共查询到20条相似文献,搜索用时 78 毫秒
1.
E. Huang J.-F. Lin J. Xu T. Huang Y.-C. Jean H.-S. Sheu 《Physics and Chemistry of Minerals》1999,26(7):576-583
Various X-ray diffraction methods have been applied to study the compression behavior of gibbsite, Al(OH)3, in diamond cells at room temperature. A phase transformation was found to take place above 3 GPa where gibbsite started
to convert to its high-pressure polymorph. The high-pressure (HP) phase is quenchable and coexists with gibbsite at the ambient
conditions after being unloaded. This HP phase was identified as nordstrandite based on the diffraction patterns obtained
at room pressure by angle dispersive and energy dispersive methods. On the basis of this structural interpretation, the bulk
modulus of the two polymorphs, i.e., gibbsite and nordstrandite, could be determined as 85 ± 5 and 70 ± 5 GPa, respectively,
by fitting a Birch-Murnaghan equation to the compression data, assuming their Ko
′ as 4. Molar volume cross-over occurs at 2 GPa, above which the molar volume of nordstrandite is smaller than that of gibbsite.
The differences in the molar volume and structure between the two polymorphs are not significant, which accounts for the irreversibility
of the phase transition. In gibbsite, the axial compressibility behaves as c/c
o > a/a
o > b/b
o. This is due to the fact that the dioctahedral sheets along the c-axis are held by the relatively weak hydrogen bonding, which results in the greater compressibility along this direction.
In nord- strandite, the axial compressibility is b/b
o > c/c
o > a/a
o, which can also be interpreted as resulting from the the existence of hydrogen bonds along the b-axis.
Received: 28 September 1998 / Revised, accepted: 22 December 1998 相似文献
2.
S. Ono E. Ito T. Katsura A. Yoneda M. J. Walter S. Urakawa W. Utsumi K. Funakoshi 《Physics and Chemistry of Minerals》2000,27(9):618-622
In situ synchrotron X-ray experiments in the system SnO2 were made at pressures of 4–29 GPa and temperatures of 300–1400 K using sintered diamond anvils in a 6–8 type high-pressure
apparatus. Orthorhombic phase (α-PbO2 structure) underwent a transition to a cubic phase (Pa3ˉ structure) at 18 GPa. This transition was observed at significantly lower pressures in DAC experiments. We obtained the
isothermal bulk modulus of cubic phase K
0 = 252(28) GPa and its pressure derivative K
′=3.5(2.2). The thermal expansion coefficient of cubic phase at 25 GPa up to 1300 K was determined from interpolation of the
P-V-T data obtained, and is 1.7(±0.7) × 10−5 K−1 at 25 GPa.
Received: 7 December 1999 / Accepted: 27 April 2000 相似文献
3.
The second-order elastic constants of CaF2 (fluorite) have been determined by Brillouin scattering to 9.3 GPa at 300 K. Acoustic velocities have been measured in the
(111) plane and inverted to simultaneously obtain the elastic constants and the orientation of the crystal. A notable feature
of the present inversion is that only the density at ambient condition was used in the inversion. We obtain high-pressure
densities directly from Brillouin data by conversion to isothermal conditions and iterative integration of the compression
curve. The pressure derivative of the isentropic bulk modulus and of the shear modulus determined in this study are 4.78 ± 0.13
and 1.08 ± 0.07, which differ from previous low-pressure ultrasonic elasticity measurements. The pressure derivative of the
isothermal bulk modulus is 4.83 ± 0.13, 8% lower than the value from static compression, and its uncertainty is lower by a
factor of 3. The elastic constants of fluorite increase almost linearly with pressure over the whole investigated pressure
range. However, at P ≥ 9 GPa, C
11 and C
12 show a subtle structure in their pressure dependence while C
44 does not. The behavior of the elastic constants of fluorite in the 9–9.3 GPa pressure range is probably affected by the onset
of a high-pressure structural transition to a lower symmetry phase (α-PbCl2 type). A single-crystal Raman scattering experiment performed in parallel to the Brillouin measurements shows the appearance
of new features at 8.7 GPa. The new features are continuously observed to 49.2 GPa, confirming that the orthorhombic high-pressure
phase is stable along the whole investigated pressure range, in agreement with a previous X-ray diffraction study of CaF2 to 45 GPa. The high-pressure elasticity data in combination with room-pressure values from previous studies allowed us to
determine an independent room-temperature compression curve of fluorite. The new compression curve yields a maximum discrepancy
of 0.05 GPa at 9.5 GPa with respect to that derived from static compression by Angel (1993). This comparison suggests that
the accuracy of the fluorite pressure scale is better than 1% over the 0–9 GPa pressure range.
