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1.
The dielectric constants and dissipation factors of synthetic tephroite (Mn2SiO4), fayalite (Fe3SiO4) and a forsteritic olivine (Mg1.80Fe0.22SiO4) were measured at 1 MHz using a two-terminal method and empirically determined edge corrections. The results are: tephroite, κ′a= 8.79 tan δa = 0.0006 κ′b = 10.20 tan δb = 0.0006 κ′c= 8.94 tan δc= 0.0008 fayalite, gk′a = 8.80 tan δa = 0.0004 gk′b= 8.92 tan δb = 0.0018 gk′c = 8.58 tan δc = 0.0010 olivine, gk′a = 7.16 tan δa = 0.0006 gk′b = 7.61 tan δb = 0.0008 gk′c = 7.03 tan δc = 0.0006 The low dielectric constant and loss of the fayalite indicate an exceptionally low Fe3+ content. An FeO polarizability of 4.18 Å3, determined from αD(FeO) = [αD (Fe2SiO4)-αD(SiO2)]/2, is probably a more reliable value for stoichiometric FeO than could be obtained from FexO where x = 0.90–0.95. The agreement between measured dielectric polarizabilities as determined from the Clausius-Mosotti equation and those calculated from the sum of oxide polarizabilities according to αD(M2M′X2) = 2αD(MX) + αD(M′X2) is ～+2.8% for tephroite and +0.2% for olivine. The deviation from additivity in tephroite is discussed.  相似文献   

2.
The thermo-elastic behavior of a natural epidote [Ca1.925 Fe0.745Al2.265Ti0.004Si3.037O12(OH)] has been investigated up to 1,200 K (at 0.0001 GPa) and 10 GPa (at 298 K) by means of in situ synchrotron powder diffraction. No phase transition has been observed within the temperature and pressure range investigated. P–V data fitted with a third-order Birch–Murnaghan equation of state (BM-EoS) give V 0 = 458.8(1)Å3, K T0 = 111(3) GPa, and K′ = 7.6(7). The confidence ellipse from the variance–covariance matrix of K T0 and K′ from the least-square procedure is strongly elongated with negative slope. The evolution of the “Eulerian finite strain” vs “normalized stress” yields Fe(0) = 114(1) GPa as intercept values, and the slope of the regression line gives K′ = 7.0(4). The evolution of the lattice parameters with pressure is slightly anisotropic. The elastic parameters calculated with a linearized BM-EoS are: a 0 = 8.8877(7) Å, K T0(a) = 117(2) GPa, and K′(a) = 3.7(4) for the a-axis; b 0 = 5.6271(7) Å, K T0(b) = 126(3) GPa, and K′(b) = 12(1) for the b-axis; and c 0 = 10.1527(7) Å, K T0(c) = 90(1) GPa, and K’(c) = 8.1(4) for the c-axis [K T0(a):K T0(b):K T0(c) = 1.30:1.40:1]. The β angle decreases with pressure, βP(°) = βP0 −0.0286(9)P +0.00134(9)P 2 (P in GPa). The evolution of axial and volume thermal expansion coefficient, α, with T was described by the polynomial function: α(T) = α0 + α1 T −1/2. The refined parameters for epidote are: α0 = 5.1(2) × 10−5 K−1 and α1 = −5.1(6) × 10−4 K1/2 for the unit-cell volume, α0(a) = 1.21(7) × 10−5 K−1 and α1(a) = −1.2(2) × 10−4 K1/2 for the a-axis, α0(b) = 1.88(7) × 10−5 K−1 and α1(b) = −1.7(2) × 10−4 K1/2 for the b-axis, and α0(c) = 2.14(9) × 10−5 K−1 and α1(c) = −2.0(2) × 10−4 K1/2 for the c-axis. The thermo-elastic anisotropy can be described, at a first approximation, by α0(a): α0(b): α0(c) = 1 : 1.55 : 1.77. The β angle increases continuously with T, with βT(°) = βT0 + 2.5(1) × 10−4 T + 1.3(7) × 10−8 T 2. A comparison between the thermo-elastic parameters of epidote and clinozoisite is carried out.  相似文献   

