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1.
Valentina Lacivita Philippe D’Arco Roberto Orlando Roberto Dovesi Alessio Meyer 《Physics and Chemistry of Minerals》2013,40(10):781-788
The static linear optical properties (refractive indices, birefringence and axial angle) of andradite–grossular (Ca3Fe2Si3O12–Ca3Al2Si3O12) solid solutions have been computed at the ab initio quantum-mechanical level through the Coupled Perturbed Kohn–Sham scheme, using an all-electron Gaussian-type basis set. Geometry relaxation after substitution of 1–8 Al for Fe atoms in the primitive cell of andradite yields 23 non-equivalent configurations ranging from cubic to triclinic symmetry. Refractive indices vary quite regularly between the andradite (1.860) and grossular (1.671) end-members; the birefringence δ and the axial angle 2V at intermediate compositions can be as large as 0.02° and 89°, respectively. Comparison with experiments suffers from inhomogeneities and impurities of natural samples; however, semi-quantitative agreement is observed. 相似文献
2.
The heat capacities of synthetic pyrope (Mg3Al2Si2O12), grossular (Ca3Al2Si3O12) and a solid solution pyrope60grossular40 (Mg1.8Ca1.2Al2Si3O12) have been measured by adiabatic calorimetry in the temperature range 10–350 K. The samples were crystallized from glasses in a conventional piston-cylinder apparatus.The molar thermophysical properties at 298.15 K (J mol?1 K?1) are:
Cop | So298?So0 | Ho298?Ho0/T | |
Pyrope | 325.31 | 266.27 | 47852 |
Grossular | 333.17 | 260.12 | 47660 |
Py60Gr40 | 328.32 | 268.32 | 47990 |
6.
S. Quartieri G. Antonioli C. A. Geiger G. Artioli P. P. Lottici 《Physics and Chemistry of Minerals》1999,26(3):251-256
The incorporation and site preference of minor amounts (about 1 wt%) of Yb3+ in synthetic pyrope (Mg3Al2Si3O12) and grossular (Ca3Al2Si3O12) garnet were studied by X-ray Absorption Fine-Structure (XAFS) Spectroscopy. The measurements, performed in the temperature
range 77–343 K at both Yb LI- and LIII-edges, demonstrate that Yb3+ enters the garnet structure and is located in the dodecahedral site in both samples. The coordination environment of Yb3+ in the two samples was compared to that of the X-site cation in end-member synthetic pyrope and grossular and in Yb3Al5O12 as determined by single-crystal X-ray diffraction. The local geometry around Yb3+ is different from that of Mg and Ca in the bulk of the garnet, and also from that of Yb3+ in Yb3Al5O12.
Τhe XAFS results indicate that, (1) structural relaxation occurs around Yb3+ in the garnet structure; (2) the host garnet matrix exerts a major structural control on the incorporation of Yb3+, and (3) minor amounts of Yb3+ in garnet are located in structural sites and not in ill-defined defects.
Received: 15 January 1998/ Revised, accepted: 21 July 1998 相似文献
7.
An in situ, high-temperature, powder diffraction investigation was performed for iron-free clinopyroxenes with compositions Ca0.40Mg1.60Si2O6, Ca0.52Mg1.46Al0.05Si1.98O6, Ca0.59Mg1.41Si2O6 and Ca0.70Mg1.30Si2O6, up to 850 °C using synchrotron radiation (ESRF, Grenoble). In samples with compositions Ca0.52Mg1.46Al0.05Si1.98O6 and Ca0.59Mg1.41Si2O6, evidence of for the P21/c-C2/c displacive phase transition was seen in changes in lattice parameters at T 550 and 300 °C respectively. Landau modelling of the phase transition behaviour for the sample with composition Ca0.52Mg1.46Al0.05Si1.98O6 shows a tricritical behaviour [T
c
=547(16)]. Comparison with the transition behaviour in other samples with lower Ca contents along the join diopside–enstatite indicates that a decrease in T
c
, and a switch from first-order to tricritical behavior occurs with increasing Ca content. The change in the transition behaviour was related to an interaction with the antiphase domains at the nanoscale. 相似文献
8.
