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1.
Geometrical changes induced by cation substitutions {Si4+/Al3+}[Mg2+/Al3+], {2Si4+/2Al3+} [2Mg2+/2Al3+], {Si4+/Fe3+} [Mg2+/Al3+] or [Mg2+/Fe3+], where {} and [] indicate tetrahedral and octahedral sheet in lizardite 1T, are studied by ab-initio quantum chemistry calculations. The majority of the models are based on the chemical compositions
reported for various lizardite polytypes with the amount of Al in the tetrahedral sheets reported to vary from 3.5% to 8%
in the 1T and 2H
1, up to ~30% in the 2H
2 polytype. Si4+ by Fe3+ substitution in the tetrahedral sheet with an Al3+ (Fe3+) in the role of a charge compensating cation in the octahedral sheet is also examined. The cation substitutions result in
the geometrical changes in the tetrahedral sheets, while the octahedral sheets remain almost untouched. Substituted tetrahedra
are tilted and their basal oxygens pushed down from the plane of basal oxygens. Ditrigonal deformation of tetrahedral sheets
depends on the substituting cation and the degree of substitution. 相似文献
2.
This paper presents an improved generalisation of cation distribution determination based on an accurate fit of all crystal-chemical
parameters. Cations are assigned to the tetrahedral and octahedral sites of the structure according to their scattering power
and a set of bond distances optimised for spinel structure. A database of 295 spinels was prepared from the literature and
unpublished data. Selected compositions include the following cations: Mg2+, Al3+, Si4+, Ti4+, V3+, Cr3+, Mn2+, Mn3+, Fe2+, Fe3+, Co2+, Ni2+, Zn2+ and vacancies. Bond distance optimisation reveals a definite lengthening in tetrahedral distance when large amounts of Fe3+ or Ni2+ are present in the octahedral site. This means that these cations modify the octahedral angle and hence the shared octahedral
edge, causing an increase in the tetrahedral distance with respect to the size of the cations entering it. Some applications
to published data are discussed, showing the capacity and limitations of the method for calculating cation distribution, and
for identifying inconsistencies and inaccuracies in experimental data.
Received: 19 February 2001 / Accepted: 1 June 2001 相似文献
3.
The hydroxy groups of the crystal lattice of dioctahedral 2:1 phyllosilicates were investigated by means of quantum-mechanical calculation. The standard Kohn-Sham self-consistent density functional theory (DFT) method was applied using the generalized gradient approximation (GGA) with numerical atomic orbitals and double-zeta polarized functions as basis set. Isomorphous cation substitution of different cations in the octahedral and tetrahedral sheet was included along with several interlayer cations reproducing experimental crystal lattice parameters. The effect of these substitutions and the interlayer charge on the hydroxyl group properties was also studied. These structures represent different cation pairs among Al3+, Fe3+ and Mg2+ in the octahedral sheet of clays joined to OH groups. The geometrical disposition of the OH bond in the crystal lattice and the hydrogen bonds and other electrostatic interactions of this group were analyzed. The frequencies of different vibrational modes of the OH group [(OH), (OH) and (OH)] were calculated and compared with experimental data, finding a good agreement. These frequencies depend significantly on the nature of cations which are joined with, and the electrostatic interactions with, the interlayer cations. Besides, hydrogen-bonding interactions with tetrahedral oxygens are important for the vibrational properties of the OH groups; however, also the electrostatic interactions of these OH groups with the rest of tetrahedral oxygens within the tetrahedral cavity should be taken into account. The cation substitution effect on the vibration modes of the OH groups was analyzed reproducing the experimental behaviour.Dr. V. Botella passed away last February 相似文献
4.
X-ray single crystal diffraction data of natural and heated Al-rich orthopyroxenes were used to study the cation ordering and the geometrical changes induced by Si+R 2+=AlIV+R 3+ substitution. The calculated site populations and the observed bond distances in tetrahedral and octahedral sites suggest a total ordering of AlIV in the TB tetrahedron and of R 3+ cations in the M1 octahedron, even in samples heated at 1000° C. The mismatch between the tetrahedral and octahedral layers along the c axis seems to play a crucial role in determining the limits of Si/AlIV substitution. 相似文献
5.
