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1.
The synthesis boundaries of the phase transformation; ++ in (Mg0.9, Fe0.1)SiO4, have been clarified at temperatures to 2000° C and pressures up to 20 GPa in order to synthesize single crystals of high quality. A single crystal of (Mg0.9, Fe0.1)2SiO4 was grown successfully to a size of 500 m. The crystal structure has been refined from single-crystal X-ray intensities. The ferrous ions prefer M1 and M3 sites to over the larger M2 site. The volume change of all the occupied polyhedra does not contribute to the decrease of total volume in the transformation; rather it tends to increase the bulk volume through the expansion of occupied tetrahedra. The volume reduction in the phase transformations is accounted for by unoccupied polyhedra, with the octahedra contributory 60% and the tetrahedra 40% to the V of the transition. The volume change in the transformation is caused also partly by the volume decrease of MO 6 (25%), partly the unoccupied tetrahedra (45%) and octahedra (30%).  相似文献   

2.
Celadonite from the northwestern Mojave Desert area of California was examined by detailed Mössbauer spectroscopy at temperatures from 10 K to 400 K. In addition to the predominant Fe3+ doublet with isomer shift 0.4 mm s–1 and quadrupole splitting 0.4 mm s–1, another Fe3+ doublet with 0.4, 1.2 mm/s and two Fe2+ doublets with 1.1, 1.7, 2.7 mm s–1 at 300 K were distinguished. The minor Fe3+ component is ascribed to dehydroxylated surface sites. Most of the remaining Fe(90%) is M2 cis-OH octahedral in an ordered M+–M2+ array. However, about 10% is M1 trans-OH Fe2+. Isomer shift vs. T gives Debye temperatures of 570 K for Fe3+ in M2 and 380 K for both Fe2+ sites, indicating greater vibrational freedom for Fe2+. Quadrupole splitting vs. T for Fe2+ gives a valence electronic energy splitting of 760 cm–1 between the ground and first excited state for M2. The M1 sites have a more drastic variation in vs. T which indicates not only a lower first excited state but a rhombic distortion at these sites. A proposed explanation is a neighboring M2 site vacancy. The soil clay formed from this celadonite, which is mostly Fe-rich smectite, was also studied by Mössbauer spectroscopy. About half the Fe2+ has been oxidized in the clay, but the isomer shifts and quadrupole splittings are essentially the same as in the original celadonite. A texture orientation in the clay absorber was detected by measuring the absorber at 55° to the source radiation. This texture effect produces asymmetric doublets in the usual 90° measurement.  相似文献   

3.
Titania, TiO2, precipitation in natural blue sapphire (Fe, Ti: -Al2O3) has been investigated using high resolution and analytical transmission electron microscopy. The structure and habit of the TiO2 precipitate depends on both the Ti4+ concentration and the temperature at which the precipitate formed. Tetragonal TiO2 (Rutile) grows at 1350° C but at 1150° C an orthorhombic non-equilibrium TiO2 polymorph precipitates. Both TiO2 polymorphs nucleate in the (0001)s plane as lens shaped discs twinned along their diameter. The crystallographic alignment of each type of TiO2 precipitate with respect to the -Al2O3 host matrix provides a high degree of structural coherency with minimal lattice mismatch. Electron diffraction analysis established the following precipitate/host orientation relationships: tetragonal TiO2: {011}r {11 07B;100}r(0001)s and 01 r10 0s twinned along the (011)r planeand orthorhombic TiO2: {021}{11 0}s, {100}(0001)s and 0 2 10 0s twinned along the (021) plane.  相似文献   

4.
Trapped holes located on Al-O-Al bonds in kaolinite were studied by electron paramagnetic resonance spectroscopy (EPR) at 9.3 and 35 GHz applied to well-crystallized, X-ray irradiated and oriented samples. The Q-band EPR spectrum is characterized by three clearly separated groups of 11 quasi-equidistant superhyperfine lines centered at gxx=2.040±0.0005, gyy=2.020±0.0005 and gzz=2.002±0.001. In each of these groups, the 11 superhyperfine lines exhibit intensities according to the ratios 12345654321. An angular dependence of the Q-band EPR spectrum with respect to the magnetic field is demonstrated by measurements on oriented films of kaolinite. An appropriate numerical treatment of the EPR spectra is described, which allowed extraction of the SuperHyperfine Structures (SHFS). X-and Q-band spectra have also been simulated. It is concluded from these experiments that only one type of center is present. This center, labelled the B-center in the literature, is very probably a hole trapped on oxygen (O- center) atoms coupled to two octahedral aluminium.  相似文献   

