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1.
Ilvaite, Ca(Fe2+,Fe3+)Fe2+Si2O8(OH) shows two magnetic phase transitions, which have been studied by Mössbauer spectroscopy within the temperature range 120–4 K. The continued charge localization between Fe2+ and Fe3+ ions in octahedral A-sites causes the Fe2+-Fe3+ interaction to be ferromagnetic, although the overall magnetic order is antiferromagnetic. The thermal evolution of the hyperfine fields at the Fe2+ (A) and Fe3+ (A) sites indicates B hf: 328 and 523 kOe respectively at 0 K and T N1= 116K. The corresponding values for Fe2+ (B) site are: B hf 186 kOe and T N2=36K. An additional hyperfine field exists at the Fe2+(B) site within the temperature range 116–36K due to short-range order induced by the spin ordering in A sites. The considerable difference between the two magnetic transition temperatures is due to spin frustration, because the Fe2+ (B) site occurs on a corner common between two triangles with respect to two sets of Fe2+ (A) and Fe3+ (A) sites with opposite spin directions.  相似文献   

2.
Summary Vivianite from Catavi Mine, Llallagua, Bolivia, has a near ideal composition with traces of Mg, Zn and Mn. Total rare-earth elements are < 1,gmg/g. Mössbauer spectroscopy shows FeIII/(FeII + FeIII) is approximately 0.04.a = 10.030Å,b = 13.434Å,c = 4.714Å, = 102.73dg. The middle-infrared powder spectrum shows H2O-related bands at 3490, 3290, 3130 cm–1 (stretch), 1618 cm–1 (bend), 825 cm–1 (rock), and at 665 cm–1 a possible M-OH2 twist. P04 bands occur at 1045-940 cm–1 (stretch) and 570-450 cm–1 (bend). Corresponding laser Raman microprobe bands occur at 1051 (ms), 986 (m), 948 (vs), 867 (mw), 828 (w), 568, 532, 453 (m), 442 (mw). Weak Raman bands at about 342, 303, 270 (w), 235 (ms), 227 (sh, ms), 196 (ms), 187 (sh, m), 162 (mw), and 126 (m) may arise from lattice vibrations. Differential thermal responses include a major endotherm from 115–235°C with a shoulder at 170°C and a maximum at 210°C resulting from loss of structural water combined with oxidation of Fe2+, and two small exotherms with maxima at 605 and 780°C related to structural transformations.
Charakterisierung des Vivianits von Catavi, Llallagua, Bolivien
Zusammenfassung Vivianit von der Catavi Mine, Llallagua, Bolivien zeigt annähernd ideale Zusammensetzung mit Spuren von Mg, Zn und Mn. Der gesamte Gehalt an seltenen EvolElementen ist < 1 ppm. Die Mössbauer Spektroskopie liefert ein Fe3+/(Fe2+ + Fe3+) Verhältnis von ungefähr 0.04.a = 10.030,b = 13.434,c = 4.714 Å, = 102.73°. Das Infrarot-Pulverspektrum zeigt dem H20 zuzuordnende Banden bei 3490, 3290, 3130 cm–1 (Streckschwingungen), 1618 cm–1 (Deformationsschwingung), 825 cm–1 (Schaukelschwingung) und eine mögliche M-OH2 Torsionsschwingung bei 665 cm–1. PO4 Banden liegen bei 1045-940 cm–1 (Streckschwingung) und 570-450 cm–1 (Deformations-schwingung). Entsprechende Banden der Laser Raman Mikrosonde liegen bei 1051 (mst), 986 (m), 948 (sst) 867 (mschw), 828 (schw), 568, 532, 453 (m), 442 (mschw). Raman Banden bei etwa 342, 303, 270 (schw), 235 (mst), 227 (Schulter, mst), 196 (mst), 187 (Schulter, m), 162 (mschw) und 126 (m) können auf Gitterschwingungen zurückgeführt werden. Differential-thermoanalytische Untersuchungen zeigen einen endothermen Bereich von 115–235°C mit einer Schulter bei 170 und einem Maximum bei 210°C, was auf den Verlust von strukturellem Wasser, das an eine Oxidation des Fe2+ gebunden ist, zurückzuführen ist; zwei auf strukturelle Transformationen zurückzuführende exotherme Maxima liegen bei 605 und 780°C.

