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1.
Hongwu Xu Yusheng Zhao Sven C. Vogel Donald D. Hickmott Luke L. Daemen Monika A. Hartl 《Physics and Chemistry of Minerals》2010,37(2):73-82
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
2.
G. Diego Gatta Marco Merlini Hanns-Peter Liermann André Rothkirch Mauro Gemmi Alessandro Pavese 《Physics and Chemistry of Minerals》2012,39(5):385-397
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
3.
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
4.
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
5.
P. Comodi G. D. Gatta P. F. Zanazzi D. Levy W. Crichton 《Physics and Chemistry of Minerals》2002,29(8):538-544
Powder diffraction measurements at simultaneous high pressure and temperature on samples of 2M1 polytype of muscovite (Ms) and paragonite (Pg) were performed at the beamline ID30 of ESRF (Grenoble), using the Paris-Edinburgh
cell. The bulk moduli of Ms, calculated from the least-squares fitting of V–P data on each isotherm using a second-order Birch–Murnaghan EoS, were: 57.0(6), 55.1(7), 51.1(7) and 48.9(5) GPa on the isotherms
at 298, 573, 723 and 873 K, respectively. The value of (∂K
T
/∂T)
was −0.0146(2) GPa K−1. The thermal expansion coefficient α varied from 35.7(3) × 10−6 K−1 at P ambient to 20.1(3) × 10−6 K−1 at P = 4 GPa [(∂α/∂P)
T
= −3.9(1) × 10−6 GPa−1 K−1]. The corresponding values for Pg on the isotherms at 298, 723 and 823 K were: bulk moduli 59.9(5), 55.7(6) and 53.8(7) GPa,
(∂K
T
/∂T)
−0.0109(1) GPa K−1. The thermal expansion coefficient α varied from 44.1(2) × 10−6 K−1 at P ambient to 32.5(2) × 10−6 K−1 at P = 4 GPa [(∂α/∂P)
T
= −2.9(1) × 10−6 GPa−1 K−1]. Thermoelastic coefficients showed that Pg is stiffer than Ms; Ms softens more rapidly than Pg upon heating; thermal expansion
is greater and its variation with pressure is smaller in Pg than in Ms.
Received: 28 January 2002 / Accepted: 5 April 2002 相似文献
6.
Behavior of epidote at high pressure and high temperature: a powder diffraction study up to 10 GPa and 1,200 K 总被引:1,自引:0,他引:1
G. Diego Gatta Marco Merlini Yongjae Lee Stefano Poli 《Physics and Chemistry of Minerals》2011,38(6):419-428
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
7.
Philippe E. Raison Claudiu C. Pavel Regis Jardin Emmanuelle Suard Richard G. Haire Karin Popa 《Physics and Chemistry of Minerals》2010,37(8):555-559
The thermal expansion of cubic pyrochlore Ce2Zr2O7 has been measured from room temperature to 898 K on polycrystalline material in conjunction with structural analyses using
neutron diffraction. This compound has a thermal expansion coefficient in line with the other comparable lanthanoide pyrochlore
oxides. The coefficient can be expressed as α(T) = 8.418 × 10−6 + 0.9861 × 10−9 × T. The structural refinements performed for each measured temperature showed a comparable linear evolution of the Ce–O/Zr–O
distances (within 0.57%). 相似文献
8.
