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1.
The effect of silica concentration on the solubility of Al and Ti in diopsidic pyroxenes has been investigated at one atmosphere in the system diopside-CaTiAl2O6-SiO2 at temperatures between 1150–1420° C. The composition of pyroxene in the system diopside-CaTiAl2O6-SiO2 is influenced by the total SiO2 content. Near the join diopside-CaTiAl2O6, the pyroxene forms a solid solution with the CaTiAl2O6 molecule, and co-exists with perovskite for compositions greater than 11 weight percent CaTiAl2O6. Anorthite is an accompanying phase. With increasing total SiO2 content a series of mineralogical changes involving Ti-bearing phases occur. Sphene solid solution co-exists with diopside solid solution, anorthite, and perovskite in a small compositional range near the diopside-CaTiAl2O6 join. Additional total SiO2 results in the elimination of perovskite and a decrease of solid solution in the pyroxenes. With further increase in SiO2 content, tridymite appears and the pyroxene is approximately pure diopside. Rutile joins diopside, anorthite, sphene solid solution and tridymite over a broad compositional range in the Ti, Si-rich part of the system. These results demonstrate that increased silica concentration decreases the solubility of Al and Ti in diopsidic pyroxenes and controls the stability of co-existing Ti-bearing phases.  相似文献   

2.
The behaviour of tetrahedrally coordinated and octahedrally coordinated Cr3+ ions in diopside is discussed from the study on the join CaMg-Si2O6-CaCrCrSiO6. The molecule CaCrCrSiO6 decomposes into uvarovite+eskolaite and its maximum solubility in diopside is 6.7 wt percent at 940 ° C. Crystalline phases are diopside ss (ss is abbreviation of solid solution), uvarovite ss, wollastonite ss, spinel and eskolaite. The diopside ss is blue in colour. Its optical spectra were measured in the wavelenght range of 325–2600 nm, and assigned after tetrahedral configuration Td and octahedral configuration Oh. It is estimated that octahedral Cr3+ ions are in high spin state, while tetrahedral Cr3+ ions may be probably in low spin state. The t and B are 10,300–10,370 cm–1 and 429–432 cm–1. The CFSE for tetrahedral low spin Cr3+ ions is nearly the same as that for octahedral high spin Cr3+ ions. The ionic radii of tetrahedral low spin Cr3+ ions calculated are 0.47–0.53 Å, shrinked from the radius of octahedral high spin Cr3+ ion (0.615 Å) as much as 14–24 percent. Petrologic implications of the result are also discussed.The first half of the D. Sc. dissertation of K. Ikeda presented to Hokkaido University in June, 1976  相似文献   

3.
The structure of glasses and melts of Na2O· 0.5Fe2O3·3SiO2 and Na2O·FeO·3SiO2 compositions have been measured using high temperature Raman spectroscopy. For the oxidized sample it has been demonstrated that there is a close structural relationship between melt and glass. No coordination changes of Fe3+ with temperature and no new anionic species have been observed in the oxidized melt. The Raman spectra of the reduced sample clearly show a decrease in the degree of polymerization, as determined by the observation of the polarization character of the spectra and the details of the change of the Raman intensities during heating in hydrogen. Mössbauer spectra suggest that Fe3+ is tetrahedrally coordinated in the oxidized glass and part of the Fe2+ is tetrahedrally coordinated in the reduced glass.  相似文献   

4.
The surface tension between silicate melts and air has been measured for melt compositions lying on the diopside-anorthite (Di-An) join from 1300° C to 1580° C. It ranges from 300 dyne/cm to 400 dyne/cm, and decreases with increasing temperature, except for a pure diopside composition. At relatively high temperatures, the surface tension decreases as the anorthite content increases, whereas at lower temperature it is almost constant. These results suggest that diopside melt has a more discrete structure at higher temperatures, whereas, anorthite-bearing melts do not dissociate in the temperature range studied. They also suggest that the structure of both the surface and interior parts of the melt are almost identical at lower temperatures, but at higher temperatures, the surface part has a more polymerized structure with Al2O3 enrichment. The surface energy, obtained from the relationship between surface tension and temperature, increases from 294 erg/cm2 (Di composition) to 1013 erg/cm2 (Di40An60) with increasing anorthite content.  相似文献   

