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1.
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
2.
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
3.
Durgesh C Rai 《Journal of Earth System Science》2003,112(3):421-429
The current designs of supporting structures of elevated water tanks are extremely vulnerable under lateral forces due to
an earthquake and the Bhuj earthquake provided another illustration when a great many water tank stagings suffered damage
and a few collapsed. The more popular shaft type stagings suffer from poor ductility of thin shell sections besides low redundancy
and toughness whereas framed stagings consist of weak members and poor brace-column joints. A strength analysis of a few damaged
shaft type stagings clearly shows that all of them either met or exceeded the strength requirements of IS:1893-1984, however,
they were all found deficient when compared with requirements of the International Building Code. IS:1893-1984 is unjustifiably
low for these systems which do not have the advantage of ductility and redundancy and are currently being underestimated at
least by a factor of 3 and need an upward revision of forces immediately. 相似文献
4.
5.
Raman spectra of a single-crystal fragment of hydrous γ-Mg2SiO4, synthesized in a multianvil press, have been measured in a diamond-anvil cell with helium as pressure-transmitting medium
to 56.5 GPa at room temperature. All five characteristic spinel Raman modes shift continuously up to the highest pressure,
showing no evidence for a major change in the crystal structure despite compression well beyond the stability field of ringwoodite
in terms of pressure. At pressures above ∼30 GPa a new mode on the low-frequency site of the two silicate-stretching modes
is clearly identifiable, indicating a modification in the spinel structure which is reversible on pressure release. The frequency
of the new mode (802 cm−1 extrapolated to 1 bar) suggests the presence of Si–O–Si linkages and/or a partial increase in the coordination of Si. Direct
determination of the subtle structural change causing the new Raman mode would require high-pressure, single-crystal synchrotron
X-ray diffraction experiments. The Raman modes of hydrous and anhydrous Mg-end-member ringwoodite are nearly identical up
to 20 GPa, suggesting that protonation has only minor effect on the lattice dynamics over the entire pressure stability range
for ringwoodite in the mantle.
Received: 7 December 2001 / Accepted: 16 April 2002 相似文献
6.
7.
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
8.
Taku Okada Takehiko Yagi Daisuke Nishio-Hamane 《Physics and Chemistry of Minerals》2011,38(4):251-258
The phase relations and compression behavior of MnTiO3 perovskite were examined using a laser-heated diamond-anvil cell, X-ray diffraction, and analytical transmission electron
microscopy. The results show that MnTiO3 perovskite becomes unstable and decomposes into MnO and orthorhombic MnTi2O5 phases at above 38 GPa and high temperature. This is the first example of ABO3 perovskite decomposing into AO + AB2O5 phases at high pressure. The compression behavior of volume, axes, and the tilting angle of TiO6 octahedron of MnTiO3 perovskite are consistent with those of other A2+B4+O3 perovskites, although no such decomposition was observed in other perovskites. FeTiO3 is also known to decompose into two phases, instead of transforming into the CaIrO3-type post-perovskite phase and we argue that one of the reasons for the peculiar behavior of titanate is the weak covalency
of the Ti–O chemical bonds. 相似文献
9.
10.
U-Pb systems were examined in samples (ranging from 4 to 10 cm3 in volume) of ore material taken from along a 3.5-m profile across a zone of U mineralization exposed in an underground mine at the Strel’tsovskoe U deposit in eastern Transbaikalia. The behaviors of two isotopic U-Pb systems (238U-206Pb and 235U-207Pb) are principally different in all samples from our profile. While the individual samples are characterized by a vast scatter of their T(206Pb/238U) age values (from 112 to 717 Ma), the corresponding T(207Pb/235U) values vary much less significantly (from 127 to 142 Ma) and are generally close to the true age of the U mineralization. The main reason for the distortion of the U-Pb system is the long-lasting (for tens of million years) migration of intermediate decay products in the 238U-206Pb(RD238U) in the samples. This process resulted in the loss of RD238U from domains with high U concentrations and the subsequent accommodation of RD238U at sites with low U concentrations. The long-term effect of these opposite processes resulted in a deficit or excess of 206Pb as the final product of 238U decay. The loss or migration of RD238U are explained by the occurrence of pitchblende in association with U oxides that have higher Si and OH concentrations than those in the pitchblende and a higher +6U/+4U ratio. The finely dispersed character of the mineralization and the loose or metamict texture of the material are the principal prerequisites for RD238U loss and an excess of 206Pb in adjacent domains with low U concentrations. Domains with low U contents in the zone with U mineralization serve as geochemical barriers (because of sulfides contained in them) at which long-lived RD238U(226Ra, 210Po, 210Bi, and 210Pb) were accommodated and subsequently caused an excess of 206Pb. The 235U-207Pb system remained closed because of the much briefer lifetime of the 235U decay products. This may account for the significant discrepancies between the T(206Pb/238U) and T(207Pb/235U) age values. RD238U was most probably lost via the migration of radioisotopes at the middle part and end of the 238U family (starting with 226Ra). The heavy Th, Pa, and U radioisotopes (234Th, 234Pa, 234U, and 230Th) that occur closer to the beginning of 238U decay, before 226Ra, only relatively insignificantly participated in the process. Our results show that the loss and migration of RD238U are, under certain conditions, the main (or even the only) process responsible for the distortion of the U-Pb system. 相似文献
11.
