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1.
Fine textures of exsolution lamellae and interface boundaries between augite and pigeonite in augite crystals from Skaergaard ferrogabbro 4430 have been studied by high resolution electron microscopy and X-ray methods. Thick pigeonite lamellae have higher densities of (100) stacking faults than thin lamellae. The displacement vector of the faults has been determined as 5/6c from the measured density of faults and the relative rotation of the augite and pigeonite lattices. The augite and pigeonite lattices are apparently coherent, and no growth ledges were observed at the interfaces. The stacking faults are often combined with the antiphase boundary of pigeonite resulting in a total displacement vector of 1/2(a+b)+5/6c. The observation of thick and thin pigeonite lamellae indicated that the thickening of (001) pigeonite lamellae was controlled by coherency strains accumulated at the interfaces between augite and pigeonite.  相似文献   

2.
Two natural clinopyroxene single crystals were investigated, an aegirine-augite (AEG) and a magnesian hedenbergite (HED). Both samples were carefully characterized by electron microprobe, X-ray diffraction, and Mössbauer spectroscopy. Magnetic susceptibility measurements of powdered samples reveal low temperature antiferromagnetic coupling and Curie-Weiss behaviour with T N =7.5(5)?K, Θ P =?19(1)?K for AEG, and T N =31(1)?K, Θ P =+21(1)?K for HED, respectively. Low temperature Mössbauer spectra exhibit relaxation phenomena. Magnetic susceptibility measurements of the single crystals show the direction of the magnetic moments to be lying within the a/c plane for both samples: 50(±2)° from a and 57(±2)° from c in AEG, and 45(±2)° from a and 60(±2)° from c in HED, respectively. The antiferromagnetic interchain interaction competes with the ferromagnetic intrachain interaction in both pyroxenes. In the magnesian hedenbergite a field induced magnetic transition is found. Its dependence on temperature, magnetic field and crystallographic direction is investigated and described.  相似文献   

3.
The orthopyroxene crystal structure can be viewed as the stacking of alternating tetrahedral and octahedral layers parallel to the (100) plane. Easy glide occurs in the (100) plane at the level of the octahedral layer to prevent breakage of the strong Si-O bonds. Dislocations with c and b Burgers vectors have been activated in (100) by room temperature indentation in an orthoenstatite gem quality single crystal. Investigations in transmission electron microscopy show that the b dislocations (b?9 Å) are not dissociated while the c's (c=5.24 Å) are dissociated into four partials. This result is interpreted by considering the oxygen sublattice as a distorted FCC one. The four c partials are thus Shockley partials bounding three stacking faults. For the two outer ones, synchroshear of the cations is necessary to keep unchanged their sixfold coordination; the oxygen sublattice is locally transformed into a HCP lattice. This accounts for the observed low splitting (?100 Å) of these faults as compared to the median one (?500 Å) which does not affect the oxygen sublattice and does not require cation synchroshear. In a Fe rich orthopyroxene (eulite), semi coherent exsolution lamellae have been studied. Either only c edge dislocations or both b and c edge dislocations occur in the phase boundaries depending upon the thickness of the lamellae. Only the c dislocations are dissociated. From the observed spacing between these mismatch dislocations a crude estimate of the exsolution temperature is proposed T ex ? 700° C.  相似文献   

4.
The electronic absorption spectra of Fe2+ in non-chromium beryls are examined. Fe2+ in the Al-rich six-coordinate site produces absorption bands at about 820 nm and 970 nm polarizedE‖c. Fe2+ in the channel produces bands at 820 nm (⊥c) and 2100 nm (‖c). Some blue beryls which are more intensely colored than most aquamarines, have an absorption band at ～700 nm (‖c) which is suggested to arise from an Fe2+/Fe3+ intervalence interaction. Fe2+ in both the six-coordinate site and the channel is identified in the Mössbauer spectra. The Mössbauer spectra of deep blue beryls are unusual and have not been satisfactorily explained. Color changes which accompany heating and irradiation are strongly influenced by the channel iron.  相似文献   