5.
Thirteen energy-dispersive x-ray diffraction spectra for -Fe2SiO4 (spinel) collected in situ at 400° C and pressures to 24 GPa constitute the basis for an elevated-temperature static compression isotherm for this important high-pressure phase. A Murnaghan regression of these molar volume measurements yields 177.3 (±17.4) GPa and 5.4(±2.5) for the 400° C, room pressure values of the isothermal bulk modulus (K P 0) and its first pressure derivative (K P 0), respectively. When compared to the room-Tdeterminations of K P 0 available in the literature, our 400° C K P 0 yields -4.1 (±6.2)×10-2 GPa/degree for the average value of (K/T) P 0 over the temperature interval 25° C<><400°>A five-parameter V(P, T) equation for -Fe2SiO4 based on simultaneous regression of our data combined with the elevated P-Tdata of Yagi et al. (1987) and the extrapolated thermal expansion values from Suzuki et al. (1979) yields isochores which have very little curvature [(2 T/P 2) v 0], in marked contrast to the isochores for fayalite (Plymate and Stout 1990) which exhibit pronounced negative curvature [(T/P 2) v <0]. along=" the=">-Fe2SiO4 reaction boundary VRvaries from a minimum of approximately 8.3% at approximately 450° C to approximately 8.9% at 1200° C. Extrapolation of the fayalite and -Fe2SiO4 V(P, T) relationships to the temperature and pressure of the 400 km discontinuity suggests a V R of approximately 8.4% at that depth, approximately 10% less than the 9.3% V R at ambient conditions.  相似文献   

6.
Brillouin spectroscopy was used to measure the single crystal elastic properties of a pure synthetic pyrope and a natural garnet containing 89.9 mol% of the pyrope end member (Mg3Al2Si3O12). The elastic moduli, c ij , of the two samples are entirely consistent and agree with previous estimates of the elastic properties of pyrope based upon the moduli of solid solutions. Our results indicate that the elastic moduli of pyrope end-member are c 11=296.2±0.5, c 12=111.1±0.6, c 44=91.6±0.3, Ks=172.8±0.3, =92.0±0.2, all in units of GPa. These results differ by several percent from those reported previously for synthetic pyrope, but are based upon a much larger data set. Although the hydrous components of the two samples from the present study are substantially different, representing both dry and saturated samples, we find no discernable effect of structurally bound water on the elastic properties. This is due to the small absolute solubility of water in pyrope, as compared with other garnets such as grossular.  相似文献   

7.
Data on the mechanisms of mantle phase transformations have come primarily from studies of analogue systems reacted experimentally at low pressures. In order to study transformation mechanisms in Mg2SiO4 at mantle pressures, forsterite () has been reacted in the stability field of -phase, at 15 GPa and temperatures up to 900° C, using a multianvil split-sphere apparatus. Transmission electron microscope studies of samples reacted for times ranging from 0.25–5.0 h show that forsterite transforms to -phase by an incoherent nucleation and growth mechanism involving nucleation on olivine grain boundaries. This mechanism and the resultant microstructures are very similar to those observed at much lower pressures in analogue systems (Mg2GeO4 and Ni2SiO4) as the result of the olivine to spinel () transformation. Metastable spinel () also forms from Mg2SiO4 olivine at 15 GPa, in addition to -phase, by the incoherent nucleation and growth mechanism. With time, the spinel progressively transforms to the stable -phase. After 1 h, spinels exhibit a highly striated microstructure along {110} and electron diffraction patterns show streaking parallel to [110] which indicates a high degree of structural disorder. High resolution imaging shows that the streaking results from thin lamellae of -phase intergrown with the spinel. The two phases have the orientation relationship [001]//[001] and [010]//[110] so that the quasi cubic-close-packed oxygen sublattices are continuous between both phases. These microstructures are similar to those observed in shocked meteorites and show that spinel transforms to -phase by a martensitic (shear) mechanism. There is also evidence that the mechanism changes to one involving diffusion-controlled growth at conditions close to equilibrium.  相似文献   

