrahedral rotation angle at ambient condition is proposed on the ground of new measurements and literature data. Dehydroxylation processes were observed in 2M 1, starting at 1,000 K in 3T at 800 and 945 K in synthetic muscovite. Rietveld refinements allowed a determination of structural variations upon heating of phengite samples and their dehydroxylate phases. The phengite structure expands by regularizing the tetrahedral sheet and by reducing the bond length differences between the outer and inner coordination shell of the interlayer site. The dehydroxylate phase derived from 2M 1 is characterized by fivefold polyhedra in the low temperature form as a consequence of two OH groups reacting to form H2O + O (residual). The dehydroxylate exhibits an increase of the cation–cation distances along the M–Or–M bonds with respect to low-temperature phengite structures. For the 3T phase, we were unable to achieve completion of dehydroxylation. The refined structural model of the dehydroxylate phase shows two hydroxyl sites, but at a short distance from one another. This result suggests that the dehydroxylation reaction did not proceed to completion. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

2.
Illite is a dioctahedral K-deficient mica with an interlayer cation content of 0.6–0.85 atoms per formula unit. 1M and 2M1 are the illite polytypes more abundant in nature. Because illite is one of the major component of clays used for the production of traditional ceramics, the understanding of its high temperature transformations is of paramount importance for the knowledge of the structural and microstructural properties of fired ceramic products. To our knowledge, the study of the illite dehydroxylation kinetics has not been attempted to date. Hence, this work presents the investigation of the reaction mechanism of dehydroxylation of illite for the first time. The natural sample investigated in this study is a 1M-polytype from Hungary. Several classical methods of kinetic analysis were used (isoconversional method, Avrami method, direct fit with kinetic expressions, and others) to achieve a complete picture of the dehydroxylation mechanism. The proposed model for the dehydroxylation of illite is a multi-step reaction sequence with (1) condensation of the water molecule in the octahedral layer; (2) one-dimensional diffusion of the water molecules through the tetrahedral ring (rate limiting step of the reaction); (3) two-dimensional diffusion of the water molecules through the interlayer region (rate limiting step of the reaction).  相似文献   

3.
 Dehydroxylation of muscovite in the form of small lamellae at 923 <T <1173 K was studied by Electron Spin Resonance (ESR) on Fe3+. The kinetics of the process has been established to be described by the model of continuous nucleation on the large surface planes of the small plates. Determined by experimental data the rate constant of the process k is shown to be that of dehydroxylation itself. The activation energy obtained by data at T<1100 K is 97.5 KJ·mol−1. The nonlinear dependence of ln(k) on 1/T is explained by the theory of transitions induced by the fluctuative preparation of a potential barrier as a result of thermal oscillations of ions in the lattice. At high temperatures the potential curve of the hydroxyl's proton is transformed so that it can overcome the barrier from one potential well to the other (from one hydroxyl site to the adjacent one). Such transformations of the curve can be caused by the oscillations of large structural clusters (∼1·10−22 kg) with the frequency ∼4.5·1012 s−1. Received: 3 August 1995 / Accepted: 13 April 1997  相似文献   

4.
The decomposition reaction of kaolinite has been investigated as a function of the defectivity of the starting material and the temperature of reaction. Time resolved energy-dispersive powder diffraction patterns have been measured using synchrotron radiation, both under a constant heating rate (heating rates from 10 to 100° C/min) and in isothermal conditions (in the temperature range 500 to 700° C). The apparent activation energy of the dehydroxylation process is different for kaolinites exhibiting a different degree of stacking fault density. The results of the analysis of the kinetic data indicate that the starting reaction mechanism is controlled by diffusion in the kaolinite particle. The diffusion process is dependent on the defective nature of both kaolinite and metakaolinite. At high temperatures, and at higher heating rates, the reaction mechanism changes and the resistance in the boundary layer outside the crystallites becomes the rate-limiting factor, and nucleation begins within the reacting particle. During the final stage of the dehydroxylation process the reaction is limited by heat or mass transfer, and this might be interpreted by the limited diffusion between the unreacted kaolinite domains and the metakaolinite matrix.  相似文献   