I. Gavrieli Alan Matthews J. B. Holland 《Contributions to Mineralogy and Petrology》1996,125(2-3):251-262
The hydrothermal reaction between grossular and 1 molar manganese chloride solution was studied at 2 kbar and 600 °C at various
bulk Ca/(Ca+Mn) compositions:
Ca3Al2Si3O12+3Mn2+(aq) ⇔ Mn3Al2Si3O12+3Ca2+(aq)
The reaction products are garnets of the spessartine-grossular solid-solution series which discontinuously armour the dissolving
grossular grains. The first garnet to crystallize is spessartine rich (X
gt
Mn≥0.95), reflecting the high Mn content of the solution, but as the reaction proceeds more calcium-rich garnets progressively
overgrow the initial products. The armouring product layer is detached from the dissolving grossular, which allows the progressive
overgrowth to occur on both its external and internal surfaces and results in the development of a two directional Ca/(Ca+Mn)
zoning pattern in the product grains. The compositional changes in the run products are consistent with attainment of heterogeneous
equilibrium between the external rims of the spessartine-grossular garnets and the bulk solutions in runs of duration ≥24
hours. Plots of ln KD versus X
gt
Ca maxima show linear variations that are not consistent with the ideal mixing that has been proposed for spessartine-grossular
garnets at temperatures of 900 to 1200 °C. The data rather fit a regular solution model with the parameters ΔG° (600 °C, 2 kbar)=−8.0±0.8 kJ/mol and w
gt
CaMn=2.6±2.0 kJ/mol. Existing solubility measurements and thermodynamic data from other Ca and Mn silicates support the calculated
data. Grossular activities calculated using the w
gt
CaMn parameter indicate that even in manganese-rich metapelites pressure estimates calculated using the garnet-plagioclase-Al2SiO5-quartz barometer will not be increased by more than 0.2 kbar.
Received: 18 January 1995/Accepted: 4 June 1996 相似文献
9.
I. E. Paukov N. K. Moroz Yu. A. Kovalevskaya I. A. Belitsky 《Physics and Chemistry of Minerals》2002,29(4):300-306
The heat capacity of paranatrolite and tetranatrolite with a disordered distribution of Al and Si atoms has been measured
in the temperature range of 6–309 K using the adiabatic calorimetry technique. The composition of the samples is represented
with the formula (Na1.90K0.22Ca0.06)[Al2.24Si2.76O10]·nH2O, where n=3.10 for paranatrolite and n=2.31 for tetranatrolite. For both zeolites, thermodynamic functions (vibrational entropy, enthalpy, and free energy function)
have been calculated. At T=298.15 K, the values of the heat capacity and entropy are 425.1 ± 0.8 and 419.1 ±0.8 J K−1 mol−1 for paranatrolite and 381.0 ± 0.7 and 383.2 ± 0.7 J K−1 mol−1 for tetranatrolite.
Thermodynamic functions for tetranatrolite and paranatrolite with compositions corrected for the amount of extraframework
cations and water molecules have also been calculated. The calculation for tetranatrolite with two water molecules and two
extraframework cations per formula yields: C
p
(298.15)=359.1 J K−1 mol−1, S(298.15) −S(0)=362.8 J K−1 mol−1. Comparing these values with the literature data for the (Al,Si)-ordered natrolite, we can conclude that the order in tetrahedral
atoms does not affect the heat capacity. The analysis of derivatives dC/dT for natrolite, paranatrolite, and tetranatrolite has indicated that the water- cations subsystem within the highly hydrated
zeolite may become unstable at temperatures above 200 K.
Received: 30 July 2001 / Accepted: 15 November 2001 相似文献
10.
The enthalpies of mixing of synthetic grossular (Ca3Al2Si3O12)-uvarovite (Ca3Cr2Si3O12) solid solutions have been determined by oxide melt calorimetry at 970 K. The results indicate that the solid solution exhibits a very small negative deviation from Raoult's law. In terms of the regular solution model a chromium-aluminum interaction parameter of between 0 and ?1000 cal/gm atom is consistent with the data. 相似文献
11.
