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1.
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2.
The tetrahedral-site order-disorder transformation in gallium albite (NaGaSi3O8) has been investigated using Rietveld structure refinement. Study of gallium-substituted albite (in contrast to pure albite [NaAlSi3O8]) is facilitated by a relatively rapid order-disorder transformation and the large difference in X-ray scattering efficiencies of gallium and silicon. High albite-structure NaGaSi3O8, grown in a Na2WO4 flux, was ordered by hydrothermal annealing below 820° C and dry annealing above 820° C, to avoid melting, using a load pressure of approximately 1 kbar. Equilibration of the order-disorder reaction has been verified by three independent reversals of ordering. The transformation between low gallium albite and high gallium albite occurs over the temperature range 890° C 970° C. The gallium content of the T 1o site increases continuously with decreasing temperature. The gallium contents of the T 1m and T 2m sites decrease smoothly with increasing ordering while the gallium content of the T 2o site decreases, then increases and then decreases again with decreasing temperature. Unit-cell parameters and the triclinic obliquity vary throughout the order-disorder transformation and undergo abrupt changes at 913±3° C and 937±3° C. These abrupt changes correlate with changes in the gallium content of the T 2o site, the X and Z ordering parameters and the configurational entropy. The order-disorder transformation in gallium-aluminum albite (NaGa0.5Al0.5Si3O8) occurs in the temperature range 765° C-850° C, at a temperature intermediate to the transformation in albite (50% order at about 680±20° C) and gallium albite.  相似文献   

3.
The elastic moduli of magnesioferrite spinel, MgFe2O4, and their temperature dependence have been determined for the first time by ultrasonic measurements on a polycrystalline specimen. The measurements were carried out at 300 MPa and to 700°C in a gas-medium high-pressure apparatus. On heating, both the elastic bulk (K S) and shear (G) moduli decrease linearly to 350°C. By combining with extant thermal-expansion data, the values for the room-temperature K S and G, and their temperature derivatives are as follows: K 0 = 176.3(7) GPa, G 0 = 80.1(2) GPa, (∂K S/∂T) P = −0.032(3) GPa K−1 and (∂G/∂T) P = −0.012(1) GPa K−1. Between 350 and 400°C, there are abrupt increases of 1.4% in both of the elastic moduli; these closely coincide with the magnetic Curie transition that was observed by thermal analyses at about 360°C.  相似文献   

4.
The published 29Si NMR data on synthetic Mg-cordierites have been used to estimate the changes in configurational Al-Si entropy of the samples due to metastable disorder. The results show that with the increase of the time of annealing in the range of 2 min-2000 h at 1185 °C the entropy of disorder in cordierite decreases from 17.1 to 6.4 J/mol K, while at 1400 °C in the range of 2 min–88 h the entropy changes from 15.4 to 8.8 J/mol K. The decrease in entropy is followed by the appearance and increase of long-range ordering which is reflected in changes of T1 and T2 site occupancies, decrease in the number of Si-O-Si and Al-O-Al groupings around O1 oxygens and in a decrease in the number of Al-O-Si-O-Al contacts among hexagonal 6T2-rings. The derived values of entropy effects together with published calorimetric data suggest that the enthalpy of metastable disordering strongly depends on the temperature of annealing.  相似文献   

5.
The kinetics of monodomain order-disorder processes in monoclinic (I2/c) BaAl2Ge2O8-feldspar have been investigated by X-ray powder diffraction, Hard Mode IR Spectroscopy, and TEM darkfield imaging on quenched samples. Compared to the behaviour predicted by the TDGL approximation ordering kinetics observed at low temperatures slow down significantly when equilibrium is approached. Such a delay is not observed in disordering experiments starting from essentially ordered cation distributions. The deviation from TDGL behaviour is interpreted in terms of partial order parameter conservation in a non-uniformly ordered phase. Modifications to the uniform TDGL rate equation are tested against the available data. An activation energy of 352 ± 28 kJ/mol is obtained for Al,Ge ordering. The mixing coefficient ξc 2/ξ2, which describes the degree of order parameter conservation, is obtained as a function of temperature. While this coefficient vanishes in the vicinity of the transformation temperature T tr, it saturates towards a level of ξc 2/ξ2≈0.4 for T→0. ξ c 2/ξ2 determines the kinetic stability of ordered clusters quenched from T≈T tr. Received: 21 April 1999 / Revised, accepted: 19 July 1999  相似文献   

