Structured diffuse scattering, displacive flexibility and polymorphism in Ba-hexacelsian

 The results of a temperature-dependent electron diffraction study of the low frequency modes of distortion of Ba-hexacelsian and their relationship to the α-β polymorphic phase transition therein are presented. Cs- and Rb-doped Ba-hexacelsian specimens are also investigated. An extremely strong and characteristic diffuse intensity distribution in the form of polarized sheets of diffuse intensity perpendicular to the <1 1 0> directions is found for the high temperature polymorph and the doped specimens. The diffuse distribution appears to result from coupled tetrahedral rotation of <1 1 0> columns of corner-connected (Al,Si)O₄ tetrahedra about the [0 0 1] axis (uncorrelated from column to column as a result of the positioning of the rotation axes). Received: 25 January 1999 / Revised, accepted: 13 July 1999     

Electron microscopy studies of akermanites (Ca1−xSrx)2CoSi2O7 with modulated structure

Single crystals of akermanite (Ca_1–x Sr _x )₂Co-Si₂O₇ solid solution were grown in nitrogen by the floating zone method using a lamp-image furnace. The grown crystals were 6 mm in diameter by 50 mm in length. Microprobe analyses indicate uniform strontium content x except in the initially crystallized part. Synthetic crystals with x from 0.0 to 0.3 give, at room temperature, satellite reflections and circular diffuse scatterings in the electron diffraction pattern, which are related to an incommensurate phase and microdomains, respectively. With increasing Sr content the wavelength of a modulation increases and the intensity of satellites decreases, but the intensity of circular diffuse scattering increases up to x=0.15 and then decreases until eventually the satellites and the circular diffuse scatterings disappear at x = 0.3. The circular diffuse scattering is explained by the cluster model for the transition state, proposed by De Ridder et al. (1976).     

Structural and magnetic properties of Co2Al4Si5O18 and Mn2Al4Si5O18 cordierite

The crystal structures, lattice dynamics and magnetic properties of synthetic Co-cordierite, Co₂Al₄Si₅O₁₈, and Mn-cordierite, Mn₂Al₄Si₅O₁₈ have been studied by neutron powder diffraction, infrared spectroscopy and magnetisation measurements. Due to different synthesis conditions, the Co-cordierite used here crystallised in the hexagonal α-cordierite structure with a disordered Si/Al distribution in the framework, while for the Mn-cordierite the orthorhombic β-structure has been determined. The experimentally determined paramagnetic moments, _exp (Mn) = 5.47(6) _B and _exp (Co) = 3.88(4) _B , are in good agreement with theoretical predictions for octahedrally coordinated Mn²⁺ and Co²⁺, respectively. In both compounds there is no magnetic long-range order down to at least 1.5 K. However, the onset of an anti-ferromagnetic short-range correlation of magnetic moments along [001] has been observed for Mn-cordierite by magnetisation and neutron diffraction measurements. This short-range magnetic correlation becomes evident from diffuse scattering observed at 2 K. The diffuse scattering has been interpreted in terms of a Blech-Averbach function. Received: 30 June 1998 / Revised, accepted: 3 March 1999     

The dehydration process of gypsum under high pressure

The effects of pressure on the dehydration of gypsum materials were investigated up to 633 K and 25 GPa by using Raman spectroscopy and synchrotron X-ray diffraction with an externally heated diamond anvil cell. At 2.5 GPa, gypsum starts to dehydrate around 428 K, by forming bassanite, CaSO₄ hemihydrate, which completely dehydrates to γ-anhydrite at 488 K. All the sulphate modes decrease linearly between 293 and 427 K with temperature coefficients ranging from −0.119 to −0.021 cm⁻¹ K⁻¹, where an abrupt change in the ν₃ mode and in the OH-stretching region indicates the beginning of dehydration. Increasing the temperature to 488 K, the OH-stretching modes completely disappear, marking the complete dehydration and formation of γ-anhydrite. Moreover, the sample changes from transparent to opaque to transparent again during the dehydration sequence gypsum-bassanite-γ-anhydrite, which irreversibly transforms to β-anhydrite form at 593 K. These data compared with the dehydration temperature at room pressure indicate that the dehydration temperature increases with pressure with a ΔP/ΔT slope equal to 230 bar/K. Synchrotron X-ray diffraction experiments show similar values of temperature and pressure for the first appearance of bassanite. Evidence of phase transition from β-anhydrite structure to the monazite type was observed at about 2 GPa under cold compression. On the other hand at the same pressure (2 GPa and 633 K), β-anhydrite was found, indicating a positive Clausis-Clayperon slope of the transition. This transformation is completely reversible as showed by the Raman spectra on the sample recovered after phase transition.     