Wen Su Ming Zhang Simon A. T. Redfern Jun Gao Reiner Klemd 《International Journal of Earth Sciences》2009,98(6):1299-1309
Chemically-zoned amphibole porphyroblast grains in an eclogite (sample ws24-7) from the western Tianshan (NW-China) have been
analyzed by electron microprobe (EMP), micro Fourier-transform infrared (micro-FTIR) and micro-Raman spectroscopy in the OH-stretching
region. The EMP data reveal zoned amphibole compositions clustering around two predominant compositions: a glaucophane end-member
(
B
Na2
C
M2+
3 M3+
2
T
Si8(OH)2) in the cores, whereas the mantle to rim of the samples has an intermediate amphibole composition (
A
0.5
B
Ca1.5Na0.5
C
M
2+
4.5 M
0.53+
T
Si7.5Al0.5(OH)2) (A = Na and/or K; M
2+ = Mg and Fe2+; M
3+ = Fe3+ and/or Al) between winchite (and ferro-winchite) and katophorite (and Mg-katophorite). Furthermore, we observed complicated
FTIR and Raman spectra with OH-stretching absorption bands varying systematically from core to rim. The FTIR/Raman spectra
of the core amphibole show three lower-frequency components (at 3,633, 3,649–3,651 and 3,660–3,663 cm−1) which can be attributed to a local O(3)-H dipole surrounded by
M(1) M(3)Mg3,
M(1) M(3)Mg2Fe2+ and
M(1) M(3) Fe2+
3, respectively, an empty A site and
T
Si8 environments. On the other hand, bands at higher frequencies (3,672–3,673, 3,691–3,697 and 3,708 cm−1) are observable in the rims of the amphiboles, and they indicate the presence of an occupied A site. The FTIR and Raman data from the OH-stretching region allow us to calculate the site occupancy of the A, M(1)–M(3), T sites with confidence when combined with EPM data. By contrast M(2)- and M(4) site occupancies are more difficult to evaluate. We use these samples to highlight on the opportunities and limitations
of FTIR OH-stretching spectroscopy applied to natural high pressure amphibole phases. The much more detailed cation site occupancy
of the zoned amphibole from the western Tianshan have been obtained by comparing data from micro-chemical and FTIR and/or
Raman in the OH-stretching data. We find the following characteristic substitutions Si(T-site) (Mg, Fe)[M(1)–M(3)-site] → Al(T-site) Al[M(1)–M(3)-site] (tschermakite), Ca(M4-site)□ (A-site) → Na(M4-site) Na + K(A-site) (richterite), and Ca(M4-site) (Mg, Fe) [M(1)–M(3)-site] → Na(M4-site) Al[M(1)–M(3)-site] (glaucophane) from the configurations observed during metamorphism. 相似文献
9.
A. Pavese V. Diella V. Pischedda M. Merli R. Bocchio M. Mezouar 《Physics and Chemistry of Minerals》2001,28(4):242-248
The thermoelastic parameters of natural andradite and grossular have been investigated by high-pressure and -temperature
synchrotron X-ray powder diffraction, at ESRF, on the ID30 beamline. The P–V–T data have been fitted by Birch-Murnaghan-like EOSs, using both the approximated and the general form. We have obtained for
andradite K
0=158.0(±1.5) GPa, (dK/dT )0=−0.020(3) GPa K−1 and α0=31.6(2) 10−6 K−1, and for grossular K
0=168.2(±1.7) GPa, (dK/dT)0=−0.016(3) GPa K−1 and α0=27.8(2) 10−6 K−1. Comparisons between the present issues and thermoelastic properties of garnets earlier determined are carried out.
Received: 7 July 2000 / Accepted: 20 October 2000 相似文献
10.
Sicheng Wang Xi Liu Yingwei Fei Qiang He Hejing Wang 《Physics and Chemistry of Minerals》2012,39(3):189-198
Using a conventional high-T furnace, the solid solutions between magnesiochromite and manganochromite, (Mg1−x
Mn
x
)Cr2O4 with x = 0.00, 0.19, 0.44, 0.61, 0.77 and 1.00, were synthesized at 1,473 K for 48 h in open air. The ambient powder X-ray diffraction
data suggest that the V–x relationship of the spinels does not show significant deviation from the Vegard’s law. In situ high-T powder X-ray diffraction measurements were taken up to 1,273 K at ambient pressure. For the investigated temperature range,
the unit-cell parameters of the spinels increase smoothly with temperature increment, indicating no sign of cation redistribution
between the tetrahedral and octahedral sites. The V–T data were fitted with a polynomial expression for the volumetric thermal expansion coefficient (aT = a0 + a1 T + a2 T - 2 \alpha_{T} = a_{0} + a_{1} T + a_{2} T^{ - 2} ), which yielded insignificant a
2 values. The effect of the composition on a
0 is adequately described by the equation a
0 = [17.7(8) − 2.4(1) × x] 10−6 K−1, whereas that on a
1 by the equation a
1 = [8.6(9) + 2.1(11) × x] 10−9 K−2. 相似文献
11.