6.
The nature of the stability of an incommensurate 3D modulation (ITM) in the structure of Baikal lazurite was evaluated using the methods of experimental geochemistry and X-ray photoelectron spectroscopy. It was shown that ITM with a period of 4.6a is preserved in the lazurite structure at 550°C almost without changes within the time interval from t = 100 h to at least 2000 h, although its initial (t = 0) development was not restored. In contrast to higher temperatures (≥ 600°C), the activities of gas species have no significant influence on the process of modulation release, except for the region of low O2, S2, and SO2 fugacities, where the type of modulation changes, and the monosulfide ion appears in the lazurite composition. At T = 550°C and probably at lower temperatures, SO2 fugacity ceases to be the critical parameter of ITM existence. The ordered state of polysulfide and sulfate clusters corresponding to the ITM period of Baikal cubic lazurite is stable at T = 550°C and is an example of forced equilibrium. It develops in response to a crystal chemical event occurring at a temperature of T x within 600–550°C and is related to the thermal compression of the structure resulting in the isolation of structural cages containing clusters with different states of sulfur. Their mutual interaction, which leads to the rapid release of the modulation at higher temperatures owing to the equalizing of cluster sizes in the cages, ceases. As a result, the proportions of reduced (S22−, and S x 2−) and oxidized (SO42−, So32−, and S2O32− sulfur species show negligible variations, and there is only partial reduction of sulfate to sulfite and thiosulfate. Lazurite samples with disulfide and polysulfide ions behave similarly, which suggests that an important condition for the preservation of ITM is the presence of sulfur-bearing anions with different sizes rather than particular sulfur species in structural cages. The degree of ordering in the distribution of clusters attained at T x remains unchanged owing to the development of forced equilibrium maintained by the energy balance between framework deformation and cluster ordering. Natural lazurite with an ITM structure could not form at temperatures higher than T x , i.e., above 550–600°C  相似文献   

7.
In this study, we present ac susceptibility measurements for a synthetic and a natural hemo-ilmenite (HI) solid solution (x)FeTiO3–(1 − x)Fe2O3 with compositions x = 0.87(1) and 0.88(8), respectively. The focus of the investigation is the magnetic ordering at the Curie temperature T C and the spin-glass-like freezing at the freezing temperature T f. The sharpness of T C for the synthetic solid solution with well-defined structure indicates the chemical homogeneity of the solution, whereas the disperse magnetic ordering of the natural solid solution reveals inhomogeneities described as spin glass system ofvariations in composition x. The frequency dispersion of T f was determined between 10 Hz and 10 kHz and was found to obey a dynamic scaling power law. The relaxation rates deviate by five orders of magnitude where the synthetic solid solution exhibits ω0 = 3(1) × 104 Hz and the natural one 5.5 × 109 Hz. The strong deviation is attributed to the difference in the ordered state above T f. These findings provide an insight into the cooling-rate effects of natural solid solutions and how magnetic thermodynamics can be used to probe the chemical homogeneity of such systems.  相似文献   

8.
On heating the paramagnetic clay mineral nontronite for ≈ 30 h at 970 °C in air, a new ferrimagnetic phase forms which was studied by magnetic techniques, microprobe analysis, x-ray diffraction and Mössbauer spectroscopy. The new phase has a Curie temperature T c ≈ 240°C and high magnetic anisotropy at room temperature with a spontaneous magnetization >12 Am2/kg. Semiquantitative microprobe analyses show Fe to be the dominating consistuent. X-ray analysis points to a lattice which may be similar to that of ?-Fe2O3 but differs from it in detail. 57Fe Mössbauer spectra, taken between 78 K and 295 °C, can be deconvoluted into three sextet subpatterns in the ferrimagnetic region which are well resolved at room temperature and exhibit a rather small line width. Above T c, a doublet is visible which is typical for Fe3+ ions.  相似文献   