3.
The elastic behaviour and the high-pressure structural evolution of a natural topaz, Al2.00Si1.05O4.00(OH0.26F1.75), have been investigated by means of in situ single-crystal X-ray diffraction up to 10.55(5) GPa. No phase transition has been observed within the pressure range investigated. Unit-cell volume data were fitted with a third-order Birch-Murnaghan Equation of State (III-BM-EoS). The III-BM-EoS parameters, simultaneously refined using the data weighted by the uncertainties in P and V, are: V 0=345.57(7) Å3, K T0=164(2) GPa and K′=2.9(4). The axial-EoS parameters are: a 0=4.6634(3) Å, K T0(a)=152(2) GPa, K′(a)=2.8(4) for the a-axis; b 0=8.8349(5) Å, K T0(b)=224(3) GPa, K′(b)=2.6(6) for the b-axis; c 0=8.3875(7) Å, K T0(c)=137(2) GPa, K′(c)=2.9(4) for the c-axis. The magnitude and the orientation of the principal Lagrangian unit-strain ellipsoid were determined. At P−P 0=10.55 GPa, the ratios ε1:ε2:ε3 are 1.00:1.42:1.56 (with ε1||b, ε2||a, ε3||c and |ε3| > |ε2| > |ε1|). Four structural refinements, performed at 0.0001, 3.14(5), 5.79(5) and 8.39(5) GPa describe the structural evolution in terms of polyhedral distortions.  相似文献   

4.
The thermoelastic behavior of a natural clintonite-1M [with composition: Ca1.01(Mg2.29Al0.59Fe0.12)Σ3.00(Si1.20Al2.80)Σ4.00O10(OH)2] has been investigated up to 10 GPa (at room temperature) and up to 960°C (at room pressure) by means of in situ synchrotron single-crystal and powder diffraction, respectively. No evidence of phase transition has been observed within the pressure and temperature range investigated. P–V data fitted with an isothermal third-order Birch–Murnaghan equation of state (BM-EoS) give V 0 = 457.1(2) ?3, K T0 = 76(3)GPa, and K′ = 10.6(15). The evolution of the “Eulerian finite strain” versus “normalized stress” shows a linear positive trend. The linear regression yields Fe(0) = 76(3) GPa as intercept value, and the slope of the regression line leads to a K′ value of 10.6(8). The evolution of the lattice parameters with pressure is significantly anisotropic [β(a) = 1/3K T0(a) = 0.0023(1) GPa−1; β(b) = 1/3K T0(b) = 0.0018(1) GPa−1; β(c) = 1/K T0(c) = 0.0072(3) GPa−1]. The β-angle increases in response to the applied P, with: βP = β0 + 0.033(4)P (P in GPa). The structure refinements of clintonite up to 10.1 GPa show that, under hydrostatic pressure, the structure rearranges by compressing mainly isotropically the inter-layer Ca-polyhedron. The bulk modulus of the Ca-polyhedron, described using a second-order BM-EoS, is K T0(Ca-polyhedron) = 41(2) GPa. The compression of the bond distances between calcium and the basal oxygens of the tetrahedral sheet leads, in turn, to an increase in the ditrigonal distortion of the tetrahedral ring, with ∂α/∂P ≈ 0.1°/GPa within the P-range investigated. The Mg-rich octahedra appear to compress in response to the applied pressure, whereas the tetrahedron appears to behave as a rigid unit. The evolution of axial and volume thermal expansion coefficient α with temperature was described by the polynomial α(T) = α0 + α1 T −1/2. The refined parameters for clintonite are as follows: α0 = 2.78(4) 10−5°C−1 and α1 = −4.4(6) 10−5°C1/2 for the unit-cell volume; α0(a) = 1.01(2) 10−5°C−1 and α1(a) = −1.8(3) 10−5°C1/2 for the a-axis; α0(b) = 1.07(1) 10−5°C−1 and α1(b) = −2.3(2) 10−5°C1/2 for the b-axis; and α0(c) = 0.64(2) 10−5°C−1 and α1(c) = −7.3(30) 10−6°C1/2for the c-axis. The β-angle appears to be almost constant within the given T-range. No structure collapsing in response to the T-induced dehydroxylation was found up to 960°C. The HP- and HT-data of this study show that in clintonite, the most and the less expandable directions do not correspond to the most and the less compressible directions, respectively. A comparison between the thermoelastic parameters of clintonite and those of true micas was carried out.  相似文献   