Steeve Gréaux Yoshio Kono Norimasa Nishiyama Takehiro Kunimoto Kouhei Wada Tetsuo Irifune 《Physics and Chemistry of Minerals》2011,38(2):85-94
The thermoelastic parameters of synthetic Ca3Al2Si3O12 grossular garnet were examined in situ at high-pressure and high-temperature by energy dispersive X-ray diffraction, using
a Kawai-type multi-anvil press apparatus coupled with synchrotron radiation. Measurements have been conducted at pressures
up to 20 GPa and temperatures up to 1,650 K: this P, T range covered the entire high-P, T stability field of grossular garnet. The analysis of room temperature data yielded V
0,300 = 1,664 ± 2 ?3 and K
0 = 166 ± 3 GPa for K¢0 K^{\prime}_{0} fixed to 4.0. Fitting of our P–V–T data by means of the high-temperature third order Birch–Murnaghan or the Mie–Grüneisen–Debye thermal equations of state,
gives the thermoelastic parameters: (∂K
0,T
/∂T)
P
= −0.019 ± 0.001 GPa K−1 and α
0,T
= 2.62 ± 0.23 × 10−5 K−1, or γ
0 = 1.21 for fixed values q
0 = 1.0 and θ
0 = 823 (Isaak et al. Phys Chem Min19:106–120, 1992). From the comparison of fits from two different approaches, we propose to constrain the bulk modulus of grossular garnet
and its pressure derivative to K
T0 = 166 GPa and K¢T0 K^{\prime}_{T0} = 4.03–4.35. Present results are compared with previously determined thermoelastic properties of grossular-rich garnets. 相似文献
12.
The thermal expansion of gehlenite, Ca2Al[AlSiO7], (up to T=830 K), TbCaAl[Al2O7] (up to T=1100 K) and SmCaAl[Al2O7] (up to T=1024 K) has been determined. All compounds are of the melilite structure type with space group
Thermal expansion data were obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches
Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α1=7.2(4)×10−6×K−1+3.6(7)×10−9ΔT×K−2 and α3=15.0(1)×10−6×K−1. For TbCaAl[Al2O7] the respective values are: α1=7.0(2)×10−6×K−1+2.0(2)×10−9ΔT×K−2 and α3=8.5(2)×10−6×K−1+2.0(3)×10−9ΔT×K−2, and the thermal expansion coefficients for SmCaAl[Al2O7] are: α1=6.9(2)×10−6×K−1+1.7(2)×10−9ΔT×K−2 and α3=9.344(5)×10−6×K−1. The expansion mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements
of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been
observed. While gehlenite behaves like a ‘proper’ layer structure, the aluminates show increased framework structure behavior.
This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging
cations due to the coupled substitution (Ca2++Si4+)–(Ln
3++Al3+) in the melilite-type structure.
This article has been mistakenly published twice. The first and original version of it is available at . 相似文献
13.
The heat capacity at constant pressure, C
p, of chlorapatite [Ca5(PO4)3Cl – ClAp], and fluorapatite [Ca5(PO4)3F – FAp], as well as of 12 compositions along the chlorapatite–fluorapatite join have been measured using relaxation calorimetry
[heat capacity option of the physical properties measurement system (PPMS)] and differential scanning calorimetry (DSC) in
the temperature range 5–764 K. The chlor-fluorapatites were synthesized at 1,375–1,220°C from Ca3(PO4)2 using the CaF2–CaCl2 flux method. Most of the chlor-fluorapatite compositions could be measured directly as single crystals using the PPMS such
that they were attached to the sample platform of the calorimeter by a crystal face. However, the crystals were too small
for the crystal face to be polished. In such cases, where the sample coupling was not optimal, an empirical procedure was
developed to smoothly connect the PPMS to the DSC heat capacities around ambient T. The heat capacity of the end-members above 298 K can be represented by the polynomials: C
pClAp = 613.21 − 2,313.90T
−0.5 − 1.87964 × 107
T
−2 + 2.79925 × 109
T
−3 and C
pFAp = 681.24 − 4,621.73 × T
−0.5 − 6.38134 × 106
T
−2 + 7.38088 × 108
T
−3 (units, J mol−1 K−1). Their standard third-law entropy, derived from the low-temperature heat capacity measurements, is S° = 400.6 ± 1.6 J mol−1 K−1 for chlorapatite and S° = 383.2 ± 1.5 J mol−1 K−1 for fluorapatite. Positive excess heat capacities of mixing, ΔC
pex, occur in the chlorapatite–fluorapatite solid solution around 80 K (and to a lesser degree at 200 K) and are asymmetrically
distributed over the join reaching a maximum of 1.3 ± 0.3 J mol−1 K−1 for F-rich compositions. They are significant at these conditions exceeding the 2σ-uncertainty of the data. The excess entropy of mixing, ΔS
ex, at 298 K reaches positive values of 3–4 J mol−1 K−1 in the F-rich portion of the binary, is, however, not significantly different from zero across the join within its 2σ-uncertainty. 相似文献
14.
