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1.
BaAl2Ge2O8-Feldspar undergoes an order-disorder phase transition I2/c↔C2/m at T tr ≈1690 K. The thermodynamics of the Al,Ge cation ordering process is described in terms of the compressible Ising model in mean field approximation. The mean field potential predicts a first order character of the phase transition. This is compared to antiferromagnetic ordering in a two-dimensional square Ising model with NN-pair interactions and four-spin interactions on alternating squares. Calculated order parameters and short range ordering are in good agreement with the corresponding properties observed in BaAl2Ge2O8-feldspar by means of X-ray diffraction, hard mode infrared spectroscopy and TEM. Using known calorimetric data a similar model is postulated for Al,Si ordering in anorthite, CaAl2Si2O8, for which the derived potential describes a transition with slightly stronger first order character at T tr ≈1928 K. Received: 30 January 1998 / Revised, accepted: 29 August 1998  相似文献   

2.
The main driving force behind Al/Si ordering in tetrahedral framework aluminosilicates is nearest-neighbour Al/Al avoidance. Computer simulation is used to explore the direct consequences of such Al/Al avoidance. The main result is that the order-disorder transition temperature T c falls dramatically as the concentration x of Al in the structure is reduced, and if the only interactions are those associated with nearest-neighbour Al/Al avoidance, T c becomes zero for x less than some critical value x c , where x c =0.31 for the feldspar framework and x c =0.34 for cordierite. Also a large degree of short range order is found above T c . Both results differ radically from the standard Bragg-Williams model. Plots of entropy and enthalpy of ordering are given as functions of x and T, which may be used to interpret experimental data or for extrapolation into ranges of x and T inaccessible to experiment. Received: 14 May 1997 / Revised, accepted: 2 June 1997  相似文献   

3.
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4.
A selected set of five different kyanite samples was analysed by electron microprobe and found to contain chromium between <0.001 and 0.055 per formula unit (pfu). Polarized electronic absorption spectroscopy on oriented single crystals, R1, R2-sharp line luminescence and spectra of excitation of λ3- and λ4-components of R1-line of Cr3+-emission had the following results: (1) The Fe2+–Ti4+ charge transfer in c-parallel chains of edge connected M(1) and M(2) octahedra shows up in the electronic absorption spectra as an almost exclusively c(||Z′)-polarized, very strong and broad band at 16000 cm−1 if <, in this case the only band in the spectrum, and at an invariably lower energy of 15400 cm−1 in crystals with  ≥ . The energy difference is explained by an expansion of the Of–Ok, and Ob–Om edges, by which the M(1) and M(2) octahedra are interconnected (Burnham 1963), when Cr3+ substitutes for Al compared to the chromium-free case. (2) The Cr3+ is proven in two greatly differing crystal fields a and b, giving rise to two sets of bands, derived from the well known dd transitions of Cr3+ 4A2g→4T2g(F)(I), →4T1g(F)(II), and →4T1g(P)(III). Band energies in the two sets a and b, as obtained by absorption, A, and excitation, E, agree well: I: 17300(a, A), 17200(a, E), 16000(b, A), 16200(b, E); II: 24800(a, A), 24400(a, E); 22300(b, A), 22200(b, E); III: 28800(b,A) cm−1. Evaluation of crystal field parameters from the bands in the electronic spectra yield Dq(a)=1730 cm−1, Dq(b)=1600 cm−1, B(a)=790 cm−1, B(b)=620 cm−1 (errors ca. ±10 cm−1), again in agreement with values extracted from the λ3, λ4 excitation spectra. The CF-values of set a are close to those typical of Cr3+ substituting for Al in octahedra of other silicate minerals without constitutional OH− as for sapphirine, mantle garnets or beryl, and are, therefore, interpreted as caused by Cr3+ substituting for Al in some or all of the M(1) to M(4) octaheda of the kyanite structure, which are crystallographically different but close in their mean Al–O distances, ranging from 1.896 to 1.919 A (Burnham 1963), and slight degrees of distortion. Hence, band set a originates from substitutive Cr3+ in the kyanite structural matrix. The CF-data of Cr3+ type b, expecially B, resemble those of Cr3+ in oxides, especially of corundum type solid solutions or eskolaite. This may be interpreted by the assumption that a fraction of the total chromium contents might be allocated in a precursor of a corundum type exsolution. Received: 3 January 1997 / Revised, accepted: 2 May 1997  相似文献   

