Non-convergent ordering and displacive phase transition in pigeonite: in situ HT XRD study

A natural Ca-rich pigeonite (En₄₇Fs₄₃Wo₁₀), free of augite exsolution products, was studied by in situ high-temperature single-crystal X-ray diffraction. The sample, monoclinic P2 ₁ /c (a=9.719(7) Å, b=8.947(9) Å, c=5.251(3) Å, β=108.49(5), V=433.0(6) ų), was annealed up to 1000 °C to induce a phase transition from P2 ₁ /c to C2/c symmetry. Complete single-crystal X-ray diffraction data collections were carried out in situ at 650, 750, 850 and 950 °C after the crystal had reached equilibrium for the Fe–Mg intracrystalline exchange reaction at each temperature. The variation, with increasing temperature, of lattice parameters, of intensity of hkl reflections with h + k=2n + 1 (which vanish at high temperature) and of some geometrical parameters from structure refinement, showed that the displacive phase transition P2 ₁ /c?C2/c was continuous in character. This contrasts with the first-order character for the HT phase transition in pigeonite containing significantly less calcium.     

High-pressure isosymmetrical phase transition in calaverite

Using density functional theory, we perform ab initio calculations of the behaviour of calaverite, AuTe₂, at high pressures. Calaverite has a distorted CdI₂ structure, that presents a pronounced two-dimensional character and a rather anisotropic response to pressure. Increasing the pressure, we predict an isosymmetrical phase transition between 55 and 60 GPa, that is accompanied by an important distortion of the structure, observed in all its geometrical parameters, especially the c lattice parameter. Relaxing the pressure, the reverse phase transition is observed between 30 and 25 GPa.     

Rigid Unit Modes in disordered nepheline: a study of a displacive incommensurate phase transition

 Calculations of the Rigid Unit Modes (RUMs) allowed in the nepheline structure are used to explain the diffuse scattering previously seen in electron diffraction experiments. The RUM calculations also show that the modulation wavelength for incommensurate nephelines is essentially determined by the framework topology. X-ray diffraction is used to measure the intensity of the diffuse scattering as a function of temperature. The diffuse intensity increases sharply at 308 K. This effect is interpreted as being due to the softening of a phonon mode, indicating a phase transition. Measurements of this phase transition below the transition temperature are made using hard mode infrared spectroscopy. Received: 17 February 1999 / Revised, accepted. 15 October 1999     

X-ray diffraction study of the displacive phase transition in anorthoclase,grain-size effects and surface relaxations

The temperature evolution of the displacive order parameter of hypersolvus, Al-Si disordered alkali feldspars with composition Or₃₁ and Or₂₀ was measured using X-ray powder diffractometry. The monoclinic — triclinic transition shows second-order behaviour and bilinear order parameter-strain coupling. The transition temperatures are 443 K (Or₃₁) and 750 K (Or₂₀). Temperature evolution of the peak width, Γ, of the 132 reflection was found to depend on the grain size of the sample with an anomalous increase of Γ at T _c in fine-grained material. This effect has been rationalised in terms of surface relaxations occuring as T approaches T _c . No anomalous line broadening occurs in coarse-grained material.     

天然文石-方解石的高温相变及热膨胀性质

利用高温粉末X射线衍射研究了高纯地质成因文石从室温到1 073 K的相变过程以及文石和方解石的热膨胀性质,并分析了地质成因与生物成因文石的差异和影响因素。结果表明:斜方晶系的文石在693～733 K转变为三方晶系的方解石,相变临界温度为723 K,摩尔体积增加5.97%;文石在300～663 K的体积热膨胀系数α(V)(10-5/K)随绝对温度T(K)的变化规律为:α(V)=3.59(79)+7.17(170)×10-3T,文石的热膨胀具有强烈的各向异性[轴向热膨胀系数α(c)α(b)α(a)];方解石在733～973 K的热膨胀系数α(10-5/K)为:α(V)=3.78(25),α(a)=-0.27(2),α(c)=4.31(29),a轴具有负热膨胀。生物成因的文石相变温度比合成和地质成因文石低60～140 K,粉末状文石相变温度低于单晶和未被破坏的整块文石;粉末状的生物成因文石和方解石与非生物成因的文石和方解石的热膨胀系数接近,然而整块的生物成因的文石有更小的热膨胀系数。     

High-pressure behavior of MnGeO3 and CdGeO3 perovskites and the post-perovskite phase transition

The stability and high-pressure behavior of perovskite structure in MnGeO₃ and CdGeO₃ were examined on the basis of in situ synchrotron X-ray diffraction measurements at high pressure and temperature in a laser-heated diamond-anvil cell. Results demonstrate that the structural distortion of orthorhombic MnGeO₃ perovskite is enhanced with increasing pressure and it undergoes phase transition to a CaIrO₃-type post-perovskite structure above 60 GPa at 1,800 K. A molar volume of the post-perovskite phase is smaller by 1.6% than that of perovskite at equivalent pressure. In contrast, the structure of CdGeO₃ perovskite becomes less distorted from the ideal cubic perovskite structure with increasing pressure, and it is stable even at 110 GPa and 2,000 K. These results suggest that the phase transition to post-perovskite is induced by a large distortion of perovskite structure with increasing pressure.     