8.
Al-Si ordering in Sr-feldspar has been followed by isothermal annealing, starting from a disordered metastable configuration. Ordering could not be followed by changes in the spontaneous strain as cell parameters did not show significant changes with thermal treatment from 0.016 h to 452 h at T=1350° C, while, on the contrary, significant changes in IR spectra are observed. A single crystal obtained from melt (Q od 0) has been progressively heated up to 678 h at T=1350° C and the relevant structural refinements enabled to monitor changes in degree of Al-Si order up to Qod = 0.86. In isothermal treatment for Sr-feldspar it is observed a significantly lower Q od than in anorthite after the same annealing time. TEM observation has shown in Sr-feldspar, also for shortest annealing, b type reflections, while in anorthite, in the same conditions, e type reflections have been observed (Carpenter 1991a). In the first stages of ordering b APDs sized 100 Å (at T=1350° C, 0.33 h) have been observed in Sr-feldspar; APD coarsening occurs with an activation energy of 120±7 kcal mol-1, not significantly different from anorthite. The ordering process seems to be a slower process in Sr-feldspar than in anorthite, even though data from longer annealing suggest that the Q od close to the equilibrium is the same in Sr and Ca-feldspar (Q od = 0.86 at T=1350° C).  相似文献   

9.
Diffusion rates of18O tracer in quartz ( c, 1 Kb H2O) and Amelia albite ( 001, 2 Kb H2O) have been measured, using Secondary Ion Mass Spectrometry (SIMS). A new technique involving hydrothermal deposition of labelled materials has removed the possibility of pressure solution-reprecipitation processes adversely affecting the experiments. Reported diffusion constants are:-quartz ( c), ,Q=98±7 KJ mol–1 (600–825° C, 1 Kb); Amelia albite ( 001), ,Q=85±7 KJ mol–1, (400–600° C, 2 Kb). Measured quartz18O diffusivities decrease discontinuously at the- transition, reflecting strong structural influences. The reported albite data agree with previously recorded studies, but-quartz data indicate significantly lower activation energies. Possible causes of this discrepancy, and some geological consequences, are noted.  相似文献   

10.
The acid/base properties of the hematite/water interface and surfacecomplexation with gold has been studied by potentiometric titrations in thefour component system H+ – FeOH –AuCl 4 - – Cl-. Equilibrium measurementswere performed in NaCl media at 298.2 K. In the evaluation of equilibriummodel from experimental data the constant capacitance model was applied. Theacid/base properties were investigated in 0.1 M NaCl in the range 2.6 pH 7.4. The resulting intrinsic constants for protonation anddeprotonation of hydroxyl groups at the surface were log 1,1,0,0(int) s = 7.10 ± 0.06 andlog -1,1,0,0(int) s = - 7.80 ±0.06. The density of proton active surface sites was 2.85nm-2 and the specific capacitance 2.5 C V-1 m-2. In the investigation of surface complexation of gold, thepotentiometric titrations were performed in the range 2.0 pH 10.2.Titration data was supplemented with analysis of Au in the aqueous phase byatomic absorbance spectrometry. The equilibrium model proposed consists ofthe following monodentate surface complexes: FeOHAuCl3(log 0,1,1,-1 s = 1.45 ± 0.03),FeOHAuCl2OH (log -1,1,1,-2 s = -3.89 ± 0.02), FeOHAu(OH)3 (log -3,1,1,-4 s = -21.94 ± 0.05). Aslightly better fit could be obtained by assuming formation of a bidentatecomplex with the composition(FeO)2Au(OH)H2O. However, based onstructural arguments this complex was rejected.  相似文献   

