The α-β phase transition in AlPO4 cristobalite: Symmetry analysis,domain structure and transition dynamics

Despite their crystallographic differences, the mechanisms of the α-β phase transitions in the cristobalite phases of SiO₂ and AlPO₄ are very similar. The β→α transition in AlPO₄ cristobalite is from cubic ( $\left( {F\bar 43m} \right)$ ) to orthorhombic (C222₁), whereas that in SiO₂ cristobalite is from cubic ( $\left( {Fd\bar 3m} \right)$ ) to tetragonal (P4₃2₁2 or P4₁2₁2). These crystallographic differences stem from the fact that there are two distinct cation positions in AlPO₄ cristobalite as opposed to one in SiO₂ cristobalite and the ordered (Al,P) distribution is retained through the phase transition. As a result, there are significant differences in their crystal structures, domain configurations resulting from the phase transition and Landau free energy expressions. A symmetry analysis of the “improper ferroelastic” transition from $F\bar 43m \to C222_1$ in AlPO₄ cristobalite has been carried out based on the Landau formalism and the projection operator methods. The six-component order parameter, η driving the phase transition transforms as the X₅ representation of $F\bar 43m$ and corresponds to the simultaneous translation and rotation of the [AlO₄] and [PO₄] tetrahedra coupled along 110. The Landau free energy expression contains a third order invariant, the minimization of which requires a first-order transition, consistent with experimental results. The tetrahedral configurations of twelve α phase domains resulting from the β→α transition in AlPO₄ cristobalite are of two types: (1) transformation twins from a loss of the 3-fold axis, and (2) antiphase domains from the loss of the translation vectors 1/2[101] and 1/2[011] (F→C). In contrast to α-SiO₂ cristobalite, the α-AlPO₄ cristobalite (C222₁) does not have chiral elements (4₃, 4₁) and hence, enantiomorphous domains are absent. These transformation domains are essentially macroscopic and static in the α phase and microscopic and dynamic in the β phase. The order parameter, η couples with the strain components, which initiates the structural fluctuations causing the domain configurations to dynamically interchange in the β phase. An analysis of the MAS NMR data (²⁹Si, ¹⁷O, ²⁷Al) on the α α-β transitions in SiO₂ and AlPO₄ cristobalites (Spearing et al. 1992, Phillips et al. 1993) essentially confirms the dynamical model proposed earlier for SiO₂ cristobalite (Hatch and Ghose 1991) and yields a detailed picture of the transition dynamics. In both cases, small atomic clusters with the configuration of the low temperature α phase persist considerably above the transition temperature, T₀. The NMR data on the β phases above T₀ cannot be explained by a softening of the tetrahedral rotational and translational modes alone, but require the onset of an order-disorder mechanism resulting in a dynamic averaging due to rapidly changing domain configurations considerably below T₀.     

Infrared and Raman spectroscopy studies of the α–β phase transition in cristobalite

Infrared and Raman spectra of cristobalite are presented as a function of temperature through the phase transition. The modes are assigned and the assignments compared to those of earlier workers. The compatibility of modes at the G-point of the a-phase with the X and G-points of the ß-phase is given. In the transition region of ca. 500–550 K, smooth changes in intensity, frequency and linewidths are seen in many modes, indicative of coexistence of a- and ß-forms.     

Dynamics of the α-β phase transitions in quartz and cristobalite as observed by in-situ high temperature 29Si and 17O NMR

Relaxation times (T₁) and lineshapes were examined as a function of temperature through the - transition for ²⁹Si in a single crystal of amethyst, and for ²⁹Si and ¹⁷O in cristobalite powders. For single crystal quartz, the three ²⁹Si peaks observed at room temperature, representing each of the three differently oriented SiO₄ tetrahedra in the unit cell, coalesce with increasing temperature such that at the - transition only one peak is observed. ²⁹Si T₁'s decrease with increasing temperature up to the transition, above which they remain constant. Although these results are not uniquely interpretable, hopping between the Dauphiné twin related configurations, ₁ and ₂, may be the fluctuations responsible for both effects. This exchange becomes observable up to 150° C below the transition, and persists above the transition, resulting in -quartz being a time and space average of ₁ and ₂. ²⁹Si T₁'s for isotopically enriched powdered cristobalite show much the same behavior as observed for quartz. In addition, ¹⁷O T₁'s decrease slowly up to the - transition at which point there is an abrupt 1.5 order of magnitude drop. Fitting of static powder ¹⁷O spectra for cristobalite gives an asymmetry parameter () of 0.125 at room T, which decreases to <0.040 at=" the=" transition=" temperature.=" the=" electric=" field=" gradient=" (efg)=" and=" chemical=" shift=" anisotropy=" (csa),=" however,=" remain=" the=" same,=" suggesting=" that=" the=" decrease=" in="> is caused by a dynamical rotation of the tetrahedra below the transition. Thus, the mechanisms of the - phase transitions in quartz and cristobalite are similar: there appears to be some fluctuation of the tetrahedra between twin-related orientations below the transition temperature, and the -phase is characterized by a dynamical average of the twin domains on a unit cell scale.     