The crystal structure of Bi2Al4−x
Fe
x
O9 compounds (x = 0–4) has striking similarities with the crystal structure of mullite. A complete substitution of Al by Fe3+ in both octahedral and tetrahedral sites is a particular structural feature. The infrared (IR) spectra of the Bi2M4O9 compounds (M = Al, Fe3+) are characterised by three band groups with band maxima in the 900–800, 800–600 and 600–400 cm−1 region. Based on the spectroscopic results obtained from mullite-type phases, the present study focuses on the composition-dependent analysis of the 900–800 cm−1 band group, which is assigned to Al(Fe3+)–O stretching vibrations of the corner-sharing MO4 tetrahedra. The Bi2Al4O9 and Bi2Fe4O9 endmembers display single bands with maxima centred at 922 and 812 cm−1, respectively. Intermediate Bi2Al4−x
Fe
x
O9 compounds exhibit a distinct splitting into three relatively sharp bands, which is interpreted in terms of ordering effects within the tetrahedral pairs. Thereby the high-energy component band of the band triplet relates to Al–O–Al conjunctions and the low-energy component band to Fe–O–Fe conjunctions. The intermediate band is assigned to stretching vibrations of Al–O–Fe or Fe–O–Al configurations of the corner-sharing tetrahedral pairs. Bands in the 800–600 cm−1 range are assigned to low-energy stretching vibrations of the MO4 tetrahedra and to M–O–M bending vibrations of the tetrahedral pairs. Absorptions in the 600–400 cm−1 range are essentially determined by M–O stretching modes of the M cations in octahedral coordination. 相似文献
15.
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
16.
P. Comodi M. Drábek M. Montagnoli M. Rieder Z. Weiss P. F. Zanazzi 《Physics and Chemistry of Minerals》2003,30(4):198-205
The crystal structure of a synthetic Rb analog of tetra-ferri-annite (Rb–TFA) 1M with the composition Rb0.99Fe2+
3.03(Fe3+ 1.04 Si2.96)O10.0(OH)2.0 was determined by the single-crystal X-ray diffraction method. The structure is homooctahedral (space group C2/m) with M1 and M2 occupied by divalent iron. Its unit cell is larger than that of the common potassium trioctahedral mica,
and similar lateral dimensions of the tetrahedral and octahedral sheets allow a small tetrahedral rotation angle α=2.23(6)°.
Structure refinements at 0.0001, 1.76, 2.81, 4.75, and 7.2 GPa indicate that in some respects the Rb–TFA behaves like all
other micas when pressure increases: the octahedra are more compressible than the tetrahedra and the interlayer is four times
more compressible than the 2:1 layer. However, there is a peculiar behavior of the tetrahedral rotation angle α: at lower
pressures (0.0001, 1.76, 2.81 GPa), it has positive values that increase with pressure [from 2.23(6)° to 6.3(4)°] as in other
micas, but negative values −7.5(5)° and −8.5(9)° appear at higher pressures, 4.75 and 7.2 GPa, respectively. This structural
evidence, together with electrostatic energy calculations, shows that Rb–TFA has a Franzini A-type 2:1 layer up to at least
2.81 GPa that at higher pressure yields to a Franzini B-type layer, as shown by the refinements at 4.75 and 7.2 GPa. The inversion
of the α angle is interpreted as a consequence of an isosymmetric displacive phase transition from A-type to B-type structure
between 2.81 and 4.75 GPa. The compressibility of the Rb–TFA was also investigated by single-crystal X-ray diffraction up
to a maximum pressure of 10 GPa. The lattice parameters reveal a sharp discontinuity between 3.36 and 3.84 GPa, which was
associated with the phase transition from Franzini-A to Franzini-B structure.
Received: 21 October 2002 / Accepted: 25 February 2003 相似文献
17.
Summary Fine-grained homogeneous powder samples of thirteen trioctahedral micas, mostly intermediate members of the phlogopite – annite
solid solution series, and samples close to the phlogopite, fluor-phlogopite and tetra-ferriphlogopite end members have been
examined at the potassium K-edge by X-ray absorption fine structure spectroscopy. The interlayer K+ cation is in a coordination that is certainly lower than 12, in contrast to what is expected from the ideal hexagonal symmetry
model of the mica structure, and approaches – but it does not reach – coordination 6, as it should be when the effective ligands
are the three nearest outer bridging oxygens of two facing upper and lower tetrahedral sheets. The observed range of coordinations
implies that only some of the three inner bridging oxygen atoms in each sheet are involved, thus leading to 6±(1 … 6) effective
configurations depending on the composition of the individual mica terms. The effective coordination number was found to vary
continuously with composition from 11 to 7 and to be related to the tetrahedral rotation angle (α) according to two different
linear relationships for the phlogopite – annite series (Fe2+Mg−1 exchange vector, involving the octahedral sheet only) and the phlogopite – tetra-ferriphlogopite series (Fe3+Al−1 vector, involving the tetrahedral sheet), respectively. Substitutions affecting either the A cation in the interlayer or
the X anion in the octahedral sheet also affect the observed trends. In particular, the latter substitution effect is best
seen in two near end member phlogopites, where the fluorine to hydroxyl substitution (F− (OH)−−1 exchange vector), which greatly changes the α tetrahedral rotation angle is, reflected in the experimental K XANES spectra
by modifying not only the energy but also the intensities of most multiple scattering features. 相似文献
18.