S. Quartieri J. Chaboy G. Antonioli C. A. Geiger 《Physics and Chemistry of Minerals》1999,27(2):88-94
We present an X-ray absorption near-edge structure study performed at the Yb LI- and LIII-edges on synthetic pyrope (Mg3Al2Si3O12) and grossular (Ca3Al2Si3O12) garnets containing about 1% wt of Yb. For the first time Yb L-edge XANES spectra are analyzed by full multiple scattering
theory using clusters of different sizes and different final-state potentials. A comparison between experimental spectra and
model calculations indicates that Yb3+ enters the dodecahedral X-site in both pyrope and grossular, in agreement with the results of an EXAFS study. Based on the
present results, the charge balancing substitution mechanism required by the replacement of divalent Mg and Ca cations with
trivalent Yb3+ is discussed in terms of vacancies in dodecahedral sites surrounding the central Yb3+ absorber.
Received: 7 December 1998 / Revised, accepted: 7 May 1999 相似文献
12.
Wendy J. Harrison 《Geochimica et cosmochimica acta》1981,45(9):1529-1544
Partition coefficients for the rare earth elements (REE) Ce, Sm and Tm between coexisting garnets and hydrous liquids have been determined at high pressure and temperatures (30 kbar and 1300 and 1500°C). Two synthetic systems were studied, Mg3Al2Si3O12-H2O and Ca3Al2Si3O12-H2O, in addition to a natural pyrope-bearing system.Deviations from Henry's Law behaviour occur at geologically relevant REE concentrations. At concentrations < 3 ppm Ce, < 12 ppm Sm, < 80 ppm Tm in pyrope and < 100 ppm Ce, < 250 ppm Sm, < 1000 ppm Tm in grossular (at 30 kbar and 1300°C), Dgarnet liquidREE increases as the REE concentration in the garnet decreases. At higher concentrations, DREE is constant. Dgrossular liquidREE also constant when the garnet contains less than about 2 ppm Sm or Tm. The REE concentration at which DREE becomes constant increases with increasing temperature, decreasing REE ionic radius and increasing Ca content of the garnet.Partitioning behaviour of Ce, Sm and Tm between a natural pyrope-rich garnet and hydrous liquid is analogous to that in the synthetic systems and substantiates the substitution model proposed by Harrison and Wood (1980).Values of DREEgarnet/liquid for which Henry's Law is obeyed are systematically higher for grossular than for pyrope (Dpyrope/liquid = 0.067(Ce), 0.108(Sm), 0.155(Tm) and Dgrossular/Liquid = 0.65(Ce), 0.75(Sm), 4.55(Tm).The implications of non-Henry's Law partitioning of REE for models of basalt petrogenesis involving garnet are far-ranging. Deviations from Henry's Law permit refinements to be made to calculated REE abundances once basic model parameters have been defined. 相似文献
13.
K.-D. Grevel A. Navrotsky W. A. Kahl D. W. Fasshauer J. Majzlan 《Physics and Chemistry of Minerals》2001,28(7):475-487
Calorimetric and P–V–T data for the high-pressure phase Mg5Al5Si6O21(OH)7 (Mg-sursassite) have been obtained. The enthalpy of drop solution of three different samples was measured by high-temperature
oxide melt calorimetry in two laboratories (UC Davis, California, and Ruhr University Bochum, Germany) using lead borate (2PbO·B2O3) at T=700 ∘C as solvent. The resulting values were used to calculate the enthalpy of formation from different thermodynamic datasets;
they range from −221.1 to −259.4 kJ mol−1 (formation from the oxides) respectively −13892.2 to −13927.9 kJ mol−1 (formation from the elements). The heat capacity of Mg5Al5Si6O21(OH)7 has been measured from T=50 ∘C to T=500 ∘C by differential scanning calorimetry in step-scanning mode. A Berman and Brown (1985)-type four-term equation represents
the heat capacity over the entire temperature range to within the experimental uncertainty: C
P
(Mg-sursassite) =(1571.104 −10560.89×T
−0.5−26217890.0 ×T
−2+1798861000.0×T
−3) J K−1 mol−1 (T in K). The P
V
T behaviour of Mg-sursassite has been determined under high pressures and high temperatures up to 8 GPa and 800 ∘C using a MAX 80 cubic anvil high-pressure apparatus. The samples were mixed with Vaseline to ensure hydrostatic pressure-transmitting
conditions, NaCl served as an internal standard for pressure calibration. By fitting a Birch-Murnaghan EOS to the data, the
bulk modulus was determined as 116.0±1.3 GPa, (K
′=4), V
T,0
=446.49 3 exp[∫(0.33±0.05) × 10−4 + (0.65±0.85)×10−8
T dT], (K
T/T)
P
= −0.011± 0.004 GPa K−1. The thermodynamic data obtained for Mg-sursassite are consistent with phase equilibrium data reported recently (Fockenberg
1998); the best agreement was obtained with Δf
H
0
298 (Mg-sursassite) = −13901.33 kJ mol−1, and S
0
298 (Mg-sursassite) = 614.61 J K−1 mol−1.