5.
Experiments using V2O5 as a high-temperature solvent have produced compositional reversals defining the miscibility gap between enstatite and diopside on the join Mg2Si2O6-CaMgSi2O6 between 925° and 1,175° C at atmospheric pressure. These experiments locate an equilibrium near 1,000° C among diopside, protoenstatite, and orthoenstatite; they verify the stable coexistence of diopside and protoenstatite above 1,000° C and disprove the hypothesis that orthoenstatite has a stability field which is continuous from temperatures below 1,000° C to the solidus. The phase relations suggest that the orthorhombic low-Ca pyroxene on the solidus in this system (formerly identified as orthoenstatite) is a phase distinct from the orthoenstatite stable with diopside at low subsolidus temperatures. Data locating the orthoenstatite-diopside miscibility gap validate the use at low pressures of symmetric orthopyroxene and asymmetric clinopyroxene solution models in this system.  相似文献   

6.
Three new crystalline phases differing in Si/Al ratio have been synthesized from compositions along the join NiAl2O4-Ni2SiO4. Four reversible univariant equilibria involving these new phases plus Ni2SiO4 (olivine) have been located within the P-T region studied (1 atm–40 kb, 1000–1700° C); an invariant point occurs near 22 kb, 1150°C.All three new phases are orthorhombic. Precession photographs and electron microprobe analyses yield the following information:Phase I: 5NiO·3Al2O3·SiO2 = 3NiAl2O4·Ni2SiO4, Pmma, a=5.67, b=11.51, c=8.10 (Å)Phase II: 7NiO·3Al2O3·2SiO2 = 3NiAl2O4· 2Ni2SiO4, Imma, a=5.66, b=17.32, c=8.11Phase III: 3NiO· Al2O3· SiO2 = NiAl2O4·Ni2SiO4, Imma, a=5.68, b=11.49, c=8.12Comparison with known structures suggests that these three phases plus NiAl2O4 spinel and high pressure Ni2SiO4 spinel belong to a homologous series based on a cubic close oxygen packing of the formula: M2n O n}-1 (T n O3n+1) where M and T are octahedrally and tetrahedrally coordinated cations, respectively. When n=1 the formula for spinel is obtained; n = 2 for phase I and phase III, both similar to the beta-phase of orthosilicates; and n = 3 for phase II which is related to the manganostibite structure.Similar phase equilibria and structural relations may occur on other joins of the aluminateorthosilicate type. Furthermore, the occurrence of such structural modifications between the spinel (aluminate) and olivine (orthosilicate) compositions suggests that there could be a corresponding polymorphic series between the olivine and spinel forms of orthosilicates.  相似文献   

7.
In the system CaSiO3-CaMnSi2O6-CaFeSi2O6 extensive miscibility gaps between pyroxenoids and clinopyroxenes are observed. The miscibility gap between Mn-bustamite and Mn-wollastonite has been determined experimentally by a hydrothermal technique between 400° and 1200° C at P f= 2 kbar. Further experiments have been performed at P f=9 kbar, which revealed a shifting of the miscibility gap towards more Ca-rich compositions. The bustamite phase is stabilized by high pressures and the wollastonite structure is the stable phase at high temperatures.Similar phase relations as along the join CaSiO3-CaMnSi2O6 exist along the join CaSiO3-CaFeSi2O6 but with a more extensive two-phase field of bustamite-clinopyroxene.Possible phase relations along the joins CaSiO3-CaMnSi2O6, CaSiO3-CaFeSi2O6 and CaFeSi2O6-CaMnSi2O6 are given in temperature-composition diagrams for low pressures, based on natural and experimental data.  相似文献   