5.
Single crystals of hexagonal and monoclinic pyrrhotite, Fe1?xS, have been experimentally deformed by uniaxial compression at 300 MPa confining pressure, and at a strain rate of 1 × 10?5 s?1 in the temperature range from 200° C to 400° C. Very high anisotropy characterizes the mechanical behaviour of the crystal structure. During compression parallel to thec-axis, when no slip system may be activated, the maximum strength is observed. One or two degrees of non-parallelism between [c] and σ1 results in slip on the basal plane, illustrating the very low resistance of the lattice against shear in this plane. At σ1 Λ(0001)=45°, i.e. when maximum resolved shear stress is attained on the basal plane, the strength reaches a minimum. Thecritical resolved shear stress (CRSS) increases from less than 4.7 MPa at 400° C to 52 MPa at 200° C. A new slip system, \((10\overline 1 0)\parallel \left\langle {1\overline 2 10} \right\rangle \) prism slip, is described. It is activated only at high angles (>70°) between σ1 and [c]. The CRSS of the prism slip ranges from 7 MPa (400° C) to 115 MPa (200° C). Twinning on \((10\overline 1 2)[(10\overline 1 2):(1\overline 2 10)]\) , earlier reported by several authors, has been produced only at the highest temperature either as secondary feature during pressure release (compression ‖[c]) or in heterogeneously strained areas (compression ⊥[c]). As twinning and prism slip attain their maximum values of the Schmidt factor under nearly equal stress conditions it is postulated that the former of the two deformation modes has the higher shear resistance.  相似文献   

6.
Combining a miniature diamond-anvil pressure cell with a single crystal four-circle diffractometer, the crystal structure of a synthetic ZrO2 has been studied in situ up to 51 kbar at room temperature. The space group of the unquenchable orthorhombic high pressure phase is Pbcm. The directions of the b and c axes are preserved through the transition and the transformation is displacive. The coordination configurations of the Zr atoms and oxygen atoms are the same in the high pressure and low pressure phases. The orthorhombic high pressure phase has a higher entropy than that of low pressure monoclinic phase.  相似文献   

7.
The polarized (E‖a′, E‖b and E‖c) electronic absorption spectra of five natural chromium-containing clinopyroxenes with compositions close to chromdiopside, omphacite, ureyite-jadeite (12.8% Cr2O3), jadeite, and spodumene (hiddenite) were studied. The polarization dependence of the intensities of the Cr3+ bands in the clinopyroxene spectra cannot be explained by the selection rules for the point groups C 2 or C 2v but can be accounted for satisfactorily with the help of the higher order pseudosymmetry model, i.e. with selection rules for the point symmetry group C 3v. The trigonal axis of the pseudosymmetry crystal field forms an angle of 20.5° with the crystallographic direction c in the (010) plane. D q increases from diopside (1542 cm?1) through omphacite (1552 cm?1), jadeite (1574 cm?1) to spodumene (1592 cm?1). The parameter B which is a measure of covalency for Cr3+-O bonds at M1 sites in clinopyroxene depends on the Cr3+ concentration and the cations at M2 sites.  相似文献   

8.
The structural deformation of an andalusite single crystal, shockloaded up to 400 kb with shock wave direction approximately parallel to c, was investigated by means of X-ray powder (Guinier) and single crystal techniques (Weissenberg, precession). Exposure to the dynamic pressure revealed a fracturing of the crystal into lattice blocks, with a mean size >1,000 Å. No change of the lattice constants could be observed after pressure release. From the streaks of X-ray reflection spots measured within the hk0, h0l, 0kl, and hhl planes the shock-induced lattice deformation is interpreted in terms of rotational gliding and/or microfracturing. The distortion mode is highly structure controlled. It follows preferrably two different structural motion systems: (1) Gliding parallel to (001) occurs, which produces lamellae parallel to (001), mainly arranged in two sublattices with common c-axis. The stacking sequence of lamellae along c is irregular. The lamellae-type structure may also result from an orientated transformation into a high pressure phase of lower symmetry and subsequent inversion into the original phase after pressure release. (2) Gliding parallel to (100) occurs. In this case the deformation mode is asymmetrical with respect to the undistorted crystal. The common direction b of the (001) and (100) deformation planes is probably the main direction of the shock-induced lattice deformation.  相似文献   