5.
Using powder X-ray diffraction of heated solids to pressures reaching 68 GPa, the pressure-volume-temperature (PVT) data on corundum Al2O3 and ɛ-Fe were determined with the following results: *Corundum,*Iron, *Al2O3*ɛ-Fe Isothermal bulk*258 (2)*164 (3)  modulus K'300, 1 (GPa) Pressure derivative K300, 1*4.88 (4)*5.36 (16) Temperature derivative*–0.020 (2)*–0.043 (3)  (∂K T,1 /∂T) P (GPa/K) Molar volume V300,1*25.59 (2)*6.76 (2)  (cm3/mol) Isobaric thermal expansion at 1 atm (0.101 MPa) is given by (K–1): α T =2.6 (2) 10–5+1.81 (9) 10–9 T–0.67 (6)/T 2 for corundum, and α T =5.7 (4) 10–5+4.2 (4) 10–9 T–0.17 (7)/T 2 for iron ɛ-Fe. Received: 1 March 1997 / Revised, accepted: 21 August 1997  相似文献   

6.
The kinetics of monodomain order-disorder processes in monoclinic (I2/c) BaAl2Ge2O8-feldspar have been investigated by X-ray powder diffraction, Hard Mode IR Spectroscopy, and TEM darkfield imaging on quenched samples. Compared to the behaviour predicted by the TDGL approximation ordering kinetics observed at low temperatures slow down significantly when equilibrium is approached. Such a delay is not observed in disordering experiments starting from essentially ordered cation distributions. The deviation from TDGL behaviour is interpreted in terms of partial order parameter conservation in a non-uniformly ordered phase. Modifications to the uniform TDGL rate equation are tested against the available data. An activation energy of 352 ± 28 kJ/mol is obtained for Al,Ge ordering. The mixing coefficient ξc 2/ξ2, which describes the degree of order parameter conservation, is obtained as a function of temperature. While this coefficient vanishes in the vicinity of the transformation temperature T tr, it saturates towards a level of ξc 2/ξ2≈0.4 for T→0. ξ c 2/ξ2 determines the kinetic stability of ordered clusters quenched from T≈T tr. Received: 21 April 1999 / Revised, accepted: 19 July 1999  相似文献   

7.
The synthetic solid solutions between lead fluorapatite and lead fluorvanadate apatite, Pb10[(PO4)6−x (VO4) x ]F2 with x equal to 0, 1, 2, 3, 4, 5, and 6, were compressed up to about 9 GPa at ambient temperature by using a diamond-anvil cell coupled with synchrotron X-ray radiation. A second-order Birch–Murnaghan equation of state was used to fit the data. As the substitution of the PO4 3− cations by the VO4 3− cations progresses, the isothermal bulk modulus steadily decreases, with a maximum reduction of about 16% (from 68.4(16) GPa for Pb10(PO4)6F2 to 57.2(28) GPa for Pb10(VO4)6F2). For the entire composition range, the a-axis dimension remains more compressible than the c-axis dimension, with the ratio of the axial bulk moduli (K T−c :K T−a ) larger than 1. The ratio of K T−c to K T−a increases from about 1.04(4) to 1.23(14) as the composition parameter x increases from 0 to 6, suggesting that the apatite solid solutions Pb10[(PO4)6−x (VO4) x ]F2 become more elastically anisotropic.  相似文献   