5.
Isothermal thermogravimetric experiments have been carried out to determine the reaction kinetics of the dehydration processes in fuller's earth, a natural Ca-montmorillonite. Dehydration in swelling clays is a complex reaction, and analysis of the thermogravimetric data using empirical rate equations and time-transformation analysis reveals that the nature of the rate controlling mechanism is dependent upon both the temperature regime of the sample as well as the extent of reaction. For fuller's earth, we find that the dehydration kinetics are dominated by a nucleation and growth mechanism at low temperatures and fractions transformed (stage I), but above 90 °C the last stages of the reaction are diffusion controlled (stage II). The activation energy for dehydration during stage I is around 35 kJ · mol−1, whereas the removal of water during stage II requires an activation energy of around 50 kJ · mol−1. These two stages of dehydration are associated with primary collapse of the interlayer (stage I) and movement of water that is hydrated to cations within the interlayer (stage II). Received: 28 August 1998 / Revised, accepted: 27 January 1999  相似文献   

6.
The application of Fourier transform infrared (FTIR) spectroscopy to the analysis of the hydroxyl groups bands' intensities of montmorillonite from Texas shows four regions of intensity loss rate for thermally shocked samples at 290<T<1100 K for 24 h. The first three regions are associated with the dehydroxylation process; while the fourth region suggests the loss of the remaining (～10%) hydroxyls via thermal dissociation into hydrogen atoms and oxygen centers. The dehydroxylation process appears to be homogeneous with adjacent trans OH ions interacting to form H2O molecules below the hexagonal hole or cavity. The vibrational analysis of the stretching and bending modes of water and hydroxyl groups at 290<T<553 K indicates not only that water is desorbed in this range, resulting in the perturbation of the octahedral hydroxyl structure due to the close approach of exchangeable cations to the hexagonal holes, but also that surface hydroxyls and AlFe3+-OH groups are dehydroxylated. AT 553<T< 773 K, the intensity loss of AlAl-OH and AlMg-OH groups almost varies linearly as a function of thermal shock temperature with the AlMg-OH vibration disappearing at T> 673 K. However, what is surprising is the persistence of very weak water stretching (～3470 cm?1) and bending (～1628 cm?1) vibrations at 553<T<773 K. It is speculated that this water, formed because of dehydroxylation, is trapped in the hexagonal cavities of the dehydrated montmorillonite lattice. However, conclusive evidence will require surface-sensitive spectroscopic measurements as this water could also be adsorbed on the external surfaces of processed samples. In the range 773<T<823 K, the main dehydroxylation of the AlAl-OH group results, and this reaction induces structural transformations in the montmorillonite lattice. FTIR measurements at 803 K for 0<t< 25 h were used to determine the kinetics mechanism of dehydroxylation in montmorillonite from Texas. The experimental data was tested, using diffusion controlled as well as six decomposition models to ascertain the kinetics mechanism of the AlAl-OH group's dehydroxylation. It appears that the dehydroxylation process can be described by the contracting spherical movement model rather than by a diffusion controlled model, suggesting surface nucleation, growth over the surface, and then advancement of the dehydroxylated/hydroxylated interface toward the center of the montmorillonite particles.  相似文献   

7.
 Polygonal serpentine (PS) from selected serpentinite were studied using transmission electron microscopy. Fiber axis selected-area electron diffraction (SAED) patterns and electron micrographs reveal orthogonal and monoclinic lizardite polytypes. The PS models by Chisholm (1992) and Baronnet et al. (1994) do not fit SAED measurements. Experimental results are matched with calculated diffraction geometry and intensities, as well as with simulated images, indicating inversion of the tetrahedral layer at sector boundaries. The structural relationships between chrysotile and PS are discussed. Two types of 30-sectored PS are distinguished. In “regular PS” the fiber axis is [100], in “helical PS” the fiber axis points into a [uν0] direction with large u value (u≫ν). Helical PS can be regarded as a lizardite analogue of helical chrysotile. Received December 6, 1995/Revised, accepted May 8, 1996  相似文献   

8.
The dissolution of chrysotile is studied in regard to the surfaces analysis by photoelectron spectrometry. After leaching of chrysotile (Provenance: Thetford; about 200 mg of fibers of 1 cm length) in nonstirred 0.1 N oxalic conditions, the composition of the mineral surfaces is determined by XPS; kinetic curves of dissolution are given in the range 22–80°C. Two conditions for the rate-limiting step are involved for the explanation of the dissolution: diffusion of Mg2+ through the fibrous gel or dissociation of chrysotile. By the former, some values of the diffusion coefficient are proposed: D varies from 5·10?19 cm2s?1 to 5·10?16 cm2s?1, in the range 22–80°C. By the second model, the leaching rate is estimated from 3 Å (22°C) per h to 250 Å (80°C) per h. For the 2 models, the activation heat energy is in the range 15–20 Kcal.  相似文献   