Chiara Elmi Maria Franca Brigatti Luca Pasquali Monica Montecchi Angela Laurora Daniele Malferrari Stefano Nannarone 《Physics and Chemistry of Minerals》2010,37(8):561-569
Microprobe analysis, single crystal X-ray diffraction, X-ray photoelectron spectroscopy, atomic force microscopy, and X-ray absorption spectroscopy were applied on Fe-rich osumilite from the volcanic massif of Mt. Arci, Sardinia, Italy. Osumilite belongs to the space group P6/mcc with unit cell parameters a = 10.1550(6), c = 14.306(1) Å and chemical formula (K0.729)C (Na0.029)B (Si10.498 Al1.502)T1 (Al2.706 Fe 0.294 2+ )T2 (Mg0.735 Mn0.091 Fe 1.184 2+ )AO30. Structure refinement converged at R = 0.0201. Unit cell parameter a is related to octahedral edge length as well as to Fe2+ content, unlike the c parameter which does not seem to be affected by chemical composition. The determination of the amount of each element on the mineral surface, obtained through X-ray photoelectron spectroscopy high-resolution spectra in the region of the Si2p, Al2p, Mg1s and Fe2p core levels, suggests that Fe presents Fe2+ oxidation state and octahedral coordination. Two peaks at 103.1 and 100.6 eV can be related to Si4+ and Si1+ components, respectively, both in tetrahedral coordination. The binding energy of Al2p, at 74.5 eV, indicates that Al is mostly present in the distorted T2 site, whereas the Mg peak at 1,305.2 eV suggests that this cation is located at the octahedral site. X-ray absorption at the Fe L2,3-edges confirms that iron is present in the mineral structure, prevalently in the divalent state and at the A octahedral site. 相似文献
6.
7.
Emily A. Hamecher Paula M. Antoshechkina Mark S. Ghiorso Paul D. Asimow 《Contributions to Mineralogy and Petrology》2013,165(1):25-43
We define and calibrate a new model of molar volume as a function of pressure, temperature, ordering state, and composition for spinels in the supersystem (Mg, Fe2+)(Al, Cr, Fe3+)2O4 ? (Mg, Fe2+)2TiO4. We use 832 X-ray and neutron diffraction measurements performed on spinels at ambient and in situ high-P, T conditions to calibrate end-member equations of state and an excess volume model for this system. The effect on molar volume of cation ordering over the octahedral and tetrahedral sites is captured with linear dependence on Mg2+, Al3+, and Fe3+ site occupancy terms. We allow standard-state volumes and coefficients of thermal expansion of the end members to vary within their uncertainties during extraction of the mixing properties, in order to achieve the best fit. Published equations of state of the various spinel end members are analyzed to obtain optimal values of the bulk modulus and its pressure derivative, for each explicit end member. For any spinel composition in the supersystem, the model molar volume is obtained by adding excess volume and cation order-dependent terms to a linear combination of the five end-member volumes, estimated at pressure and temperature using the high-T Vinet equation of state. The preferred model has a total of 9 excess volume and order-dependent parameters and fits nearly all experiments to within 0.02 J/bar/mol, or better than 0.5 % in volume. The model is compared to the current MELTS spinel model with a demonstration of the impact of the model difference on the estimated spinel-garnet lherzolite transition pressure. 相似文献
8.
Summary Fine-grained homogeneous powder samples of thirteen trioctahedral micas, mostly intermediate members of the phlogopite – annite
solid solution series, and samples close to the phlogopite, fluor-phlogopite and tetra-ferriphlogopite end members have been
examined at the potassium K-edge by X-ray absorption fine structure spectroscopy. The interlayer K+ cation is in a coordination that is certainly lower than 12, in contrast to what is expected from the ideal hexagonal symmetry
model of the mica structure, and approaches – but it does not reach – coordination 6, as it should be when the effective ligands
are the three nearest outer bridging oxygens of two facing upper and lower tetrahedral sheets. The observed range of coordinations
implies that only some of the three inner bridging oxygen atoms in each sheet are involved, thus leading to 6±(1 … 6) effective
configurations depending on the composition of the individual mica terms. The effective coordination number was found to vary
continuously with composition from 11 to 7 and to be related to the tetrahedral rotation angle (α) according to two different
linear relationships for the phlogopite – annite series (Fe2+Mg−1 exchange vector, involving the octahedral sheet only) and the phlogopite – tetra-ferriphlogopite series (Fe3+Al−1 vector, involving the tetrahedral sheet), respectively. Substitutions affecting either the A cation in the interlayer or
the X anion in the octahedral sheet also affect the observed trends. In particular, the latter substitution effect is best
seen in two near end member phlogopites, where the fluorine to hydroxyl substitution (F− (OH)−−1 exchange vector), which greatly changes the α tetrahedral rotation angle is, reflected in the experimental K XANES spectra
by modifying not only the energy but also the intensities of most multiple scattering features. 相似文献
9.