Received: 10 July 2001 / Accepted: 7 March 2002 相似文献
4.
The empirical linear relation between volume and logarithm of bulk modulus of a material, discovered by Grover, Getting and
Kennedy is taken as the basis for our equation of state. Using the latest experimental information on the adiabatic bulk modulus,
the equation of state is applied to the three polymorphs of Mg2SiO4 to develop a consistent dataset of their thermodynamic properties in the temperature range of 200–2273 K and a pressure range
of 0.1 MPa–30 GPa. The results imply that the bulk sound velocity contrast (v
β−v
α)/v
α increases with temperature along the α–β phase boundary and reaches the value 8.9% at 13.5 GPa, a pressure equivalent to
410 km depth in the Earth. The bulk sound velocity contrast (v
γ−v
β)/v
β decreases with temperature along the β–γ phase boundary and becomes less than 0.7% at temperatures and pressures equivalent
to those associated with the 520-km seismic discontinuity in the Earth.
Received: 1 August 2000 / Accepted: 1 March 2001 相似文献
5.
Synchrotron radiation S K-edge XANES spectra and unit-cell parameters are used to investigate the local electronic structure
of non-stoichiometric binary and ternary Fe-Co-Ni monosulfide solid solution (mss; M0.923S, M = Fe, Co, Ni) quenched from 800 °C and low pressure. The prominent absorption edge feature of the XANES spectra represents
transition of S 1s core level electrons to unoccupied S 3p σ* antibonding orbitals hybridized with empty metal 3d(eg) orbitals. There is a progressive increase in area of the edge peak from Fe0.923S to Ni0.923S and Co0.923S, which correlates with progressive decrease in c and a parameters for the NiAs-type subcell and increase in metallic character, and reflects increase in the number and availability
of empty eg
β orbitals and covalence of metal-S bonds. More generally, the area of the edge peak exhibits an inverse linear correlation
with a, c and unit-cell volume of binary and ternary mss. This inverse linear correlation is attributed to progressive increase in
covalence and M-S-M bonding interaction in the c-axis direction, through metal-S [M 3d(eg) - S 3p (or 3d)] π bonding. However, the area of the edge peak does not correlate very well with the average number of 3d
electrons per metal atom in these solid solutions, showing that the absorption of synchrotron radiation reflects the local
electronic structure of individual absorber atoms (i.e. the SM6 cluster), and is not a group (crystal energy band) effect.
Received: 21 March 2000 / Accepted: 14 July 2000 相似文献
6.
The structural behavior of synthetic gahnite (ZnAl2O4) has been investigated by X-ray powder diffraction at high pressure (0–43 GPa) and room temperature, on the ID9 beamline
at ESRF. The equation of state of gahnite has been derived using the models of Birch–Murnaghan, Vinet and Poirier–Tarantola,
and the results have been mutually compared (the elastic bulk modulus and its derivatives versus P determined by the third-order Birch–Murnaghan equation of state are K
0=201.7(±0.9) GPa, K
′
0=7.62(±0.09) and K
″
0=−0.1022 GPa−1 (implied value). The compressibilities of the tetrahedral and octahedral bond lengths [0.00188(8) and 0.00142(5) GPa−1 at P=0, respectively], and the␣polyhedral volume compressibilities of the four-␣and␣sixfold coordination sites [0.0057(2) and
0.0041(2) GPa−1 at P=0, respectively] are discussed.
Received: 15 January 2001 / Accepted: 23 April 2001 相似文献
7.