9.
 The partitioning of Fe and Mg between the M1 and M2 octahedral sites of olivine has been investigated by in situ time-of-flight neutron powder diffraction. The degree of M-cation order was determined from direct measurements of site occupancies in a synthetic sample of Fo50Fa50 heated to 1250 °C at the Fe-FeO oxygen buffer. Fe shows slight preference for M1 at temperatures below about 600 °C, progressively disordering on heating to this temperature. Above 630 °C, the temperature at which site preferences cross over (T cr), Fe preferentially occupies M2, becoming progressively more ordered into M2 on increasing temperature. The cation-ordering behaviour is discussed in relation to the temperature dependence of the M1 and M2 site geometries, and it is suggested that vibrational entropy, crystal field effects and changes in bond characteristics play a part in the cross-over of partitioning behaviour. The temperature dependence of site ordering is modelled using a Landau expansion of the free energy of ordering of the type ΔG = −hQ + gTQ +  (T − T c)Q 2 +  Q 4, with a/h = 0.00406 K−1, b/h = 2.3, T c = 572 K and g/h = 0.00106 K−1. These results suggest that the high-temperature ordering behaviour across the forsterite-fayalite join will have a bearing on the activity-composition relations of this important rock-forming mineral, and indicate that Fe-Mg olivine solid solutions become less ideal as temperature increases. Received: 12 August 1999 / Accepted: 25 April 2000  相似文献   

10.
We have studied cation ordering in dolomite in situ as a function of pressure, temperature, and experimental time using the multi-anvil apparatus and synchrotron radiation. Starting with ordered dolomite, we observe the onset of disordering taking place at 950°C, while complete disordering is achieved at 1,070 (±20)°C, for pressures ranging between 3.37 and 4.05 GPa. Pressure does not appear to have significant effect on the order/disorder transition over the investigated range. We find that dolomite can reach its equilibrium ordering state above 900°C within duration of laboratory experiment (few hours), both from disordered state and from ordered state. In addition, we have reversed the dolomite breakdown reaction [magnesite + aragonite = dolomite] between 4.5 and 5.5 GPa, by monitoring diffraction peak intensity. We also have determined that dolomite is stable up to 7.4 GPa at 1,100°C. We confirm some earlier studies where a change in slope (dP/dT) has been observed, but we find a non-zero slope in the low pressure range. Combining the values of entropy obtained from dolomite degree of ordering with enthalpy values deduced from our bracketing of [magnesite + aragonite = dolomite] equilibrium, we model the location of dolomite breakdown in the P–T space as a function of cation ordering. By comparing previous conflicting studies, we show that, although kinetics of order/disorder is fast, disequilibrium dolomite breakdown is possible. Our modeling shows that subducted disordered dolomite present in carbonated sediments could be decomposed to [magnesite + aragonite] at lower pressure (3.5 GPa) than usually considered (>5 GPa). This 2-GPa (60 km) difference is valid on a fast subduction path and is possible if disorder inherited from sedimentation is preserved. On a slow subduction path, however, dolomite breakdown is encountered at about 250 km depth, which is 100 km deeper than currently considered.  相似文献   