With 4 Figures  相似文献   

3.
Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO4 solutions. Single-crystal XRD refinement with R1=0.0232 for the unique observed reflections (|Fo| > 4F) and wR2=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, Vo=160.11(4) cm3, and fractional positions for all atoms except the H in the H3O groups. The chemical composition of this sample is described by the formula (H3O)0.91Fe2.91(SO4)2[(OH)5.64(H2O)0.18]. The enthalpy of formation (Hof) is –3694.5 ± 4.6 kJ mol–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H2O, and -MgSO4. The entropy at standard temperature and pressure (So) is 438.9±0.7 J mol–1 K–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (Cp) data between 273 and 400 K were fitted to a Maier-Kelley polynomial Cp(T in K)=280.6 + 0.6149T–3199700T–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol–1. Speciation and activity calculations for Fe(III)–SO4 solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the Cp data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in Cp, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H3O)Fe3(SO4)2(OH)6 was estimated: Gof= –3226.4 ± 4.6 kJ mol–1, Hof=–3770.2 ± 4.6 kJ mol–1, So=448.2 ± 0.7 J mol–1 K–1, Cp (T in K)=287.2 + 0.6281T–3286000T–2 (between 273 and 400 K).  相似文献   

4.
A new thermodynamic model for multi-component spinel solid solutions has been developed which takes into account thermodynamic consequences of cation mixing in spinel sublattices. It has been applied to the evaluation of thermodynamic functions of cation mixing and thermodynamic properties of Fe3O4–FeCr2O4 spinels using intracrystalline cation distribution in magnetite, lattice parameters and activity-composition relations of magnetite–chromite solid solutions. According to the model, cation distribution in binary spinels, (Fe1-x2+ Fex3+)[Fex2+Fe2-2y-x3+Cr2y]O4, and their thermodynamic properties depend strongly on Fe2+–Cr3+ cation mixing. Mixing of Fe2+–Fe3+ and Fe3+–Cr3+ can be accepted as ideal. If Fe2+, Fe3+ and Cr are denoted as 1, 3 and 4 respectively, the equation of cation distribution is –RT ln(x2/((1–x)(2–2y–x)))= G13* + (1–2x)W13+y(W14–W13–W34) where G13* is the difference between the Gibbs energy of inverse and normal magnetite, Wij is a Margules parameter of cation mixing and G13*, J/mol =–23,000+13.4 T, W14=36 kJ/mol, W13=W34=0. The positive nonconfigurational Gibbs energy of mixing is the main reason for changing activity–composition relations with temperature. According to the model, the solvus in Fe3O4–FeCr2O4 spinel has a critical temperature close to 500°C, which is consistent with mineralogical data.  相似文献   

5.
Summary Anandite has an approximate formula of Ba(Fe3+, Fe2+)3[Si2(Fe3+, Fe2+, Si)2O10–x(OH)x] (S, Cl) (OH), withx=0–1, and belongs to the 2 O brittle mica group. It is orthorhombic; space groupPnmn;a=5.468(9) Å,b=9.489(18)Å,c=19.963(11) Å;Z=4.The structure was determined from 3dim. Weissenberg-data, starting with an approximate structure in the pseudo space groupCcmm. Least squares refinement resulted inR=0.061 for 409 photometric intensities, andR=0.131 for all 853 observedhkl-reflexions.The iron of the tetrahedral layer is concentrated in one of the two crystallographically different kinds of tetrahedra. The basal oxygen rings of the tetrahedral layer form approximate hexagons and have not the ditrigonal configuration of the common micas. This peculiarity is considered to be a consequence of the size and charge of the barium ion. The role of OH in the common micas is played partly by S2– and Cl– in anandite.
Die Kristallstruktur des 2 O Sprödglimmers Anandit
Zusammenfassung Anandit hat die ungefähre Formel Ba(Fe3+, Fe2+)3[Si2(Fe3+, Fe2+, Si)2O10–x(OH)x] (S, Cl) (OH) mitx=0–1 und gehört zur 2O Sprödglimmergruppe. Er ist rhombisch; RaumgruppePnmn; a=5,468(9) Å,b=9,489(18) Å,c=19,963(11) Å;Z=4.Die Struktur wurde aus Weissenberg-Daten bestimmt, wobei mit einer approximativen Struktur in der PseudoraumpruppeCcmm begonnen wurde. Die Verfeinerung nach der Methode der kleinsten Quadrate führte für 409 photometrierte Reflexe aufR=0,061 und für alle 853 beobachtetenhkl-Reflexe aufR=0,131.Der Eisengehalt der Tetraederschicht ist in einer der beiden kristallographisch verschiedenen Tetraederarten konzentriert. Die basalen Sauerstoffringe der Tetraederschicht bilden annäherungsweise Sechsecke und haben nicht die ditrigonale Konfiguration der gewöhnlichen Glimmer. In Anandit spielen S2– und Cl– teilweise die Rolle der Hydroxylgruppen in den gewöhnlichen Glimmern.