9.
Two crystals of natural chalcopyrite, CuFeS2, experimentally deformed at 200° C have been studied by means of transmission electron microscopy (TEM). The activated glide planes are (001) and {112}. The dislocations in (001) have the Burgers vector [110] and a predominating edge character. They are split into two colinear partials b=1/2[110] and can cross split into {112}. The dislocations in {112} consist of straight segments along low index lattice lines. They are often arranged in dipoles generating trails of loops. Few dislocations with b=1/2[ \(\overline {11} \) 1] and [1 \(\bar 1\) 0] are present and dislocations with b=[0 \(\bar 2\) 1] occur in low angle subgrain boundaries. From weak beam contrasts it is presumed that most of the dislocations gliding in {112} have b=1/2〈3 \(\overline {11} \) 〉. They are dissociated into up to four partials. Microtwins and different types of stacking faults in {112} also occur. Models of the dissociation of dislocations are discussed.  相似文献   

10.
Ar, N2 and CO2 were introduced into the structural cavities of channel-evacuated single-crystals of White Well cordierite with the composition: K0.01Na0.03(Mg1.91Fe0.09Mn0.01)Al3.98Si5.01O18. The gas refilling experiments were carried out in conventional hydrothermal bombs at 6–7 kbar and 600–700°C. The increase in the mean refractive indices for gas-treated crystals, as determined with a spindle-stage equipped microscope, was used along with point-dipole calculations to estimate the percentage of occupied structural cavities. The steep increase of the electronic polarizability parallel to the a-axis, which can be derived from the increase of the refractive index n γ (Z∥a) upon introduction of volatiles, indicates that N2 and CO2 are preferentially aligned parallel to the a-axis of cordierite. Single-crystal structure refinements at room temperature confirm these predictions. Additionally, decreased C–O and N–N bond lengths suggest a librational motion with a mean rotary oscillation angle of 35° (N2) and 25° (CO2) about a, where c is the rotation axis. Mean libration angles of 40° (N2) and 28° (CO2) were estimated from the electronic polarizability tensors of CO2 and N2. Site occupancy refinements of the channel position are in good agreement with the optically derived values for the volatile concentrations, both indicating about 70% and 60% filled cavities for Ar- and N2-cordierite, respectively. Chemical analyses and point-dipole calculations confirm that about 45% of the cavities are occupied in the CO2-treated crystal. The structural framework of cordierite is slightly but specifically altered by the various channel occupants.  相似文献   

11.
Deformation-induced stacking defects in dolomite have been characterised following examination at the cation sublattice level using high-resolution electron microscopy at 500kV. Slip on c (≡{0001}) is observed to produce stacking faults, often de-localised laterally, which are terminated by partial dislocations with Burgers vectors of the form 1/3 [1 \(\overline 1 \) 00]: a model for the faulted dolomite lattice has been constructed which agrees with the image appearance. Slip on f (≡{10 \(\overline 1 \) 2}) produces long planar faults which are established as not being stacking faults, in the normal sense, since there appear to be no offsets of the cation sublattice across the faults, nor any general indication of any terminating partial dislocations: it is proposed that the contrast arises from rotational disorder in CO3 groups which has resulted from the prior passage of partial dislocations during deformation.  相似文献   

12.
The power law regression equation, <R(M–O)> = 1.46(<ρ(r c)>/r)?0.19, relating the average experimental bond lengths, <R(M–O)>, to the average accumulation of the electron density at the bond critical point, <ρ(r c)>, between bonded pairs of metal and oxygen atoms (r is the row number of the M atom), determined at ambient conditions for oxide crystals, is similar to the regression equation R(M–O) = 1.41(ρ(r c)/r)?0.21 determined for three perovskite crystals at pressures as high as 80 GPa. The pair are also comparable with the equation <R(M–O)> = 1.43(<s>/r)?0.21 determined for oxide crystals at ambient conditions and <R(M–O)> = 1.39(<s>/r)?0.22 determined for geometry-optimized hydroxyacid molecules that relate the geometry-optimized bond lengths to the average Pauling bond strength, <s>, for the M–O bonded interactions. On the basis of the correspondence between the equations relating <ρ(r c)> and <s> with bond length, it seems plausible that the Pauling bond strength might serve a rough estimate of the accumulation of the electron density between M–O bonded pairs of atoms. Similar expressions, relating bond length and bond strength hold for fluoride, nitride and sulfide molecules and crystals. The similarity of the expressions for the crystals and molecules is compelling evidence that molecular and crystalline M–O bonded interactions are intrinsically related. The value of <ρ(r c)> = r[(1.41)/<R(M–O)>]4.76 determined for the average bond length for a given coordination polyhedron closely matches the Pauling’s electrostatic bond strength reaching each the coordinating anions of the coordinated polyhedron. Despite the relative simplicity of the expression, it appears to be more general in its application in that it holds for the bulk of the M–O bonded pairs of atoms of the periodic table.  相似文献   