A model is proposed for the thermodynamic properties of multicomponent pyroxenes in the composition space defined by the end-member component CaMgSi2O6 and the exchange components Fe(Mg)-1, TiAl2(MgSi2)-1, Fe3+(Al)-1, Fe3+Al(MgSi)-1, and Mg(Ca)-1. It is formulated for the simplifying assumptions that: (1) a molecular mixing type approximation describes changes in the molar configurational entropy associated with the coupled exchange substitutions TiAl2MgSi2, Fe3+AlMgSi, and Al2MgSi (and their ferroan equivalents), and (2) Fe2+ and Mg2+, and Al3+ and Fe3+ display long-range non-convergent ordering between M2 and octahedral M1 sites, and octahedral M1 and tetrahedral sites, respectively. The molar vibrational Gibbs energy is described by a Taylor expansion of second degree in seven linearly independent composition and ordering variables, which is extended to third degree to account for asymmetry in the mixing of Ca and Mg, and Ca and Fe on the M2 site, and is further modified for the assumption that the standard state properties of Ca end-member components of clinopyroxenes are linearly dependent on the coordination number of Ca2+ on the M2 site. The model is shown to be consistent with miscibility gap feaures of pyroxenes in the system CaMgSi2O6–CaTiAl2O6–CaAl2SiO6. In subsequent papers, the model is calibrated for the simplifying assumptions that: (1) all regular-solution-type parameters are constants independent of temperature, (2) Pbca and C2/c end-members have identical heat capacities and coefficients of thermal expansion and compressibility, and (3) the heat capacities and coefficients of thermal expansion and compressibility are zero for all reciprocal reactions relating Pbca and pigeonite or high-calcium pyroxene C2/c endmember components. 相似文献
10.
T. S. Zaitseva I. M. Gorokhov T. A. Ivanovskaya B. B. Zvyagina N. N. Mel’nikov O. V. Yakovleva 《Lithology and Mineral Resources》2005,40(4):353-363
The paper presents results of lithological-mineralogical, Mossbauer, and isotope-geochronological study of globular phyllosilicates (glauconite and illite) from the Lower Cambrian Virbalis Formation in western Lithuania. K-Ar dates of these minerals (382 and 374 Ma) do not correspond to stratigraphic positions of the studied samples and indicate the loss of radiogenic 40Ar, probably, in Middle Devonian. Simulation of cation distribution in the mineral structure and comparison of the obtained data with Mossbauer spectral characteristics suggest that loss of 40Ar was caused by the structural rearrangement of globular phyllosilicates during the postdiagenetic substitution of Fe2+, Mg2+, and Fe3+ by Al3+, with the subsequent ordering of cation distribution in octahedral layers. These processes were presumably related to the same Caledonian tectonic events that were responsible for metasomatic dolomitization of Lower Paleozoic rocks in adjacent areas of the Baltic region at the terminal Silurian-Devonian. Diffraction analysis showed that globules consist of two micaceous phases with different Fe contents (illite and glauconite). Two alternative models are considered to explain the formation of two-phase globules: (1) disequilibrium conditions of diagenetic mineral formation; (2) transformation of glauconite into illite. Although the available data are insufficient to make an unambiguous choice between these models, the second mechanism seems to be more preferable.__________Translated from Litologiya i Poleznye Iskopaemye, No. 4, 2005, pp. 403–415.Original Russian Text Copyright © 2005 by Zaitseva, Gorokhov, Ivanovskaya, Zvyagina, Mel’nikov, Yakovleva. 相似文献
11.