With 4 Figures  相似文献   

6.
The infrared reflectivity spectra of two natural cassiterite single crystals from Portugal and Vietnam have been studied and analysed in the frequency range of 15–4000 cm–1 at room temperature. The optical mode parameters are deduced by simulation of the experimental spectra using the factorised form of the dielectric function. The difference with synthetic SnO2 spectra is a dip near 500 cm–1 understood as the activation of an infrared forbidden E g mode due to the amount of Fe3+ and Ti4+ impurities. Another result of this work is the derivation of the correct values of the static dielectric constant of cassiterite.  相似文献   

7.
The temperature dependence of the absorption spectra of ilvaite, Ca(Fe2+,Fe3+)Fe2+Si2O8(OH), shows strongly one dimensional transport behaviour with no singularity at the Pnam-P21/a phase transition point near 335 K. Polarized single crystal transmission measurements were carried out between 300 K and 450 K in a frequency range between 600 and 23 000 cm−1. No Drude —absorption at low energies was found at any temperature. A macroscopic, thermodynamic model based on Landau-Ginzburg theory is given which accounts for the observed macroscopic properties of the structural phase transition and its coupling with the Fe2+-Fe3+ ordering. This ordering scheme is discussed on an atomistic level and compared with the behaviour of magnetite and trans-(CH) x .  相似文献   

8.
This work reports the synthesis of ferri-clinoholmquistite, nominally Li2(Mg3Fe3+2)Si8O22(OH)2, at varying fO2 conditions. Amphibole compositions were characterized by X-ray (powder and single-crystal) diffraction, microchemical (EMPA) and spectroscopic (FTIR, Mössbauer and Raman) techniques. Under reducing conditions ( NNO+1, where NNO = Nickel–Nickel oxide buffer), the amphibole yield is very high (>90%), but its composition, and in particular the FeO/Fe2O3 ratio, departs significantly from the nominal one. Under oxidizing conditions ( NNO+1.5), the amphibole yield is much lower (<60%, with Li-pyroxene abundant), but its composition is close to the ideal stoichiometry. The exchange vector of relevance for the studied system is M2(Mg,Fe2+) M4(Mg,Fe2+) M2Fe3+–1 M4Li–1, which is still rather unexplored in natural systems. Amphibole crystals of suitable size for structure refinement were obtained only at 800 °C, 0.4 GPa and NNO conditions (sample 152), and have C2/m symmetry. The X-ray powder patterns for all other samples were indexed in the same symmetry; the amphibole closest to ideal composition has a = 9.428(1) Å, b = 17.878(3) Å, c = 5.282(1) Å, = 102.06(2)°, V = 870.8(3) Å3. Mössbauer spectra show that Fe3+ is strongly ordered at M2 in all samples, whereas Fe2+ is disordered over the B and C sites. FTIR analysis shows that the amount of CFe2+ increases for increasingly reducing conditions. FTIR data also provide strong evidence for slight but significant amounts of Li at the A sites.  相似文献   

