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1.
The crystal structure of the unstable mineral alumoklyuchevskite K3Cu3AlO2(SO4)4 [monoclinic, I2, a = 18.772(7), b = 4.967(2), c = 18.468(7) Å, β = 101.66(1)°, V = 1686(1) Å] was refined to R 1 = 0.131 for 2450 unique reflections with F ≥ 4σF hkl. The structure is based on oxocentered tetrahedrons (OAlCu 3 7+ ) linked into chains via edges. Each chain is surrounded by SO4 tetrahedrons forming a structural complex. Each complex is elongated along the b axis. This type of crystal structure was also found in other fumarole minerals of the Great Tolbachik Fissure Eruption (GTFE, Kamchatka Peninsula, Russia, 1975–1976), klyuchevskite, K3Cu3Fe3+O2(SO4)4; and piypite, K2Cu2O(SO4)2. 相似文献
2.
We present results from low-temperature heat capacity measurements of spinels along the solid solution between MgAl2O4 and MgCr2O4. The data also include new low-temperature heat capacity measurements for MgAl2O4 spinel. Heat capacities were measured between 1.5 and 300 K, and thermochemical functions were derived from the results.
No heat capacity anomaly was observed for MgAl2O4 spinel; however, we observe a low-temperature heat capacity anomaly for Cr-bearing spinels at temperatures below 15 K. From
our data we calculate standard entropies (298.15 K) for Mg(Cr,Al)2O4 spinels. We suggest a standard entropy for MgAl2O4 of 80.9 ± 0.6 J mol−1 K−1. For the solid solution between MgAl2O4 and MgCr2O4, we observe a linear increase of the standard entropies from 80.9 J mol−1 K−1 for MgAl2O4 to 118.3 J mol−1 K−1 for MgCr2O4. 相似文献
3.
M. Zhang G. J. Redhammer E. K. H. Salje M. Mookherjee 《Physics and Chemistry of Minerals》2002,29(9):609-616
Synthetic aegirine LiFeSi2O6 and NaFeSi2O6 were characterized using infrared spectroscopy in the frequency range 50–2000 cm−1, and at temperatures between 20 and 300 K. For the C2/c phase of LiFeSi2O6, 25 of the 27 predicted infrared bands and 26 of 30 predicted Raman bands are recorded at room temperature. NaFeSi2O6 (with symmetry C2/c) shows 25 infrared and 26 Raman bands. On cooling, the C2/c–P21/c structural phase transition of LiFeSi2O6 is characterized by the appearance of 13 additional recorded peaks. This observation indicates the enlargement of the unit
cell at the transition point. The appearance of an extra band near 688 cm−1 in the monoclinic P21/c phase, which is due to the Si–O–Si vibration in the Si2O6 chains, indicates that there are two non-equivalent Si sites with different Si–O bond lengths. Most significant spectral
changes appear in the far-infrared region, where Li–O and Fe–O vibrations are mainly located. Infrared bands between 300 and
330 cm−1 show unusually dramatic changes at temperatures far below the transition. Compared with the infrared data of NaFeSi2O6 measured at low temperatures, the change in LiFeSi2O6 is interpreted as the consequence of mode crossing in the frequency region. A generalized Landau theory was used to analyze
the order parameter of the C2/c–P21/c phase transition, and the results suggest that the transition is close to tricritical.
Received: 21 January 2002 / Accepted: 22 July 2002 相似文献
4.
L. A. Olsen K. Friese E. Makovicky T. Balić-Žunić W. Morgenroth A. Grzechnik 《Physics and Chemistry of Minerals》2011,38(1):1-10
The crystal structure of Pb6Bi2S9 is investigated at pressures between 0 and 5.6 GPa with X-ray diffraction on single-crystals. The pressure is applied using diamond anvil cells. Heyrovskyite (Bbmm, a = 13.719(4) Å, b = 31.393(9) Å, c = 4.1319(10) Å, Z = 4) is the stable phase of Pb6Bi2S9 at ambient conditions and is built from distorted moduli of PbS-archetype structure with a low stereochemical activity of the Pb2+ and Bi3+ lone electron pairs. Heyrovskyite is stable until at least 3.9 GPa and a first-order phase transition occurs between 3.9 and 4.8 GPa. A single-crystal is retained after the reversible phase transition despite an anisotropic contraction of the unit cell and a volume decrease of 4.2%. The crystal structure of the high pressure phase, β-Pb6Bi2S9, is solved in Pna2 1 (a = 25.302(7) Å, b = 30.819(9) Å, c = 4.0640(13) Å, Z = 8) from synchrotron data at 5.06 GPa. This structure consists of two types of moduli with SnS/TlI-archetype structure in which the Pb and Bi lone pairs are strongly expressed. The mechanism of the phase transition is described in detail and the results are compared to the closely related phase transition in Pb3Bi2S6 (lillianite). 相似文献
5.