5.
Diffusion coefficients of Cr and Al in chromite spinel have been determined at pressures ranging from 3 to 7 GPa and temperatures ranging from 1,400 to 1,700°C by using the diffusion couple of natural single crystals of MgAl2O4 spinel and chromite. The interdiffusion coefficient of Cr–Al as a function of Cr# (=Cr/(Cr + Al)) was determined as D Cr–Al = D 0 exp {−(Q′ + PV*)/RT}, where D 0 = exp{(10.3 ± 0.08) × Cr#0.54±0.02} + (1170 ± 31.2) cm2/s, Q′ = 520 ± 81 kJ/mol at 3 GPa, and V* = 1.36 ± 0.25 cm3/mol at 1,600°C, which is applicable up to Cr# = 0.8. The estimation of the self-diffusion coefficients of Cr and Al from Cr–Al interdiffusion shows that the diffusivity of Cr is more than one order of magnitude smaller than that of Al. These results are in agreement with patterns of multipolar Cr–Al zoning observed in natural chromite spinel samples deformed by diffusion creep.  相似文献   

6.
The dielectric constants and dielectric loss values of 4 Ca-containing minerals were determined at 1 MHz using a two-terminal method and empirically determined edge corrections. The results are: vesuvianitel κ′ a=9.93 tan δ=0.006 κ′ c=9.79 tan δ=0.005 vesuvianitel κ′ a=10.02 tan δ=0.002 κ′ c=9.85 tan δ=0.003 zoisite1 κ′ a =10.49 tan δ=0.0006 κ′ b =15.31 tan δ=0.0008 κ′ c=9.51 tan δ=0.0008 zoisite2 κ′ a =10.55 tan δ=0.0011 κ′ b =15.45 tan δ=0.0013 κ′ c=9.39 tan δ=0.0008 epidote κ′ 11= 9.52 tan δ=0.0008 κ′ 22=17.1 tan δ=0.0009 κ′ 33= 9.37 tan δ=0.0006 fluorapatite1 κ′ a =10.48 tan δ=0.0008 κ′ c = 8.72 tan δ=0.0114 fluorapatite2 κ′ a =10.40 tan δ=0.0010 κ′ c=8.26 tan δ=0.0178 The deviation (δ) between measured dielectric polarizabilities as determined from the Clausius-Mosotti equation and those calculated from the sum of oxide polarizabilities according to α D (mineral)=∑ α D (oxides) for vesuvianite is ～ 0.5%. The large deviations of epidote and zoisite from the additivity rule with Δ=+ 10.1 and + 11.7%, respectively, are attributed to “rattling” Ca ions. The combined effects of both a large F thermal parameter and possible F-ion conductivity in fluorapatite are believed to be responsible for Δ=+2–3%. Although variation of oxygen polarizability with oxygen molar volume (Vo) is believed to affect the total polarizabilities, the variation of Vo in these Ca minerals is too small to observe the effect.  相似文献   

7.
High-pressure crystal structure refinements and axial compressibilities have been determined by x-ray methods for the olivine isomorph chrysoberyl, Al2BeO4. Unlike silicate olivines, which are more than twice as compressible along b than along a, chrysoberyl (space group Pbnm) has nearly isotropic compressibility with β a =1.12±0.04, β b =1.46±0.05, and β c =1.31±0.03 (all×10?4 kbar?1). The resultant bulk modulus is 2.42±0.05 Mbar, with K′ assumed to be 4. The axial compression ratios of chrysoberyl are 1.00:1.30:1.17, compared to axial compression ratios 1.00:2.02:1.60 for forsterite. These differences in compression anisotropy arise from differences in relative bond compressibilities. In chrysoberyl the average aluminum-oxygen and beryllium-oxygen bond compressibilities are similar, yielding nearly isotropic compression, but in silicate olivines octahedral cation-oxygen bonds are significantly more compressible than Si-O bonds, so that compression parallel to a is much more restricted than that parallel to b. The inherent anisotropy of the olivine structure is not, by itself, sufficient to cause anisotropic compression. It appears that in the case of olivine the distribution of cations of different valences, in conjunction with the structure type, leads to anisotropies in physical properties.  相似文献   