13.
Polarized electronic absorption spectra, E∥a(∥X), E∥b(∥Y) and E∥c(∥Z), in the energy range 3000–5000?cm–1 were obtained for the orthorhombic thenardite-type phase Cr2SiO4, unique in its Cr2+-allocation suggesting some metal-metal bonding in Cr2+Cr2+ pairs with Cr-Cr distance 2.75?Å along [001]. The spectra were scanned at 273 and 120?K on single crystal platelets ∥(100), containing optical Y and Z, and ∥(010), containing optical X and Z, with thicknesses 12.3 and 15.6?μm, respectively. Microscope-spectrometric techniques with a spatial resolution of 20?μm and 1?nm spectral resolution were used. The orientations were obtained by means of X-ray precession photographs. The xenomorphic, strongly pleochroic crystal fragments (X deeply greenish-blue, Y faint blue almost colourless, Z deeply purple almost opaque) were extracted from polycrystalline Cr2SiO4, synthesized at 35?kbar, above 1440?°C from high purity Cr2O3, Cr (10% excess) and SiO2 in chromium capsules. The Cr2SiO4-phase was identified by X-ray diffraction (XRD). Four strongly polarized bands, at about 13500 (I), 15700 (II), 18700 (III) and 19700 (IV) cm–1, in the absorption spectra of Cr2SiO4 single crystals show properties (temperature behaviour of linear and integral absorption coefficients, polarization behaviour, molar absorptivities) which are compatible with an assignment to localized spin-allowed transitions of Cr2+ in a distorted square planar coordination of point symmetry C2. The crystal field parameter of Cr2+ is estimated to be 10?Dq?10700?cm–1. A relatively intense, sharp band at 18400?cm–1 and three other minor features can, from their small half widths, be assigned to spin-forbidden dd-transitions of Cr2+. The intensity of such bands strongly decreases on decreasing temperature. The large half widths, near 5000?cm–1 of band III are indicative of some Cr-Cr interactions, i.e. δ-δ* transitions of Cr2 4+, whereas the latter alone would be in conflict with the strong polarization of bands I and II parallel [100]. Therefore, it is concluded that the spectra obtained can best be interpreted assuming both dd-transitions of localized d-electrons at Cr2+ as well as δ-δ* transitions of Cr2 4+ pairs with metal-metal interaction. To explain this, a dynamic exchange process 2 Crloc 2+?Cr2, cpl 4+ is suggested wherein the half life times of the ground states of both exchanging species are significantly longer than those of the respective optically excited states, such that the spectra show both dd- and δ-δ*-transitions.  相似文献   

14.
Metamorphic biotites examined by transmission electron microscopy contain planar defects on the (001) plane, superlattices, twins and a microstructure causing streaking of k≠3n rows. Analysis of the fringe contrast shows that the fault vectors associated with the planar defects are either R 1=±1/3 [010], R 2=±1/6 [310] or R 3=±1/6 [3 \(\bar 1\) 0]. Structural considerations indicate that a stacking fault R 1, R 2 or R 3 is most likely to exist in the octahedral layer rather than the potassium layer. The result of such a fault on a unit layer of mica is effectively to rotate it through ±120° about c* (equivalent to the common mica twin law). These stacking faults can provide the mechanism for producing the ±120° rotations associated with the common mica polytypes. Furthermore, many of the observed microstructures can be generated by these stacking faults.  相似文献   