11.
Emerald deposits in Swat, northwestern Pakistan, occurring in talc-magnesite and quartz-magnesite assemblages, have been investigated through stable isotope studies. Isotopic analyses were performed on a total of seven emeralds, associated quartz (seven samples), fuchsite (three samples) and tourmaline (two samples) from the Mingora emerald mines. The oxygen isotopic composition ( 18O SMOW) of emeralds shows a strong enrichment in18O and is remarkably uniform at + 15.6 ± 0.4 (1,n = 7). Each of the two components of water in emerald (channel and inclusion) has a different range of hydrogen isotopic composition: the channel waters being distinctly isotopically heavier (D = –51 to –32 SMOW) than the other inclusion waters (D = –96 to –70 SMOW). Similarly the oxygen isotopic compositions of tourmaline and fuchsite are relatively constant ( 18O = + 13 to + 14 SMOW) and show enrichment in18O. The 18O values of quartz, ranging from + 15.1 to + 19.1 SMOW, are also high (+ 16.9 ± 1.4 1, n = 7). The meanD of channel waters measured from emerald (–42 ± 6.6 SMOW) and that of fluid calculated from hydrous mineralsDcalculated (–47 ± 7.1 SMOW) are consistent with both metamorphic and magmatic origin. However, the close similarity between the measuredD values of the hydroxyl hydrogen in fuchsite (–74 to –6 SMOW) and tourmaline (–84 and –69 SMOW) with pegmatitic muscovite and tourmaline suggests that the mineralization was probably caused by modified (18O-enriched) hydrothermal solutions derived from an S-type granitic magma. The variation in the carbon and oxygen isotopic composition of magnesite, locally associated with emerald mineralization, is also very restricted ( 13 –3.2 ± 0.7%, PDB; 18O + 17.9 ± 1.27 SMOW). On the basis of the isotopic composition of fluid ( 13C –1.8 ± 0.7 PDB; 18O + 13.6 ± 1.2 SMOW calculated for the 250-550 °C temperature), it is proposed that the Swat magnesites formed due to the carbonation of previously serpentinized ultramafic rocks by a CO2-bearing fluid of metamorphic origin.  相似文献   

12.
Divariant oxide plus metal assemblages potentially make useful redox sensors for use in hydrothermal and other high pressure experiments. Here we report the calibration of the (Ni, Mn)O/Ni redox sensor in which the Ni/NiO (NNO) oxygen buffer is displaced to lower oxygen chemical potentials (O2), by the solid solution of MnO in the oxide phase. This assemblage was chosen because: (1) it covers a useful range of O2; (2) the system can be calibrated very accurately. Values of O2 defined by the (Ni, Mn)O/Ni assemblage were determined electrochemically, from 900 to 1300 K, using calcia-stabilized zirconia solid electrolytes. The oxide compositions (8 in total, ranging from 0.1X NiO0.8) were analysed afterwards by electron microprobe, and were checked for internal consistency by measuring the lattice parameters (a0), using powder XRD. The accuracies of the measurements, both assessed theoretically and established empirically, are (1): ±80J/mol in O2, ±0.0002 Å in a0 and ±0.002 to 0.005 in X NiO. Activity-composition relations were fitted to the Redlich-Kister formalism. There is a slight asymmetry (corresponding to a subregular model) across the solution with A 0 G =9577(±45) J/mol, and A 1 G =–477(±80) J/mol. The experimental data were also used to derive the parameters Vex, Hex and Sex. There is no obvious relationship between excess volumes and enthalpies of mixing, nor between excess volumes and excess entropies. The experimental data from this study have been used to formulate the (Ni, Mn)O/Ni redox sensor expression: O2 = 2(NNO) + 2RTlnX NiO + 2(1 – X NiO)2[11483 – 1.697T] – 477(4X NiO – 1)(900 < T(K) < 1300) where O2(NNO)=–478967+248.514T–9.7961 T In T, from O'Neill and Pownceby(1993a).  相似文献   

13.
We show the steps followed for obtaining the principal reflectances of an absorbing uniaxial mineral, ilmenite, by use of the inference method derived from statistical reflectance parameters of the sample. The values obtained in air, at 580 nm, with this method are: R =19.6±0.3 and R =17.8±0.3.  相似文献   

14.
The compressibility of -Mns (alabandite) was determined by x-ray analysis using a Mao-Bell type diamond anvil cell. The zero pressure bulk modulus (K0) is 74±2 GPa with the pressure derivative of the bulk modulus (Ko) fixed at four. Allowing (Ko) to vary yielded a statistically better fit with K0 = 88±6 GPa and k0 = 2.2±0.6. Our data combined with the data of McCammon (1991) gave Ko = 73±1 GPa with ko fixed at four. A fit with ko allowed to vary yielded ko = 75±2 GPa and ko = 3.7±0.4. Alabandite transformed from the B1 structure (NaCl-type) to an unknown high-pressure phase at 26 GPa. The high-pressure phase has lower than hexagonal symmetry and it is stable to at least 46±4 GPa.Also affiliated with the James Franck Institute, University of Chicago  相似文献   