8.
A single crystal X-ray diffraction study on lithium tetraborate Li2B4O7 (diomignite, space group I41 cd) has been performed under pressure up to 8.3 GPa. No phase transitions were found in the pressure range investigated, and hence the pressure evolution of the unit-cell volume of the I41 cd structure has been described using a third-order Birch–Murnaghan equation of state (BM-EoS) with the following parameters: V 0  = 923.21(6) Å3, K 0  = 45.6(6) GPa, and K′ = 7.3(3). A linearized BM-EoS was fitted to the axial compressibilities resulting in the following parameters a 0  = 9.4747(3) Å, K 0a  = 73.3(9) GPa, K′ a  = 5.1(3) and c 0  = 10.2838(4) Å, K 0c  = 24.6(3) GPa, K′ c  = 7.5(2) for the a and c axes, respectively. The elastic anisotropy of Li2B4O7 is very large with the zero-pressure compressibility ratio β 0c /β 0a  = 3.0(1). The large elastic anisotropy is consistent with the crystal structure: A three-dimensional arrangement of relatively rigid tetraborate groups [B4O7]2− forms channels occupied by lithium along the polar c–axis, and hence compression along the c axis requires the shrinkage of the lithium channels, whereas compression in the a direction depends mainly on the contraction of the most rigid [B4O7]2− units. Finally, the isothermal bulk modulus obtained in this work is in general agreement with that derived from ultrasonic (Adachi et al. in Proceedings-IEEE Ultrasonic Symposium, 228–232, 1985; Shorrocks et al. in Proceedings-IEEE Ultrasonic Symposium, 337–340, 1981) and Brillouin scattering measurements (Takagi et al. in Ferroelectrics, 137:337–342, 1992).  相似文献   

9.
Summary Sarkinite is a basic manganese arsenate, Mn2AsO4(OH). The lattice parameters are:a=12.779 (2) Å,b=13.596 (2) Å,c=10.208 (2) Å, =108°53 (6). Space groupP21/a,Z=16. The crystal structure has been solved by direct methods from three-dimensional X-ray diffractometer data and refined by least-squares methods toR=0.052 for 3519 independent reflections. The crystal structure is built up by a three-dimensional framework of MnO4(OH)2 octahedra, MnO4(OH) trigonal bipyramids and AsO4 tetrahedra, as found in wagnerite. Isotypy of sarkinite with triploidite is confirmed.
Die Kristallstruktur des Sarkinits, Mn2AsO4(OH)
Zusammenfassung Die Kristallstruktur des basischen Manganarsenates Sarkinit, Mn2AsO4(OH), mit den Gitterkonstantena=12,779 (2) Å,b=13,596 (2) Å,c=10,208 (2) Å, =108°53 (6). RaumgruppeP21/a,Z=16, wurde mit dreidimensionalen Röntgendiffraktometermessungen durch direkte Methoden gelöst und nach dem kleinste-Quadrate-Verfahren verfeinert (R=0,052 für 3519 unabhängige Reflexe). Die Struktur besteht aus einem dreidimensionalen Gerüst aus MnO4(OH)2-Oktaedern, trigonalen Bipyramiden von MnO4(OH) und AsO4-Tetraedern wie in Wagnerit. Die Isotypie von Sarkinit mit Triploidit wurde bestätigt.

With 1 Figure  相似文献   

10.
The compressibility at room temperature and the thermal expansion at room pressure of two disordered crystals (space group C2/c) obtained by annealing a natural omphacite sample (space group P2/n) of composition close to Jd56Di44 and Jd55Di45, respectively, have been studied by single-crystal X-ray diffraction. Using a Birch–Murnaghan equation of state truncated at the third order [BM3-EoS], we have obtained the following coefficients: V 0 = 421.04(7) Å3, K T0 = 119(2) GPa, K′ = 5.7(6). A parameterized form of the BM3 EoS was used to determine the axial moduli of a, b and c. The anisotropy scheme is β c  ≤ β a  ≤ β b , with an anisotropy ratio 1.05:1.00:1.07. A fitting of the lattice variation as a function of temperature, allowing for linear dependency of the thermal expansion coefficient on the temperature, yielded αV(1bar,303K) = 2.64(2) × 10−5 K−1 and an axial thermal expansion anisotropy of α b  ≫ α a  > α c . Comparison of our results with available data on compressibility and thermal expansion shows that while a reasonable ideal behaviour can be proposed for the compressibility of clinopyroxenes in the jadeite–diopside binary join [K T0 as a function of Jd molar %: K T0 = 106(1) GPa + 0.28(2) × Jd(mol%)], the available data have not sufficient quality to extract the behaviour of thermal expansion for the same binary join in terms of composition.  相似文献   