The thermal expansion of gehlenite, Ca2Al[AlSiO7], (up to T=830 K), TbCaAl[Al2O7] (up to T=1,100 K) and SmCaAl[Al2O7] (up to T=1,024 K) has been determined. All compounds are of the melilite structure type with space group
Thermal expansion data was obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α1=7.2(4)×10−6 K−1+3.6(7)×10−9ΔT K−2 and α3=15.0(1)×10−6 K−1. For TbCaAl[Al2O7] the respective values are: α1=7.0(2)×10−6 K−1+2.0(2)×10−9ΔT K−2 and α3=8.5(2)×10−6 K−1+2.0(3)×10−9ΔT K−2, and the thermal expansion coefficients for SmCaAl[Al2O7] are: α1=6.9(2)× 10−6 K−1+1.7(2)×10−9ΔT K−2 and α3=9.344(5)×10−6 K−1. The expansion-mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements
of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been
observed. While gehlenite behaves like a ’proper’ layer structure, the aluminates show increased framework structure behaviour.
This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging
cations due to the coupled substitution (Ca2++Si4+)-(Ln
3++Al3+) in the melilite-type structure.
Electronic Supplementary Material Supplementary material is available for this article at 相似文献
19.
Virender K. Sharma Ria A. Yngard Zoltan Homonnay Abhishek Dey Chun He 《Aquatic Geochemistry》2010,16(3):483-490
The kinetics of the formation of the purple-colored species between FeIII-EDTA and peroxynitrite were studied as a function of pH (10.4–12.3) at 22°C in aqueous solutions using a stopped-flow technique.
A purple-colored species was immediately formed upon mixing, which had an absorbance maximum at 520 nm. The increase in absorbance
with time could be fit empirically by a power function with two parameters a and b. The power equation determined was absorbance = a*t
b
, where a increased linearly with pH and the concentration of peroxynitrite, while b almost remained constant with a value of ~0.25. The molar extinction coefficient ε520 nm for the colored species was determined as 13 M−1cm−1, which is much lower than ε520 nm = 520 M−1 cm−1 for the [FeIII(EDTA)O2]3−, a purple species observed in the FeIII–EDTA–H2O2 system. The results of kinetics and spectral measurements of the present study are briefly discussed and compared with those
of the reaction between Fe(III)-EDTA and hydrogen peroxide. 相似文献
20.
The accepted standard state entropy of titanite (sphene) has been questioned in several recent studies, which suggested a
revision from the literature value 129.3 ± 0.8 J/mol K to values in the range of 110–120 J/mol K. The heat capacity of titanite
was therefore re-measured with a PPMS in the range 5 to 300 K and the standard entropy of titanite was calculated as 127.2
± 0.2 J/mol K, much closer to the original data than the suggested revisions. Volume parameters for a modified Murgnahan equation
of state: V
P,T
= V
298° × [1 + a°(T − 298) − 20a°(T − 298)] × [1 – 4P/(K
298 × (1 – 1.5 × 10−4 [T − 298]) + 4P)]1/4 were fit to recent unit cell determinations at elevated pressures and temperatures, yielding the constants V
298° = 5.568 J/bar, a° = 3.1 × 10−5 K−1, and K = 1,100 kbar. The standard Gibbs free energy of formation of titanite, −2456.2 kJ/mol (∆H°f = −2598.4 kJ/mol) was calculated from the new entropy and volume data combined with data from experimental reversals on the
reaction, titanite + kyanite = anorthite + rutile. This value is 4–11 kJ/mol less negative than that obtained from experimental
determinations of the enthalpy of formation, and it is slightly more negative than values given in internally consistent databases.
The displacement of most calculated phase equilibria involving titanite is not large except for reactions with small ∆S. Re-calculated baric estimates for several metamorphic suites yield pressure differences on the order of 2 kbar in eclogites
and 10 kbar for ultra-high pressure titanite-bearing assemblages. 相似文献