8.
 P–V–T measurements on magnesite MgCO3 have been carried out at high pressure and high temperature up to 8.6 GPa and 1285 K, using a DIA-type, cubic-anvil apparatus (SAM-85) in conjunction with in situ synchrotron X-ray powder diffraction. Precise volumes are obtained by the use of data collected above 873 K on heating and in the entire cooling cycle to minimize non-hydrostatic stress. From these data, the equation-of-state parameters are derived from various approaches based on the Birch-Murnaghan equation of state and on the relevant thermodynamic relations. With K′0 fixed at 4, we obtain K0=103(1) GPa, α(K−1)=3.15(17)×10−5 +2.32(28)×10−8 T, (∂KT/∂T)P=−0.021(2) GPaK−1, (dα/∂P)T=−1.81×10−6 GPa−1K−1 and (∂KT/∂T)V= −0.007(1) GPaK−1; whereas the third-order Birch-Murnaghan equation of state with K′0 as an adjustable parameter yields the following values: K0=108(3) GPa, K′0=2.33(94), α(K−1)=3.08(16)×10−5+2.05(27) ×10−8 T, (∂KT/∂T)P=−0.017(1) GPaK−1, (dα/∂P)T= −1.41×10−6 GPa−1K−1 and (∂KT/∂T)V=−0.008(1) GPaK−1. Within the investigated P–T range, thermal pressure for magnesite increases linearly with temperature and is pressure (or volume) dependent. The present measurements of room-temperature bulk modulus, of its pressure derivative, and of the extrapolated zero-pressure volumes at high temperatures, are in agreement with previous single-crystal study and ultrasonic measurements, whereas (∂KT/∂T)P, (∂α/∂P)T and (∂KT/∂T)V are determined for the first time in this compound. Using this new equation of state, thermodynamic calculations for the reactions (1) magnesite=periclase+CO2 and (2) magnesite+enstatite=forsterite+CO2 are consistent with existing experimental phase equilibrium data. Received September 28, 1995/Revised, accepted May 22, 1996  相似文献   

9.
In this article, the shear behavior of discontinuities caused by bedding planes of weakness between two different rock types with high strength difference is investigated. The effect of roughness and compressive strength of joint wall in such discontinuities are studied. The designed profiles consist of two regular and three irregular artificial joints molded by three types of plaster mortars with different uniaxial compressive strengths. Firstly, it is demonstrated that the shear behavior of discontinuities with different joint wall compressive strengths (JCS) is different from rock joints with identical wall compressive strengths by showing that Barton’s empirical criterion is not appropriate for the former discontinuities. After that, some correlation equations are proposed between the joint roughness coefficient (JRC) parameter and some surface statistical/fractal parameters, and the normal stress range of Barton’s strength criterion is also modified to be used for such discontinuities. Then, a new empirical criterion is proposed for these discontinuities in such a way that a rational function is used instead of JRC log10(JCS/σ n) as i 0(σ c/σ n)a/[b + (σ c/σ n) a ] by satisfying the peak dilation angle boundary conditions under zero and very high normal stress (physical infinite normal stress causing zero peak dilation angle). The proposed criterion has three surface parameters: i 0, a, and b. The reason for separation of i 0 from JRC is indicated and the method of its calculation is mentioned based on the literature. The two remaining coefficients (a and b) are discussed in detail and it is shown that a shows a power-law relationship with b, introducing the coefficient c through b = c a . Then, it is expressed that a is directly related to discontinuity surface topography. Finally, it is shown that the coefficient c has higher values in irregular profiles in comparison with regular profiles and is dominated by intensity of peak dilation angle reduction (majorly related to the surface irregularity and minorly related to roughness). The coefficient c is to be determined by performing regression analysis on experimental data.  相似文献   

