Analysis of cation distribution in the octahedral sheet of dioctahedral 2:1 phyllosilicates by using inverse Monte Carlo methods

An inverse Monte Carlo (MC) method was developed to determine the distribution of octahedral cations (Al³⁺, Fe³⁺, and Mg²⁺) in bentonite illite–smectite (I–S) samples (dioctahedral 2:1 phyllosilicates) using FT–IR and ²⁷Al MAS NMR spectroscopies. FT–IR allows determination of the nature and proportion of different cation pairs bound to OH groups measuring the intensities of OH-bending bands. ²⁷Al MAS NMR data provide information about cation configuration because ²⁷Al MAS NMR intensity depends on Fe distribution. MC calculations based on FT–IR data alone show Fe segregation by short-range ordering (Fe clusters within 9 to 15?Å from a given Fe atom). Fe segregation increases with illite proportion. MC calculations based on IR and ²⁷Al NMR simultaneously yield similar configurations in which Fe clusters are smaller. The latter calculations fail to build appropriate cation distributions for those samples with higher number of illite layers and significant Fe content, which is indicative of long-range Fe ordering that cannot be detected by FT–IR and ²⁷Al MAS NMR. The proportion of Mg–Mg pairs is negligible in all samples, and calculations, in which the number of Mg atoms, as second neighbours, is minimised, create appropriate configurations.     

Theoretical modelling of cis -vacant and trans -vacant configurations in the octahedral sheet of illites and smectites

 The cis-vacant configurations of smectites and illites have been studied theoretically by using transferable empirical interatomic potentials. A wide range of compositions of octahedral and tetrahedral cation and interlayer charge has been considered. All results have been compared with the trans-vacant configurations in each sample. The calculated values reproduce the differences in the lattice parameters between the cis- and trans-vacant configurations of experimental studies. Taking into account the cis-/trans-vacant proportion, the calculated structures agree with experiment for the main structural features of the crystal lattice. The effect of the cation substitution in the octahedral and tetrahedral sheets on the cell parameters has been also studied, finding good linear relationships. The calculated cation substitution effects are consistent with experimental results. Although the energy difference between the cis- and trans-vacant configurations is small, the cis-vacant is more stable when the composition of clays is more smectitic, like the experimental behaviour. Similar trends of the cation substitution effect on the cis-/trans-vacant proportion to the experimental results are found. The structure of the hydroxy groups has also been analysed. The OH bond length, the orientation of the O–H bond with respect to the (001) plane and the non-bonding H...O distances have been studied. Received: 4 September 2000 / Accepted: 29 January 2001     

Structural thermal behavior of paragonite and its dehydroxylate: a high-temperature single-crystal study

 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: α_a = 1.51(8) × 10⁻⁵, α_b = 1.94(6) × 10⁻⁵, α_c = 2.15(7) ×  10⁻⁵ °C⁻¹, and α_V = 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     

Structure of Cu-bearing orthopyroxene, Mg(Cu.56,Mg.44)Si2O6, and behavior of Cu2+ in the orthopyroxene structure

Cu-bearing pyroxene, Mg(Cu.₅₆,Mg.₄₄)Si₂O₆, has been synthesized by a flux method and crystal structure refinement has been performed by single crystal X-ray diffraction. It is found that the crystal structure is orthorhombic (space group Pbca) with unit cell dimensions of a=18.221(4), b=8.890(1), c=5.2260(7)Å and the cell volume of 846.5( )3ų. In the M2-site one of the M-O bonds(M-O3B) is extremely expanded from 2.444(2) in enstatite to 2.732(2), thus the coordination polyhedron around M2-site is regarded as square pyramidal rather than square planar or octahedral. It is also found that the M1-site in the pyroxene structure is occupied almost exclusively by Mg, while the M2-site is almost evenly occupied by Mg and Cu. The observed extreme site preference shown by Cu²⁺ is unusual among the divalent cations with similar ionic sizes.     