11.
A model is developed for the thermodynamic properties of Fe2+–Mg2+-aluminate-titanate-ferrite spinels of space group Fd3m. The model incorporates an expression for the configurational entropy of mixing which accounts for long-range order over tetrahedral and octahedral sites. Short-range order or departures from cubic symmetry are not considered. The non-configurational Gibbs energy is formulated as a second degree Taylor expansion in six linearly independent composition and ordering variables. The model parameters are calibrated to reproduce miscibility gap constraints, order-disorder phenomena in MgAl2O4 and MgFe2O4, and Fe2+–Mg2+ partitioning data between olivine and: (1) aluminate spinels; (2) ferrite spinels; (3) titanate spinels; (4) mixed aluminate-ferrite spinels. This calibration is achieved without invoking non-configurational excess entropies of mixing. The model predicts that the ordering state of FeAl2O4 is more normal than that of MgAl2O4. It also successfully accounts for heat of solution measurements and activity-composition relations in the constituent binaries. Phase equilibrium constraints require that the structure of Fe3O4 is more inverse than random at all temperatures and that Mg2+ has a strong tetrahedral site preference with respect to that of Fe2+. The analysis suggests that in the titanates short range order on octahedral sites may be significant at temperatures as high as 1300° C. Constraints developed from calibrating the thermodynamic properties of Fe2+–Mg2+-aluminatetitanate-ferrite spinel solid solutions permit extension of the database of Berman (1988) to include estimates of the end-member properties of hercynite (FeAl2O4), ulvöspinel (Fe2TiO4), MgFe2O4 and cubic Mg2TiO4. In constructing these estimates, provision is made for low-temperature magnetic entropy contributions and the energetic consequences of disordering the aluminates and the ferrites. These estimates are consistent with all of the available low-temperature adiabatic calorimetry, high-temperature heat content, and heat of solution measurements on the end-members. The analysis implies that there is a substantial heat capacity anomaly in the range 300°–900° C associated with disordering of the MgAl2O4 structure while that in FeAl2O4 becomes significant at temperatures above 700° C. The same heat capacity response in the ferrites indicates that the order/disorder transformation is coupled to the antiferromagnetic-paramagnetic transition in MgFe2O4 but takes place well above the ferrimagnetic-paramagnetic transition in magnetite. The proposed model is internally consistent with solution theory reported elsewhere for Fe2+–Mg2+ olivines and orthopyroxenes (Sack and Ghiorso 1989), rhombohedral oxides (Ghiorso 1990a) and the remaining end-member properties of Berman (1988).  相似文献   

12.
We determined the forward rate constant (K+) for the Fe2+–Mg order–disorder between the M2 and M1 sites of orthopyroxene (OPx), which is described by the homogeneous reaction Fe2+ (M2) + Mg(M1) ↔ Mg(M2) + Fe2+ (M1), by both ordering and disordering experiments at isothermal condition and also by continuous cooling experiments. The rate constant was determined as a function of temperature in the range of 550–750°C, oxygen fugacity between quartz–fayalite–iron and Ni–NiO buffers, and at compositions of 16 and 50 mol% ferrosilite component. The K+ value derived from disordering experiment was found to be larger than that derived from ordering experiment at 550°C, while at T>580°C, these two values are essentially the same. The fO2 dependence of the rate constant can be described by the relation K+ α (fO2) n with n=5.5–6.5, which is compatible with the theoretically expected relation. The Arrhenius relation at the WI buffer condition is given by
where C o represents the total number of M2 + M1 sites occupied by Fe2+ and Mg per unit volume of the crystal. The above relation can be used to calculate the cooling rates of natural OPx crystals around the closure temperature (T c) of Fe–Mg ordering, which are usually below 300°C for slowly cooled rocks. We determined the Fe–Mg ordering states of several OPx crystals (∼ Fs50) from the Central Gneissic Complex (Khtada Lake), British Columbia, which yields T c ∼290°C. Numerical simulation of the change of Fe2+-Mg ordering in OPx as a function of temperature using the above expression of rate constant and a non-linear cooling model yields quenched values of ordering states that are in agreement with the observed values for cooling rates of 11–17°C/Myr below 300°C. The inferred cooling rate is in agreement with the available geochronological constraints.  相似文献   

13.
A thermometer based on the MgFe?1 exchange equilibrium between garnet and clinopyroxene is formulated by using new experimental data measured at 600° to 950°C, 0.8 to 3.0 GPa, and f(O2) defined by the fayalite-quartz-magnetite buffer in the basalt-H2O system. The new formulation is T = 3820 / 1.828 + lnKD (1 + a(2.2 ? p)), where T is temperature (K), P is pressure (GPa), KD is the Fe-Mg partition coefficient between garnet and clino-pyroxene, defined as KD = (Fe2+/Mg)garnet/(Fe2+/Mg) clinopyroxene, and a = 132/T. Application of the thermometer to rocks in amphibolite, granulite, and eclogite terranes yields temperatures that are in reasonable agreement with other well-calibrated thermometers and the experimental calibrations by Ellis and Green (1979) and Pattison and Newton (1989).  相似文献   