10.
 The melting reaction: albite(solid)+ H2O(fluid) =albite-H2O(melt) has been determined in the presence of H2O–NaCl fluids at 5 and 9.2 kbar, and results compared with those obtained in presence of H2O–CO2 fluids. To a good approximation, albite melts congruently at 9 kbar, indicating that the melting temperature at constant pressure is principally determined by water activity. At 5 kbar, the temperature (T)- mole fraction (X (H2O) ) melting relations in the two systems are almost coincident. By contrast, H2O–NaCl mixing at 9 kbar is quite non-ideal; albite melts ∼70 °C higher in H2O–NaCl brines than in H2O–CO2 fluids for X (H2O) =0.8 and ∼100 °C higher for X (H2O) =0.5. The melting temperature of albite in H2O–NaCl fluids of X (H2O)=0.8 is ∼100 °C higher than in pure water. The P–T curves for albite melting at constant H2O–NaCl show a temperature minimum at about 5 kbar. Water activities in H2O–NaCl fluids calculated from these results, from new experimental data on the dehydration of brucite in presence of H2O–NaCl fluid at 9 kbar, and from previously published experimental data, indicate a large decrease with increasing fluid pressure at pressures up to 10 kbar. Aqueous brines with dissolved chloride salt contents comparable to those of real crustal fluids provide a mechanism for reducing water activities, buffering and limiting crustal melting, and generating anhydrous mineral assemblages during deep crustal metamorphism in the granulite facies and in subduction-related metamorphism. Low water activity in high pressure-temperature metamorphic mineral assemblages is not necessarily a criterion of fluid absence or melting, but may be due to the presence of low a (H2O) brines. Received: 17 March 1995/Accepted: 9 April 1996  相似文献   

11.
 In situ x-ray data on molar volumes of periclase and tungsten have been collected over the temperature range from 300 K to melting. We determine the temperature by combining the technique of spectroradiometry and electrical resistance wire heating. The thermal expansion (α) of periclase between 300 and 3100 K is given by α=2.6025 10−5+1.3535 10−8 T+6.5687 10−3 T−1−1.8281 T−2. For tungsten, we have (300 to 3600 K) α=7.862 10−6+6.392 10−9 T. The data at 298 K for periclase is: molar volume 11.246 (0.031) cm3, α=3.15 (0.07) 10−5 K−1, and for tungsten: molar volume 9.55 cm3, α=9.77 (10.08) 10−6 K−1. Received: July 18, 1996 / Revised, accepted: February 14, 1997  相似文献   

12.
Inelastic magnetic neutron scattering has been used to determine the energy of the 4 A 2→4 T 2 transition in CoAl2O4 spinel and the δ1 transition in Co2[Al4Si5]O18 cordierite. The observed crystal field splitting in Co-spinel is 485 meV (3900 cm−1), which corresponds to a crystal field stabilization energy of 56.2 kJmol−1. The transition energy of the δ1 transition in Co-cordierite has been determined to be 21 meV (170 cm−1). The present data demonstrate that magnetic neutron scattering can be used to measure crystal field transitions at energies of interest in the study of 3d-containing silicates. It may be used to measure transition energies when the use of optical spectroscopy is inappropriate. Received: 30 January 1997 / Accepted: 5 July 1997  相似文献   