15.
Two new protoamphibole-type amphiboles with space group type Pnmn, have been found in nature: protoferro-anthophyllite (Fe0.80Mn0.20)2 (Fe0.98Mg0.02)5 (Si4O11)2(OH)2, and protomangano-ferro-anthophyllite, (Mn0.70Fe0.30)2 (Fe0.82Mg0.18)5 (Si4O11)2(OH)2. Protoferro-anthophyllite (PFA) occurs in pegmatites at both Gifu Prefecture, Japan and at Cheyenne Mountain, El Paso County, Colorado, USA. Protomangano-ferro-anthophyllite, (PMFA) occurs in pegmatites at Fukushima Prefecture and in a Mn mine at Tochigi Prefecture, Japan. Structure determinations of the two amphiboles show that both are isostructural with the synthetic fluorian-amphibole, protoamphibole (= protofluorian-lithian-anthophyllite). A calculation of the procrystal electron density distributions, the bond paths and the bond critical point properties of PFA, PMFA, grunerite and protoamphibole indicates that the M4 cation in these amphiboles is 4-coordinated. A calculation of the electron density distributions at the Becke3LYP/6-311G(2d,p) level for model silicate tetrahedra for these amphiboles and anthophyllite reveals that the value of the electron density at the bond critical points, ρ(r c ), for the SiO(nbr) bonds is larger, on average (0.93 e/Å3), than that for the SiO(br) bonds (0.90 e/Å3). The observed SiO bond lengths decrease linearly with increasing ρ(r c ) while the magnitudes of the curvatures of ρ(r c ) both perpendicular and parallel to the bonds and the Laplacian of ρ(r c ) each increases. These trends are associated with an increase in the electronegativity of the Si cation, a possible increase in the covalent character of the SiO bond and a tendency for SiO(nbr) bonds to be involved in wider OSiO angles than SiO(br) bonds. It is possible, if not likely, that protoanthophyllite has often been misidentified as anthophyllite.  相似文献   

16.
The electron paramagnetic resonance (EPR) spectrum of Cr3+ in synthetic crystals of forsterite consists primarily of lines of Cr3+ “isolated” at the M1 and M2 positions in a “perfect” crystal environment without local charge compensation. In addition it shows two nonequivalent superhyperfine-split sextets with different intensities which are due to strong interaction of the Cr3+ electron spin S (S=3/2) with an adjacent nuclear spin I(I=5/2). Electron nuclear double resonance (ENDOR) experiments revealed that the sextets result from Cr3+ (M1) - Al3+ and Cr3+ (M2) - Al3+ pairs, Al being located at adjacent tetrahedral Si sites. The g, D, A, and A′ tensor components of the Cr3+ - Al3+ pairs have been determined at room temperature. The values of the pairs are distinct although they are not very different from the corresponding data of “isolated” Cr3+. From the intensities of the EPR spectra the relative concentration of the Cr3+ - Al3+ pairs with respect to “isolated” Cr3+ has been estimated.  相似文献   

17.
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18.
Polycrystalline material of a sulfate apatite with chemical composition Na6Ca4(SO4)6F2 or (Na2Ca4)Na4(SO4)6F2 has been synthesized by solid state reactions. Basic crystallographic data are as follows: hexagonal symmetry, a?=?9.3976(1) Å, c?=?6.8956(1) Å, V?=?527.39(1) Å3, Z?=?1, space group P63/m. For structural investigations the Rietveld method was employed. Thermal expansion has been studied between 25 and 600 °C. High temperature (HT) powder diffraction data as well as thermal analysis indicate that the apatite-type compound undergoes a reconstructive phase transition in the range between 610 and 630 °C. Single-crystals of the HT-polymorph were directly grown from the melt. Structural investigations based on single-crystal diffraction data of the quenched crystals performed at ?100 °C showed orthorhombic symmetry (space group Pna21) with a?=?12.7560(8) Å, b?=?8.6930(4) Å, c?=?9.8980(5) Å, V?=?1097.57(10) Å3 and Z?=?2. Unit cell parameters for a quenched polycrystalline sample of the HT-form obtained at ambient conditions from a LeBail-fit are as follows: a?=?12.7875(1) Å, b?=?8.7255(1) Å, c?=?9.9261(1) Å, V?=?1107.53(2) Å3. The lattice parameters of both modifications are related by the following approximate relationships: a HT?≈?2c RT, b HT?≈?-(½a RT?+?b RT), c HT?≈?a RT. The HT-modification is isotypic with the corresponding potassium compound K6Ca4(SO4)6F2. The pronounced disorder of the sulphate group even at low temperatures has been studied by maximum entropy calculations. Despite the first-order character of the transformation clusters of sulfate groups surrounding the fluorine anions can be identified in both polymorphs. Each of the three next neighbor SO4-tetrahedra within a cluster is in turn surrounded by 8–9 M-cations (M: Na,Ca) defining cage-like units. However, in the apatite structure the corresponding three tricapped trigonal prisms are symmetry equivalent. Furthermore, the central fluorine atom of each cluster is coordinated by three next M-neighbors (FM3-triangles), whereas in the HT-polymorph a four-fold coordination is observed (FM4-tetrahedra).  相似文献   