Mina Yutani Takehiko Yagi Hitoshi Yusa Tetsuo Irifune 《Physics and Chemistry of Minerals》1997,24(5):340-344
In situ X-ray diffraction experiments of calcium ferrite-type MgAl2O4 have been carried out using a diamond anvil cell combined with synchrotron radiation and an imaging plate X-ray detector
under hydrostatic pressures up to 9 GPa. The observed unit-cell volumes at various pressures were fitted to the Birch-Murnaghan
equation of state, yielding a bulk modulus of K
T
0= 241(3) GPa when K′
T
0=4 is assumed. This relatively large bulk modulus of calcium ferrite-type MgAl2O4 is consistent with that expected from the systematic relation between bulk modulus and molar volume for the most compounds
possessing fcc oxygen packing.
Received March 5, 1996/Revised, accepted October 15, 1996 相似文献
8.
G. D. Gwanmesia J. Liu G. Chen S. Kesson S. M. Rigden R. C. Liebermann 《Physics and Chemistry of Minerals》2000,27(7):445-452
Dense isotropic polycrystalline specimens of majorite-rich garnets (Py100, Py62Mj38, Py50Mj50, Py21Mj79 and Mj100) along the pyrope (Mg3Al2Si3O12 = Py100)-majorite (MgSiO3 = Mj100) join were fabricated in a 2000-ton uniaxial split-sphere anvil apparatus (USSA-2000) at pressures from 10 to 18.5 GPa and
temperatures from 1200 to 1850 °C, within their stability fields in runs of 2–4-h duration, using hot-pressing techniques
developed by Gwanmesia et al. (1993). These specimens are single-phased, fine-grained (≤5 mm), free of microcracks, and have
bulk densities greater than 99% of the corresponding single-crystal X-ray density. Elastic compressional (P) and shear (S) wave velocities were determined at room pressure and temperature for these polycrystalline garnet specimens by phase comparison
ultrasonic interferometry. For Mj100, the P and S wave velocities are within 1% of the Hashin-Shtrikman averages calculated from the single crystal elastic moduli measured
by Brillouin spectroscopy. Both the elastic bulk modulus (K) and the shear modulus (G) decrease continuously with increasing majorite content from pyrope garnet (Py100) to pure majorite garnet (Mj100). The compositional dependence of K and G are given by K = 172.3 (40) − 0.085X, and G = 91.6 (10) − 0.038X, where X = mol% majorite), respectively, indicating that substitution of Si for Mg and Al decreases both K and G by about 5% along the solid solution series.
Received: 25 March 1999 / Accepted: 12 July 1999 相似文献
9.
J. Zhang 《Physics and Chemistry of Minerals》2000,27(3):145-148
Isobaric volume measurements for MgO were carried out at 2.6, 5.4, and 8.2 GPa in the temperature range 300–1073 K using
a DIA-type, large-volume apparatus in conjunction with synchrotron X-ray powder diffraction. Linear fit of the thermal expansion
data over the experimental pressure range yields the pressure derivative, (∂α/∂P)
T
, of −1.04(8) × 10−6 GPa−1 K−1 and the mean zero-pressure thermal expansion α0,
T
= 4.09(6) × 10−5 K−1. The α0,
T
value is in good agreement with results of Suzuki (1975) and Utsumi et al. (1998) over the same temperature range, whereas
(∂α/∂P)
T
is determined for the first time on MgO by direct measurements. The cross-derivative (∂α2/∂P∂T) cannot be resolved because of large uncertainties associated with the temperature derivative of α at all pressures. The
temperature derivative of the bulk modulus, (∂K
T/∂T)
P
, of −0.025(3) GPa K−1, obtained from the measured (∂α/∂P)
T
value, is in accord with previous findings.
Received: 2 April 1999 / Revised, accepted: 22 June 1999 相似文献
10.
H. Morishima E. Ohtani T. Kato T. Kubo A. Suzuki T. Kikegawa O. Shimomura 《Physics and Chemistry of Minerals》1999,27(1):3-10
The high-pressure and temperature equation of state of majorite solid solution, Mj0.8Py0.2, was determined up to 23 GPa and 773 K with energy-dispersive synchrotron X-ray diffraction at high pressure and high temperature
using the single- and double-stage configurations of the multianvil apparatuses, MAX80 and 90. The X-ray diffraction data
of the majorite sample were analyzed using the WPPD (whole-powder-pattern decomposition) method to obtain the lattice parameters. A least-squares fitting using the third-order Birch-Murnaghan equation
of state yields the isothermal bulk modulus, K
T0
= 156 GPa, its pressure derivative, K′ = 4.4(±0.3), and temperature derivative (∂K
T
/∂T)
P
= −1.9(±0.3)× 10−2 GPa/K, assuming that the thermal expansion coefficient is similar to that of pyrope-almandine solid solution.