13.
 The crystal chemical response of basalt clinopyroxene to increasing pressure was investigated by means of crystal-structure simulation (a procedure that enables modeling of the structural parameters of a clinopyroxene of known chemistry without requiring direct X-ray diffraction analysis) using available experimental chemical data. Pressure proved the main physical variable governing clinopyroxene behavior in a magmatic environment. The general internal consistency of the simulation data permitted construction of an empirical geobarometer based on the relationship of cell volume (Vc) vs M1-site volume (VM1). The straightforward geobarometric formulation in the absence of direct X-ray analysis is: P(kbar)=698.443+4.985⋅AlT−26.826⋅Fe2+ M1−3.764⋅Fe3+ +53.989⋅AlM1+3.948⋅Ti+14.651⋅Cr −700.431⋅Ca−666.629⋅Na−682.848⋅MgM2−691.138⋅Fe2+ M2−688.384⋅Mn−6.267⋅(MgM2)2−4.144⋅(Fe2+ M2 where: (Fe2+ M1⋅MgM2)/(Fe2+ M2⋅MgM1)=e**(0.238⋅R3++0.289⋅CNM−2.315), CNM=Ca+Na+Mn, and R3+=AlM1+Fe3++Ti+Cr, with cations in atoms per formula unit. The geobarometer reproduces experimental pressures within ±2 kbar (=1σ; max. dev. ≤5 kbar; N=29) in the range 0–24 kbar and is applicable to near-liquidus C2/c clinopyroxenes crystallized from basaltic melts in the absence of garnet (excepting high-Al2O3 basalts). It is therefore suitable for many natural clinopyroxenes occurring as mega- or phenocrysts or forming well-preserved cumulate pyroxenites. If the above restrictions are not wholly satisfied, the Vc vs VM1 plot can also be used qualitatively to deduce the relative pressure conditions of clinopyroxenes forming from similar batches of magma. The structural simulation of experimental data also provided insight into the influence of minor chemical changes of the parental magma on the crystal chemistry of clinopyroxene at high pressure. Within the considered compositional space at given P-T, a CaO and a SiO2 in the melt have opposite effects on M2- and T-site cation populations. As a result, under similar physical conditions, clinopyroxenes from higher-CaO or more undersaturated basalts have higher VM2, VT and Vc and lower VM1. For basalts with normal contents of Al2O3 (<18 wt %), variations of major elements in the melt do not reduce the accuracy of the geobarometer. Received: 3 April 1994 / Accepted: 23 December 1995  相似文献   

14.
The ratios M R = E/σ c for 11 heterogeneous carbonate (dolomites, limestones and chalks) rock formations collected from different regions of Israel were examined. Sixty-eight uniaxial compressive tests were conducted on weak-to-strong (5 MPa < σ c < 100 MPa) and very strong (σ c > 100 MPa) rock samples exhibiting wide ranges of elastic modulus (E = 6100–82300 MPa), uniaxial compressive strength (σ c = 14–273.9 MPa), Poisson's ratio (ν = 0.13–0.49), and dry bulk density (ρ = 1.7–2.7 g/cm3). The observed range of M R = 60.9–1011.4 and mean value of M R = 380.5 are compared with the results obtained by Deere (Rock mechanics in engineering practice, Wiley, London, pp 1–20, 1968) for limestones and dolomites, and the statistical analysis of M R distribution is performed. Mutual relations between E, σ c, ρ, M R for all studied rocks, and separately for concrete rock formations are revealed. Linear multiple correlations between E on the one hand and σ c and ρ on the other for Nekorot and Bina limestone and Aminadav dolomite are obtained. It is established that the elastic modulus and M R in very strong carbonate samples are more correlated with ρ−σ c combination and ε a max, respectively, than in weak to strong samples. The relation between M R and maximum axial strain (ε a max) for all studied rock samples (weak-to-strong and very strong) is discussed.  相似文献   

15.
 The partitioning of Fe and Mg between the M1 and M2 octahedral sites of olivine has been investigated by in situ time-of-flight neutron powder diffraction. The degree of M-cation order was determined from direct measurements of site occupancies in a synthetic sample of Fo50Fa50 heated to 1250 °C at the Fe-FeO oxygen buffer. Fe shows slight preference for M1 at temperatures below about 600 °C, progressively disordering on heating to this temperature. Above 630 °C, the temperature at which site preferences cross over (T cr), Fe preferentially occupies M2, becoming progressively more ordered into M2 on increasing temperature. The cation-ordering behaviour is discussed in relation to the temperature dependence of the M1 and M2 site geometries, and it is suggested that vibrational entropy, crystal field effects and changes in bond characteristics play a part in the cross-over of partitioning behaviour. The temperature dependence of site ordering is modelled using a Landau expansion of the free energy of ordering of the type ΔG = −hQ + gTQ +  (T − T c)Q 2 +  Q 4, with a/h = 0.00406 K−1, b/h = 2.3, T c = 572 K and g/h = 0.00106 K−1. These results suggest that the high-temperature ordering behaviour across the forsterite-fayalite join will have a bearing on the activity-composition relations of this important rock-forming mineral, and indicate that Fe-Mg olivine solid solutions become less ideal as temperature increases. Received: 12 August 1999 / Accepted: 25 April 2000  相似文献   