15.
The timescale of structural relaxation in a silicate melt defines the transition from liquid (relaxed) to glassy (unrelaxed) behavior. Structural relaxation in silicate melts can be described by a relaxation time, , consistent with the observation that the timescales of both volume and shear relaxation are of the same order of magnitude. The onset of significantly unrelaxed behavior occurs 2 log10 units of time above . In the case of shear relaxation, the relaxation time can be quantified using the Maxwell relationship for a viscoelastic material; S = S/G (where S is the shear relaxation time, G is the shear modulus at infinite frequency and S is the zero frequency shear viscosity). The value of G known for SiO2 and several other silicate glasses. The shear modulus, G , and the bulk modulus, K , are similar in magnitude for every glass, with both moduli being relatively insensitive to changes in temperature and composition. In contrast, the shear viscosity of silicate melts ranges over at least ten orders of magnitude, with composition at fixed temperature, and with temperature at fixed composition. Therefore, relative to S, G may be considered a constant (independent of composition and temperature) and the value of S, the relaxation time, may be estimated directly for the large number of silicate melts for which the shear viscosity is known.For silicate melts, the relaxation times calculated from the Maxwell relationship agree well with available data for the onset of the frequency-dependence (dispersion) of acoustic velocities, the onset of non-Newtonian viscosities, the scan-rate dependence of the calorimetric glass transition, with the timescale of an oxygen diffusive jump and with the Si-O bond exchange frequency obtained from 29Si NMR studies.  相似文献   

16.
Water in microcrystalline quartz of volcanic origin: Agates   总被引：2，自引：0，他引：2  
Agates of volcanic origin, containing the different quartz species, fibrous, length-fast chalcedony (CH), granular fine quartz (FQ), and fibrous, length-slow, to lepidospheric quartzine (QN), have been investigated to evaluate possible relations between microstructure, i.e. crystallite size and texture, refractive indices, densities, contents of trace elements and of water, as well as dehydration behaviour. By means of near infrared spectroscopy, total water contents , could be differentiated quantitatively into contents of molecular water, , and silanole-group water, . Despite the low total water contents of the agates studied ( between 1 and 2 wt.%), near infrared spectroscopy results in reliable data on and .Wall-layering CH consists of fibrous quartz crystals and exhibits higher C-ratios, , than horizontally layered FQ which consists predominantly of granular quartz crystals (C CH=0.45±0.11 (N=6), C FQ=0.36±0.10 (N=4). This result is interpreted to be due to analogy with the behaviour of C-ratios in fluid phase-deposited opals-AN (hyalithe) and liquid phase-deposited opals-AG (non-crystalline opal) or -CT (common opal) (Langer and Flörke 1974).Translucent layers of CH show mostly lower refractive indices, when measured parallel than when measured perpendicular to the axes of the quartz fibers. The same is true for milky layers of CH. Crystallite sizes are smaller in the latter than in the former.For all samples studied, exists a positive correlation between at% (1/2Ca+1/2Mg+Na+K+Li) and at% (Al3++Fe3+). This indicates that at least parts of (A13++ Fe3+) substitute for Si in the quartz structure. The charge is balanced by incorporation of di- and mono-valent cations in structural interstices. When the quantity at % H+, as obtained from , is included into the sum at% (1/2 Me2++Me+), the above correlation is destroyed. This result could be indicative for a strong concentration of the Si-OH groups in the surface of the quartz microcrystallites.  相似文献   

17.
Neutron powder diffraction measurements of the temperature dependence of superlattice reflections in calcite have shown that there is a continuous phase transition at 1260 K. The change in space group symmetry and the halving of the unit cell size on heating indicate that this transition is an orientational order/disorder transition. The intensities of the superlattice reflections show that the temperature dependence of the order parameter, Q, is of the form (T c –T), where is 0.25, indicating that the transition is tricritical. The transition is accompanied by a large contraction along the c axis on cooling, defining a spontaneous strain e3 which is related to the order parameter (and hence temperature) via e3 Q 2. No evidence for critical lowering of the value of was found. These measurements confirm that, apart from the detailed critical behaviour, the phase transition in calcite is similar to that observed in NaNO3.  相似文献   