11.
CoGeO3 was synthesized at 1,273 and 1,448 K using ceramic sintering techniques in the monoclinic and orthorhombic modification, respectively. The two compounds were analysed by magnetic susceptibility measurements and neutron diffraction in order to study magnetic ordering and spin structures at low temperature. The monoclinic form of CoGeO3 has C2/c symmetry and orders magnetically below 36 K with a small negative paramagnetic Curie temperature θ P = −4.6 (2) K. The magnetic structure can be described with k = (1, 0, 0) in the magnetic space group C2′/c′ having a ferromagnetic spin arrangement within the chains of M1 sites, but a dominating antiferromagnetic coupling between the chains. At the M1 sites the magnetic spins are aligned within the a–c plane forming an angle of 120° with the +a-axis and they are not parallel to the spins at M2. Here spins are also ferromagnetically coupled within, but antiferromagnetically coupled between the M1/M2 site bands. The orthorhombic phase of CoGeO3 displays Pbca symmetry and transforms to an antiferromagnetically ordered state [θ P = −18.6(2) K] below 33 K. The magnetic spin structure can be described with k = (0, 0, 0) in space group Pbca′ and it is similar to the one of the C2/c phase except that it is non-collinear in nature, i.e. there are components of the magnetic moment along all three crystallographic axes. Small magneto-elastic coupling is observed in the orthorhombic phase.  相似文献   

12.
The thermoelastic behaviour of anthophyllite has been determined for a natural crystal with crystal-chemical formula ANa0.01 B(Mg1.30Mn0.57Ca0.09Na0.04) C(Mg4.95Fe0.02Al0.03) T(Si8.00)O22 W(OH)2 using single-crystal X-ray diffraction to 973 K. The best model for fitting the thermal expansion data is that of Berman (J Petrol 29:445–522, 1988) in which the coefficient of volume thermal expansion varies linearly with T as α V,T  = a 1 + 2a 2 (T − T 0): α298 = a 1 = 3.40(6) × 10−5 K−1, a 2 = 5.1(1.0) × 10−9 K−2. The corresponding axial thermal expansion coefficients for this linear model are: α a ,298 = 1.21(2) × 10−5 K−1, a 2,a  = 5.2(4) × 10−9 K−2; α b ,298 = 9.2(1) × 10−6 K−1, a 2,b  = 7(2) × 10−10 K−2. α c ,298 = 1.26(3) × 10−5 K−1, a 2,c  = 1.3(6) × 10−9 K−2. The thermoelastic behaviour of anthophyllite differs from that of most monoclinic (C2/m) amphiboles: (a) the ε 1 − ε 2 plane of the unit-strain ellipsoid, which is normal to b in anthophyllite but usually at a high angle to c in monoclinic amphiboles; (b) the strain components are ε 1 ≫ ε 2 > ε 3 in anthophyllite, but ε 1 ~ ε 2 ≫ ε 3 in monoclinic amphiboles. The strain behaviour of anthophyllite is similar to that of synthetic C2/m ANa B(LiMg) CMg5 TSi8 O22 W(OH)2, suggesting that high contents of small cations at the B-site may be primarily responsible for the much higher thermal expansion ⊥(100). Refined values for site-scattering at M4 decrease from 31.64 epfu at 298 K to 30.81 epfu at 973 K, which couples with similar increases of those of M1 and M2 sites. These changes in site scattering are interpreted in terms of Mn ↔ Mg exchange involving M1,2 ↔ M4, which was first detected at 673 K.  相似文献   

13.
The high-pressure elastic behaviour of a synthetic zeolite mordenite, Na6Al6.02Si42.02O96·19H2O [a=18.131(2), b=20.507(2), c=7.5221(5) Å, space group Cmc21], has been investigated by means of in situ synchrotron X-ray powder diffraction up to 5.68 GPa. No phase transition has been observed within the pressure range investigated. Axial and volume bulk moduli have been calculated using a truncated second-order Birch–Murnaghan equation-of-state (II-BM-EoS). The refined elastic parameters are: V 0=2801(11) Å3, K T0= 41(2) GPa for the unit-cell volume; a 0=18.138(32) Å, K T0(a)=70(8) GPa for the a-axis; b 0=20.517(35) Å, K T0(b)=29(2) GPa for the b-axis and c 0=7.531(5) Å, K T0(c)=38(1) GPa for the c-axis [K T0(a): K T0(b): K T0(c)=2.41:1.00:1.31]. Axial and volume Eulerian finite strain versus “normalized stress” plots (fe–Fe plot) show an almost linear trend and the weighted linear regression through the data points yields the following intercept values: Fe(0)=39(4) GPa for V; Fe a (0)=65(18) GPa for a; Fe b (0)=28(3) GPa for b; Fe c (0)=38(2) GPa for c. The magnitudes of the principal Lagrangian unit-strain coefficients, between 0.47 GPa (the lowest HP-data point) and each measured P>0.47 GPa, were calculated. The unit-strain ellipsoid is oriented with ε1 || b, ε2 || c, ε3 || a and |ε1|> |ε2|> |ε3|. Between 0.47 and 5.68 GPa the relationship between the unit-strain coefficient is ε1: ε2: ε3=2.16:1.81:1.00. The reasons of the elastic anisotropy are discussed.An erratum to this article can be found at  相似文献   