9.
Muscovite-2M1 shows a major phase transition at about 800°C, which is generally attributed in the literature to the structural dehydroxylation process, although a number of structural models have been proposed for the dehydroxylated phase, and different transformation mechanisms have also been put forward. The observed first order transformation involves an increase in the cell volume, and it is not clear to date how the cell expansion is related to the loss of hydroxyl groups. The phase change has been re-investigated here by in situ high temperature powder diffraction, both in non-isothermal and isothermal modes, to combine for the first time the structural and the kinetic interpretation of the transformation. The results unequivocally confirm that the reaction taking place in the temperature range 700–1000°C is truly a dehydroxylation process, involving the nucleation and growth of the high temperature dehydroxylated phase, having Al in 5-fold coordination. Structural simulations of the basal peaks of the powder diffraction patterns indicate that the model originally proposed by Udagawa et al. (1974) for the dehydroxylated phase correctly describes the high temperature phase. The kinetic analysis of the isothermal data using an Avrami-type model yields values for the reaction order compatible with a reaction mechanism limited by a monodimensional diffusion step. Apparent activation energy of the process in vacuum is about 251 kJ/mol. Experiments carried out at temperatures much higher than the onset temperature of the reaction show that the dehydroxylation reaction overlaps with the reaction of formation of mullite, the final product in the reaction pathway. Received: 24 April 1998 / Revised, accepted: 12 October 1998  相似文献   

10.
 The kinetics of hydrothermal crystallisation of sodium zeolites from a natural mixture of halloysite and amorphous silica with Si/Al ≈ 4 was investigated. The sample collected at Scarpara (Tuscania, Italy) is the final product of an intense hydrothermal alteration process on the pre-existing leucitic tufites. In order to enhance its reactivity in the NaOH solution, the sample was thermally activated at 600 °C for 1 h. The hydrothermal crystallisation sequence of zeolites formed in the range 90–150 °C has been followed using real-time synchrotron powder diffraction. The reaction kinetics of Na-X, Na-P and analcime were analysed using a model developed for the study of the kinetic data from X-ray diffraction experiments. Na-X and Na-P cocrystallize with an autocatalytic nucleation at lower isothermal temperatures and with a heterogeneous nucleation at higher isothermal temperatures. Na-X tends to dissolve before Na-P, which in turn transforms into analcime. This work is part of a general project on the kinetics of formation of zeolites from clay precursors which is important for either engineering and production of valuable industrial materials and for the interpretation of poorly understood processes of formation of zeolites in natural hydrothermal environments. Received: 7 November 2000 / Accepted: 19 March 2001  相似文献   

11.
The effects of deformation on the kinetics of the net-transfer reaction anorthite + forsterite → cpx + opx + spinel ± gt were studied using static and shear deformation experiments. Experiments were performed on dry anorthite-olivine (An92–Fo93) samples at 900°C and pressures between 1,000 and 1,600 MPa in a Griggs apparatus. Deformed (‘non-hydrostatic’) and undeformed (‘static’) samples are compared in terms of phase petrology, reaction rate and reaction mechanisms. Anorthite + olivine reactions are diffusion-controlled as seen from reaction rim structures. In undeformed samples, delayed reaction onset and low reaction rates demonstrate sluggish nucleation of reaction products and slow rates of diffusion at dry conditions, even at 700–900 MPa confining pressure overstepping. The reaction rate is enhanced in deformed An–Fo samples. The higher rate is mainly attributed to a combination of high stresses and viscous deformation processes of the reactants and products, which cause an increase in the nucleation rate of products. The results imply that viscous deformation processes alone can be responsible for the initiation and localisation of metamorphic reactions in dry rocks in the absence of fluid infiltration. A. A. de Ronde was supported by the Swiss National Fond grants 2100-057092.99 and 2000-065041.01.  相似文献   