High-pressure phase transition in MnTiO3 from the ilmenite to the LiNbO3 structure

Crystals of a high-pressure phase of MnTiO₃ have been synthesized at pressures of 60 kbar using the SAM-85 cubic-anvil high pressure apparatus. Although all crystals examined were twinned on (10 \(\bar 1\) \(\bar 2\) ), a set of diffraction intensities that are essentially unaffected by the twinning were obtained. Three possible structure models were considered: (1) the corundum (completely disordered Mn and Ti), (2) the partially-disordered ilmenite, and (3) the LiNbO₃ structures. The R factors of the corundum and the disordered ilmenite models were much larger than that of LiNbO₃. Using structure factors unaffected by twinning, the final LiNbO₃-type refinement gave R _w=0.037 and R=0.034. The averaged bond lengths for Mn-O and Ti-O were consistent with ones calculated using Shannon and Prewitt's (1969) radii. The study concludes that MnTiO₃ II actually has an ordered LiNbO₃-type structure rather than the disordered one as reported previously. From the analysis of the two MnTiO₃ structures, the transition can be related to a cation reordering process, in which half of the cations participate, accompanied by the rotation of oxygens to accommodate the cations.     

High-pressure investigations on the isostructural phase transition and metallization in realgar with diamond anvil cells

The high-pressure structural,vibrational and electrical properties for realgar were investigated by in-situ Raman scattering and electrical conductivity experiments combined with first-principle calculations up to~30.8 GPa.It was verified that realgar underwent an isostructural phase transition at~6.3 GPa and a metallization at a higher pressure of~23.5 GPa.The isostructural phase transition was well evidenced by the obvious variations of Raman peaks,electrical conductivity,crystal parameters and the As–S bond length.The phase transition of metallization was in closely associated with the closure of bandgap rather than caused by the structural phase transition.And furthermore,the metallic realgar exhibited a relatively low compressibility with the unit cell volume V₀=718.1.4?³and bulk modulus B₀=36.1 GPa.     

P-T-X data on P21/c-clinopyroxenes and their displacive phase transitions

The P2₁/c clinopyroxene kanoite (ideally MnMgSi₂O₆) was studied as a function of pressure and temperature using powder X-ray diffraction, differential scanning calorimetry (DSC) and optical methods. The temperature of the P2₁/c to high-temperature (HT) C2/c transition ranges from 425?°C in endmember MnMgSi₂O₆ to 125?°C in natural samples with an aegirine component. Compiling pigeonite and clinoenstatite–clinoferrosilite literature data, the temperature of the transformation was found to decrease linearly with M2 cation size. A synchrotron powder diffraction study in a heated diamond-anvil cell (DAC) yielded compression and thermal expansion data for low kanoite of composition Mn_1.2Mg_0.4Fe_0.4Si₂O₆. The high-pressure (HP) phase transition from P2₁/c to HPC2/c was reversed at 5.8 GPa at 417?°C. The high-temperature phase transition from P2₁/c to HTC2/c was rather indistinct and occurred at approximately 530?°C and 0.76 GPa. In a separate experiment, the HT transition was observed optically in a hydrothermal DAC between 0.0 and 0.4 GPa. The in-situP-T data of both experiments yielded an increase in transition temperature with increasing pressure (approx. 149?°C/GPa) and suggest a change in character of the transition from first order to continuous with increasing pressure. The data indicate that the HTC2/c and HPC2/c polymorphs are distinct phases with different stability fields. Since the high-temperature and the high-pressure polymorphs of kanoite were shown to be isotypic with other low-Ca clinopyroxenes such as the (Mg,Fe)SiO₃ series, the conclusions we draw from this study are valid for all clinopyroxenes with small (<0.88 Å) M1 and M2 cation sizes. The petrologic implications of these conclusions for the occurrence of “clinoenstatite” in the Alpe Arami peridotite are discussed.     