18.
We have performed a detailed Mössbauer study of synthetic annites on the (OH, F)-join. Recently developed data treatment and spectral analysis methods were used to extract true intrinsic Fe2+ quadrupole splitting distributions (QSDs) that represent the most information that can be resolved from the spectra. The overall room temperature (RT) QSDs can be consistently interpreted in terms of four QSD contributions (or populations) centered at: QSHH2.55 mm/s for Fe2+O4(OH)2 octahedra (cis and trans not resolved), QSHF 2.35 mm/s for Fe2+O4(OH)F octahedra (cis and trans not resolved), QScFF2.15 mm/s for cis-Fe2+O4F2 octahedra, and QStFF 1.5 mm/s for trans-Fe2+O4F2 octahedra. Each such contribution has a width ( 0.2 mm/s) caused by distortions of the octahedra. Minor contributions due to Fe2+O5(OH) and Fe2+O5F octahedra probably also contribute to the overall Fe2+ QSDs. The ferric iron spectral components were also characterized. Here, two distinct types of octahedral Fe3+ contributions are seen and interpreted as being due mainly to Fe3+O5OH and Fe3+O5F octahedra, respectively. Tetrahedral Fe3+ is seen only in the OH-annite end-member and the total Fe3+ content drops significantly on addition of F. On leave from: Department of Materials Physics, University of Science and Technology Beijing, 100083 Beijing, China  相似文献   

19.
Thermal treatments of anorthite carried out at up to 1,547° C show that the unit cell parameter changes as a function of the treatment temperature. The best fit curve found by non-linear least squares analysis is: =91.419-(0.327·10-6)T 2+(0.199·10-12)T 4-(0.391·10)T 6. The results obtained support significant Al,Si disorder (Al0.10, where Al=t 1(0)-1/3 [t 1(m)+t 2(0)+t 2(m)], Ribbe 1975), in anorthite equilibrated near the melting point and confirm a high temperature series differentiated from the low temperature series for calcic plagioclases in the An85–An100 range also. In the plot vs. An-content the high and low temperature curves intersect at An85 composition and progressively diverge in the An85–An100 range. The trends of the high and low temperature curves in this range are interpretable on the basis of the degree of Al, Si order in the average structures of calcic plagioclases.  相似文献   

20.
We present new experimental data on Mg tracer diffusion in oriented single crystals of forsterite (Fo100) and San Carlos olivine (Fo92) between 1000–1300° C. The activation energies of diffusion are found to be 400 (±60) kJ/mol (96 kcal/mol) and 275 (±25) kJ/mol (65 kcal/ mol) in forsterite and San Carlos olivine, respectively, along [001] at a fO2 of 10–12 bars. There is no change in activation energy of Mg tracer diffusion within this temperature range. Mg tracer diffusion in a nominally pure forsterite is found to be anisotropic (Dc > Da > D b) and a function of fO2. This fO2 dependence is different from that in olivine containing Fe as a major element, which suggests that the diffusion mechanism of Mg in forsterite is different from that in Fe-bearing olivine at least over some range of fO2. The diffusion mechanism in nominally pure forsterites may involve impurities present below the limits of detection or alternately, Si or Fe3+ interstitial defects, Fe being present as impurity (ppm level) in forsterite. Pressure dependence of Mg tracer diffusivity in forsterite measured to 10 GPa in a multianvil apparatus yields an activation volume of approximately 1–3.5 cm3/ mol. It is found that presence of small amounts of hydrogen bearing species in the atmosphere during diffusion anneal (fH2 0.2 bars, fH20 0.24 bars) do not affect Mg tracer diffusion in forsterite within the resolution of our measurement at a total pressure of 1 bar. The observed diffusion process is shown to be extrinsic; hence extrapolation of the diffusion data to lower temperatures should not be plagued by uncertainties related to change of diffusion mechanism from intrinsic to extrinsic.  相似文献   

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