Raman spectroscopic study of K-lingunite at various pressures and temperatures

K-lingunite is a high-pressure modification of K-feldspar that possesses the tetragonal hollandite structure. Variations of the Raman spectra of K-lingunite were studied up to ~31.5 GPa at room temperature, and in the range 79–823 K at atmospheric pressure. The Raman frequencies of all bands were observed to increase with increasing pressure, and decrease with increasing temperature for K-lingunite. This behavior is in line with those observed for most of other materials. New sharp Raman bands appear at pressures greater than 13–15 GPa, suggesting a phase transition in K-lingunite with increasing pressure. The transition is reversible when pressure was released. The appearance of these new Raman bands may correspond to the phase transition revealed earlier at around 20 GPa by X-ray diffraction studies. Instead of transforming back to its stable minerals, such as orthoclase, microcline or sanidine, K-lingunite became amorphous in the temperature range 803–823 K at atmospheric pressure.     

Linear birefringence and X-Ray diffraction studies of the structural phase transition in titanite,CaTiSiO5

The antiferroelectric phase transition in titanite characterised by a collinear displacement of Ti-atoms from their central octahedral position is investigated using linear optical birefringence and X-ray diffraction techniques. Both methods indicate a continuous transition near 496 K and extra contributions to δΔn and X-ray intensity signals at higher temperatures. The critical exponent of the macroscopic order parameter is found to be β = 0.14 ± 0.02 and the transformation is interpreted in terms of a two-dimensional quasi-spin model. Topological features of the structure agree well with the spatial distribution of the diffuse scattering of the superstructure reflection 40 \(\bar 3\) .     

Negative thermal expansion in beta-quartz

Computer modelling and theoretical analysis are used to explain the nearly zero and slightly negative coefficients of thermal expansion in β-quartz well above the α-β phase transition temperature. Quartz was selected for study as an archetypal material with a framework structure of stiff units, namely SiO₄ tetrahedra, linked through shared oxygen atoms as very flexible hinges. The contributions of the soft mode, the Vallade mode, the TA_z phonon branch and the phonon spectrum as a whole are discussed in detail. The results fully support and illustrate a recent theory of the negative contribution to thermal expansion in framework structures. It is a geometrical effect due to the rotation of the tetrahedral units, folding together as they vibrate. The very rapid increase in the lattice parameters for about 20 K above the transition temperature is well accounted for within quasiharmonic theory, and is therefore not evidence for critical fluctuations or fluctuating patches of α ₊, α ₋ structure. Received August 14 1997 / Revised, accepted January 26 1998     

Structural modifications of CaGeO3-wollastonite under room temperature pressurization

 In-situ X-ray diffraction measurements of CaGeO₃-wollastonite at high pressure at room temperature have been performed using a diamond anvil cell with an X-ray source. A new structural modification of CaGeO₃-wollastonite is observed at about 6GPa and the characteristic reflections of the high pressure form are preserved on decompression to an ambient pressure. A rhodonite-like structure is proposed as a high pressure form from the crystal chemical consideration. The rhodonite-like phase is further transformed into a perovskite-form at about 15 GPa. The rhodonite-like-form of CaGeO₃ seems not to be a stable phase from the heating experiments under high pressures. The metastable transition path from the wollastonite to the perovskite polymorph through the rhodonite-like structure is kinetically favored under room temperature pressurization. No pressure-induced amorphization is observed during the transition into the perovskite-form, although the transition is accompanied by the coordination change of Ge atoms from fourfold to sixfold. Received: July 19, 1995 / Revised, accepted: August 1996     

An infrared spectroscopic and single-crystal X-ray study of malayaite, CaSnSiO5

Powder infrared spectroscopy and X-ray diffraction techniques on single crystals were used to study the thermal behaviour of malayaite, CaSnSiO₅. Infrared spectra show a discontinuity in the temperature evolution of phonon frequencies and absorbance near 500 K. However, crystal structure data collected at 300, 450, 550, 670, and 750 K show no evidence of a symmetry-breaking phase transition and no split positions. The most obvious change with heating is a tumbling motion of the SnO₆ octahedra and an increase of the anisotropic displacement factors of Ca. The thermal evolution of the mean-square vibrational amplitude of the Ca atom shows a pronounced change in slope near 500 K. The evidence suggests that the 500 K anomaly in malayaite is more similar in character to the 825 K (β-γ) transition as opposed to the 496 K (α-β) transition in synthetic titanite. Received: 26 March 1998 / Revised, accepted: 23 December 1998     

Circular diffuse scattering of akermanite studied by the optical diffraction method

Circular diffuse scattering appears when the incommensurate phase of akermanite transforms partly to either the normal phase or the commensurate phase by exchanging Ca atoms for larger alkali-earth atoms such as Sr or by exchanging Mg atoms for larger atoms such as Fe and/or by increasing the temperature. The scattering effect has been investigated by using an optical diffraction method. To induce the appearance of circular satellite reflections around the Bragg reflections, the modulation waves must repeat with a phase difference in one direction, x or y, together with a wavelength change. If the modulation waves repeat with phase differences in both x and y directions, circular satellite reflection will be induced without varying the modulation wavelength. Experimental reproduction of circular diffuse scattering shows that this phenomenon is ascribed to modulation waves repeating with a layer-to-layer phase difference and with a constant phase difference within each layer of the akermanite structure.     