12.
We determined the lithium isotope fractionation between synthetic Li-bearing serpentine phases lizardite, chrysotile, antigorite, and aqueous fluid in the P,T range 0.2–4.0 GPa, 200–500°C. For experiments in the systems lizardite-fluid and antigorite-fluid, 7Li preferentially partitioned into the fluid and Δ7Li values followed the T-dependent fractionation of Li-bearing mica-fluid (Wunder et al. 2007). By contrast, for chrysotile-fluid experiments, 7Li weakly partitioned into chrysotile. This contrasting behavior might be due to different Li environments in the three serpentine varieties: in lizardite and antigorite lithium is sixfold coordinated, whereas in chrysotile lithium is incorporated in two ways, octahedrally and as Li-bearing water cluster filling the nanotube cores. Low-temperature IR spectroscopic measurements of chrysotile showed significant amounts of water, whose freezing point was suppressed due to the Li contents and the confined geometry of the fluid within the tubes. The small inverse Li-isotopic fractionation for chrysotile-fluid results from intra-crystalline Li isotope fractionation of octahedral Li[6] with preference to 6Li and lithium within the channels (Li[Ch]) of chrysotile, favoring 7Li. The nanotubes of chrysotile possibly serve as important carrier of Li and perhaps also of other fluid-mobile elements in serpentinized oceanic crust. This might explain higher Li abundances for low-T chrysotile-bearing serpentinites relative to high-T serpentinites. Isotopically heavy Li-bearing fluids of chrysotile nanotubes could be released at relatively shallow depths during subduction, prior to complete chrysotile reactions to form antigorite. During further subduction, fluids produced during breakdown of serpentine phases will be depleted in 7Li. This behavior might explain some of the Li-isotopic heterogeneities observed for serpentinized peridotites.  相似文献   

13.
The effects of molecular diffusivity of H2SO4 and NH3 vapours on nucleated particles of SO42− and NO3− species are reported. Condensation sink and source rate of H2SO4 and NH3 vapours, growth rates and ratios of real to apparent nucleation rates are calculated for SO4– and NO3− aerosols using fractional contributions of them in total aerosol size-distribution during the measurement period at Pune, reported in Chate and Pranesha (2004). The percentage of nucleated SO42− and NO3− aerosols of mid-point diameter 13 nm are 2% and 3% respectively of the total particles (13 nm ≤ D p ≤ 750 nm) for both H2SO4 and NH3 diffusion. In the diameter range 75 nm ≤ D p ≤ 133 nm, it is 48% and 45% of SO42− and NO3− aerosols, respectively for NH3 diffusion and 43% and 36% of SO42− and NO3− for H2SO4 diffusion. Increase in percentage of nucleated particles of these species corresponding to mid-point diameter 133 nm around 0900 h IST is significantly higher than that of mid-point diameter 13 nm and it is due to photo-chemical nucleation, coagulation and coalescence among nucleated clusters. The ratios of real to apparent formation rates for SO42− and NO3− aerosols are 12% and 11% respectively, corresponding to mid-point diameter 13 nm, 17% and 13%, for midpoint diameter 133 nm and 12% and 9.5%, for mid-point diameter 750 nm. The results indicate that nucleation involving H2SO4 and acidic NH3 diffusion on SO42− and NO3− particles is the most relevant mechanism in this region.  相似文献   

14.
Although pseudomorphic mineral replacement reactions are common in all geological environments, and have long been considered important to many geological processes such as metamorphism, metasomatism, diagenesis, and chemical weathering, their mechanisms are still not well known. We present a combined textural and kinetic study of the replacement of pentlandite, (Fe,Ni)9S8, by violarite (NiFe)3S4, and describe the mechanisms and kinetic behavior of this reaction by considering the role of the fluid phase, the causes of coupling between pentlandite dissolution and violarite precipitation, the rate-limiting steps controlling the kinetic behavior, and the origin of the length scale of the features preserved during pseudomorphism.The experiments were conducted under mild hydrothermal conditions (80-210 °C, vapor saturated pressures). Reaction kinetics shows a complex behavior depending on various physical and chemical parameters including temperature, pH, concentrations of various reaction species, solid-weight-to-fluid-volume-ratio and specific surface area. The rate of replacement (i) increases with temperature from 80 to 125 °C, then decreases as temperature further increases to 210 °C, (ii) first increases then decreases with decreasing pH from pH 6 to 1, (iii) increases with increasing concentration of oxidants such as O2(aq), H2O2, and KMnO4, but decreases with increasing concentration of Ni2+ and Fe3+, and with increasing solid-weight-to-fluid-volume ratio, (iv) increases linearly with the specific surface area. This kinetic behavior as well as the resulting textures revealed a coupled dissolution-reprecipitation reaction mechanism.Nanometer-scale pseudomorphic replacement, through which the crystallographic orientation of pentlandite is inherited by violarite, occurs only between 1 < pH < 6, and spatial coupling between dissolution and reprecipitation is controlled by the local solution chemistry as well as by epitaxial nucleation mediated by the pentlandite substrate. The kinetic results show that pentlandite dissolution is rate-limiting under mild acidic to neutral conditions (1 < pH < 6), while violarite precipitation is rate-limiting under strong acidic conditions (pH 1). The difference in rate-limiting steps influences the coupling mechanism and causes the different degrees of preservation (length scale of pseudomorphism) and different morphologies observed at high and low pHs: pentlandite dissolution being rate-limiting results in nanoscale coupling between dissolution and precipitation and thus nanoscale pseudomorphism (length scale <20 nm), in which the replacement precisely preserves the morphology and internal details, resembling remarkably the natural pentlandite/violarite assemblages. In contrast, violarite precipitation being rate-limiting results in microscale pseudomorphism (length scale ∼10 μm): the morphology of the pentlandite grains is only roughly preserved and internal details are not preserved.This case study illustrates some general principles of replacement reactions proceeding via the coupled dissolution-reprecipitation mechanism: (i) primary mineral dissolution needs to be rate-limiting compared to the secondary mineral precipitation in order to achieve a high degree pseudomorphic replacement; (ii) the effects of solution composition on reaction kinetics can be qualitatively rationalized by considering the rate-limiting step reaction.  相似文献   