8.
The join diopside (CaMgSi2O6) — ureyite (NaCrSi2O6) was studied at pressures of 1 atm, 1 kb, 5 kb, and 20 kb using gel mixtures as starting materials. All runs except those at 1 atm were made under hydrous conditions. The data show that the solubility of ureyite in diopside decreases with increasing pressure. At 20 kb the maximum ureyite content of diopside is 13 weight percent (4.6% Cr2O3) as compared to 24 weight percent at 1 atm. It is predicted that pyroxenes that have equilibrated at depths >140 km will not contain a ureyite component; rather Cr will enter diopside in the form of a CaCr(CrSi)O6 component. Pyroxenes containing this component were found as metastable phases at 20 kb.  相似文献   

9.
A series of alumina-free micas was synthesized hydrothermally in the potassium-poor portion of the system K2O-MgO-SiO2-H2O. One end member of this series has the composition KMg2.5[Si4O10](OH)2, which, because of its octahedral occupancy, is intermediate between the dioctahedral and trioctahedral micas.From this end member a series of mica solid solutions extends towards more Mg-rich compositions. Single phase micas were obtained along the substitution line 2Mg for Si which appears to involve incorporation of part of the Mg in tetrahedral sites. It leads to a theoretical end member with a structural formula KMg3[Si3.5Mg0.5O10](OH)2. Solid solutions containing up to 75 mole % of this theoretical end member could be synthesized. The observed densities, water contents, and a one-dimensional Fourier synthesis are consistent with the assumed substitution.At 1 kb fluid pressure and 620° C the Si-rich end member KMg2.5[Si4O10](OH)2 decomposes to a more Mg-rich mica, the roedderite phase K2Mg5Si12O30, liquid, and H2O-rich vapor. With increasing Mg-content the thermal stability of the mica solid solutions increases up to 860°C at a composition of about K2O·6.2MgO·7.4SiO2·2H2O, i.e. KMg2.8[Si3.7Mg0.3O10](OH)2. This mica disintegrates directly into forsterite + liquid + H2O-rich vapor. The mica phase richest in Mg with a composition of about K2O·6.5MgO·7.25SiO2·2H2O, i.e. KMg2.875 [Si3.625Mg0.375O10](OH)2, breaks down at 765° C into forsterite, a more Si-rich mica, liquid, and H2O-rich vapor.This binary series of alumina-free micas forms a complete series of ternary solid solutions with normal phlogopite, KMg3[Si3AlO10](OH)2. Analyses of some natural phlogopites showing Si in excess of 3.0 (up to 3.18) per formula unit can be explained through this ternary miscibility range.  相似文献   

10.
The effect of Cr on the silicate system has been studied in air at 1 atm by adding a small amount of MgCr2O4 (0.2–0.5 wt.%) to the join Mg2SiO4 (forsterite) — CaAl2Si2O8 (anorthite) — CaMgSi2O6 (diopside), which has been considered to form a thermal divide in the system CaO-MgO-Al2O3-SiO2. The spinel primary field is enlarged compared with that in the Cr-free join at the expense of the anorthite primary field. The piercing points forsterite+anorthite+diopside+liquid and forsterite+anorthite+spinel+liquid approach each other with increasing MgCr2O4, meet at the join with 0.25 wt.% MgCr2O4 (0.20 wt.% Cr2O3) to form the ‘isobaric quaternary invariant point’ forsterite+anorthite+diopside+spinel+liquid, and then separate again as new ‘piercing points’ of diopside+spinel+anorthite+liquid and forsterite+diopside+ spinel+liquid. This process indicates that the join Mg2SiO4-CaAl2Si2O8-CaMgSi2O6 containing more than 0.2 wt.% Cr2O3 cannot be a thermal divide in the basalt tetrahedron. The results of the present study show that the presence of a minor amount of Cr causes a significant effect on the phase relations and therefore, the role of Cr must be taken into account in the formulation of a petrologic model.  相似文献   