16.
The blue-green color of amazonite has been assigned by various authors to ions Pb+ (6 s)2 (6 p) and/or Pb3+ (6 s) in site of K+ of microcline. Owing to the complex which forms between the ion Pb3+ and the lone pairs of the oxygen atoms surrounding it, the peripheral electron of Pb3+ passes on the levels (6 p) of the latter, which results in a great similarity of the spectra of Pb+ and Pb3+ in amazonite (the transition energies are multiplied by a factor greater than 1), whereas, in the isolated state, these spectra are completely different from one another. An analytical development of the crystal field around a site K+ is established. Under the effect of the crystal field, the transition 2 P 1/2→2 P 3/2 (6 p) is split into two double transitions. The lower transition only falls in the visible domain (1.6–1.8 eV for Pb+), the second in U−V. The green color would arise from the ion Pb+, whereas the blue one would be attributed to the ion Pb3+. Received: 23 January 1997 / Revised, accepted: 10 September 1997  相似文献   

17.
The temperature induced structural evolution and thermoelastic behaviour of a natural (Pbca) orthopyroxene (Opx), with chemical formula M2(Mg0.856Ca0.025Fe2+ 0.119) M1(Mg0.957Fe2+ 0.011Fe3+ 0.016Cr0.011Al0.005)Al0.032Si1.968O6, from a suite of high pressure ultramafic nodules of mantle origin, have been investigated by in-situ neutron powder diffraction at several temperatures starting from 1,200°C down to 150°C. Unit-cell parameter variations as a function of T show no phase transition within this temperature range. The volume thermal expansion coefficient, α = V −1(∂V/∂T) P0, varies linearly with T. The axial thermal expansion coefficients, αj = l j−1(∂l j/∂T)P0, increase non-linearly with T. The principal Lagrangian unit-strain coefficients (ɛ//a, ɛ//b, ɛ//c), increase continuously with T. However, the orientation of the unit-strain ellipsoid appears to change with T. With decreasing T, the values of the unit-strain coefficients along the b and c axes tend to converge. The orientation at ΔT = 1,080°C is maintained down to the lowest temperature (150°C). The two non-equivalent tetrahedral chains, TA n OA3n and TB n OB3n , are kinked differently. At room-T, the TB n OB3n chain is more strongly kinked by about 23° than the TA n OA3n chain. With increasing T, the difference decreases by 3° for the TB n OB3n chain. The intersite cation exchange reaction between M1 and M2 (Mg2+ and Fe2+) shows a slight residual order at 1,200°C followed by reordering with decreasing temperature although seemingly not with a definite progressive trend. At the lowest temperature reached (150°C), reordering has occurred with the same value of partitioning coefficient K D as that before heating. The absence of the expected phase transition is most likely due to the presence of minor amounts of Fe3+, Al, Ca and Cr which must play a crucial role on the thermoelastic behaviour and phase stability fields in natural Opx, with consequent important petrologic and geological implications.  相似文献   

18.
The equation of state and crystal structure of pyrope were determined by single crystal X-ray diffraction under hydrostatic conditions to 33 GPa, a pressure that corresponds to a depth of about 900 km in the lower mantle. The bulk modulus K T0 and its pressure derivative K ' T0 were determined simultaneously from an unweighted fit of the volume data at different pressures to a third order Birch-Murnaghan equation of state. They are 171(2) GPa and 4.4(2), respectively. Over the whole pressure range, MgO8 polyhedra showed the largest compression of 18.10(8)%, followed by AlO6 and SiO4 polyhedra, with compression of 11.7(1)% and 4.6(1)%, respectively. The polyhedral bulk moduli for MgO8, AlO6 and SiO4 are 107(1), 211(11) and 580(24) GPa, respectively, with K ' T0 fixed to 4. Significant compression of up to 1.8(1)% in the very rigid Si−O bonding in pyrope could be detected to 33 GPa. Changes in the degree of polyhedral distortion for all three types of polyhedra could also be observed. These changes could be found for the first time for AlO6 and SiO4 in pyrope. It seems that the compression of pyrope crystal structure is governed by the kinking of the Al−O−Si angle between the octahedra and tetrahedra. No phase transition could be detected to 33 GPa. Received: 24 March 1997 / Revised, accepted: 29 July 1997  相似文献   