V. L. Vinograd O. G. Safonov D. J. Wilson L. L. Perchuk L. Bindi J. D. Gale B. Winkler 《Petrology》2010,18(4):447-459
Atomistic model was proposed to describe the thermodynamics of mixing in the diopside-K-jadeite solid solution (CaMgSi2O6-KAlSi2O6). The simulations were based on minimization of the lattice energies of 800 structures within a 2 × 2 × 4 supercell of C2/c diopside with the compositions between CaMgSi2O6 and KAlSi2O6 and with variable degrees of order/disorder in the arrangement of Ca/K cations in M2 site and Mg/Al in Ml site. The energy
minimization was performed with the help of a force-field model. The results of the calculations were used to define a generalized
Ising model, which included 37 pair interaction parameters. Isotherms of the enthalpy of mixing within the range of 273–2023
K were calculated with a Monte Carlo algorithm, while the Gibbs free energies of mixing were obtained by thermodynamic integration
of the enthalpies of mixing. The calculated T-X diagram for the system CaMgSi2O6-KAlSi2O6 at temperatures below 1000 K shows several miscibility gaps, which are separated by intervals of stability of intermediate
ordered compounds. At temperatures above 1000 K a homogeneous solid solution is formed. The standard thermodynamic properties
of K-jadeite (KAlSi2O6) evaluated from quantum mechanical calculations were used to determine location of several mineral reactions with the participation
of the diopside-K-jadeite solid solution. The results of the simulations suggest that the low content of KalSi2O6 in natural clinopyroxenes is not related to crystal chemical factors preventing isomorphism, but is determined by relatively
high standard enthalpy of this end member. 相似文献
6.
Shigeto Hirai Yohei Kojima Hiroaki Ohfuji Norimasa Nishiyama Tetsuo Irifune Stephan Klemme Geoffrey Bromiley J. Paul Attfield 《Physics and Chemistry of Minerals》2011,38(8):631-637
Raman spectroscopy and heat capacity measurements have been used to study the post-perovskite phase of CaIr0.5Pt0.5O3, recovered from synthesis at a pressure of 15 GPa. Laser heating CaIr0.5Pt0.5O3 to 1,900 K at 60 GPa produces a new perovskite phase which is not recoverable and reverts to the post-perovskite polymorph
between 20 and 9 GPa on decompression. This implies that Pt-rich CaIr1−xPtxO3 perovskites including the end member CaPtO3 cannot easily be recovered to ambient pressure from high P–T synthesis. We estimate an increase in the thermodynamic Grüneisen
parameter across the post-perovskite to perovskite transition of 34%, of similar magnitude to those for (Mg,Fe)SiO3 and MgGeO3, suggesting that CaIr0.5Pt0.5O3 is a promising analogue for experimental studies of the competition in energetics between perovskite and post-perovskite
phases of magnesium silicates in Earth’s lowermost mantle. Low-temperature heat capacity measurements show that CaIrO3 has a significant Sommerfeld coefficient of 11.7 mJ/mol K2 and an entropy change of only 1.1% of Rln2 at the 108 K Curie transition, consistent with the near-itinerant electron magnetism. Heat capacity results for post-perovskite
CaIr0.5Rh0.5O3 are also reported. 相似文献
7.
Dmytro M. Trots Alexander Kurnosov Leonid Vasylechko Marek Berkowski Tiziana Boffa Ballaran Daniel J. Frost 《Physics and Chemistry of Minerals》2011,38(7):561-567
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
8.