14.
The behaviour of synthetic Mg-ferrite (MgFe2O4) has been investigated at high pressure (in situ high-pressure synchrotron radiation powder diffraction at ESRF) and at high temperature (in situ high-temperature X-ray powder diffraction) conditions. The elastic properties determined by the third-order Birch–Murnaghan equation of state result in K0=181.5(± 1.3) GPa, K=6.32(± 0.14) and K= –0.0638 GPa–1. The symmetry-independent coordinate of oxygen does not show significant sensitivity to pressure, and the structure shrinking is mainly attributable to the shortening of the cell edge (homogeneous strain). The lattice parameter thermal expansion is described by a0+a1*(T–298)+a2/(T–298)2, where a0=9.1(1) 10–6 K–1, a1=4.9(2) 10–9 K–2 and a2= 5.1(5) 10–2 K. The high-temperature cation-ordering reaction which MgFe-spinel undergoes has been interpreted by the ONeill model, whose parameters are = 22.2(± 1.8) kJ mol–1 and =–17.6(± 1.2) kJ mol–1. The elastic and thermal properties measured have then been used to model the phase diagram of MgFe2O4, which shows that the high-pressure transition from spinel to orthorombic CaMn2O4-like structure at T < 1700 K is preceded by a decomposition into MgO and Fe2O3.  相似文献   

15.
The dielectric constants and dissipation factors of topaz, scapolite and orthoclase were determined at 1 MHz using a two-terminal method and empirically determined edge corrections. The results are: topaz κ′ a =6.61 tan δ=0.0005 κ′ b =6.82 tan δ=0.0007 κ′ c =6.81 tan δ=0.0007 orthoclase κ′ a =4.69 tan δ=0.0007 κ′ b =5.79 tan δ=0.0007 κ′ c =5.63 tan δ=0.0011 κ′ 11 =4.72 κ′ 22 =5.79 κ′ 33 =5.76 scapolite κ′ a =6.74 tan δ=0.0004 κ′ c =8.51 tan δ=0.0004 The deviation (Δ) between measured dielectric polarizabilities as determined from the Clausius-Mosotti equation and those calculated from the sum of ion polarizabilities according to α D (mineral)=∑αD (ions) for topaz is 2.5%. The large deviations of orthoclase and scapolite from the oxide additivity rule with δ=+7.2 and + 17.6%, respectively, are attributed to “rattling” K ions in orthoclase and “rattling” (Na,K,Ca) ions and disordered O= and Cl- ions in scapolite.  相似文献   

16.
Magnesium self-diffusion coefficients were determined experimentally for diffusion parallel to each of the three crystallographic directions in natural orthoenstatite (En88Fs12). Experiments were conducted at 1 atm in CO-CO2 gas mixing furnaces, which provided oxygen fugacities equivalent to the iron-wüstite buffer. Diffusion of 25Mg was induced in polished samples of oriented orthoenstatite using a film of isotopically enriched 25MgO as the source material. Very short (<0.15 μm) diffusional penetration profiles were measured by ion microprobe depth profiling. The diffusion coefficients determined for four temperatures (900, 850, 800, 750 °C) provide the activation energies, E a , and frequency factors, D o, where D = D o exp (−E a /RT) for Mg self-diffusion parallel to each crystallographic direction: a-axis, E a  = 360 ± 52 kJ/mole and D o = 1.10 × 10−4 m2/s; b-axis, E a  = 339 ± 77 kJ/mole and D o = 6.93 × 10−6 m2/s and c-axis, E a  = 265 ± 66 kJ/mole and D o = 4.34 × 10−9 m2/s. In this temperature range, any possible anisotropy of cation diffusion is very small, however the activation energy for diffusion parallel to the c-axis (001) is the lowest and the activation energies for diffusion parallel to the a-axis (100) and b-axis (010) are higher. Application of these diffusion results to the silicate phases of the Lowicz mesosiderite meteorite provides cooling rates for the silicate portion of the meteorite (4–11 °C/100 years) that are similar, although slower, to previous estimates. These silicate cooling rates are still several orders of magnitude faster than the cooling rates (0.1 °C/106 years) for the metal portions. Received: 22 January 1997 / Accepted: 2 October 1997  相似文献   