11.
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12.
Synthetic diopsides in the join CaMgSi2O6 CaCrAlSiO6 have been studied by means of crystal-field theory. These diopsides are either blue or pale green in colour. The former forms at lower temperatures and the latter at higher temperatures. The optical spectra and colours can be unequivocally explained based on the assumption that Cr3+ions occupy both tetrahedral and octahedral sites in the diopsides. In the blue diopsides Cr3+ions are present in two kinds of spin state, i.e., tetrahedrally coordinated low spin and octahedrally coordinated high spin. On heating the blue diopsides, tetrahedral occupancy of chromium decreases sharply due to spin transformation from tetrahedral low spin to octahedral high spin. Above 1,160° C nearly all chromium ions are present in octahedral sites with high spin state and the diopsides become pale green in colour. Some petrogenetic applications of the resultes are discussed.  相似文献   

13.
In the system CaO-MgO-Al2O3-SiO2, the tetrahedron CaMgSi2O6(di)-Mg2SiO4(fo)-SiO2-CaAl2 SiO6(CaTs) forms a simplified basalt tetrahedron, and within this tetrahedron, the plane di-fo-CaAl2Si2O8(an) separates simplified tholeiitic from alkalic basalts. Liquidus phase relations on this join have been studied at 1 atm and at 7, 10, 15, and 20 kbar. The temperature maximum on the 1 atm isobaric quaternary univariant line along which forsterite, diopside, anorthite, and liquid are in equilibrium lies to the SiO2-rich side of the join di-fo-an. The isobaric quaternary invariant point at which forsterite, diopside, anorthite, spinel, and liquid are in equilibrium passes, with increasing pressure, from the silica-poor to the silica-rich side of the join di-fo-an, which causes the piercing points on this join to change from forsterite+diopside+anorthite+liquid and forsterite +spinel+anorthite+liquid below 5 kbar to forsterite +diopside+spinel+liquid and diopside +spinel+anorthite+liquid above 5 kbar. As pressure increases, the forsterite and anorthite fields contract and the diopside and corundum fields expand. The anorthite primary phase field disappears entirely from the join di-fo-an between 15 and 20 kbar. Below about 4 kbar, the join di-fo-an represents, in simplified form, a thermal divide between alkalic and tholeiitic basalts. From about 4 to at least 12 kbar, alkalic basalts can produce tholeiitic basalts by fractional crystallization, and at pressures above about 12 kbar, it is possible for alkalic basalt to be produced from oceanite by crystallization of both olivine and orthopyroxene. If alkalic basalts are primary melts from a lherzolite mantle, they must be produced at high pressures, probably greater than about 12 kbar.Department of Geosciences, University of Texas at Dallas Contribution No. 327. Hawaii Institute of Geophysics Contribution No. 814.  相似文献   

14.
Mixtures of synthetic crystalline enstatite and diopside were reacted with small water contents in sealed capsules in piston-cylinder apparatus at 30 kb between 1000° C and 1700° C. The compositions of coexisting enstatite and diopside solid solutions were measured with an ARL-EMX electron microprobe between 1000° C and 1500° C. Between 1100° C and 1500° C the pyroxenes coexisted with H2O-undersaturated liquid which quenched to inhomogeneous pyroxene crystals. The presence of liquid facilitated growth of pyroxene crystals suitable for microprobe determinations. The solvus of Davis and Boyd (1966) is generally used in geothermometry; our enstatite solvus limb is a few mol-% richer in Mg2Si2O6 in the temperature range 1000–1400° C; our diopside solvus limb is a few mol-% richer in Mg2Si2O6 below 1100°C, in close agreement between 1100° C and 1200° C, but richer in CaMgSi2O6 between 1200° C and 1500° C. Estimated equilibration temperatures for a diopside with composition 78.7% Di is 1300° C according to our results compared with 1210° C for the Davis and Boyd solvus.  相似文献   