Received: 5 October 1998 / Revised, accepted: 24 June 1999 相似文献
11.
X-ray powder diffraction measurements have been carried out at ESRF (Grenoble, France) on the ID30 beamline to study the
equation of state of 3T phengite (Dora-Maira massif, Italian western Alps) by a large volume cell up to P = 50 kbar and T = 1000 K. Several equations of state (EOS) models (the Vinet EOS, the Birch-Murnaghan EOS and its variants, a VT-polynomial expansion) have been used to interpolate the experimental data and discussed in the light of the results achieved.
The thermoelastic properties of 3T phengite (bulk modulus, its derivatives versus pressure or temperature, bulk thermal expansion)
have been obtained and an isochoric curve with slope P/T = 0.02 kbar/K has been calculated by means of the Vinet EOS. This slope value supports either the occurrence at the peak
conditions (about 30 kbar and 1000 K) of an originally Mg/Si-richer and stiffer phengite or a non-isochoric P-T retrograde path.
Received: 5 June 1998 / Revised, accepted: 12 December 1998 相似文献
12.
The structural behavior of stuffed derivatives of quartz within the Li1−
x
Al1−
x
Si1+
x
O4 system (0 ≤ x ≤ 1) has been studied in the temperature range 20 to 873 K using high-resolution powder synchrotron X-ray diffraction (XRD).
Rietveld analysis reveals three distinct regimes whose boundaries are defined by an Al/Si order-disorder transition at x=∼0.3 and a β–α displacive transformation at x=∼0.65. Compounds that are topologically identical to β-quartz (0 ≤ x < ∼0.65) expand within the (0 0 1) plane and contract along c with increasing temperature; however, this thermal anisotropy is significantly higher for structures within the regime 0 ≤ x < ∼0.3 than for those with compositions ∼0.3 ≤ x < ∼0.65. We attribute this disparity to a tetrahedral tilting mechanism that occurs only in the ordered structures (0 ≤ x < ∼0.3). The phases with ∼0.65 ≤ x ≤ 1 adopt the α-quartz structure at room temperature, and they display positive thermal expansion along both a and c from 20 K to their α–β transition temperatures. This behavior arises mainly from a rotation of rigid Si(Al)-tetrahedra about
the <100> axes. Landau analysis provides quantitative evidence that the charge-coupled substitution of Li+Al for Si in quartz
dampens the α–β transition. With increasing Li+Al content, the low-temperature modifications exhibit a marked decrease in
spontaneous strain; this behavior reflects a weakening of the first-order character of the transition. In addition, we observe
a linear decrease in the α–β critical temperature from 846 K to near 0 K as the Li+Al content increases from x=0 to x=∼0.5.
Received: 26 June 2000 / Accepted: 1 December 2000 相似文献
13.
Dmitry L. Lakshtanov Carine B. Vanpeteghem Jennifer M. Jackson Jay D. Bass Guoyin Shen Vitali B. Prakapenka Konstantin Litasov Eiji Ohtani 《Physics and Chemistry of Minerals》2005,32(7):466-470
We have determined the P-V equation of state of Al-rich H-bearing SiO2 stishovite by X-ray powder diffraction at pressures up to 58 GPa using synchrotron radiation. The sample contained 1.8 wt%
Al2O3 and up to 500 ppm H2O, and had a composition that would coexist with Mg-silicate perovskite in a subducted slab. By fitting a third-order Birch-Murnaghan
equation of state to our compression data, we obtained a bulk modulus K
T0=298(7) GPa with K′=4.3(5). With K′ fixed to a value of 4, the bulk modulus K
T0=304(3) GPa. Our results indicate that Al3+ and H+ have a small effect on the elastic properties of stishovite. Compared with data obtained up to 43.8 GPa, peak intensities
changed and we observed a decreased quality of fit to a tetragonal unit cell at pressures of 49 GPa and higher. These changes
may be an indication that the rutile↔CaCl2 transition occurs between these pressures. After laser annealing of the sample at 58.3(10) GPa and subsequent decompression
to room conditions, the cell volume is the same as before compression, giving strong evidence that the composition of the
recovered sample is also unchanged. This suggests that Al and H are retained in the sample under extreme P-T conditions and
that stishovite can be an agent for transporting water to the deepest lower mantle. 相似文献
14.