L. G. Kuznetsova A. A. Zolotarev O. V. Frank-Kamenetskaya I. V. Rozhdestvenskaya Yu. M. Bronzova J. Spratte A. Ertl 《Geology of Ore Deposits》2011,53(8):806-817
A detailed study of the chemical composition and substitutions in calcium tourmalines from a scapolite-bearing rare-metal
pegmatite vein from the Sol’bel’der River basin has shown that their species attribution is determined by occupancy of octahedral
site Y. The composition of the yellow tourmaline most abundant in the central part of the pegmatite bodyis rather constant
and characterized by the ideal formula Ca(Mg2Li)Al6(Si6O18)(BO3)3(OH)3F. Variations in the chemical composition of zonal tourmaline crystals from the contact part of the pegmatite are controlled
by abrupt change in the chemical medium during their formation. The yellow cores of these crystals are close in composition
to tourmaline from the central part of the pegmatite vein. The Mg content abruptly decreases toward the crystal margin: Mg2+ → Fe2+, 2Mg2+ → Li+ + Al3+, and Mg2+ + OH → Al3+ + O2−. The composition of dark green marginal zones in tourmaline is characterized by the ideal formula Ca(Al1.5Li1.5)Al6(Si6O18)(BO3)3 (OH2O)(F). The results indicate specific formation conditions of pegmatite. The crystallochemical formulas of the studied tourmalines
allow us to regard them as new mineral species in the tourmaline group. 相似文献
12.
A. Katerinopoulou A. Katerinopoulos P. Voudouris A. Bieniok M. Musso G. Amthauer 《Mineralogy and Petrology》2009,95(1-2):113-124
Unusual Ti–Cr–Zr-rich garnet crystals from high-temperature melilitic skarn of the Maronia area, western Thrace, Greece, were investigated by electron-microprobe analysis, powder and single-crystal X-ray diffraction, IR, Raman and Mössbauer spectroscopy. Chemical data showed that the garnets contain up to 8 wt.% TiO2, 8 wt.% Cr2O3 and 4 wt.% ZrO2, representing a solid solution of andradite (Ca3Fe3+ 2Si3O12 ≈46 mol%), uvarovite (Ca3Cr2Si3O12 ≈23 mol%), grossular (Ca3Al2Si3O12 ≈10 mol%), schorlomite (Ca3Ti2[Si,(Fe3+,Al3+)2]O12 ≈15 mol%), and kimzeyite (Ca3Zr2[Si,Al2]3O12 ≈6 mol%). The Mössbauer analysis showed that the total Fe is ferric, preferentially located at the octahedral site and to a smaller extent at the tetrahedral site. Single-crystal XRD analysis, Raman and IR spectroscopy verified substitution of Si mainly by Al3+, Fe3+ and Ti4+. Cr3+ and Zr4+ are found at the octahedral site along with Fe3+, Al3+ and Ti4+. The measured H2O content is 0.20 wt.%. The analytical data suggest that the structural formula of the Maronia garnet can be given as: (Ca2.99Mg0.03)Σ=3.02(Fe3+ 0.67Cr0.54Al0.33Ti0.29Zr0.15)Σ=1.98(Si2.42Ti0.24Fe0.18Al0.14)Σ=2.98O12OH0.11. Ti-rich garnets are not common and their crystal chemistry is still under investigation. The present work presents new evidence that will enable the elucidation of the structural chemistry of Ti- and Cr-rich garnets. 相似文献
13.
Chemical and mineralogical analyses of the clay fraction of eleven soils containing a large amount of vermiculite clay and representing a wide range of parent materials revealed that two types of vermiculite clays exist: (1) An aluminous type in which Al3+ substitutes for Si4+ in tetrahedral positions in the same order of magnitude as in the coarse grained vermiculites and micas, and with Al3+ as the dominant octahedral ion. (2) A silicious type in which only Si4+ occupies the tetrahedral positions, and with Fe3+ and Mg2+ as the dominant octahedral ions. The aluminous vermiculite clay was found to occur in soils derived from acid igneous rocks and is usally associated with mica, whereas the silicious type was found to occur in soils derived from basic igneous rocks which do not contain mica. Because of this close association of these two types to their parent material, it was concluded that the aluminous vermiculite is a product of alteration of mica whereas the silicious type is a product of synthesis from primary oxides of silica, alumina, iron, and magnesium. Both types of vermiculite clays tend to be dioctahedral in contrast to the trioctahedral nature of the coarse-grained vermiculite. 相似文献
14.