High-pressure transformations of ilmenite to perovskite, and lithium niobate to perovskite in zinc germanate

In-situ X-ray powder diffraction measurements conducted under high pressure confirmed the existence of an unquenchable orthorhombic perovskite in ZnGeO₃. ZnGeO₃ ilmenite transformed into perovskite at 30.0 GPa and 1300±150 K in a laser-heated diamond anvil cell. After releasing the pressure, the lithium niobate phase was recovered as a quenched product. The perovskite was also obtained by recompression of the lithium niobate phase at room temperature under a lower pressure than the equilibrium phase boundary of the ilmenite–perovskite transition. Bulk moduli of ilmenite, lithium niobate, and perovskite phases were calculated on the basis of the refined X-ray diffraction data. The structural relations among these phases are considered in terms of the rotation of GeO₆ octahedra. A slight rotation of the octahedra plays an important role for the transition from lithium niobate to perovskite at ambient temperature. On the other hand, high temperature is needed to rearrange GeO₆ octahedra in the ilmenite–perovskite transition. The correlation of quenchability with rotation angle of GeO₆ octahedra for other germanate perovskites is also discussed.     

Rigid unit modes in the high-temperature phase of SiO2 tridymite: calculations and electron diffraction

Calculations of the rigid unit mode (RUM) spectrum of the high-temperature phase of SiO₂ tridymite are used to explain the patterns of diffuse scattering seen in transmission electron microscopy experiments. These results show that RUM's can occur with wave vectors on curved surfaces in reciprocal space rather than being confined to symmetry points, lines or planes. The fact that the calculations reproduce the detail seen in the diffuse scattering provides a striking nontrivial confirmation of the validity of the rigid unit mode model.     

Determination of the phase boundary between ilmenite and perovskite in MgSiO3 by in situ X-ray diffraction and quench experiments

Determination of the phase boundary between ilmenite and perovskite structures in MgSiO₃ has been made at pressures between 18 and 24 GPa and temperatures up to 2000 °C by in situ X-ray diffraction measurements using synchrotron radiation and quench experiments. It was difficult to precisely define the phase boundary by the present in situ X-ray observations, because the grain growth of ilmenite hindered the estimation of relative abundances of these phases. Moreover, the slow reaction kinetics between these two phases made it difficult to determine the phase boundary by changing pressure and temperature conditions during in situ X-ray diffraction measurements. Nevertheless, the phase boundary was well constrained by quench method with a pressure calibration based on the spinel-postspinel boundary of Mg₂SiO₄ determined by in situ X-ray experiments. This yielded the ilmenite-perovskite phase boundary of P (GPa) = 25.0 (±0.2) – 0.003 T (°C) for a temperature range of 1200–1800 °C, which is generally consistent with the results of the present in situ X-ray diffraction measurements within the uncertainty of ∼±0.5 GPa. The phase boundary thus determined between ilmenite and perovskite phases in MgSiO₃ is slightly (∼0.5 GPa) lower than that of the spinel-postspinel transformation in Mg₂SiO₄. Received: 19 May 1999 / Accepted: 21 March 2000     

Kinetics of the Coesite-Quartz Transition: Application to the Exhumation of Ultrahigh-Pressure Rocks

The kinetics of the quartz–coesite phase transition hasbeen studied in situ by X-ray diffraction in the 2·1–3·2GPa, 500–1010°C pressure–temperature range.Analysis of the data within Cahn's model of nucleation and growthat grain boundaries reveals that the prograde and retrogradereactions have different kinetics. The quartz     

Raman scattering and X-ray diffraction study of the thermal decomposition of an ettringite-group crystal

 A Raman scattering and X-ray diffraction study of the thermal decomposition of a naturally occurring, ettringite-group crystal is presented. Raman spectra, recorded with increasing temperature, indicate that the thermal decomposition begins at ≈55 °C, accompanied by dehydration of water molecules from the mineral. This is in contrast to previous studies that reported higher temperature breakdown of ettringite. The dehydration is completed by 175 °C and this results in total collapse of the crystalline structure and the material becomes amorphous. The Raman scattering results are supported by X-ray diffraction results obtained at increasing temperatures. Received: 9 July 2001 / Accepted: 14 August 2002     

Deformation of lower-mantle ferropericlase (Mg,Fe)O across the electronic spin transition