14.
A number of previous investigations have examined the ordering behavior of magnesium cordierite using X-ray diffraction, transmission electron microscopy, infrared spectroscopy and solution calorimetry. In the present investigation, one series of samples from the above studies has been examined by Raman spectroscopy. Systematic modifications in the spectra with annealing time at 1,200° C are consistent with a continuous ordering of the average Al/Si distribution from 4 h to at least 64 h, and which may begin earlier. Spectral changes are first definitely observed when the ordered domains are around 100 Å across, suggesting that Raman spectroscopy is sensitive to this distance scale. The spectra of samples annealed at 1,200° C are compared with samples annealed at 1,400°; C where ordering proceeds much faster, and the possible use of Raman spectroscopy in characterization of Al/Si order in cordierite is discussed. Finally, the Raman spectrum of Mg2Al4Si5O18 with a stuffed β-quartz structure has been obtained. Comparison of its spectrum with that of cordierite glass suggests similar structures for both, which seem different to that of disordered cordierite.  相似文献   

15.
Ferrimagnetic minerals in red paleosols of Pleistocene Epoch, eastern China   总被引：1，自引：1，他引：0  
The type,grain size and origin of ferimagnetic minerals separated from red paleosols of pleistocene Epoch(Q2)in eastern China ,were studied by using mineral magnetic measurement,X-ray powder diffraction and electron microscopy.Results showed that the iron oxider in red paleosols were composed of hematite(α-Fe2O3),maghemite(γ-Fe2O3) and goethite(α-FeOOH),Mineral magnetic parameters and X-ray diffraction patterns indicated that maghemite was the dominant remanence carrier in red paleosols,which is characterized by superparamagnetic(SP) and stable single domain(SSD) grains,The variations of magnetic susceptibility(χ） ,anhysteretic magnetic susceptibility(χRAM）and saturation isothermal remanent magnetization(SIRM) for red paleosols following heating to various temperatures showed two peak values at 700℃ and 900℃.The spherulitic magnetic particles measuring 250-1000μm in diameter in red paleosols were separated by the magnetic separation method,indicating that these magnetic particles were an assemblage of superparamagnetic and stable single domain ferrimagnetic grains,It is suggested that the ferrimagnetic minerals of red paleosols be a pedogenic ferrimagnetic component under high temperature and high humid conditions in the Pleistocene Fpoch(Q2).It is concluded that the magnetism characteristics of red paleosols can be used to evaluate the environmental changes of Quaternary in eastern China.  相似文献   

16.
The ordering of Al and Si in Mg cordierite Mg2Al4Si5O18 is considered using computer simulation. First the enthalpy of interaction J ij between sites is derived by computer modelling 101 different Al/Si configurations and analysing their energies. They are compared with similar results for three other minerals and with ab initio calculations to assess the whole approach. Secondly the ordering process is studied using Monte Carlo simulation applied to the J ij . The ordering phase transition temperature T c is found as 1800°C in reasonable agreement with the experimental estimate of 1450° C. These are much lower than the estimate T c(ABW)≈7600°C obtained from Bragg-Williams theory. Strong short-range order sets in below T c(ABW), and the reasons for much lower temperature T c of long-range ordering are discussed. Strong short-range also sets in very rapidly in a simulated anneal, in agreement with experiment. Thirdly an attempt is made to compare our calculated enthalpies directly with the results of NMR and calorimetry experiments, not completely successfully. A free energy ΔG≈4.6 eV for the activation barrier for ordering is suggested.  相似文献   

17.
Clay‐rich basins have undergone varying degrees of magnetic transformation during burial, affecting their ability to retain accurate records of Earth's dynamic magnetic field. We propose to bracket the magnetite‐out and pyrrhotite‐in temperatures in shales and slates from Taiwan and the Pyrenees by using a combination of low‐temperature magnetic transitions and geothermometers. For Tburial < 340°C, the magnetic assemblage is dominated by magnetite. Gradually with increasing burial temperature, the concentration of magnetite decreases to a few ppmv. We observe the magnetite‐out isograd at Tburial ~350°C. At Tburial >60°C and Tburial >340°C respectively, fine‐grained and coarse‐grained pyrrhotite develop. In the course of burial, a clay‐rich basin gradually loses its capability to retain a record of Earth's magnetic field. It is only during basin uplift, that coarse pyrrhotite might acquire a thermo remanent magnetization. Our results point out therefore highly contrasted magnetic properties and palaeomagnetic records between deeply buried basins and exhumed ones.  相似文献   