15.
Summary In order to define the limits of expansion of the M2 polyhedron in theC2/c clinopyroxenes of formulaX M2MgM1 [Si2O6] as the mean ionic radius in the M2 site increases, the join CaMgSi2O6–SrMgSi2O6 (Di–SrPx) has been investigated atP=1 atm and between 1090°C and 1350°C. The extent of the clinopyroxene solid solutions is limited to the compositional range Di100–Di70SrPx30. Within this range the unit-cell parameters of the clinopyroxenes show a linear variation with the increase of Sr content. The comparison of the variations caused in the unit-cell dimensions by the increase of the mean ionic radius in the M2 site (Di–SrPx series) with those caused by the decrease of the mean ionic radius in M2 (Di–En series) displays a different trend ofb in the two series. This different trend ofb suggests a different mechanism of the structure deformation in the two solid solution series. The narrow extent of the Di–SrPx solid solutions atT=1200°C shows that the increase of the mean ionic radius in the M2 site is restricted to the range 1.12–1.16 Å.
La substitution Ca–Sr dans les clinopyroxènes le long du joint CaMgSi2O6–SrMgSi2O6
Résumé Le joint CaMgSi2O6–SrMgSi2O6 (Di–SrPx) a été étudié entre 1090°C et 1350°C à 1 atm dans le but d'établir quelles sont les limites de l'expansibilité du polyhèdre M2 dans les clinopyroxènesX M2MgM1 [Si2O6] (group spatialC2/c) avec l'augmentation du rayon jonique moyen dans le site M2. La solution solide est limitée à l'intervalle de composition Di100–Di70 SrPx30. Dans ce domaine les paramètres de la maille varient d'une façon linéaire avec la teneur croissante de Sr. Si on compare les variations de la maille, déterminées par le rayon jonique moyen croissant dans le site M2 (série Di–SrPx), avec celles causées par la diminution du rayon jonique moyen dans le site M2 (série Di–En), on observe une tendance différente du paramètreb dans les deux séries. Ceci indique un mécanisme différent de la déformation structuralle dans les deux séries de solutions solides. Puisque àT=1200°C le domaine des solutions solides Di–SrPx est étroit, l'augmentation du rayon ionique moyen dans le site M2 est bornée à l'intervalle 1.12–1.16 Å.

With 5 Figures  相似文献   

16.
The pressure-temperature curve for the equilibrium anorthite+2enstatite=pyrope+diopside+quartz has been determined in the system CaO-MgO-Al2O2-SiO2 to be between 13.4 and 14.0 kbars at 900° C. The slope up to 1,240° C is 8.5 bar/K. The entropy change at 1,200 K is 20 kJ. These data, combined with data from the literature, lead to a geobarometer equation which, when applied to rocks from the Agto area (West Greenland), gives pressure estimates of 6–10 kbars at 800° C. The results are consistent for rocks of differing Fe/Mg ratios and are consistent with independent pressure estimates.  相似文献   

17.
Subsolidus phase relations have been determined in the systems SiO2-Cr-O and MgO-SiO2-Cr-O in equilibrium with metallic Cr, at 1100 to 1500℃ and 0 to 2.88 GPa. The results show that there are no ternary phases in the SiO2-Cr-O system at these conditions, i.e., only the assemblage eskolaite-Cr-metal-quartz (or tridymite) is found. In the MgO-containing system, however, extensive substitution of Cr2+ for Mg is observed in (Mg, Cr2+)2SiO4 olivine, (Mg, Cr2+)2Si2O6 pyroxene, and (Mg, Cr2+)Cr2O4 spinel. Cr3+ levels in olivine and pyroxene are below detection limits. The pyroxene is orthohombic at XCrPx2+ < 0.2, monoclinic at higher XCrPx2+ . Thestructure of the spinels becomes tetragonally distorted at XCr2+Sp >0.2. The experimental datahave been fitted to a thermodynamic model, and the authors obtained the mixing parameter (W) of Mg-Cr2+ in olivine, pyroxene and spinel, and the relation between temperatures and free energies of formation for the end-members: Cr2+-olivine (Cr2SiO4), Cr2+-pyroxene (Cr2Si2O6)  相似文献   