9.
Summary Sonoraite, FeTeO3(OH)·H2O, is monoclinic,P 21/c, witha=10.984(2),b=10.268(2),c=7.917(2) Å, =108.49(2)°. For 8 formula units per cell the calculated density is 4.179(2) g/cm3; the observed value is 3.95(1) g/cm3. The Supper-Pace automated diffractometer was used to collect 1884 independent reflections which were corrected for absorption. The structure was determined by an automated symbolic addition procedure. It was refined to a residualR of 6.2% using anisotropic temperature factors for the cations and isotropic temperature factors for the oxygen atoms. Chains of octahedra about Fe extend along [101]; edge-sharing pairs of these octahedra are joined by corner sharing. The Fe–Fe distances across the shared edges are 3.05 and 3.20 Å, short enough to suggest magnetic interactions. All but one H2O are involved in the chains. The Te4+ ions have a pseudotetrahedral coordination, with three oxygen ions forming one face of the tetrahedron and the lone electron pair of Te occupying the fourth corner. The O–Te–O average bond angle is 95°. The Fe chains are tied together by Te–O bonds in all three dimensions.
Die Kristallstruktur von Sonorait, Fe3+Te4+O3(OH).H2O
Zusammenfassung Sonorait, FeTeO3(OH)·H2O, ist monoklin, P 21/c, mit den folgenden Zelldimensionen:a=10,984(2),b=10,268(2),c=7,917(2) Å, =108,49(2)°. Mit 8 Formel-Einheiten errechnet man eine Dichte von 4,179(2) g/cm3; die gemessene Dichte beträgt 3,95(1) g/cm3. Das Supper-Pace automatische Diffraktometer wurde zur Sammlung von 1884 unabhängigen Reflexen benutzt, welche für Absorption korrigiert wurden. Die Struktur wurde mit Hilfe eines vollständig automatischen Programms für symbolische Addition bestimmt. Mit anisotropen Temperaturfaktoren für die Kationen und mit isotropen Temperaturfaktoren für die Sauerstoff-Atome wurde ein Residuum von 6,2% erreicht. Ketten von Eisen-Oktaedern erstrecken sich entlang [101]; Oktaeder-Paare mit gemeinsamen Kanten sind über Eckenverknüpfung verbunden. Die Fe–Fe-Abstände über die gemeinsamen Kanten betragen 3,05 und 3,20 Å, kurz genug, um zu magnetischer Wechselwirkung führen zu können. Nur ein H2O-Molekül ist nicht Teil einer Kette. Die Te4+-Ionen befinden sich in pseudotetraedrischer Koordination; drei Sauerstoff-Ionen bilden eine Fläche des Tetraeders, die vierte Ecke wird durch das einsame Elektronenpaar von Te besetzt. Der Mittelwert des O–Te–O-Bindungswinkels beträgt 95° Die Fe-Ketten werden durch Te–O-Bindungen dreidimensional verbunden.

With 3 Figures  相似文献   

10.
Summary  Transmission M?ssbauer spectra of synthetic Ca-free P21/c Mg0.22Fe0.78SiO3 clinopyroxene were collected at temperatures in the range 4.2 to 745 K and in an external magnetic field of 60 kOe at 180 K. The magnetic order-disorder transition temperature was determined by M?ssbauer thermoscanning to be 21 ± 3 K. Above this temperature, all M?ssbauer spectra consist of a superposition of two doublets, respectively produced by Fe2+ ions at an almost regular octahedral M1 site and at a more distorted octahedral M2 site. The temperature variation of the Fe2+ center shifts were analyzed using the Debye model for the lattice vibrations. The characteristic M?ssbauer temperatures were found to be 356 K ± 35 K for M1 and 333 K ± 25 K for M2. From the external field (60 kOe) M?ssbauer spectrum recorded at 180 K, the principal component V zz of the electric field gradient (EFG) was determined to be positive for both sites but precise values for the magnitudes of the asymmetry parameters η of the EFG could not be determined. The temperature variations of the M1 and M2 quadrupole splittings ΔE Q(T ) are consistent with the higher distortion of the M2 octahedra. Using the crystal-field model to interpret ΔE Q(T ), the energy gaps δ1 and δ2 of the first excited electronic states within the 5D orbital term were estimated to be 410 ± 50 cm−1 and 730 ± 50 cm−1 for M1, and δ1 = 1050 ± 75 cm−1 for M2. Received May 29, 2000;/revised version accepted July 13, 2001  相似文献   