The crystal structure of aP21/a polymorph of sapphirine (a=11.286(3),b=14.438(2),c=9.957(2) Å, β=125.4(2) °) of composition [Mg3.7Fe 0.1 2+ Al4.1- Fe 0.1 3+ ]IV[Si1.8Al4.2]IVO20 was refined using structure factors determined by both neutron and x-ray diffraction methods to conventionalR factors of 0.067 and 0.031. respectively, forF obs>2σ. The results of the two refinements agree reasonably well, but a half-normal probability plot (Abrahams, 1974) comparing the two data sets indicates that the pooled standard deviations of the atomic coordinates have been underestimated by a factor of two. The structure of sapphirine, solved initially by Moore (1969), consists of cubic closest packed oxygens with octahedral and predominantly tetrahedral layers alternately stacked along [100]. The layer in which 70% of the octahedral sites are occupied has an Mg-Al distribution characterized by Mg-rich octahedra sharing edges mainly with Al-rich octahedra. Mean octahedral bond lengths correlate well with Al occupancy determined by neutron site refinement if the relative number of shared octahedral edges is taken into account (see Table 1). The predominantly tetrahedral layer has 10% of the octahedral sites occupied by Al and 30% of the tetrahedral sites occupied by Al-Si in the ratio 2.33∶1. There are single chains of Al-Si tetrahedra parallel toz with corner-sharing wing tetrahedra (T5 andT6) on either side in the (100) plane. The meanT-O distance is highly correlated with Al occupancy, XAl, as determined from the neutron site refinement: $$\langle T - O\rangle = 1.656 + 0.105X_{Al} (r^2 = 0.995).$$ Details of the neutron refinement are summarized below. 相似文献
15.
The incorporation of hydrogen into ferrosilite, Fe-bearing enstatite and orthopyroxene containing different trivalent cations (Cr3+ and Al3+, Cr3+ and Fe3+) was investigated experimentally at 25 kbar. Hydrogen concentration was determined by FTIR-spectroscopy on oriented crystal sections and by secondary ion mass spectroscopy, whereas Mößbauer spectroscopy and optical spectroscopy were used to characterise the valence state of Fe in orthopyroxene. Results suggest that hydrogen incorporation in ferrosilite is achieved by a similar mechanism as in pure enstatite. In Cr-bearing samples, however, hydrogen incorporation is reduced by the presence of other trivalent cations by an increased tendency to form Tschermaks substitutions, e.g. Si T 4+ + Mg M1 2+ ? Al T 3+ + Cr M1 3+ . Thus, hydrogen solubility in natural orthopyroxenes from the Earth’s mantle, containing significant amounts of Cr3+, Al3+, and Fe3+, may be much more limited than expected from their trivalent cation content, as a large fraction of the trivalent cations does not participate in H-incorporating reactions as 2 Mg M1 2+ ? M M1 3+ + VM1 + H i + . 相似文献
16.
Georg Müller 《Contributions to Mineralogy and Petrology》1966,13(1):59-74
Structural formulas were calculated for 8 analysed coexisting biotite-muscovitepairs from granitic rocks. Characteristic components of these structural formulas were plotted against the unit cell dimensions of these micas.In accordance with the results of Gower (1957) the substitution of OH– by F– in trioctahedral micas was found to reduce c
0 · . However, in contrast to his statements, octahedral alumina was found to reduce c
0 · sin also and to an even larger extent than fluorine. This observation is in agreement with the commonly encountered compacting of the mica structure through replacement of 3 large cations (Fe2+, Mg2+, Mn2+) by two smaller ones (Al3+, Fe3+).Concerning b
0 the combined amounts of octahedral Al and tetrahedral Si cause a reduction of this value, which means indirectly that tetrahedral Al alone would increase b
0.Reductions of b
0 and c
0 · sin by Al in synthetic micas were also found by Crowley and Roy (1964) and Seifert (1966) for the substitution Mg + Si by two Al in trioctahedral micas.In an earlier paper the author (Müller, 1966) has already shown with the same mica samples that the substitutions of M2+ by Al3+ and of OH– by F– also have the strongest effects of all substitutions on the refractive indices, densities, and specific refractive energies of these micas. Therefore it is evident that the latter effects as well as the changes of lattice constants described in this paper are interrelated.