High temperature dehydroxylation of muscovite-2M1: a kinetic study by in situ XRPD

Muscovite-2M₁ shows a major phase transition at about 800°C, which is generally attributed in the literature to the structural dehydroxylation process, although a number of structural models have been proposed for the dehydroxylated phase, and different transformation mechanisms have also been put forward. The observed first order transformation involves an increase in the cell volume, and it is not clear to date how the cell expansion is related to the loss of hydroxyl groups. The phase change has been re-investigated here by in situ high temperature powder diffraction, both in non-isothermal and isothermal modes, to combine for the first time the structural and the kinetic interpretation of the transformation. The results unequivocally confirm that the reaction taking place in the temperature range 700–1000°C is truly a dehydroxylation process, involving the nucleation and growth of the high temperature dehydroxylated phase, having Al in 5-fold coordination. Structural simulations of the basal peaks of the powder diffraction patterns indicate that the model originally proposed by Udagawa et al. (1974) for the dehydroxylated phase correctly describes the high temperature phase. The kinetic analysis of the isothermal data using an Avrami-type model yields values for the reaction order compatible with a reaction mechanism limited by a monodimensional diffusion step. Apparent activation energy of the process in vacuum is about 251 kJ/mol. Experiments carried out at temperatures much higher than the onset temperature of the reaction show that the dehydroxylation reaction overlaps with the reaction of formation of mullite, the final product in the reaction pathway. Received: 24 April 1998 / Revised, accepted: 12 October 1998     

Variation of the oxygen content and point defects in olivines, (Fe x Mg 1−x )2SiO4, 0.2 ≤ x ≤ 1.0

 The variation of the oxygen content in olivines, (Fe _x Mg_{1− x} )₂SiO₄, with 0.2 ≤ x ≤ 1.0, was investigated by thermogravimetric measurements. Mass changes occurring upon oxygen activity changes were measured as a function of oxygen activity and cationic composition at 1130 and 1200 °C. During the measurements the samples were in direct contact with gases containing CO, CO₂ and N₂ and, at a few spots at the bottom of the sample stack, also with SiO₂. By fitting experimental data of mass changes to equations derived using point defect thermodynamics, it was shown for olivines with 0.2 ≤ x ≤ 1.0 at 1130 °C and 0.2 ≤ x ≤ 0.7 at 1200 °C within the oxygen activity ranges investigated that the observed variations in the oxygen contents are compatible with cation vacancies and Fe³⁺ ions on M sites and Fe³⁺ ions on silicon sites as majority defects if it is assumed that only three types of point defects occur as majority defects. Different cases were considered, closed systems, taking into account that ξ=[Si]/([Si]+[Fe]+[Mg]) is not necessarily equal to 1/3, and olivines in equilibrium with SiO₂ or pyroxenes. The oxygen content variations observed in this study are significantly smaller than those reported previously in the literature. It is proposed that these differences are related to the dissolution of Fe into noble metal containers used as sample holders in earlier studies and/or to the presence of secondary phases. Received: 1 November 1995 / Accepted: 15 September 2002 Acknowledgements This work was supported by the Cornell Center for Materials Research (CCMR), a Materials Research Science and Engineering Center of the National Science Foundation (DMR-0079992). The authors thank Mr. Daniel M. DiPasquo and Mr. Jason A. Schick for helping in experimental work.     

The Effect of Cr2O3 on the Partial Melting of Spinel Lherzolite in the System CaO-MgO-Al2O3-SiO2-Cr2O3 at 1{middle dot}1 GPa

Chromium as Cr³⁺ substitutes for octahedrally coordinated Alin upper-mantle minerals, thereby reducing the activity of Al₂O₃in the system and hence the concentration of Al₂O₃ in partialmelts. The effect of Cr₂O₃ on melt compositions multiply saturatedwith the spinel lherzolite phase assemblage has been quantifiedin the system CaO–MgO–Al₂O₃–SiO₂–Cr₂O₃at 1·1 GPa as a function of 100 Cr/(Cr + Al) in the spinel(Cr#_sp). The decrease of Al₂O₃ in the melt with increasing Cr#_spis accompanied by increasing MgO and SiO₂, whereas CaO remainsalmost constant. Consequently, the CaO/Al₂O₃ ratio of the meltincreases with Cr#_sp, and the melt becomes richer in normativediopside, hypersthene and quartz. The effect may explain certainmantle melts with unusually high CaO/Al₂O₃ ratios. The concentrationof Cr₂O₃ in the melt remains low even at high Cr#_sp, which meansthat the strong effect of Cr₂O₃ on partial melting equilibriais not readily apparent from its concentration in the melt itself.The existence of a highly refractory major component such asCr₂O₃ nullifies simplified conclusions from the ‘inverseapproach’ in the experimental study of basalt petrogenesis,as there is insufficient information in the composition of thepartial melt to reconstruct the conditions of melting. KEY WORDS: basalt petrogenesis; partial melting; reversal experiment; spinel lherzolite; system CMAS–Cr₂O₃; CaO/Al₂O₃ of melt; effect of Cr₂O₃