11.
The influence on the structure of Fe2+ Mg substitution was studied in synthetic single crystals belonging to the MgCr2O4–FeCr2O4 series produced by flux growth at 900–1200 °C in controlled atmosphere. Samples were analyzed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption-, infrared- and Mössbauer spectroscopy. The Mössbauer data show that iron occurs almost exclusively as IVFe2+. Only minor Fe3+ (<0.005 apfu) was observed in samples with very low total Fe. Optical absorption spectra show that chromium with few exceptions is present as a trivalent cation at the octahedral site. Additional absorption bands attributable to Cr2+ and Cr3+ at the tetrahedral site are evident in spectra of end-member magnesiochromite and solid-solution crystals with low ferrous contents. Structural parameters a0, u and T–O increase with chromite content, while the M–O bond distance remains nearly constant, with an average value equal to 1.995(1) Å corresponding to the Cr3+ octahedral bond distance. The ideal trend between cell parameter, T–O bond length and Fe2+ content (apfu) is described by the following linear relations: a0=8.3325(5) + 0.0443(8)Fe2+ (Å) and T–O=1.9645(6) + 0.033(1)Fe2+ (Å) Consequently, Fe2+ and Mg tetrahedral bond lengths are equal to 1.998(1) Å and 1.965(1) Å, respectively.  相似文献   

12.
A Raman spectroscopic study of Fe-rich sphalerite (Zn1 − x Fe x S) has been carried out for six samples with 0.10 ≤ x ≤ 0.24. Both the intensities and frequencies of the TO and LO modes of sphalerite are approximately independent of Fe concentration. However, the substitution of Zn by Fe results in five additional bands with frequencies between the TO (271 cm−1) and LO (350 cm−1) modes. Three of these bands are attributed to resonance modes (i.e. Y 1, Y 2 and Y 3 modes). The fourth band (B mode) is assigned to a breathing mode of the nearest-neighbor sulfur atoms around the Fe atoms. The band at 337 cm−1 is attributed to the presence of Fe3+. The excellent correlations between the normalized intensities of these five different modes and x Fe show that these modes depend on Fe-content. Another extra mode at 287 cm−1 is assigned to the presence of Cd in sphalerite.  相似文献   

13.
The local structural heterogeneity and energetic properties of 22 natural Mg–Fe cordierites, ideal formula (Mg,Fe)2Al4Si5O18·x(H2O,CO2), were investigated at length scales given by powder infrared spectroscopy (IR) and also by published electronic absorption spectra. The studied samples have iron mole fractions from XFe = 0.06 to 0.82 and cover most of the Mg–Fe cordierite binary. Variations in wavenumbers and line widths of the IR bands were determined as a function of composition. Most modes shift linearly to lower wavenumbers with increasing XFe, except those at high wavenumbers located between 900 and 1,200 cm-1. They are vibrations that have a large internal (Si,Al)O4 character and are not greatly affected by Mg–Fe exchange on the octahedral site. The lower wavenumber modes can be best characterized as lattice vibrations having mixed character. The systematics of the wavenumber shifts suggest small continuous variations in the "average" cordierite structure with Mg–Fe exchange and are consistent with an ideal volume of mixing, Vmix= 0, behavior (Boberski and Schreyer 1990). IR line broadening was measured using the autocorrelation function for three wavenumber regions in order to determine the range of structural heterogeneity between roughly 2 and 100 Å (0.2–10.0 nm) in the solid solution. In order to do this, an empirical correction was first made to account for the effect that small amounts of channel Na have on the phonon systematics. The results show that between 1,200 and 540 cm-1 the line widths of the IR bands broaden slightly and linearly with increasing XFe. Between 350 and 125 cm-1 nonlinear behavior was observed and it may be related to dynamic effects. These results suggest minimal excess elastic enthalpies of mixing for Mg–Fe cordierite solid solutions. Channel Na should affect measurably the thermodynamic properties of natural cordierites as evidenced by variations in the IR spectra of Na-containing samples. Occluded H2O (Class I) and CO2 should have little interaction with the framework and can be considered nearly "free" molecules. They should not give rise to measurable structural heterogeneity in the framework. The contribution of the crystal field stabilization energy (CFSE) of octahedral Fe2+ to the energetics of Mg–Fe cordierites was also investigated using published electronic absorption spectra (Khomenko et al. 2001). Two bands are observed between 8,000 and 10,500 cm-1 and they represent electronic dd-excitations of octahedral Fe2+ derived from the 5T2g 5Eg transition. They shift to higher wavenumbers with increasing XMg in cordierite. An analysis gives slightly asymmetric excess -CFSE across the Mg–Fe cordierite join with a maximum of about –550 J/mole towards iron-rich compositions.Editorial responsibility: J. Hoefs  相似文献   