Synchrotron X-ray powder diffraction experiments at high pressure conditions (0.0001–13 GPa) were performed at ESRF (Grenoble-F),
on the beamline ID9, to investigate the bulk elastic properties of natural P2/n-omphacites, with quasi-ideal composition. The monoclinic cell parameters a, b, c and β were determined as a function of pressure, and their compressibility coefficients are 0.00277(7), 0.00313(8), 0.00292(5)
and 0.00116(4) GPa−1, respectively. The third-order Birch-Murnaghan equation of state was used to interpolate the experimental P−V data, obtaining K
0=116.6(±2.5) GPa and K′0=6.03(±0.60). K
0 was also determined by means of the axial and angular compressibilities [122.5(±1.7) GPa], and of the finite Lagrangian strain
theory [121.5(±1.0) GPa]. The discrepancies on K
0 are discussed in the light of a comparison between techniques to determine the bulk modulus of crystalline materials from
static compression diffraction data.
Received: 22 February 2000 / Accepted: 10 July 2000 相似文献
15.
High-pressure and high-temperature Raman spectra of CaGeO3 tetragonal garnet have been collected to 11.5 GPa and 1225 K, respectively, in order to investigate possible intrinsic anharmonic
behaviour in this phase. The Raman peak positions were observed to vary linearly with pressure and temperature within the
ranges studied, with the higher-energy peaks showing larger P- and T-induced shifts than the low energy modes. The observed T-induced shifts are similar to those reported for grossular and andradite, while the observed P-induced shifts are generally larger than those of aluminosilicate and MgSiO3 majorite garnets (Gillet et al. 1992; Rauch et al. 1996) due to the larger bulk modulus of CaGeO3 garnet. The observed mode shifts of CaGeO3 garnet were used to determine the isothermal and isobaric mode Grüneisen parameters for this phase. These parameters are
similar in value to those reported previously for grossular and andradite (Gillet et al. 1992). The calculated intrinsic anharmonic
parameters, a
i
, for CaGeO3 garnet were determined to be nonzero, indicating significant anharmonic behaviour for this phase. These values, which range
from −3.8 × 10−5 K−1 to −1.3 × 10−5 K−1, are also similar to those reported for andradite and grossular, but smaller than those determined for pyrope (Gillet et al.
1992). Hence, we expect MgSiO3 majorite to show greater anharmonicity than the germanate analogue studied by us. The anharmonic parameters determined for
CaGeO3 tetragonal garnet may now be introduced into quasiharmonic vibrational heat capacity models to account for the observed anharmonic
behaviour.
Received: 21 April 1999 / Revised, accepted: 11 September 1999 相似文献
16.