Received: 21 September 2000 / Accepted: 26 February 2001 相似文献
14.
Gianluca Iezzi Mario Tribaudino Giancarlo Della Ventura Fabrizio Nestola Fabio Bellatreccia 《Physics and Chemistry of Minerals》2005,32(7):515-523
The synthetic amphibole Na0.95(Li0.95Mg1.05)Mg5Si8O22(OH)2 was studied in situ at high-T, using IR OH-stretching spectroscopy and synchrotron X-ray powder diffraction. At room-T the sample has P21
/m symmetry, as shown by the FTIR spectrum. It shows in the OH region two well-defined and intense absorptions at 3,748 and
3,712 cm−1, respectively, and two minor bands at 3,667 and 3,687 cm−1. The main bands are assigned to the two independent O–H groups in the primitive structure. The two minor bands evidencing
the presence of small amount of vacant A-site (A□0.05). With increasing T, these bands shift continuously and merge into a unique absorption at high temperature. A change as a function of increasing
T is revealed by the evolution of the refined unit-cell parameters, whose trend shows a transition to C2/m at about 320–330°C. The spontaneous scalar strain, fitted with a tricritical 2–6 Landau potential, gives a T
c of 325(10)°C (β parameter = 0.27). Comparison with the second-order P21
/m ⇔ C2/m phase transition at 255°C for synthetic amphibole ANa0.8B(Na0.8Mg1.2)CMg5Si8O22(OH)2 indicates that the substitution of Na with Li at the B-sites strongly affects the thermodynamic character and the T
c of the phase transition. The comparison of LNMSH amphiboles with cummingtonitic ones shows that the high-T thermodynamic behaviour is affected by A-site occupancy. 相似文献
15.
Klaus Schollenbruch Alan B. Woodland Daniel J. Frost 《Physics and Chemistry of Minerals》2010,37(3):137-143
The stability of hercynite (FeAl2O4) has been investigated experimentally between 7 and 24 GPa and 900 and 1,700°C. Hercynite breaks down to its constituent
oxides at 7–8.5 GPa and temperatures >1,000°C. The incorporation of a small magnetite component in the hercynite necessitated
a small correction to fix the location of the endmember reaction: FeAl2O4 = Al2O3 + FeO in P–T space. After making this correction, the position of the phase boundary was used to evaluate thermodynamic data for hercynite.
Our results support a relatively large S
298° for hercynite, on the order of 115 J mol−1 K−1. Experiments up to 24 GPa and 1,400°C failed to detect any high-pressure polymorph of FeAl2O4; only corundum + wüstite were detected. This behaviour contrasts with that observed for the analogous MgAl2O4 system where the constituent oxides recombine at high pressure to produce “post-spinel” phases with CaFe2O4-type and CaTi2O4-type structures. 相似文献
16.