High-pressure phase transition and behavior of protons in brucite Mg(OH)2: a high-pressure–temperature study using IR synchrotron radiation

 Infrared absorption spectra of brucite Mg (OH)₂ were measured under high pressure and high temperature from 0.1 MPa 25 °C to 16 GPa 360 °C using infrared synchrotron radiation at BL43IR of Spring-8 and a high-temperature diamond-anvil cell. Brucite originally has an absorption peak at 3700 cm⁻¹, which is due to the OH dipole at ambient pressure. Over 3 GPa, brucite shows a pressure-induced absorption peak at 3650 cm⁻¹. The pressure-induced peak can be assigned to a new OH dipole under pressure. The new peak indicates that brucite has a new proton site under pressure and undergoes a high-pressure phase transition. From observations of the pressure-induced peak under various P–T condition, a stable region of the high-pressure phase was determined. The original peak shifts to lower wavenumber at −0.25 cm⁻¹ GPa⁻¹, while the pressure-induced peak shifts at −5.1 cm⁻¹ GPa⁻¹. These negative dependences of original and pressure-induced peak shifts against pressure result from enhanced hydrogen bond by shortened O–H···O distance, and the two dependences must result from the differences of hydrogen bond types of the original and pressure-induced peaks, most likely from trifurcated and bent types, respectively. Under high pressure and high temperature, the pressure-induced peak disappears, but a broad absorption band between 3300 and 3500 cm⁻¹ was observed. The broad absorption band may suggest free proton, and the possibility of proton conduction in brucite under high pressure and temperature. Received: 16 July 2001 / Accepted: 25 December 2001     

Nucleation of augite at antiphase boundaries in pigeonite

Pigeonites in coarse grained dolerites from the Whin Sill have been examined by transmission electron microscopy. The observed micro-structures involve coarse, heterogeneous (001) augite lamellae and antiphase boundaries (APB's), some of which have nucleated fine (001) plates of augite. APB's approximately parallel to (211) and \((\bar 211)\) are Ca enriched and those approximately parallel to (120) are not (or at least are less so), the former changing their orientation according to the local Ca content of the pigeonite and providing suitable sites for the heterogeneous nucleation of augite. Simple structural models show how (211) and \((\bar 211)\) APB's provide more suitable sites for Ca²⁺ ions that those parallel to (120). The development of the antiphase domains is discussed. Concentrating Ca²⁺ ions onto a restricted number of sites is not favoured by entropy and therefore possibly does not occur at high temperatures. The final antiphase domain scale is a complex function of the Ca content and cooling rate of the pigeonite.     

Formation mechanism of pigeonite lamellae in skaergaard augite

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.     

Preferred orientation of antiphase boundaries in pigeonite as a cooling ratemeter

Antiphase domains (APD's) of pigeonite lamellae in natural and heated augite crystals from the Hakonetoge andesite have been examined by a transmission electron microscope (TEM). Antiphase boundaries (APB's) of the pigeonite lamellae in natural specimens have a sigmoidal shape cutting the c axis in (010) sections. APB's in specimens heated at temperatures above the high-low inversion and then quenched are nearly parallel to the c axis with almost straight boundaries. These observations indicate that the preferred orientation of APB's in (010) sections depends on cooling rate; at fast colling rates the APB's are nearly parallel to the c axis, whereas at slower cooling rates they are inclined to the c axis. The cooling rate of the natural augite specimen from Hakonetoge is estimated to be about 0.01 °C/h from the experimentally determined time-temperature-transformation (TTT) diagram for the APB orientations. APD sizes are large in specimens quenched from above the inversion temperature; they are at a minimum after cooling rates of around 1–0.1 °C/h, and then become larger with slower cooling rates.     

High-temperature phase transition and local structure of a hydrous anorthoclase

The in situ Raman spectra of a hydrous anorthoclase at temperatures of 20–800 °C have been measured using a LABRAM-HR spectrometer and Linkam TS 1500 heating stage. The frequencies of modes at 54, 99, 130 and 162 cm^?1 related to M–O vibrations decrease sharply and then increase drastically or keep steady at temperatures above 200 °C. A knee point can be clearly seen at about 200 °C for those modes. The frequency of the mode at 282 cm^?1 shows little temperature dependence. However, for the two strongest modes at 471 and 512 cm^?1, the frequencies decrease linearly with increasing temperature. From evolution of the frequencies of modes at 54, 99, 130 and 162 cm^?1 with temperature, the following conclusions can be drawn: (1) The distance of the local M–O bond shortens rather than lengthens at temperatures above 200 °C; (2) The abrupt changes of the local structure of M site induce a collapse of the framework structure and displacive phase transition at 200 °C; and (3) The H atoms incorporated in anorthoclase are located at the M site. These results are indicative for the structure and properties of anorthoclase at deep earth conditions.     