Planewave pseudopotential calculations of supercell total energies were used as bases for first-principles calculations of
the CaCO3–MgCO3 and CdCO3–MgCO3 phase diagrams. Calculated phase diagrams are in qualitative to semiquantitative agreement with experiment. Two unobserved
phases, Cd3Mg (CO3)4 and CdMg3(CO3)4, are predicted. No new phases are predicted in the CaCO3–MgCO3 system, but a low-lying metastable Ca3Mg(CO3)4 state, analogous to the Cd3Mg(CO3)4 phase is predicted. All of the predicted lowest-lying metastable states, except for huntite CaMg3(CO3)4, have dolomite-related structures, i.e. they are layer structures in which A
m
B
n
cation layers lie perpendicular to the rhombohedral [111] vector.
Received: 6 May 2002 / Accepted: 23 October 2002
Acknowledgements This work was partially supported by NSF contract DMR-0080766 and NIST. 相似文献
9.
Philippe Léone Charlotte Doussier-Brochard Gilles André Yves Moëlo 《Physics and Chemistry of Minerals》2008,35(4):201-206
Mn2+Sb2S4, a monoclinic dimorph of clerite, and benavidesite (Mn2+Pb4Sb6S14) show well-individualized single chains of manganese atoms in octahedral coordination. Their magnetic structures are presented
and compared with those of iron derivatives, berthierite (Fe2+Sb2S4) and jamesonite (Fe2+Pb4Sb6S14). Within chains, interactions are antiferromagnetic. Like berthierite, MnSb2S4 shows a spiral magnetic structure with an incommensurate 1D propagation vector [0, 0.369, 0], unchanged with temperature.
In berthierite, the interactions between identical chains are antiferromagnetic, whereas in MnSb2S4 interactions between chains are ferromagnetic along c-axis. Below 6 K, jamesonite and benavidesite have commensurate magnetic structures with the same propagation vector [0.5, 0, 0]:
jamesonite is a canted ferromagnet and iron magnetic moments are mainly oriented along the a-axis, whereas for benavidesite, no angle of canting is detected, and manganese magnetic moments are oriented along b-axis. Below 30 K, for both compounds, one-dimensional magnetic ordering or correlations are visible in the neutron diagrams
and persist down to 1.4 K. 相似文献
10.
The high-pressure behavior of a vanadinite (Pb10(VO4)6Cl2, a = b = 10.3254(5), c = 7.3450(4) Å, space group P63/m), a natural microporous mineral, has been investigated using in-situ HP-synchrotron X-ray powder diffraction up to 7.67 GPa with a diamond anvil cell under hydrostatic conditions. No phase transition has been observed within the pressure range investigated. Axial and volume isothermal Equations of State (EoS) of vanadinite were determined. Fitting the P–V data with a third-order Birch-Murnaghan (BM) EoS, using the data weighted by the uncertainties in P and V, we obtained: V 0 = 681(1) Å3, K 0 = 41(5) GPa, and K′ = 12.5(2.5). The evolution of the lattice constants with P shows a strong anisotropic compression pattern. The axial bulk moduli were calculated with a third-order “linearized” BM-EoS. The EoS parameters are: a 0 = 10.3302(2) Å, K 0(a) = 35(2) GPa and K′(a) = 10(1) for the a-axis; c 0 = 7.3520(3) Å, K 0(c) = 98(4) GPa, and K′(c) = 9(2) for the c-axis (K 0(a):K 0(c) = 1:2.80). Axial and volume Eulerian-finite strain (fe) at different normalized stress (Fe) were calculated. The weighted linear regression through the data points yields the following intercept values: Fe a (0) = 35(2) GPa for the a-axis, Fe c (0) = 98(4) GPa for the c-axis and Fe V (0) = 45(2) GPa for the unit-cell volume. The slope of the regression lines gives rise to K′ values of 10(1) for the a-axis, 9(2) for the c-axis and 11(1) for the unit cell-volume. A comparison between the HP-elastic response of vanadinite and the iso-structural apatite is carried out. The possible reasons of the elastic anisotropy are discussed. 相似文献
11.
12.
13.
14.