17.
The structure of deuterated jarosite, KFe3(SO4)2(OD)6, was investigated using time-of-flight neutron diffraction up to its dehydroxylation temperature. Rietveld analysis reveals that with increasing temperature, its c dimension expands at a rate ~10 times greater than that for a. This anisotropy of thermal expansion is due to rapid increase in the thickness of the (001) sheet of [Fe(O,OH)6] octahedra and [SO4] tetrahedra with increasing temperature. Fitting of the measured cell volumes yields a coefficient of thermal expansion, α = α0 + α1 T, where α0 = 1.01 × 10−4 K−1 and α1 = −1.15 × 10−7 K−2. On heating, the hydrogen bonds, O1···D–O3, through which the (001) octahedral–tetrahedral sheets are held together, become weakened, as reflected by an increase in the D···O1 distance and a concomitant decrease in the O3–D distance with increasing temperature. On further heating to 575 K, jarosite starts to decompose into nanocrystalline yavapaiite and hematite (as well as water vapor), a direct result of the breaking of the hydrogen bonds that hold the jarosite structure together.  相似文献   

18.
Zusammenfassung Die Struktur von Kristallen der Tieftemperaturmodifikation des K2Li[AlF6] wurden untersucht. Es ergaben sich folgende Daten: Kristallklasse –3m–D 3d: ditrigonal-skalenoedrisch; rhomboedrisches Translationsgitter; RaumgruppeR –3m–D 3d (5). Hexagonale Aufstellung:a 0=5,574 Åc 0=13,648 Å ;c/a=2,4485. Inhalt der Zelle 3 · K2LiAlF6. Rhomboedrische Aufstellung: R = 5,573 Å;=60° 01; Inhalt dieser Zelle 1 · K2LiAlF6;D x = 3,066. Die vollständige Struktur wird mitgeteilt und mit der sehr ähnlichen Struktur des kubischen Minerals Elpasolith, K2Na[AIF6], verglichen; es besteht zwischen beiden Strukturen Homöotypie, Außerdem werden die optischen Daten und die Spaltbarkeit dieser beiden Kristallarten miteinander verglichen und die Unterschiede qualitativ auf Grund der Kristallstrukturen erklärt. Weitere Homöotypiebeziehungen werden aufgezeigt.  相似文献   

19.
Fe-bearing dense hydrous magnesium silicate Phase A, Mg6.85Fe0.14Si2.00O8(OH)6 has been studied by single-crystal X-ray diffraction at ambient conditions and by high-pressure powder diffraction using synchrotron radiation to 33 GPa. Unit cell parameters at room temperature and pressure from single crystal diffraction are a=7.8678 (4) Å, c=9.5771 (5) Å, and V=513.43 (4) Å3. Fitting of the P–V data to a third-order Birch-Murnaghan isothermal equation of state yields V 0=512.3 (3) Å3, K T,0=102.9 (28) GPa and K′=6.4 (3). Compression is strongly anisotropic with the a-axes, which lie in the plane of the distorted close-packed layers, approximately 26% more compressible than the c-axis, which is normal to the plane. Structure refinement from single-crystal X-ray intensity data reveals expansion of the structure with Fe substitution, mainly by expansion of M-site octahedra. The short Si2–O6 distance becomes nearly 1% shorter with ~2% Fe substitution for Mg, possibly providing additional rigidity in the c-direction over the Mg end member. K T obtained for the Fe-bearing sample is ~5.5% greater than reported previously for Fe-free Phase A, despite the larger unit cell volume. This study represents a direct comparison of structure and K T–ρ relations between two compositions of a F-free dense hydrous magnesium silicate (DHMS) phase, and may help to characterize the effect of Fe substitution on the properties of other DHMS phases from studies of the Fe-free end-members.  相似文献   

20.
 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   

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