High-pressure phase transitions of anorthosite crust in the Earth's deep mantle

We investigated phase relations, mineral chemistry, and density of lunar highland anorthosite at conditions up to 125 GPa and 2000 K. We used a multi-anvil apparatus and a laser-heated diamond-anvil cell for this purpose. In-situ X-ray diffraction measurements at high pressures and composition analysis of recovered samples using an analytical transmission electron microscope showed that anorthosite consists of garnet, CaAl₄Si₂O₁₁-rich phase (CAS phase), and SiO₂ phases in the upper mantle and the mantle transition zone. Under lower mantle conditions, these minerals transform to the assemblage of bridgmanite, Ca-perovskite, corundum, stishovite, and calcium ferrite-type aluminous phase through the decomposition of garnet and CAS phase at around 700 km depth. Anorthosite has a higher density than PREM and pyrolite in the upper mantle, while its density becomes comparable or lower under lower mantle conditions. Our results suggest that ancient anorthosite crust subducted down to the deep mantle was likely to have accumulated at 660–720 km in depth without coming back to the Earth's surface. Some portions of the anorthosite crust might have circulated continuously in the Earth's deep interior by mantle convection and potentially subducted to the bottom of the lower mantle when carried within layers of dense basaltic rocks.     

High-pressure phase transitions of potassium aluminosilicates with an emphasis on leucite

Phase behaviors of kalsilite (KAlSiO₄), leucite (KAlSi₂O₆) and sanidine (KAlSi₃O₈) at high pressures and temperatures have been reviewed. New experimental data for leucite composition were obtained in a diamond-anvil press coupled with laser heating. At about 1,000° C, the leucite composition breaks down into an assemblage of kalsilite +kyanite+K₂Si₄O₉ (wadeite-type) in the range 60 to 120 kbar, of kalsilite+KAlSi₃O₈ (hollandite-type) in the range 120 to 150 kbar, and of KAlSi₃O₈ (hollandite-type) + KAlO₂ (?) at 170 kbar or above. The suggestion that kalsilite is the most appropriate potassium silicate in the anhydrous upper mantle needs to be revised. It is suggested that the wadeite-type K₂Si₄O₉ is the most appropriate host for potassium in the upper mantle at depths greater than about 150 km.     

High-pressure behavior of natural single-crystal epidote and clinozoisite up to 40 GPa

The comparative compressibility and high-pressure stability of a natural epidote (0.79 Fe-total per formula unit, Fe_tot pfu) and clinozoisite (0.40 Fe_tot pfu) were investigated by single-crystal X-ray diffraction and Raman spectroscopy. The lattice parameters of both phases exhibit continuous compression behavior up to 30 GPa without evidence of phase transformation. Pressure–volume data for both phases were fitted to a third-order Birch–Murnaghan equation of state with V ₀ = 461.1(1) ų, K ₀ = 115(2) GPa, and \(K_{0}^{'}\) = 3.7(2) for epidote and V ₀ = 457.8(1) ų, K ₀ = 142(3) GPa, and \(K_{0}^{'}\) = 5.2(4) for clinozoisite. In both epidote and clinozoisite, the b-axis is the stiffest direction, and the ratios of axial compressibility are 1.19:1.00:1.15 for epidote and 1.82:1.00:1.19 for clinozoisite. Whereas the compressibility of the a-axis is nearly the same for both phases, the b- and c-axes of the epidote are about 1.5 times more compressible than in clinozoisite, consistent with epidote having a lower bulk modulus. Raman spectra collected up to 40.4 GPa also show no indication of phase transformation and were used to obtain mode Grüneisen parameters (γ _i) for Si–O vibrations, which were found to be 0.5–0.8, typical for hydrous silicate minerals. The average pressure coefficient of Raman frequency shifts for M–O modes in epidote, 2.61(6) cm^?1/GPa, is larger than found for clinozoisite, 2.40(6) cm^?1/GPa, mainly due to the different compressibility of FeO₆ and AlO₆ octahedra in M3 sites. Epidote and clinozoisite contain about 2 wt% H₂O are thus potentially important carriers of water in subducted slabs.     

富镁与贫镁坡缕石在热处理下的结构变化研究

研究了安徽明光富镁坡缕石和江苏盱眙贫镁坡缕石热处理后的结构变化,结果表明:富镁坡缕石八面体片对称性好,晶体结构稳定性高,结晶度高,热稳定性好;贫镁坡缕石八面体片中存在连续八面体空位,对称性差,晶体结构稳定性低,结晶度差,热稳定性差。在脱除结晶水和羟基过程中,富镁坡缕石由正交晶系转变为单斜晶系,层间距变小,孔道变形、塌陷但一直保持链层结构,显示晶质特性;而贫镁坡缕石的晶体结构发生折叠,链层结构逐步破坏,700℃煅烧后部分四面体片遭到破坏,虽然显示多晶特性为主,但开始出现非晶化现象。