15.
The thermal behaviour of ripidolite, an iron-rich chlorite, has been studied in situ by infrared emission spectroscopy up to 800 °C. The more di,trioctahedral nature due to significant amounts of Fe3+ is reflected, in addition to the two bands around 3420 and 3560 cm−1, by an extra band around 3345 cm−1. This extra band is absent in pure dioctahedral chlorites without Fe3+. These bands have been assigned to (AlAl)O-OH, (SiAl)O-OH and (SiSi)O-OH stretching modes with increasing frequencies. The bands disappear upon dehydroxylation around 650 °C. A similar behaviour is observed for the corresponding libration modes around 716, 759 and 802 cm−1. The stretching and bending modes of the inner-OH of the octahedral sheet in the 2:1 clay-like layer are observed around 3645, 943 and 904 cm−1. Although the bands decrease in intensity, they remain present up to 800 °C as dehydroxylation of the octahedral sheet is not yet complete at this temperature. The presence of two bending modes is explained as being due to a differentiation between Mg-OH and Fe-OH modes. At 650 °C a new sharp band is observed around 502 cm−1 assigned to a (Fe,Mg)-O-Al bending mode caused by the formation of a spinel-like interlayer phase after dehydroxylation. Received: 4 June 1999 / Accepted: 6 August 1999  相似文献   

16.
 Using a combination of dielectric spectroscopy and atomistic computer simulation techniques, the dynamical behaviour of the loosely bound (Na+ and K+) channel ions in nepheline has been investigated. The low-frequency dielectric properties of a natural Bancroft nepheline have been studied from room temperature to 1100 K. At each temperature, the dielectric constant, conductivity and dielectric loss were determined over a range of frequencies from 100 Hz to 10 MHz. At high temperatures a distinct Debye-type relaxation in the dielectric loss spectrum was observed; the activation energy for this process was determined to be 1.38 ± 0.02 eV. Atomistic simulation techniques were used to elucidate the mechanism and energetics of cation migration. A mechanism involving the hopping of Na+ ions between oval sites and partially occupied hexagonal (K+) sites, via a bottleneck consisting of a distorted sixfold ring of (Al,Si)O4 tetrahedra, was found to give a calculated energy barrier in very good agreement with the experimentally determined activation energy. These results confirm the nature of the process responsible for the observed dielectric behaviour. Overall, this study demonstrates the intrinsic, microscopic control of cation diffusion processes in rock-forming minerals. Identifying specific energy barriers and preferred diffusion pathways is fundamental to the prediction of diffusion energetics. Received: 8 May 2000 / Accepted: 21 July 2000  相似文献   