14.
Kojitani  H.  Nishimura  K.  Kubo  A.  Sakashita  M.  Aoki  K.  Akaogi  M. 《Physics and Chemistry of Minerals》2003,30(7):409-415
Raman spectroscopy of calcium ferrite type MgAl2O4 and CaAl2O4 and heat capacity measurement of CaAl2O4 calcium ferrite were performed. The heat-capacity of CaAl2O4 calcium ferrite measured by a differential scanning calorimeter (DSC) was represented as CP(T)=190.6–1.116 × 107T–2 + 1.491 × 109T–3 above 250 K (T in K). The obtained Raman spectra were applied to lattice dynamics calculation of heat capacity using the Kieffer model. The calculated heat capacity for CaAl2O4 calcium ferrite showed good agreement with that by the DSC measurement. A Kieffer model calculation for MgAl2O4 calcium ferrite similar to that for CaAl2O4 calcium ferrite was made to estimate the heat capacity of the former. The heat capacity of MgAl2O4 calcium ferrite was represented as CP(T)=223.4–1352T –0.5 – 4.181 × 106T –2 + 4.300 × 108T –3 above 250 K. The calculation also gave approximated vibrational entropies at 298 K of calcium ferrite type MgAl2O4 and CaAl2O4 as 97.6 and 114.9 J mol–1 K–1, respectively.  相似文献   

15.
Examination of schorlomite from ijolite at Magnet Cove (USA) and silicocarbonatite at Afrikanda (Russia), using electron-microprobe and hydrogen analyses, X-ray diffraction and Mössbauer spectroscopy, shows the complexity of substitution mechanisms operating in Ti-rich garnets. These substitutions involve incorporation of Na in the eightfold-coordinated X site, Fe2+ and Mg in the octahedrally coordinated Y site, and Fe3+, Al and Fe2+ in the tetrahedrally coordinated Z site. Substitutions Ti4+Fe3+Fe3+–1Si–1 and Ti4+Al3+Fe3+–1Si–1 are of major significance to the crystal chemistry of schorlomite, whereas Fe2+ enters the Z site in relatively minor quantities (<3% Fe). There is no evidence (either structural or indirect, such as discrepancies between the measured and calculated Fe2+ contents) for the presence of [6]Ti3+ or [4]Ti4+ in schorlomite. The simplified general formula of schorlomite can be written as Ca3Ti4+2[Si3-x(Fe3+,Al,Fe2+)xO12], keeping in mind that the notion of end-member composition is inapplicable to this mineral. In the published analyses of schorlomite with low to moderate Zr contents, x ranges from 0.6 to 1.0, i.e. Ti4+ in the Y site is <2 and accompanied by appreciable amounts of lower-charged cations (in particular, Fe3+, Fe2+ and Mg). For classification purposes, the mole percentage of schorlomite can be determined as the amount of [6]Ti4+, balanced by substitutions in the Z site, relative to the total occupancy in the Y site: ([6]Ti4+–[6]Fe2+–[6]Mg2+– [8]Na+)/2. In addition to the predominant schorlomite component, the crystals examined in this work contain significant (>15 mol.%) proportions of andradite (Ca3Fe3+2Si3O12), morimotoite (Ca3Fe2+TiSi3O12), and Ca3MgTiSi3O12. The importance of accurate quantitative determination and assignment of Fe, Ti and other cations to the crystallographic sites for petrogenetic studies is discussed.
A. R. ChakhmouradianEmail: Phone: +1-204-4747278Fax: +1-204-4747623
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16.
A series of amphiboles along the magnesioriebeckite—Na2Mg3Fe3+ 2Si8O22(OH)2– ferri-clinoholmquistite—Li2Mg3Fe3+ 2Si8O22(OH)2 - join, defined by the BLiB Na–1 exchange vector, were hydrothermally synthesized at 700°C, 0.4 GPa, NNO + 1 redox conditions. Powder XRD and SEM-EDAX showed a very high (> 90%) amphibole yield for all samples. X-ray patterns were indexed in the C2/m space group; refined cell-parameters show a linear decrease of a and as a function of chemistry. IR spectra in the OH-stretching region show four main and rather sharp bands; these are assigned to Mg and Fe2+ at M(1,3), and indicate that the obtained amphiboles depart from the nominal octahedral composition (M1,3Mg3). The IR spectra also show that there is an increasing filling-up of the A-site for increasing Na in the system (increasing solid-solution toward, arfvedsonite). Mössbauer spectra show four well-defined quadrupole doublets which are assigned to Fe3+ at M2 and to Fe2+ at M1, M3 and M4, respectively. The Fe3+/Fe2+ content derived from fitted peak areas show variable Fe3+ concentration along the series. Mössbauer spectra also show a distinct alteration of 57Fe hyperfine parameters with changing Na–Li at M4. The most evident variation is observed for the quadrupole splitting of Fe3+ at M2, which increases by 50% from ferri-clinoholmquistite to magnesio-riebeckite; this suggest that the M2 octahedron in ferri-clinoholmquistite is much closer to the ideal geometry than the M2 octahedron in magnesio-riebeckite. Mössbauer spectra show also a well-defined increase in the Fe2+ quadrupole splitting of the M1 and M3 octahedra, which is attributed to the Na–Li distribution at the B-sites.  相似文献   