Defect structure of the low temperature α-cristobalite phase and the cristobalite ⇆ tridymite transformation in (Si-Ge)O2

Using minimum exposure techniques, it is feasible to perform high resolution electron microscopy on the α-cristobalite phase of (Si_0.9 Ge_0.1)O₂, which is extremely radiation sensitive. Such images reveal atomic scale information of twins and tridymite-like stacking faults on (1 1 1)_β planes, as well as of domain boundaries resulting from the β→α transition. Polytype structures are formed in certain cases. Morphological features suggest that the phase transformation cristobalite → tridymite proceeds by means of a zonal dislocation mediated synchro-shear process on (1 1 1)_β planes; the geometry of this process is analyzed. Received: 13 June 1999 / Accepted: 30 October 1999     

Dauphiné twinning in deformed quartzites: Implications of an in situ TEM study of the α-β phase transformation

The occurrence of Dauphiné twinning in deformed quartzites has been investigated by means of hotstage high voltage transmission electron microscopy (TEM). In-situ observations show that Dauphiné twins created during the - phase transition interact strongly with dislocation substructures, with the result that some twins persist at temperatures many degrees below the phase transition temperature, and probably to room temperature. Attempts were made to establish whether Dauphiné twinning was responsible for the differences in preferred orientations between positive and negative rhombs, reported by Tullis and Tullis (1972) in quartzites experimentally loaded below the yield stress at various temperatures. The results were inconclusive. We could not identify any Dauphiné twinning in the samples, even in regions where there were concentrations of dislocations.     

The Mesolithic–Neolithic transition in southern Iberia

New data and a review of historiographic information from Neolithic sites of the Malaga and Algarve coasts (southern Iberian Peninsula) and from the Maghreb (North Africa) reveal the existence of a Neolithic settlement at least from 7.5 cal ka BP. The agricultural and pastoralist food producing economy of that population rapidly replaced the coastal economies of the Mesolithic populations. The timing of this population and economic turnover coincided with major changes in the continental and marine ecosystems, including upwelling intensity, sea-level changes and increased aridity in the Sahara and along the Iberian coast. These changes likely impacted the subsistence strategies of the Mesolithic populations along the Iberian seascapes and resulted in abandonments manifested as sedimentary hiatuses in some areas during the Mesolithic–Neolithic transition. The rapid expansion and area of dispersal of the early Neolithic traits suggest the use of marine technology. Different evidences for a Maghrebian origin for the first colonists have been summarized. The recognition of an early North-African Neolithic influence in Southern Iberia and the Maghreb is vital for understanding the appearance and development of the Neolithic in Western Europe. Our review suggests links between climate change, resource allocation, and population turnover.     

The nature of megafaunal extinctions during the MIS 3–2 transition in Japan

The nature of late Quaternary megafaunal extinctions has been the subject of intense debate since the 1960s. Traditionally, scientists cite either climatic changes or human predation as the primary reason for worldwide megafaunal extinctions. In many island cases (e.g., Madagascar, New Zealand), scientists have had a tendency to lean toward humans as being the direct or indirect dominant cause for the relatively quick extirpation of indigenous megafaunas. This study evaluates the record for megafaunal (e.g., Palaeoloxodon, Mammuthus, Sinomegaceros) extinctions in the Japanese islands and draw the tentative conclusion that: (1) humans directly and/or indirectly influenced the extinction of some large herbivores; and (2) the megafaunal extinctions likely began earlier than originally proposed; during the marine isotope stage (“MIS”) 3–2 transition (～30–20 ka) rather than during the MIS 2–1 (～15–10 ka) shift that roughly coincides with the advent of the Jomon period in Japan. However, we temper our findings due to the current paucity of sites in Japan that have associated archaeology and vertebrate paleontological materials that date to the MIS 3–2 transition.     