Recent high-pressure studies have shown that an electronic spin transition of iron in ferropericlase, an expected major phase of Earth’s lower mantle, results in changes in its properties, including density, incompressibility, radiative thermal conductivity, electrical conductivity, and sound velocities. To understand the rheology of ferropericlase across the spin transition, we have used in situ radial X-ray diffraction techniques to examine ferropericlase, (Mg_0.83,Fe_0.17)O, deformed non-hydrostatically in a diamond cell up to 81 GPa at room temperature. Compared with recent quasi-hydrostatic studies, the range of the spin transition is shifted by approximately 20 GPa as a result of the presence of large differential stress in the sample. We also observed a reduction in incompressibility and in the unit cell volume of 3% across the spin transition. Our radial X-ray diffraction results show that the {0 0 1} texture is the dominant lattice preferred orientation in ferropericlase across the spin transition and in the low-spin state. Viscoplastic self-consistent polycrystal plasticity simulations suggest that this preferred orientation pattern is produced by {1 1 0}<1–10> slip. Analyzing our radial X-ray diffraction patterns using lattice strain theory, we evaluated the lattice d-spacings of ferropericlase and Mo as a function of the ψ angle between the compression direction and the diffracting plane normal. These analyses give the ratio between the uniaxial stress component (t) and the shear modulus (G) under constant stress condition, which represents a proxy for the supported differential stress and elastic strength. This ratio in the mixed-spin and low-spin states is lower than what is expected from previous studies of high-spin ferropericlase, indicating that the spin transition results in a reduced differential stress and elastic strength along with the volume reduction. The influence of the spin transition on the differential stress and strength of ferropericlase is expected to be less dominant across the wide spin transition zone at high pressure–temperature conditions relevant to the lower mantle.     

Thermal decomposition of Ferrian chamosite: an infrared emission spectroscopic study

The thermal behaviour of ripidolite, an iron-rich chlorite, has been studied in situ by infrared emission spectroscopy up to 800 °C. The more di,trioctahedral nature due to significant amounts of Fe³⁺ is reflected, in addition to the two bands around 3420 and 3560 cm⁻¹, by an extra band around 3345 cm⁻¹. This extra band is absent in pure dioctahedral chlorites without Fe³⁺. These bands have been assigned to (AlAl)O-OH, (SiAl)O-OH and (SiSi)O-OH stretching modes with increasing frequencies. The bands disappear upon dehydroxylation around 650 °C. A similar behaviour is observed for the corresponding libration modes around 716, 759 and 802 cm⁻¹. The stretching and bending modes of the inner-OH of the octahedral sheet in the 2:1 clay-like layer are observed around 3645, 943 and 904 cm⁻¹. Although the bands decrease in intensity, they remain present up to 800 °C as dehydroxylation of the octahedral sheet is not yet complete at this temperature. The presence of two bending modes is explained as being due to a differentiation between Mg-OH and Fe-OH modes. At 650 °C a new sharp band is observed around 502 cm⁻¹ assigned to a (Fe,Mg)-O-Al bending mode caused by the formation of a spinel-like interlayer phase after dehydroxylation. Received: 4 June 1999 / Accepted: 6 August 1999     

Orientation Distribution Within a Single Hematite Crystal

While crystallography conventionally presumes that a single crystal carries a unique crystallographic orientation, modern experimental techniques reveal that a single crystal may exhibit an orientation distribution. However, this distribution is largely concentrated; it is extremely concentrated when compared with orientation distributions of polycrystalline specimen. A case study of a deformation experiment with a single hematite crystal is presented, where the experimental deformation induced twining, which in turn changed a largely concentrated unimodal “parent” orientation distribution into a multimodal orientation distribution with a major mode resembling the parent mode and three minor modes corresponding to the progressive twining. The free and open source software MTEX for texture analysis was used to compute and visualize orientations density functions from both integral orientation measurements, i.e. neutron diffraction pole intensity data, and individual orientation measurements, i.e. electron back scatter diffraction data. Thus it is exemplified that MTEX is capable of analysing orientation data from largely concentrated orientation distributions.     

Rigid unit modes and dynamic disorder: SiO2 cristobalite and quartz

The high temperature (β) phases of SiO₂ cristobalite and quartz are studied by performing molecular dynamics simulations using a model which allows easy analysis of tetrahedral motions. The dynamic nature of the disordered high-temperature phase of cristobalite is attributed to rigid unit mode (RUM) excitations, and it is found that the entire spectrum of RUMs is responsible for the disorder. Comparisons of the results of β-cristobalite with those of β-quartz lead to the conclusion that framework structures with high degrees of geometric flexibility, and hence many RUMs, are free to deform through cooperative tetrahedral rotations even in the limit of extremely large tetrahedral stiffnesses. Received: 10 March 1998 / Revised, accepted 15 January 1999