17.
Ti-andradite (melanite) has been found in a metapyroxenite layer in the upper part of the Malenco ultramafics(Italy), coexisting with clinochlore, diopside and magnetite. Field observations, as well as major and trace elementbulk-rock composition, strongly suggest a cumulate origin for the layer. Textural relationships indicate thatTi-andradite formed during two different metamorphic stages. Under peak metamorphic conditions (400–450°C, 5±2 kbar)Ti-andradite grew in an assemblage of diopside, clinochlore, magnetite and rare ilmenite and perovskite. Later, retrograde brittle deformationinduced formation of veins containing the paragenesis Ti-andradite, vesuvianite, diopside, chlinochlore, magnetite and accessory perovskite.The Ti-andradite varies considerably in TiO2 (0.11–9.62 wt%), Fe2O3(14.3–30.5 wt%), Al2O3 (0.65–3.90 wt%), Cr2O3(>0.18–0.98 wt%) and SiO2 (32.1–36.1 wt%); this is mostly, but not entirely, due to distinct zoning.Ti-andradite contains 0.32 to 0.66 wt% H2O as determined by infrared spectroscopy and 0.83 to 1.76 wt% FeO. The CaO shows almost no variation (34.1±0.7 wt%) and Ca completely fills the dodecahedral site. Single crystal site refinements indicate that no tetrahedral Ti or Fe replaces Si. Titanium incorporation is attributed to similar degrees of substitution along the exchange vectors Ti3+ Fe3+, Ti4+ AlIV Al -1 VI Si-1 and (Fe2+, Mn2+, Mg2+)Ti4+ 2Fe -1 3+ . The presence of mixed valence states of both Fe and Ti suggests a low oxygen fugacity during crystallization of Ti-andradite. Mass balance calculations indicate an isochemical origin of the first generation of Ti-andradite in the clinopyroxenite layer. Its occurrence is restricted to antigorite-free mineral assemblages containing clinochlore of 0.95X Al>1.1. The hydrothermal crystallization of Ti-rich andradite in veins demonstrates Ti mobility in aqueous fluids under moderate P-T conditions. The zonation patterns indicate disequilibrium conditions during vein crystallization. As no fluorine-, carbonate- and phosphate-bearing minerals were found, OH- is most probably the ligand complexing Ti.  相似文献   