Hanen Azaza Lassaad Mechi Amira Doggaz Virgil Optasanu Mohamed Tlili Mohamed Ben Amor 《Arabian Journal of Geosciences》2017,10(10):220
During the production of hydrocarbons from subterranean reservoirs, scaling with calcium carbonate and barium sulfate causes flux decline and dangerous problems in production facilities. This work is intended to study the effect of calcium ions on the precipitation of barium sulfate (barite); then, the effect of the formed barite on calcium carbonate crystallization. The conductometric and pH methods were used to follow the progress of the precipitation reaction in aqueous medium. The obtained precipitates were characterized by FTIR, RAMAN, SEM, and XRD. It was shown that Ca2+ in the reaction media does not affect the microstructure of barite even for higher calcium–barium molar ratio. It influences the precipitation kinetics and the solubility of barite by the formation of CaSO4° ion pairing as a predominant role of complex formation (CaSO4) and the increase of the ionic strength. In Ca(HCO3)2-BaSO4-NaCl aqueous system, experiments have showed that added or formed barite in the reaction media accelerates calcite precipitation. No effect on the microstructure of heterogeneous formed calcite which remain calcite shape. However the presence of carbonate ions affects slightly the microstructure of barite. 相似文献
15.
Shuangmeng Zhai Weihong Xue Daisuke Yamazaki Shuangming Shan Eiji Ito Naotaka Tomioka Akira Shimojuku Ken-ichi Funakoshi 《Physics and Chemistry of Minerals》2011,38(5):357-361
High pressure in situ synchrotron X-ray diffraction experiment of strontium orthophosphate Sr3(PO4)2 has been carried out to 20.0 GPa at room temperature using multianvil apparatus. Fitting a third-order Birch–Murnaghan equation of state to the P–V data yields a volume of V 0 = 498.0 ± 0.1 Å3, an isothermal bulk modulus of K T = 89.5 ± 1.7 GPa, and first pressure derivative of K T ′ = 6.57 ± 0.34. If K T ′ is fixed at 4, K T is obtained as 104.4 ± 1.2 GPa. Analysis of axial compressible modulus shows that the a-axis (K a = 79.6 ± 3.2 GPa) is more compressible than the c-axis (K c = 116.4 ± 4.3 GPa). Based on the high pressure Raman spectroscopic results, the mode Grüneisen parameters are determined and the average mode Grüneisen parameter of PO4 vibrations of Sr3(PO4)2 is calculated to be 0.30(2). 相似文献
16.
Room-temperature-polarized single-crystal Raman spectra have been measured for both GdAlO3 and YAlO3. Both aluminates crystallize in the orthorhombic (Pbnm) perovskite structure. Of the 24 possible Raman modes in 4 symmetries,
20 and 17 modes were observed for gadolinium and yttrium aluminates, respectively. Comparisons of the Raman spectra of these
two aluminates to those of 28 other orthorhombic ABO3 perovskites revealed remarkably similar spectral patterns, regardless of chemistry or valency of the cations. Closer examination
of the effect of mass, valencies, and size of the cations on the Raman spectra versus composition revealed that for the observed
modes, the A cation plays the dominant role in determining the Raman shift. In particular, the one to two lowest energy modes
in each symmetry are determined by cation mass and valency no matter what the chemistry. For some perovskites with common
A cations, higher energy modes were also strikingly similar. In particular, the calcium perovskites had almost all Ag modes at the same energies despite the greatly varying B cations. The second to the lowest mode in Ag and B1g depended only on A cation mass for all perovskites. The volume plays a minor role throughout but is hard to separate from
mass effects because the most massive cations are also the largest. However, if the B-cation is common, for example, aluminates
or ferrites, the volume has a minor effect on the higher energy modes. These trends were not observed for all perovskites.
Notable exceptions were found if a perovskite is near a phase transition or metastable, as found for three manganites. The
effect of increased valency of the A cation from 2–4 to 3–3 perovskites expresses itself as relatively larger Raman shifts
for the lowest energy modes. Analog studies of MgSiO3 perovskites should be undertaken with only 2–4 perovskites. The increased understanding for the mode distributions of perovskites
allows for better estimates of their thermodynamic properties through vibrational modeling. 相似文献
17.