19.
The lower crust of the Serre massif (Calabria, southern Italy) provides a window into the mid- to lower crust of the south European Variscan orogenic belt. Previously, zircon U-Pb ages were employed to date high-temperature processes affecting this portion of the Variscan crust. The present paper reports new LA-ICP-MS U-Pb data on the zircon of a deformed quartz-monzodiorite dike and of three mafic granulites sampled at the base of the lower crust section. Determination of trace elements on zircon, including rare earth elements (REE), has been also performed. The end of the Variscan exhumation, dated by anatectic zircon from migmatitic metapelites, and the growth-modification of zircon with respect to the growth of Variscan metamorphic garnet have been assumed as ??time markers??. The concordant zircon ages of the metamorphic basic rocks cover a range from 744?±?20 Ma to 231?±?10 Ma with high age density from 357?±?11?Ma to 279?±?10 Ma, a few ages comprised between 418?±?14 Ma and 483?±?12 Ma and between 505?±?11 Ma and 593?±?14 Ma. Zircon from the deformed quartz-monzodiorite dike evidences a minimum age of emplacement of 323?±?5 Ma. Most of the analysed zircon domains dated between 357?±?11 Ma to 279?±?10 Ma from garnet-bearing metabasic rocks show flat patterns of heavy rare earth elements (HREE), as expected in the case of their simultaneous growth with garnet. This allows to consider (1) zircon domains giving Variscan ages as ??metamorphic?? with specific geological significance, and (2) zircon domains with ages ranging from 564?±?17 Ma to 593?±?14 Ma as dating the emplacement of the magmatic protoliths as shown by internal microtextures, fractionated patterns of HREE and Th/U ratios (0.16?C0.19). The Variscan zircon ages (357?C279?Ma) reflect effects of crustal thickening, peak metamorphism and subsequent multistage Variscan decompression documented by the statistically significant clusters of ages around 347?C340?Ma, 323?C318?Ma, 300?C294?Ma and 279?Ma. The U-Pb zircon ages of the metabasic rocks suggest a period of about 60?C70?Ma for granulite facies metamorphism and anatectic conditions. Literature data indicate that the migmatitic metapelites of the upper part of the Serre crust section also underwent a long period, about 40?Ma, of granulite facies metamorphism and anatectic conditions. A diachronism emerges through the time comparison of the Variscan evolution between the upper and the lower portions of the Serre deep crust. The duration of the Variscan processes defined in Calabria is comparable to that of other south European Variscan blocks.  相似文献   

20.
Single crystals of quartz, shock-loaded along the a axis to pressures of 22 Gpa, 24 GPa, 26 GPa and 30 GPa were examined by high-voltage transmission electron microscopy (TEM), scanning electron microscopy (SEM) and X-ray diffraction. Asymmetric broadenings of X-ray lines indicate spatial inhomogeneity of shock effects. X-ray streaking angles in the reciprocal lattice planes h0 \(\bar h\) l, 0k \(\bar k\) l and hki0 indicate a slight tilting deformation by rotation about [00.1] in (0001). TEM reveals glass lamellae which are mostly in (01 \(\bar 1\) 2) orientation, and are correlated with optical planar elements and with surface steps seen in SEM. No dislocations are found. There are (0001) lamellar features, probably Brazil twins. The (01 \(\bar 1\) 2) glass lamellae develop directly from bands of quartz in which intense deformation has produced a fine-scale lamellar to blocky structure, possibly also originating by twinning. Relics of crystalline structure are found in almost completely vitrified lamellae. Stishovite occurs in heavily deformed parts of the 22 GPa and 24 GPa specimens, in patches of densified glass distinct from the sharply bounded lamellae. The nucleationless, pervasive transformation of lamellae to glass, with preservation of their sharp boundaries, is attributed to defect coalescence analogous to vitrification by radiation damage (metamictization). Some patchy glass may be due to melting.  相似文献   

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