The partitioning of samarium and thulium between garnets and melts in the systems Mg3Al2-Si3O12-H2O and Ca3Al2Si3O12-H2O has been studied as a function of REE concentration in the garnets at 30 kbar pressure. Synthesis experiments of variable time under constant P, T conditions indicate that garnet initially crystallizes rapidly to produce apparent values of D
Sm (D
Sm=concentration of Sm in garnet/concentration of Sm in liquid) which are too large in the case of pyrope and too small in the case of grossular. As the experiment proceeds, Sm diffuses out of or into the garnet and the equilibrium value of D
Sm is approached. Approximate values of diffusion coefficients for Sm in pyrope garnet obtained by this method are 6 × 10–13 cm2 s–1 at 1,300 ° C and 2 × 10–12 cm2 s–1 at 1,500 ° C, and for grossular, 8.3 × 10–12 cm2 s–1 at 1,200 ° C and 4.6 × 10–11 cm2 s–1 at 1,300 ° C. The equilibrium values of D
Sm have been reversed by experiments with Sm-free pyrope and Sm-bearing glass, and with Sm-bearing grossular and Sm-free glass.Between 12 ppm and 1,000 ppm Sm in pyrope at 1,300 ° C and between 80 ppm and >2 wt.% Tm in pyrope at 1,500 ° C, partition coefficients are constant and independent of REE concentration. Above 100 ppm of Sm in garnet at 1,500 ° C, partition coefficients are independent of Sm concentration. At lower concentrations, however, D
Sm is dependent upon the Sm content of the garnet. The two regions may be interpreted in terms of charge-balanced substitution of Sm3Al5O12 in the garnet at high Sm concentrations and defect equilibria involving cation vacancies at low concentrations. At very low REE concentrations (< 1 ppm Tm in grossular at 1,300 ° C) DREE garnet/liquid again becomes constant with an apparent Henry's Law value greater than that at high concentrations. This may be interpreted in terms of a large abundance of cation vacancies relative to the number of REE ions.The importance of defects in the low concentration region has been confirmed by adding other REE (at 80 ppm level) to the system Mg3Al2Si3O12-H2O at low Sm concentrations. These change D
Sm in the defect region, demonstrating their role in the production of vacancies.Experiments on a natural pyropic garnet indicate that defect equilibria are of importance to REE partitioning within the concentration ranges found in nature. 相似文献
17.
In order to clarify Al2O3 content and phase stability of aluminous CaSiO3-perovskite, high-pressure and high-temperature transformations of Ca3Al2Si3O12 garnet (grossular) were studied using a MA8-type high-pressure apparatus combined with synchrotron radiation. Recovered samples
were examined by analytical transmission electron microscopy. At pressures of 23–25 GPa and temperatures of 1000–1600 K, grossular
garnet decomposed into a mixture of aluminum-bearing Ca-perovskite and corundum, although a metastable perovskite with grossular
composition was formed when the heating duration was not long enough at 1000 K. On release of pressure, this aluminum-bearing
CaSiO3-perovskite transformed to the “LiNbO3-type phase” and/or amorphous phase depending on its Al2O3 content. The structure of this LiNbO3-type phase is very similar to that of LiNbO3 but is not identical. CaSiO3-perovskite with 8 to 25 mol% Al2O3 was quenched to alternating lamellae of amorphous layer and LiNbO3-type phase. On the other hand, a quenched product from CaSiO3-perovskite with less than 6 mol% consisted only of amorphous phase. Most of the inconsistencies amongst previous studies
could be explained by the formation of perovskite with grossular composition, amorphous phase, and the LiNbO3-type phase.
Received: 11 April 2001 / Accepted: 5 July 2002 相似文献
18.
The mixing properties of Fe3Al2Si3O12-Ca3Al2Si3O12 garnet solid solutions have been studied in the temperature range 850–1100° C. The experimental method involves measuring the composition of garnet in equilibrium with an assemblage in which the activity of the Ca3Al2Si3O12 component is fixed. Experiments on the assemblage garnet solid solution, anorthite, Al2SiO5 polymorph and quartz at known pressure and temperature fix the activity of the Ca3Al2Si3O12 component through the equilibrium: 1 $$\begin{gathered} {\text{3CaAl}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{8}} \rightleftarrows {\text{Ca}}_{\text{3}} {\text{Al}}_{\text{2}} {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} \hfill \\ {\text{Anorthite garnet}} \hfill \\ {\text{ + 2Al}}_{\text{2}} {\text{SiO}}_{\text{5}} {\text{ + SiO}}_{\text{2}} \hfill \\ {\text{ sillimanite/kyanite quartz}}{\text{.}} \hfill \\ \end{gathered}$$ This equilibrium, with either sillimanite or kyanite as the aluminosilicate mineral, was used to control \({\text{a}}_{{\text{Ca}}_{\text{3}} {\text{Al}}_{\text{2}} {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} }^{{\text{gt}}} \) . The compositions of the garnet solutions produced were determined by measurement of their unit cell edges. At 1 bar Fe3Al2Si3O12-Ca3Al2Si3O12 garnets exhibit negative deviations from ideality at the Fe-rich end of the series and positive deviations at the calcium end. With increasing pressure the activity coefficients for the Ca3Al2Si3O12 component increase because the partial molar volume of this component is greater than the molar volume of pure grossular. Previous studies indicate that the activity coefficients for the Ca3Al2Si3O12 component also increase with increasing (Mg/Mg+Fe) ratio of the garnet. The region of negative deviation from ideality implies a tendency towards formation of a stable Fe-Ca garnet component. Evidence in support of this conclusion has been found in a natural Fe-rich garnet which was found to contain two different garnet phases of distinctly different compositions. 相似文献
19.