19.
To investigate the point defect chemistry and the kinetic properties of manganese olivine Mn2SiO4, the point defect relaxation time (τ) characterizing the rate of re-equilibration of electrical conductivity following a change in oxygen fugacity was measured for single crystals oriented for electrical conduction along the [010] direction. The experiments were carried out at temperatures T = 1173–1473 K and oxygen fugacities with the MnSiO3 activity controlled at unity. The value of τ, which ranges from 130 to 1463 s, increases with decreasing temperature. At 1273 K, the value of τ in the regime is a factor of ∼1.8 smaller than that in the regime. The point defect relaxation time was used to calculate the chemical diffusivity (). Values of lie in the range 2.2× 10− 10 − 2.5×10− 9 m2/s. For the regime, a semi-log plot of vs 1/T yields a concave downward curve. Based on these results combined with those from Part I of this work for the point defect structure and electrical conductivity in Mn-olivine, it is proposed that the relaxation rate of electrical conduction is determined by the coupled diffusion of manganese vacancies and electron holes which rate-control the relaxation process at low and high temperatures, respectively. Deconvolution of the curve into two straight-line segments yields values for the mobilities and the diffusivities for Mn vacancies and electron holes. These results, combined with the measured electrical conductivity data, were used to calculate the concentrations of Mn vacancies and electron holes. These results in conjunction with those published for other transition-metal silicate olivines reveal the following: The mobility of electron holes in Mn-olivine is about two orders of magnitude smaller than that in Fe-olivine and is somewhat larger than that in (Mg0.9Fe0.1)-olivine. The mobilities of metal vacancies in these three olivines are similar both in magnitude and in temperature dependence. The concentrations of the majority point defects are the highest in Fe-olivine crystals and the lowest in Co-olivine crystals, while those in Mn-olivine and (Mg0.9Fe0.1)-olivine crystals lie in between. The deviation from stoichiometry in the cation sublattice for a transition-metal silicate olivine is about two orders of magnitude lower than that for the corresponding transition-metal oxide. Received: 10 January 1996 / Revised, accepted: 29 May 1997  相似文献   

20.
The reverse Monte Carlo (RMC) method was used for modelling the three-dimensional structure of sodium tetrasilicate glass (Na2Si4O9, NS4). Neutron diffraction data over a large momentum transfer range and nuclear magnetic resonance results (Q-species distribution) as well as chemical bonding considerations have been used to constrain the RMC simulations. Very good agreement with the experimental structure factor was achieved. The three-dimensional model is analysed in terms of partial pair distribution functions, bond-angle distributions, short-range order (SRO) clusters and ring statistics. The average Si–O–Si bridging angle is different for the different Qi–Qj units. The effect of different Q species on the network connectivity is analysed by comparison with statistical SRO distributions. While the Q2 species are randomly distributed, a high preference for the formation of Q4–Q4 units in three-membered rings is found. This explains why during the initial stages of hydration of NS4 glass, Si–OH groups are preferentially formed by breaking Q4–Q4 linkages. The RMC model also provides an independent test for the assignment of bands in the Si–O stretching region of the Raman spectrum. It is shown that the bands at about 1050 and 1100 cm−1 are probably due to Q3 units surrounded by different numbers of Q4 units. Received: 7 April 1997 / Revised, accepted: 5 July 1997  相似文献   

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