18.
Experimental investigations between 800 ° to 1,100 ° C yielded no evidence for extensive substitution of Mn2++Si4+2Mn3+ in braunite, leading to a complete solid solution series between partridgeite (Mn2O3) and braunites with silica contents up to 40 wt. % as proposed by Muan (1959a, b). In the presence of excess manganese braunite of nearly ideal composition coexists at 800 ° C with partridgeite and at T1,000 ° C with hausmannite (Mn3O4). At 800 ° C and 1,000 ° C braunite coexists, in the presence of excess silica, with a SiO2-polymorph and at 1,100 ° C with rhodonite (MnSiO3). Quantitative analysis of the X-ray patterns of coexisting cristobalite and braunite confirms a maximum silica-excess in braunite of only about 2 wt.% over the ideal composition, Mn2+Mn 6 3+ SiO12.  相似文献   

19.
The structure of H2O-saturated silicate melts and of silicate-saturated aqueous solutions, as well as that of supercritical silicate-rich aqueous liquids, has been characterized in-situ while the sample was at high temperature (to 800 °C) and pressure (up to 796 MPa). Structural information was obtained with confocal microRaman and with FTIR spectroscopy. Two Al-bearing glasses compositionally along the join Na2O•4SiO2-Na2O•4(NaAl)O2-H2O (5 and 10 mol% Al2O3, denoted NA5 and NA10) were used as starting materials. Fluids and melts were examined along pressure-temperature trajectories of isochores of H2O at nominal densities (from PVT properties of pure H2O) of 0.85 g/cm3 (NA10 experiments) and 0.86 g/cm3 (NA5 experiments) with the aluminosilicate + H2O sample contained in an externally-heated, Ir-gasketed hydrothermal diamond anvil cell.Molecular H2O (H2O°) and OH groups that form bonds with cations exist in all three phases. The OH/H2O° ratio is positively correlated with temperature and pressure (and, therefore, fugacity of H2O, fH2O) with (OH/H2O°)melt > (OH/H2O°)fluid at all pressures and temperatures. Structural units of Q3, Q2, Q1, and Q0 type occur together in fluids, in melts, and, when outside the two-phase melt + fluid boundary, in single-phase liquids. The abundance of Q0 and Q1 increases and Q2 and Q3 decrease with fH2O. Therefore, the NBO/T (nonbridging oxygen per tetrahedrally coordination cations), of melt is a positive function of fH2O. The NBO/T of silicate in coexisting aqueous fluid, although greater than in melt, is less sensitive to fH2O.The melt structural data are used to describe relationships between activity of H2O and melting phase relations of silicate systems at high pressure and temperature. The data were also combined with available partial molar configurational heat capacity of Qn-species in melts to illustrate how these quantities can be employed to estimate relationships between heat capacity of melts and their H2O content.  相似文献   

20.
The kinetic problems associated with the experimental determination of reactions among complex solidsolution phases at low temperatures have hindered our understanding of the phase relations in greenschist facies rocks. In the absence of reliable experimental data, we have used the new, expanded internally-consistent thermodynamic dataset of Holland and Powell (1990), to present calculated phase equilibria for the system CaO–FeO–MgO–Al2O3–SiO2–H2O–CO2 (CaFMASCH) with quartz in eccess, in the range 400°–500°C at low to intermediate pressures, involving the minerals amphibole, chlorite, anorthite, clinozoisite, dolomite, chloritoid, garnet, margarite, andalusite, and calcite. By solving independent sets of non-linear equations formed from equilibrium relationships, we calculate not only the loci of reactions in pressuretemperature-x(CO2) space, but also the compositions of coexisting minerals in terms of the substitutions, FeMg-1 and (Fe,Mg)SiAl-1Al-1. Invariant, univariant and divariant equilibria are calculated and discussed in relation to naturally-occurring greenschist facies metabasic and siliceous dolomitic mineral assemblages. We thus avoid the use of activity-corrected curves so commonly presented in the literature as a substitute for genuine univariant phase diagram boundaries.  相似文献   

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