Incommensurate–normal phase transition in natural melilite: an in situ high-temperature X-ray single-crystal study

The structure of a natural melilite with chemical composition (Ca_1.87Sr_0.02Na_0.10K_0.02)_2.01(Mg_0.96Al_0.07)_1.03(Si_1.98Al_0.02)_2.00O₇ has been investigated by X-ray single-crystal diffraction methods within the temperature range 298–773 K. The values of the coefficient of the modulation wave vector were determined at 298 K, 323 K, 348 K, and 358 K. These values show a continuous linear decrease from 0.2833(6) at 298 K to 0.2763(9) at 358 K. The incommensurate phase undergoes a phase transition to the normal phase at 359 K. The refinements of the structure, carried out at 298 K, 348 K, 359 K, 373 K, 413 K, 463 K, 513 K, 573 K, 673 K, and 773 K, showed that the normal phase (high-temperature phase) does not significantly differ from the basic structure (the average structure of the incommensurate structure). This study confirms that in natural melilites with chemical composition close to that of åkermanite the wavelength of the incommensurate modulation increases when the temperature rises. The different behaviour of the q-vector as a function of temperature in natural and synthetic åkermanite is discussed.     

The high-pressure C2/c–P21/c phase transition along the LiAlSi2O6–LiGaSi2O6 solid solution

Two synthetic single-crystals with composition Li(Al_0.53Ga_0.47)Si₂O₆ and LiGaSi₂O₆ and space group C2/c at room conditions have been studied under pressure by means of X-ray diffraction using a diamond anvil cell. The unit-cell parameters were determined at 12 and 10 different pressures up to P = 8.849 and P = 7.320 GPa for Li(Al_0.53Ga_0.47)Si₂O₆ and LiGaSi₂O₆, respectively. The sample with mixed composition shows a C2/c to P2₁/c phase transformation between 1.814 and 2.156 GPa, first-order in character. The transition is characterised by a large and discontinuous decrease in the unit-cell volume and by the appearance of the b-type reflections (h + k = odd) typical of the primitive symmetry. The Ga end-member shows the same C2/c to P2₁/c transformation at a pressure between 0.0001 and 0.39 GPa. The low-pressure value at which the transition occurred did not allow collecting any data in the C2/c pressure stability field except that on room pressure. Our results compared with those relative to spodumene (LiAlSi₂O₆, Arlt and Angel 2000a) indicate that the substitution of Al for Ga at the M1 site of Li-clinopyroxenes strongly affects the transition pressure causing a decrease from 3.17 GPa (spodumene) to less than 0.39 GPa (LiGaSi₂O₆) and decreases the volume discontinuity at the transition. As already found for other compounds, the C2/c low-pressure phases are more rigid than the P2₁ /c high-pressure ones. Moreover, the increase of the M1 cation radius causes a decrease in the bulk modulus K _T0. The axial compressibility among the Li-bearing clinopyroxenes indicates that the c axis is the most rigid for the C2/c phases while it becomes the most compressible for the P2₁ /c phases.     

Crystallographic preferred orientation in wüstite (FeO) through the cubic-to-rhombohedral phase transition

Magnesiowüstite, (Mg_0.08Fe_0.88)O, and wüstite, Fe_0.94O, were compressed to ~36?GPa at ambient temperature in the diamond anvil cell (DAC) at the Advanced Light Source. X-ray diffraction patterns were taken in situ in radial geometry in order to study the evolution of crystallographic preferred orientation through the cubic-to-rhombohedral phase transition. Under uniaxial stress in the DAC, {100}_c planes aligned perpendicular to the compression direction. The {100}_c in cubic became { $\left\{ {10\bar 14} \right\}$ }_r in rhombohedral and remained aligned perpendicular to the compression direction. However, the {101}_c and {111}_c planes in the cubic phase split into { ${10{\bar{1}}4}$ }_r and { ${11{\bar{2}}0}$ }_r, and (0001)_r and { ${10{\bar{1}}1}$ }_r, respectively, in the rhombohedral phase. The { ${11{\bar{2}}0}$ }_r planes preferentially aligned perpendicular to the compression direction while { ${10{\bar{1}}4}$ }_r oriented at a low angle to the compression direction. Similarly, { ${10{\bar{1}}1}$ }_r showed a slight preference to align more closely perpendicular to the compression direction than (0001)_r. This variant selection may occur because the 〈 ${10{\bar{1}}4}$ 〉_r and [0001]_r directions are the softer of the two sets of directions. The rhombohedral texture distortion may also be due to subsequent deformation. Indeed, polycrystal plasticity simulations indicate that for preferred { ${10{\bar{1}}4}$ }〈 ${1{\bar{2}}10}$ 〉_r and { ${11{\bar{2}}0}$ }〈 ${{\bar{1}}101}$ 〉_r slip and slightly less active { ${10{\bar{1}}1}$ }〈 ${{\bar{1}}2{\bar{1}}0}$ 〉_r slip, the observed texture pattern can be obtained.     