17.
The dehydroxylation reactions of chrysotile Mg3Si2O5(OH)4 and brucite Mg(OH)2 were studied under inert nitrogen atmosphere using isothermal and non-isothermal approaches. The brucite decomposition was additionally studied under CO2 in order to check the influence of a competing dehydroxylation/carbonation/decarbonisation reaction on the reaction kinetics. Isothermal experiments were conducted using in situ high-temperature X-ray powder diffraction, whereas non-isothermal experiments were performed by thermogravimetric analyses. All data were treated by model-free, isoconversional approaches (‘time to a given fraction’ and Friedman method) to avoid the influence of kinetic misinterpretation caused by model-fitting techniques. All examined reactions are characterised by a dynamic, non-constant reaction-progress-resolved (‘α’-resolved) course of the apparent activation energy E a and indicate, therefore, multi-step reaction scenarios in case of the three studied reactions. The dehydroxylation kinetics of chrysotile can be subdivided into three different stages characterised by a steadily increasing E a (α ≤ 15 %, 240–300 kJ/mol), before coming down and forming a plateau (15 % ≤ α ≤ 60 %, 300–260 kJ/mol). The reaction ends with an increasing E a (α ≥ 60 %, 260–290 kJ/mol). The dehydroxylation of brucite under nitrogen shows a less dynamic, but generally decreasing trend in E a versus α (160–110 kJ/mol). In contrast to that, the decomposition of brucite under CO2 delivers a dynamic course with a much higher apparent E a characterised by an initial stage of around 290 kJ/mol. Afterwards, the apparent E a comes down to around 250 kJ/mol at α ~ 65 % before rising up to around 400 kJ/mol. The delivered kinetic data have been investigated by the z(α) master plot and generalised time master plot methods in order to discriminate the reaction mechanism. Resulting data verify the multi-step reaction scenarios (reactions governed by more than one rate-determining step) already visible in E a versus α plots.  相似文献   

18.
 The lattice constants of paragonite-2M1, NaAl2(AlSi3)O10(OH)2, were determined to 800 °C by the single-crystal diffraction method. Mean thermal expansion coefficients, in the range 25–600 °C, were: αa = 1.51(8) × 10−5, αb = 1.94(6) × 10−5, αc = 2.15(7) ×  10−5 °C−1, and αV = 5.9(2) × 10−5 °C−1. At T higher than 600 °C, cell parameters showed a change in expansion rate due to a dehydroxylation process. The structural refinements of natural paragonite, carried out at 25, 210, 450 and 600 °C, before dehydroxylation, showed that the larger thermal expansion along the c parameter was mainly due to interlayer thickness dilatation. In the 25–600 °C range, Si,Al tetrahedra remained quite unchanged, whereas the other polyhedra expanded linearly with expansion rate proportional to their volume. The polyhedron around the interlayer cation Na became more regular with temperature. Tetrahedral rotation angle α changed from 16.2 to 12.9°. The structure of the new phase, nominally NaAl2 (AlSi3)O11, obtained as a consequence of dehydroxylation, had a cell volume 4.2% larger than that of paragonite. It was refined at room temperature and its expansion coefficients determined in the range 25–800 °C. The most significant structural difference from paragonite was the presence of Al in fivefold coordination, according to a distorted trigonal bipyramid. Results confirm the structural effects of the dehydration mechanism of micas and dioctahedral 2:1 layer silicates. By combining thermal expansion and compressibility data, the following approximate equation of state in the PTV space was obtained for paragonite: V/V 0 = 1 + 5.9(2) × 10−5 T(°C) − 0.00153(4) P(kbar). Received: 12 July 1999 / Revised, accepted: 7 December 1999  相似文献   

19.
 Iron tracer diffusion experiments in diopside have been performed using natural and synthetic single crystals of diopside, and stable iron tracers enriched in 54Fe, at temperatures in the range 950–1100 °C, total pressure 1 atm, for times up to 29 days. Iron isotope diffusion profiles were determined with an ion microprobe. For experiments performed at log pO2 = −13, in directions parallel to the c axis and the b axis of two natural, low iron (Fe ∼ 1.8 at %) diopsides, the data obey a single Arrhenius relationship of the form D = 6.22−5.9 +49.6×10−15 exp(−161.5 ± 35.0 kJ mol−1/RT) m2 s−1. A single datum for iron diffusion in iron-free, single-crystal diopside at 1050 °C, is approximately 1 order of magnitude slower than in the natural crystals. The pO2 dependence of iron diffusion in natural crystals at 1050 °C (power exponent = 0.229 ± 0.036) indicates a vacancy mechanism; this is consistent with the results of unpublished atomistic simulation studies. There is no evidence of anisotropy for iron diffusion in diopside. Received: 16 March 1999 / Accepted: 10 April 2000  相似文献   

20.
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.  相似文献   

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