K.-D. Grevel A. Navrotsky W. A. Kahl D. W. Fasshauer J. Majzlan 《Physics and Chemistry of Minerals》2001,28(7):475-487
Calorimetric and P–V–T data for the high-pressure phase Mg5Al5Si6O21(OH)7 (Mg-sursassite) have been obtained. The enthalpy of drop solution of three different samples was measured by high-temperature
oxide melt calorimetry in two laboratories (UC Davis, California, and Ruhr University Bochum, Germany) using lead borate (2PbO·B2O3) at T=700 ∘C as solvent. The resulting values were used to calculate the enthalpy of formation from different thermodynamic datasets;
they range from −221.1 to −259.4 kJ mol−1 (formation from the oxides) respectively −13892.2 to −13927.9 kJ mol−1 (formation from the elements). The heat capacity of Mg5Al5Si6O21(OH)7 has been measured from T=50 ∘C to T=500 ∘C by differential scanning calorimetry in step-scanning mode. A Berman and Brown (1985)-type four-term equation represents
the heat capacity over the entire temperature range to within the experimental uncertainty: C
P
(Mg-sursassite) =(1571.104 −10560.89×T
−0.5−26217890.0 ×T
−2+1798861000.0×T
−3) J K−1 mol−1 (T in K). The P
V
T behaviour of Mg-sursassite has been determined under high pressures and high temperatures up to 8 GPa and 800 ∘C using a MAX 80 cubic anvil high-pressure apparatus. The samples were mixed with Vaseline to ensure hydrostatic pressure-transmitting
conditions, NaCl served as an internal standard for pressure calibration. By fitting a Birch-Murnaghan EOS to the data, the
bulk modulus was determined as 116.0±1.3 GPa, (K
′=4), V
T,0
=446.49 3 exp[∫(0.33±0.05) × 10−4 + (0.65±0.85)×10−8
T dT], (K
T/T)
P
= −0.011± 0.004 GPa K−1. The thermodynamic data obtained for Mg-sursassite are consistent with phase equilibrium data reported recently (Fockenberg
1998); the best agreement was obtained with Δf
H
0
298 (Mg-sursassite) = −13901.33 kJ mol−1, and S
0
298 (Mg-sursassite) = 614.61 J K−1 mol−1.
Received: 21 September 2000 / Accepted: 26 February 2001 相似文献
17.
N. S. Bagdassarov 《Physics and Chemistry of Minerals》1999,26(6):513-520
The present study deals with the small strain torsion deformation of MACOR glass-ceramic samples at high temperatures (450–850 °C)
and over a range of low frequencies (20 Hz–5 mHz). The samples of MACOR ceramic consist of 55 vol% randomly oriented, sheet-like
fluorophlogopite mica crystals (∼100–20 μm in planar size, 1–2 μm in thickness) and 45 vol% of isotropic alumino-borosilicate
glass matrix. Measurements of the complex shear modulus show that the sample does not possess the relaxed shear viscosity
even at temperatures above the glass transition temperature of the glass matrix. The maximum of the imaginary component G
′′() of the shear modulus is ∼0.15 of the unrelaxed value G
∞, the relaxation strength Δ≈0.9. The activation energy of the peak of G
′′() is ∼245 kJ mol−1. Using this value of E
a
, the data obtained at various frequencies and temperatures have been reduced to a master curve using the dimensionless variable
ωτ, where ∼0 exp(−E
a
/RT). The internal friction Q−1(ωτ) is ∝1/()0.35−0.4 in the low-temperature high-frequency range (1); passes through a maximum at ∼1 and trends asymptotically to a value Q−1∼0.25–0.30 at ≪1. The behaviour of Q
−1(ωτ) differs from that of a Caputo body by the presence of the resolved peak which may be attributed to the slow mechanical
relaxation of mica crystals due to rotation as well as flexing and bending modes of crystal deformation.
Received: 26 June 1998 / Revised, accepted: 13 January 1999 相似文献
18.
Summary
Low-temperature phase transitions of leonite-type compounds, K2Me2+(SO4)2 · 4H2O (Me = Mg, Mn, Fe), are investigated by temperature dependent measurements of single-crystal X-ray reflection intensities
and lattice parameters. The transition temperatures and the progress of the transitions are determined by birefringence data
and differential scanning calorimetry. The cause for the phase transitions of leonite-type compounds is a dynamic disorder
of sulphate groups at room temperature (C2/m), that freezes in to an ordered structure (I2/a) at −4(1) °C in leonite, K2Mg(SO4)2 · 4H2O. At −153(1) °C the crystal structure switches to another ordered phase (P21/a). The Mn analogue shows the same succession with transition temperatures at −68(1) °C and −104(1) °C. The disordered room
temperature structure of the isotypic mineral mereiterite, K2Fe(SO4)2 · 4H2O, transforms directly to the ordered P21/a structure at 3(2) °C.
Analysis of X-ray intensities and of excess birefringence reveals that the displacive I2/a ⇔ P21/a phase transition of leonite and Mn-leonite is first order. According to Landau theory the C2/m ⇔ I2/a (leonite, Mn-leonite) and C2/m ⇔ P21/a (mereiterite) order-disorder transitions are almost tricritical.