Mein Dank gilt den Herren Dr.W. Harre und Dr. H. Gundlach, Bundesanstalt für Bodenforschung, Hannover, für die Ausführung der chemischen Glimmeranalysen, sowie der Deutschen Forschungsgemeinschaft, Bad Godesberg, für ihre finanzielle Beihilfe. Herrn Dr. F. Seifert, Kiel, danke ich für zahlreiche sachliche Diskussionen und Hinweise und für die Überlassung seines Algol-Rechenprogramms, mit welchem 4 der 16 Strukturformeln elektronisch berechnet wurden. Herrn Prof. Dr. F. Liebau, Kiel, verdanke ich einige freundliche Ratschläge. 相似文献
Mein Dank gilt den Herren Dr.W. Harre und Dr. H. Gundlach, Bundesanstalt für Bodenforschung, Hannover, für die Ausführung der chemischen Glimmeranalysen, sowie der Deutschen Forschungsgemeinschaft, Bad Godesberg, für ihre finanzielle Beihilfe. Herrn Dr. F. Seifert, Kiel, danke ich für zahlreiche sachliche Diskussionen und Hinweise und für die Überlassung seines Algol-Rechenprogramms, mit welchem 4 der 16 Strukturformeln elektronisch berechnet wurden. Herrn Prof. Dr. F. Liebau, Kiel, verdanke ich einige freundliche Ratschläge. 相似文献
17.
A well crystallized and homogeneous specimen of lizardite from Monte Fico, Elba, Italy, has been studied by Mössbauer and Fourier transform infrared (FTIR) spectrometries. One of the aims was the determination of the oxidation state and the distribution of iron in the structure of this reference sample. Mössbauer data indicate the presence of octahedral ferrous iron, octahedral ferric iron and tetrahedral ferric iron (59.9, 31.3 and 8.8% of total iron, respectively). The existence of only one octahedral site, previously suggested by X-ray structure refinement, is confirmed. The occurrence of tetrahedrally coordinated iron is indicated also by FTIR spectrometry, in particular by the presence of an absorption band at 790 cm–1. Based also on new electron microprobe data, the improved crystal chemical formula for lizardite from Monte Fico is: (Mg2.74Fe2+ 0.10Fe3+ 0.05Al0.11)Σ=3.00 ?· (Si1.94Al0.05Fe3+ 0.01)Σ=2.00O5.05(OH)3.95. 相似文献
18.
Synthetic melilites on the join Ca2MgSi2O7 (åkermanite: Ak)-Ca2Fe3+AlSiO7 (ferrialuminium gehlenite: FAGeh) were studied using X-ray powder diffraction and 57Fe Mössbauer spectroscopic methods to determine the distribution of Fe3+ between two different tetrahedral sites (T1 and T2), and the relationship between ionic substitution and incommensurate (IC) structure. Melilites were synthesized from starting materials with compositions of Ak100, Ak80FAGeh20, Ak70FAGeh30 and Ak50FAGeh50 by sintering at 1,170–1,350 °C and 1 atm. The average chemical compositions and end-member components, Ak, FAGeh and Geh (Ca2Al2SiO7), of the synthetic melilites were Ca2.015Mg1.023Si1.981O7 (Ak100), Ca2.017Mg0.788Fe 0.187 3+ Al0.221Si1.791O7 (Ak78FAGeh19Geh3), Ca1.995Mg0.695Fe 0.258 3+ Al0.318Si1.723O7 (Ak69FAGeh25Geh6) and Ca1.982Mg0.495Fe 0.449 3+ Al0.519Si1.535O7 (Ak49FAGeh44Geh7), respectively. Rietveld refinements using X-ray powder diffraction data measured using CuK α -radiation at room temperature converged successfully with goodness-of-fits of 1.15–1.26. The refined Fe occupancies at the T1 and T2 sites and the Mg and Si contents determined by electron microprobe analysis gave the site populations of [0.788Mg + 0.082Fe3+ + 0.130Al]T1[0.104Fe3+ + 0.104Al + 1.792Si]T2 for Ak78FAGeh19Geh3, [0.695Mg + 0.127Fe3+ + 0.178Al]T1[0.132Fe3+ + 0.144Al + 1.724Si]T2 for Ak69FAGeh25Geh6 and [0.495Mg + 0.202Fe3+ + 0.303Al]T1[0.248Fe3+ + 0.216Al + 1.536Si]T2 for Ak49FAGeh44Geh7 (apfu: atoms per formula unit), respectively. The results indicate that Fe3+ is distributed at both the T1 and the T2 sites. The mean T1–O distance decreases with