Based on the theory of thermal conductivity, in this paper we derived a formula to estimate the prolongation period (AtL) of cooling-crystallization process of a granitic melt caused by latent heat of crystallization as follows:△tL=QL×△tcol/(TM-TC)×CP where TM is initial temperature of the granite melt, Tc crystallization temperature of the granite melt, Cp specific heat, △tcol cooling period of a granite melt from its initial temperature (TM) to its crystallization temperature (Tc), QL latent heat of the granite melt.
The cooling period of the melt for the Fanshan granodiorite from its initial temperature (900℃) to crystallization temperature (600℃) could be estimated -210,000 years if latent heat was not considered. Calculation for the Fanshan melt using the above formula yields a AtL value of -190,000 years, which implies that the actual cooling period within the temperature range of 900°-600℃ should be 400,000 years. This demonstrates that the latent heat produced from crystallization of the granitic melt is a key factor influencing the cooling-crystallization process of a granitic melt, prolongating the period of crystallization and resulting in the large emplacement-crystallization time difference (ECTD) in granite batholith. 相似文献
The cooling period of the melt for the Fanshan granodiorite from its initial temperature (900℃) to crystallization temperature (600℃) could be estimated -210,000 years if latent heat was not considered. Calculation for the Fanshan melt using the above formula yields a AtL value of -190,000 years, which implies that the actual cooling period within the temperature range of 900°-600℃ should be 400,000 years. This demonstrates that the latent heat produced from crystallization of the granitic melt is a key factor influencing the cooling-crystallization process of a granitic melt, prolongating the period of crystallization and resulting in the large emplacement-crystallization time difference (ECTD) in granite batholith. 相似文献
20.
Uvarovite (Ca3Cr2Si3O12) forms a complete solid solution series with grossularite (Ca3Al2Si3O12) below 855 ± 5 ° C at a total pressure of 1 atm. Pure uvarovite decomposes to pwo (CaSiO3) + esk (Cr2O3) at 1385 ± 10 ° C. The incorporation of about 5 wt-% of Ca3Al2 Si3O12 component in the uvarovite structure raises the thermal stability of the garnetss to 1410 ± 5 ° C, and uvarovite95 grossularite05 melts incongruently to pwo (CaSiO3) + coreskss ((Al, Cr)2O3) + L. Pure grossularite decomposes to wo (CaSi03) + geh (Ca2Al2SiO7) + and (CaAl2Si2O8) at 855 ± 5 ° C, grossularite thermal stability is increased by incorporation of Ca3Cr2Si3O12 component by 530 ° C. At 1280±5 ° C coreskss + L react to garss + geh + an defining an invariant tequilibrium of the CaO-Cr2O3-Al2O3-SiO2 quaternary system. Liquid reacts to garss + pwo + geh + an at 1263 ±5 ° C terminating univariant and divariant liquid relations occurring along the join Ca3Cr2Si3O12-Ca3Al2Si3O12. The unit-cell parameter for uvarovite is 11.996(2) Å, the refractive index 1.865(3). The substitution of Cr by Al decreases a and n almost linearly toward the grossularite end member which displays a unit-cell parameter of 11.848(2) Å and a refractive index of 1.732 (1). 相似文献