Pressure-induced structural transition in Ln2Zr2O7 (Ln = Ce, Nd, Gd) pyrochlores

The structural behavior under pressure of three lanthanide pyrochlore zirconates Ln₂Zr₂O₇ (Ln³⁺ = Ce, Nd and Gd) has been investigated by X-ray diffraction up to 50 GPa. For all three compounds, a symmetry reduction from cubic to monoclinic is observed under increasing pressure dependant on a pressure value that increases with the ionic radius of the lanthanide ions, r _Ln. The cubic and monoclinic phases coexist over a wide pressure range which increases with r _Ln. The zero-pressure bulk modulus of the cubic phase, B ₀, and its pressure derivative, B ₀′, have been determined by fitting the experimental compressibility curves to the Birch–Murnaghan equation of state.     

The P21/m↔ C2/m phase transition in synthetic amphibole Na NaMg Mg5 Si8 O22 (OH)2: thermodynamic and crystal-chemical evaluation

The P2₁/mC2/m displacive phase transition in the synthetic end-member amphibole Na NaMg Mg₅ Si₈ O₂₂ (OH)₂ has been studied by monitoring changes in unit-cell parameters and the intensities of superlattice reflections at 25–400 °C. This amphibole allows investigation of the effects of compositional variations at the A- and B-group sites upon the transition. Polynomial fitting of a 24 Landau potential to the evolution of the order parameter with T yielded a T _c of 257 ± 3 °C, and Landau coefficients compatible with a second-order transition. Structure refinement of single-crystal data collected at 25, 140, 270 and 370 °C allowed modelling of the structural changes as a function of T and symmetry. Crystal-chemical analysis suggests that differences in T _c in cummingtonites and in the crystal of this work depend mainly upon the relations between the aggregate ionic radii of the B- and C-group cations. Electronic Supplementary Material: of Table 5 is available in the online version of this article at http://dx.doi.org/10.1007/s00269-003-0348-9     

High-pressure phases in the Al2SiO5 system and the problem of aluminous phase in the Earth's lower mantle: ab initio calculations

 One of the main uncertainties in mineralogical models of the Earth's lower mantle is the nature of the aluminous mineral: it is not clear whether Al forms its own minerals or is mainly contained in (Mg,Fe)SiO₃-perovskite. This question is very important, since it is known that if Al were mainly hosted by perovskite, it would radically change Fe/Mg-partitioning and phase equilibria between mantle minerals, and also alter many physical and chemical properties of perovskite, which is currently believed to comprise ca. 70% of the volume of the lower mantle. This, in turn, would require us to reconsider many of our geochemical and geophysical models for the lower mantle. This work considers the possibility of a V₃O₅-type structured modification of Al₂SiO₅ to be the main host of Al in the lower mantle, as proposed by previous workers. We report ab initio calculations, based on density functional theory within the generalised gradient approximation (GGA) with plane wave basis set and nonlocal pseudopotentials. We consider polymorphs of Al₂SiO₅ (kyanite, andalusite, sillimanite, and hypothetical V₃O₅-like and pseudobrookite-like phases), SiO₂ (stishovite, quartz) and Al₂O₃ (corundum). Computational conditions (e.g., plane-wave energy cutoff, Brillouin zone sampling) were carefully chosen in order to reproduce small energy changes associated with phase transitions between the Al₂SiO₅ polymorphs. Good agreement of crystal structures, bulk moduli, atomisation energies and the phase diagram of Al₂SiO₅ with experimental data was found. Strong disagreement between the calculated lattice parameters and density of V₃O₅-like phase of Al₂SiO₅ and experimental values, assigned to it by previous workers, suggests that a V₃O₅-structured phase of Al₂SiO₅ was never observed experimentally. In addition, we found that the most stable high-pressure assembly in Al₂SiO₅ system is corundum+stishovite, and the value of the transition pressure at T = O K (113 kbar) is in excellent agreement with experimental estimates (95–150 kbar). We explain the instability of octahedrally coordinated silicates of Al to decomposition on the basis of Pauling's second rule. Received: 18 May 1999 / Accepted: 5 November 1999     

Detecting a magnesiowüstite phase transition in the lower mantle by inversion of geomagnetic data

Global geomagnetic data are inverted for detecting a high-conductivity layer at depths of 1500–2000 km to test the hypothesis of a magnesiowüstite phase transition in the lower mantle. We present the results of processing of both synthetic and global data—average monthly values of the geomagnetic field from 1920 to 2009. The inverted global data are consistent with the possible existence of a high-conductivity layer at great depths in the lower mantle.     