S. M. S. Niknejad H. Savoji M. Pourafshari Chenar M. Soltanieh 《International Journal of Environmental Science and Technology》2017,14(2):375-384
In this work, permeation of mixed gases H2S/CH4 through commercial polyphenylene oxide (PPO) hollow fiber and poly (ester urethane) urea (PEUU) flat membranes was studied at pressures of 345–689 kPa, at ambient temperature and at 313.15 K. Various H2S concentrations of about 100–5000 ppm in CH4 binary synthetic gas mixtures as well as a real natural gas sample obtained from a gas refinery containing 0.3360 mol.% H2S (equivalent to 3360 ppm) were tested. It was observed that the permeance of components was affected by the balance between competitive sorption and plasticization effects. Separation factors of H2S/CH4 were in the range of 1.3–2.9, 1.8–3.1 and 2.2–4.3 at pressures of 345, 517 and 689 kPa, respectively. In the range of 101–5008 ppm of H2S in CH4, the effect of temperature on the separation factor was nearly negligible; however, permeances of both components of the mixtures increased with temperature. Additionally, the results obtained by PEUU membrane indicated that it was a better choice for hydrogen sulfide separation from H2S/CH4 mixtures than PPO. For PPO membrane, removal of hydrogen sulfide from high-concentration (up to 5008 ppm) binary mixtures of H2S/CH4 was compared with that of low concentration (as low as 101 ppm) through PPO. At concentrations of 101–968 ppm, plasticization was dominant compared with the competitive sorption, while for the H2S feed concentrations of 3048 ppm, the competitive sorption effect was dominant. For H2S concentration of 5008 ppm, the balance between these two effects played an important role for explanation of its trend. 相似文献
18.
19.
Using density functional simulations within the generalized gradient approximation and projector-augmented wave method together
with thermodynamic modelling, the reciprocal solubilities of MgSiO3 and CaSiO3 perovskites were calculated for pressures and temperatures of the Earth’s lower mantle from 25 to 100 GPa and 0 to 6,000 K,
respectively. The solubility of Ca in MgSiO3 at conditions along a mantle adiabat is found to be less than 0.02 atoms per formula unit. The solubility of Mg in CaSiO3 is even lower, and most important, the extent of solid solution decreases with pressure. To dissolve CaSiO3 perovskite completely in MgSiO3 perovskite, a solubility of 7.8 or 2.3 mol% would be necessary for a fertile pyrolytic or depleted harzburgitic mantle, respectively.
Thus, for any reasonable geotherm, two separate perovskites will be present in fertile mantle, suggesting that Ca-perovskite
will be residual to low degree melting throughout the entire mantle. At the solidus, CaSiO3 perovskite might completely dissolve in MgSiO3 perovskite only in a depleted mantle with <1.25 wt% CaO. These implications may be modified if Ca solubility in MgSiO3 is increased by other major mantle constituents such as Fe and Al. 相似文献
20.
Jianmin Shi Stefan G. Ebbinghaus Klaus Dieter Becker 《Physics and Chemistry of Minerals》2008,35(1):1-9
In the olivine crystal structure, cations are distributed over two inequivalent octahedral sites, M1 and M2. Kinetics of cation
exchange between the two octahedral sites in (Co0.1Mg0.9)2SiO4 single crystal have been studied in the temperature range from 600 to 800°C by monitoring the time evolution of the absorbance
of Co2+ ions in M1 or M2 sites using optical spectroscopy after rapid temperature jumps. It was found from such temperature-jump
induced relaxation experiments that with increasing temperature the absorbance of Co2+ ions in the M1 site decreases while that in the M2 site increases. This indicates a tendency of Co2+ cations to populate the M2 site with increasing temperatures and vice versa. The experimental relaxation data can be modeled
using a triple exponential equation based on theoretical analysis. Activation energies of 221 ± 4 and 213 ± 10 kJ/mol were
derived from relaxation experiments on the M2 site and M1 site, respectively, for the cation exchange processes in (Co0.1Mg0.9)2SiO4 olivine. Implications for cation diffusion at low temperatures are discussed. 相似文献