Received March 7, 2001; revised version accepted June 27, 2001 相似文献
19.
Grain growth kinetics in CaTiO3-perovskite + FeO-wüstite aggregates were studied at the conditions of T = 1223–1623 K, P = 0.1 MPa and P = 200 MPa. Starting samples were fabricated by hot-pressing mechanically mixed powders of CaTiO3 + FeO with FeO = 0%, 1%, 3%, 6%, 10%, 20% and 100% by weight in a gas-medium apparatus at 1323 K and 300 MPa for 5 h. The
increase of grain size (G) of CaTiO3 with time (t) follows a growth law: G
n
−G
n
0 = κ·t(κ=κ0exp(−(Q/RT)). Two grain growth regimes are observed at T < 1523 K and T ≥ 1523 K. For T < 1523 K, the best fits of the data to the growth law yield growth exponents of n = 2.2 ± 0.2, 3.0 ± 0.3 and 3.5 ± 0.3 for samples with FeO = 0%, 3% and 10% respectively. Under these conditions the rate
constants, κ, obey an Arrhenius relation with Q = 206 ± 35 kJ/mol and 385 ± 65 kJ/mol for samples with FeO = 3% and 10%. Grain growth of CaTiO3 becomes sluggish when FeO content exceeds 6%. For T ≥ 1523 K, the best fits of the data to the growth law yield n = 2.5 ± 0.2 for both samples with FeO = 3% and 10%. The activation energies (Q ) were determined as 71 ± 30 kJ/mol and 229 ± 45 kJ/mol for samples with FeO = 3% and 10%, respectively. The TEM observations
show a remarkable difference in the distribution and geometry of FeO below and above 1523 K: nanometer-sized particles of
FeO were observed along CaTiO3 grain boundaries in samples annealed at T < 1523 K. No FeO particles were detected along CaTiO3 grain boundaries in samples annealed at T ≥ 1523 K, but large clusters of FeO particles are observed locally indicating a fast separation of FeO from CaTiO3. Thus we conclude that the slow growth rate of CaTiO3 at T < 1523 K is due to the pinning by FeO particles at grain boundary, and that the change of grain growth kinetics in CaTiO3 at T ≥ 1523 K may relate to the separation of FeO from CaTiO3, which we interpret as due to the phase transformation of CaTiO3 at around 1523 K.
Received: 19 June 1998 / Revised, accepted: 24 March 1999 相似文献
20.
The variation of the oxygen content in olivines, (Fe
x
Mg1−
x
)2SiO4, with 0.2 ≤ x ≤ 1.0, was investigated by thermogravimetric measurements. Mass changes occurring upon oxygen activity changes were measured
as a function of oxygen activity and cationic composition at 1130 and 1200 °C. During the measurements the samples were in
direct contact with gases containing CO, CO2 and N2 and, at a few spots at the bottom of the sample stack, also with SiO2. By fitting experimental data of mass changes to equations derived using point defect thermodynamics, it was shown for olivines
with 0.2 ≤ x ≤ 1.0 at 1130 °C and 0.2 ≤ x ≤ 0.7 at 1200 °C within the oxygen activity ranges investigated that the observed variations in the oxygen contents are compatible
with cation vacancies and Fe3+ ions on M sites and Fe3+ ions on silicon sites as majority defects if it is assumed that only three types of point defects occur as majority defects.
Different cases were considered, closed systems, taking into account that ξ=[Si]/([Si]+[Fe]+[Mg]) is not necessarily equal
to 1/3, and olivines in equilibrium with SiO2 or pyroxenes. The oxygen content variations observed in this study are significantly smaller than those reported previously
in the literature. It is proposed that these differences are related to the dissolution of Fe into noble metal containers
used as sample holders in earlier studies and/or to the presence of secondary phases.
Received: 1 November 1995 / Accepted: 15 September 2002
Acknowledgements This work was supported by the Cornell Center for Materials Research (CCMR), a Materials Research Science and Engineering
Center of the National Science Foundation (DMR-0079992). The authors thank Mr. Daniel M. DiPasquo and Mr. Jason A. Schick
for helping in experimental work. 相似文献