18.
Temporal stability of magnetic parameters of anthropogenic ferrimagnetics in model soil conditions was studied. Fly ash from a power plant was used as original contaminant material, while soil reactive medium was modeled by different soil solutions. Changes in mass-specific magnetic susceptibility (χ), percentage frequency dependent magnetic susceptibility (χFD%), hysteresis parameters and thermomagnetic curves were measured for samples which underwent different leaching time periods. Virtually constant magnetic susceptibility values were obtained, independently on the soil medium (acid, neutral). On the other hand, the original highly non-stoichiometric maghemite phase rapidly transformed to stable magnetite. In some cases (model of free-draining soils) further decrease of Curie temperature (Tc) to 550–560°C is observed.  相似文献   

19.
 Ferrian magnesian spodumene was synthesized in the MLFSH system at P=0.4 GPa, T=700 °C, fO2=NNO+2.3. The space group at room T is P21/c [a=9.638(3) ?, b=8.709(2) ?, c=5.258(2) ?, β=109.83(3)∘, V=415.2 ?3]. The structure is topologically equivalent to that of ferrian spodumene, LiFeSi2O6, and has two symmetrically independent tetrahedral chains, A and B, and two independent octahedral sites, M1 and M2. The crystal-chemical composition was determined combining EMP, SIMS and single-crystal XRD analysis, yielding M2(Li0.85Mg0.09Fe2+ 0.06) M1(Fe3+ 0.85Mg0.15)Si2O6. Li is ordered at the M2 site and Fe3+ is ordered at the M1 site, whereas Mg (and Fe2+) distribute over both octahedral sites. Structure refinements done at different temperatures (25, 70, 95, 125, 150 and 200 °C) allowed characterization of a reversible displacive P21/c→C2/c transition at 106 °C. Previous HT-XRD studies of Li-clinopyroxenes had shown that the transition temperature is inversely related to the size of the M1 cation. For the crystal of this work, the aggregate ionic radius at M1 is longer than that of ferrian spodumene, for which the transition temperature is −44 °C. The higher transition temperature observed can only be explained on the basis of the shorter aggregate radius at the M2 site (due to the presence of Mg substituting after Li), in keeping with the results obtained for ferromagnesian P21/c pyroxenes. The effects of all the chemical substitutions must be considered when modelling transition temperatures and thermodynamic behaviour in clinopyroxenes. Received: 7 May 2002 / Accepted: 23 October 2002  相似文献   

20.
Equations for the configurational entropy and homogeneous equilibria in Ca2MgSi2O7-Ca2SiAl2O7 melilites are derived for a site constraint that does not permit Mg on the smaller T2 tetrahedral sites. This constraint leads to one ordering parameter and one composition parameter. The maximum configurational entropy for perfectly ordered crystalline solutions is 3.795 cal K–1 mol–1, corresponding to the structural formula Ca2(Mg0.33Al0.67) (Si0.67Al0.33)2O7 and not the equimolar composition Ca2(Mg0.5Al0.5)(Si0.75Al0.25)2O7. Similarly, the configuration Ca2(Si0.33Al0.67)(Si0.33Al0.67)2O7 has the maximum entropy for the gehlenite end-member composition. The tabulated entropy of end-member gehlenite at 298.15 K must be corrected by at least 2Rln2, which corresponds to a substantial correction to its Gibbs energy at high temperature. The same corrections are applicable to other minerals having two crystallographically distinct sites in a 21 ratio and where the same configurational entropy equation applies: MgFe2O4 (magnesioferrite), NiFe2O4 (trevorite), TiFe2O4 (ulvospinel), TiMg2O4, TiZn2O4, CuFe2O4, and TiFe2O5 (pseudobrookite) inasmuch as these substances prefer the same inverse ordered state as gehlenite at low temperatures. The effects of the ideal enthalpy and entropy on temperatures of homogeneous equilibria in gehlenite and MgTi2O5 are evaluated. Geological-thermometer phase diagrams of the long-range ordering parameter plotted against temperature have a sigmoidal shape for these minerals owing to the fact that this type of disordering is non-convergent.  相似文献   

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