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
12.
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
13.
The structure of CaGe2O5 between room temperature and 923 K has been determined by X-ray powder diffraction. A continuous phase transition from triclinic C1¯ to monoclinic C2/c symmetry at Tc=714±3 K is observed. The transition is accompanied by a weak heat capacity anomaly. This anomaly and the strain analysis based on the measured lattice parameters indicate a classical second-order phase transition. The order parameter, as measured by the strain component e23, is associated with the displacement of the Ca cation. Electronic structure optimization by density functional methods is used to verify the centric space group of the low-temperature structure of CaGe2O5. 相似文献
14.
15.
Clive Barnett 《Geoforum》2005,36(1):7-12
Recent work on neoliberalism has sought to reconcile a Marxist understanding of hegemony with poststructuralist ideas of discourse and governmentality derived from Foucault. This paper argues that this convergence cannot resolve the limitations of Marxist theories of contemporary socio-economic change, and nor do they do justice to the degree to which Foucault’s work might be thought of as a supplement to liberal political thought. The turn to Foucault highlights the difficulty that theories of hegemony have in accounting for the suturing together of top-down programmes with the activities of everyday life. However, the prevalent interpretation of governmentality only compounds this problem, by supposing that the implied subject-effects of programmes of rule are either automatically realised, or more or less successfully ‘contested’ and ‘resisted’. Theories of hegemony and of governmentality both assume that subject-formation works through a circular process of recognition and subjection. Both approaches therefore treat ‘the social’ as a residual effect of hegemonic projects and/or governmental rationalities. This means that neither approach can acknowledge the proactive role that long-term rhythms of socio-cultural change can play in reshaping formal practices of politics, policy, and administration. The instrumental use of notions of governmentality to sustain theories of neoliberalism and neoliberalization supports a two-dimensional understanding of political power—which is understood in terms of relations of imposition and resistance—and of geographical space—which is understood in terms of the diffusion and contingent combination of hegemonic projects. Theories of neoliberalism provide a consoling image of how the world works, and in their simplistic reiteration of the idea that liberalism privileges the market and individual self-interest, they provide little assistance in thinking about how best to balance equally compelling imperatives to respect pluralistic difference and enable effective collective action. 相似文献
16.
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
17.
The standard enthalpy of formation of stannite (Cu2FeSnS4) was calculated from the calorimetric measurements of the reactions of its formation from simple synthetic sulfides: Cu2S + FeS2 + SnS → Cu2FeSnS4 and 2CuS + FeS + SnS → Cu2FeSnS4. Using published data for the binary sulfides, the standard enthalpy of formation of stannite from the elements was determined as ΔfH°298.15(Cu2FeSnS4) =–(417.28 ± 2.28) kJ mol–1. 相似文献
18.
Mingda Lv Xi Liu Sean R. Shieh Tianqi Xie Fei Wang Clemens Prescher Vitali B. Prakapenka 《Physics and Chemistry of Minerals》2016,43(4):301-306
Using a diamond-anvil cell and synchrotron X-ray diffraction, the compressional behavior of a synthetic qandilite Mg2.00(1)Ti1.00(1)O4 has been investigated up to about 14.9 GPa at 300 K. The pressure–volume data fitted to the third-order Birch–Murnaghan equation of state yield an isothermal bulk modulus (K T0) of 175(5) GPa, with its first derivative \(K_{T0}^{{\prime }}\) attaining 3.5(7). If \(K_{T0}^{{\prime }}\) is fixed as 4, the K T0 value is 172(1) GPa. This value is substantially larger than the value of the adiabatic bulk modulus (K S0) previously determined by an ultrasonic pulse echo method (152(7) GPa; Liebermann et al. in Geophys J Int 50:553–586, 1977), but in general agreement with the K T0 empirically estimated on the basis of crystal chemical systematics (169 GPa; Hazen and Yang in Am Miner 84:1956–1960, 1999). Compared to the K T0 values of the ulvöspinel (Fe2TiO4; ~148(4) GPa with \(K_{T0}^{{\prime }} = 4\)) and the ringwoodite solid solutions along the Mg2SiO4–Fe2SiO4 join, our finding suggests that the substitution of Mg2+ for Fe2+ on the T sites of the 4–2 spinels can have more significant effect on the K T0 than that on the M sites. 相似文献
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