18.
The synthesis and the chemical, structural, magnetic, and Mössbauer spectral characterization of three synthetic alluaudites, Na2Mn2Fe(PO4)3, NaMn Fe2(PO4)3 and Na2MnFeIIFeIII(PO4)3, and a natural sample with the nominal composition of NaMn Fe2(PO4)3, collected in the Buranga pegmatite, Rwanda, are reported. All four compounds have the expected alluaudite monoclinic C2/c structure with the general formula [A(2)A(2)][A(1)A(1)A(1)2]M(1)M(2)2(PO4)3 in which manganese(II) is on the M(1) site and manganese(II), iron(III) and, in some cases, iron(II) on the M(2) site. The X-ray structure of Na2Mn2Fe(PO4)3 also indicates a partially disordered distribution of NaI and MnII on the M(1) and A(1) crystallographic sites. All four compounds are paramagnetic above 40 K and antiferromagnetically ordered below. Above 40 K the effective magnetic moments of NaMnFe2(PO4)3 and Na2MnFeIIFeIII(PO4)3 are those expected of high-spin manganese(II) and iron(III) with the 6A1g electronic ground state and high-spin iron(II) with the 5T2g electronic ground state. In contrast, the effective magnetic moment of Na2Mn2Fe(PO4)3 is lower than expected as a result of enhanced antiferromagnetic exchange coupling by the manganese(II) on the M(2) site. The Mössbauer spectra of all four compounds have been measured from 4.2 to 295 K and have been found to be magnetically ordered below 40 K for Na2Mn2Fe(PO4)3 and 35 K for the remaining compounds. The Mössbauer spectra of Na2Mn2Fe(PO4)3 exhibit the two expected iron(III) quadrupole doublets and/or magnetic sextets expected for a random distribution of manganese(II) and iron(III) ions on the M(2) site. Further, the Mössbauer spectra of Na2MnFeIIFeIII(PO4)3 exhibit the two iron(II) and two iron(III) quadrupole doublets and/or magnetic sextets expected for a random distribution of iron(II) and iron(III) on the M(2) site. Surprisingly, the synthetic and natural samples of NaMnFe2(PO4)3 have 19 and 10% of iron(II) on the M(2) site; apparently the presence of some iron(II) stabilizes the alluaudite structure through the reduction of iron(III)–iron(III) repulsion. The temperature dependence of the iron(II) quadrupole splitting yields a 440 to 600 cm–1 low-symmetry component to the octahedral crystal field splitting at the M(2) site. The iron(II) and iron(III) hyperfine fields observed at 4.2 K are consistent with the presence of antiferromagnetic ordering at low temperatures in all four compounds.  相似文献   

19.
The structural behavior of -eucryptite (LiAlSiO4) has been investigated using infrared (IR) spectroscopy over a temperature range of 20 to 900 K and FT-Raman spectroscopy at room temperature. IR reflectance measurements show that -eucryptite possesses high reflectivity in the far-IR region, as is consistent with its reported superionic conductivity along the c-axis. On heating, the Li-related IR bands near 246 and 300 cm–1 (with A2 symmetry) broadened and weakened dramatically, presumably as a result of Li+ positional disordering along the structural channels parallel to c. The disordering process appears to induce a framework distortion, as is evidenced by the broadening of some vibrations of Si(Al)–O with increasing temperature. A change in slope in the temperature dependence of the phonon frequency near 300 cm–1 and the linewidth of the 760 cm–1 band at 715 K indicates that Li becomes completely disordered above this temperature. In addition, the temperature dependence of the linewidth for the 760 cm–1 band exhibits an additional change in slope at 780 K, implying the existence of an intermediate state within this temperature range. The detailed structure of this intermediate phase, however, needs further study. Our IR data provide no indication of structural changes between room temperature and 20 K.  相似文献   

20.
The thermoelastic behaviour of a natural gedrite having the crystal-chemical formula ANa0.47 B(Na0.03 Mg1.05 Fe0.862+ Mn0.02 Ca0.04) C(Mg3.44 Fe0.362+ Al1.15 Ti0.054+) T(Si6.31 Al1.69)O22 W(OH)2 has been studied by single-crystal X-ray diffraction to 973 K (Stage 1). After data collection at 973 K, the crystal was heated to 1,173 K to induce dehydrogenation, which was registered by significant changes in unit-cell parameters, M1–O3 and M3–O3 bond lengths and refined site-scattering values of M1 and M4 sites. These changes and the crystal-chemical formula calculated from structure refinement show that all Fe2+ originally at M4 migrates into the ribbon of octahedrally coordinated sites, where most of it oxidises to Fe3+, and there is a corresponding exchange of Mg from the ribbon into M4. The resulting composition is that of an oxo-gedrite with an inferred crystal-chemical formula ANa0.47 B(Na0.03 Mg1.93 Ca0.04) C(Mg2.56 Mn0.022+ Fe0.102+ Fe1.223+ Al1.15 Ti0.054+) T(Si6.31 Al1.69) O22 W[O1.122− (OH)0.88]. This marked redistribution of Mg and Fe is interpreted as being driven by rapid dehydrogenation at the H3A and H3B sites, such that all available Fe in the structure orders at M1 and M3 sites and is oxidised to Fe3+. Thermoelastic data are reported for gedrite and oxo-gedrite; the latter was measured during cooling from 1,173 to 298 K (Stage 2) and checked after further heating to 1,273 K (Stage 3). The thermoelastic properties of gedrite and oxo-gedrite are compared with each other and those of anthophyllite.  相似文献   

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