Mg-Fe partitioning between silicate spinel and magnesiowüstite at high pressure: experimental determination and calculation of phase relations in the system Mg2SiO4-Fe2SiO4

 Mg-Fe partitioning experiments between (Mg,Fe)₂SiO₄ spinel and (Mg,Fe)O magnesiowüstite were carried out at pressures of 17–21.3 GPa at temperatures of 1400 and 1600 °C, using a multi-anvil apparatus, in order to determine interaction parameters of spinel and magnesiowüstite solid solutions and also to constrain the equilibrium boundaries of the postspinel transition in the Fe-rich side in the system Mg₂SiO₄-Fe₂SiO₄. The obtained values of the interaction parameters were 3.4 ± 1.5 and 13.9 ± 1.4 kJ mol⁻¹, respectively, for spinel and magnesiowüstite solid solutions at 19 GPa and 1600 °C. The partitioning data in the system Mg₂SiO₄-Fe₂SiO₄ at 1400 and 1600 °C showed that the transition boundary between spinel and the mixture of magnesiowüstite and stishovite has a negative dP/dT slope. Using the above interaction parameters and available thermodynamic data of the Mg₂SiO₄ and Fe₂SiO₄ end members, the transition boundaries of spinel to the mixture of magnesiowüstite and stishovite were calculated. Within the uncertainties of the data used, the calculated boundaries are in good agreement with the boundaries at 1400 and 1600 °C experimentally determined in this study. The dissociation boundary of Fe₂SiO₄ spinel to wüstite and stishovite, calculated from the thermodynamic data, has a negative slope of −1.5 ± 0.6 MPa K⁻¹. Received: 18 February 1998 / Revised, accepted: 18 October 1999     

Thermal expansion and high-temperature P21/c–C2/c phase transition in clinopyroxene-type LiFeGe2O6 and comparison to NaFe(Si,Ge)2O6

A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) Å, β = 108.844(6)°, V = 442.75(16) ų, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the $(\bar{1}\,0\,1) A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) ?, β = 108.844(6)°, V = 442.75(16) ?³, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the ([`1] 0 1)(\bar{1}\,0\,1) plane, mostly along [0 1 0], and pure shear in the (0 1 0) plane due to the decrease of β. From comparison with silicate analogues, the germanate clinopyroxenes are more expansible, while the P2₁/c expands more than the C2/c phase. The evolution of Q ² (calculated as the normalized intensity of b-type reflections) with T in the framework of the Landau theory has been done using a standard expression for a first order phase transition. We observe a jump of Q ₀² = 0.538(2) at T _tr, with T _c of 481(7) K, b/a = −2,290 K, and c/a = 3,192 K, and thus far from being tri-critical point. A closely related composition (LiFe³⁺Si₂O₆) shows an equivalent phase transition at 228 K, which is very close to the tri-critical point and 561 K cooler. This result indicates that a change in the composition of tetrahedral sites can have dramatic effects on the P2₁/c ↔ C2/c displacive phase transition in clinopyroxenes. The major changes observed in the evolution of the crystal structure with T are observed in the M2 polyhedron, with a volume decrease by ca. 13.3%, compared to ca. 1.3% observed in the M1 polyhedron. The tetrahedra behave as rigid units with neither a significant change of volume at T > T _tr (<1‰), nor a change of tilting of the basal plane. No change in coordination is observed at T > T _tr in the M2 polyhedron, which remains sixfold coordinated although a strong deformation of this polyhedron is observed. This deformation is related to a strong change by 51.4° at T _tr of the kinking angle (O3–O3–O3 angle) of the B-chain of tetrahedra, which switches from O-rotated to S-rotated [from 143.3(5)° to 194.7(6)°]. The A-chain is S-rotated at T < T _tr [206.8(5)° at 703 K] and extends by 12° at the transition.