the substitution of Fe3+ + Al3+ for Mg2+ at the T1 site, whereas the mean T2–O distance increases with substitution of Fe3+ + Al3+ for Si4+ at the T2 site, causing decrease in the a dimension and increase in the c dimension. However, in spite of the successful Rietveld refinements for the X-ray powder diffraction data measured using CuK α-radiation at room temperature, each Bragg reflection measured using CuK α1-radiation at room temperature showed weak shoulders, which were not observed in those measured at 200 °C. The Mössbauer spectra of the melilites measured at room temperature consist of two doublets assigned to Fe3+ at the T1 site and two or three doublets to Fe3+ at the T2 site, implying the existence of multiple T1 and T2 sites with different site distortions. These facts can be interpreted in terms of the IC structure in all synthetic melilites at room temperature, respectively. The results of Mössbauer analysis indicate that the IC structure in melilite is caused by not only known multiple T1 site, but also multiple T2 site at room temperature. 相似文献
19.
Benaissa Rhouta Ezzouhra Zatile Lahcen Bouna Omar Lakbita Francis Maury Lahcen Daoudi Marie Christine Lafont M’Barek Amjoud François Senocq Amane Jada Ahmed Aït Aghzzaf 《Physics and Chemistry of Minerals》2013,40(5):411-424
This study is devoted to the physicochemical and mineralogical characterizations of palygorskite from Marrakech High Atlas, Morocco. The raw clay and its Na+-saturated <2 μm fraction were characterized using chemical, structural, and thermal analytical techniques. Measurements of specific surface area and porous volume are reported. The clay fraction was found to be made up of 95 % of palygorskite and 5 % of sepiolite. An original feature of this palygorskite is its deficiency in zeolitic H2O. The half-cell structural formula of its dehydrated form was determined on the basis of 21 oxygens to be (Si7.92Al0.08)(Mg2.15Al1.4Fe0.4Ti0.05 $ \square_{1} $ )(Ca0.03Na0.08K0.04)O21, while the hydrated form could be formulated as (Si7.97Al0.03)(Mg2.17Al1.46Fe0.40Ti0.05)(Ca0.03Na0.07K0,03)O20.18(OH)1.94(OH2)3.88·2.43 H2O. These formulas show that the (Al3++Fe3+)/Mg2+ ratio is around 0.84, revealing a pronounced dioctahedral character. Further, inside its octahedral sheet, it was determined that the inner M1 sites are occupied by vacancies, whereas the M2 sites are shared between 90 % of trivalent cations (78 % for Al3+ and 22 % for Fe3+), 7.5 % of Mg2+, and 2.5 % of Ti4+, all of them linked to 1.94 of structural hydroxyls. The two remaining Mg2+ by half-cell occupy edge M3 sites and are coordinated to 3.88 molecules of OH2. Channels of this palygorskite are deficient in zeolitic H2O since they contain only 2.43 H2O molecules. A correlation was found between these results and the observation of very intense and well-resolved FTIR bands arising from dioctahedral domains (mainly Al2OH, Fe2OH, and AlFeOH) along with very small responses from a trioctahedral domain (Mg3OH). Accordingly, a schematic representation of the composition of the octahedral sheet was proposed. The cation exchange capacity, specific surface area, and total pore volume were also assessed to be ca. 21.2 meq/100 g, 116 m2/g, and 0.458 cm3/g, respectively. 相似文献
20.
The Mössbauer spectra of 119Sn and 57Fe in three natural and a synthetic garnet were studied between 20 and 300 K. These spectra reveal the presence of octahedral Sn4+ as well as octahedral Fe3+ and Fe2+. Sn2+ could not be detected. On the basis of these results the following cation substitution can be derived for the tin-bearing Silicate garnets of this study: Sn4+ (oct)+Fe2+ (oct) ? 2 Fe3+ (oct). 相似文献