Order disorder in sillimanite

AP³⁺-Si⁴⁺ disordering in sillimanite cannot be considered as ideal mixing on tetrahedral sites. Ideal free energy of mixing in sillimanite corresponding to slight disordering results in changing the kyanite-sillimanite phase equilibrium boundary by impossible magnitude. A regular solution model for the sites yields the following expression for the free energy of mixing: 1 $$G_{sill}^M = W \{ (X_{Al - T1} )^2 + (X_{Al - T2} )^2 \} + RT ln X_{Al - T1} X_{Al - T2}$$ . Calculations using the phase equilibrium data show that even small disequilibrium in intra-crystalline distribution results in significant change in pressure of the kyanite-sillimanite “equilibrium”. If information on interaction energies such as W is not available for disordering silicates, it is not advisable to use the ideal configurational entropy in calculations of phase equilibria.     

Atomic ordering around the oxygen vacancies in sillimanite

Computer simulation is used to investigate the short range ordering around an isolated oxygen vacancy in sillimanite. The static lattice energy with the use of empirical potentials is calculated, for different Al/Si distributions around a vacancy in a supercell of sillimanite. A parametrisation of the total energy is built up and used to deduce the best Al/Si ordering around the oxygen vacancy. It is found that a strong ordering about the vacancy occurs. In the ab-plane two sets of aluminium cluster are found besides the vacancy, surrounded above and below by silicon atoms, a configuration that promotes local charge balance. By placing two vacancies on sites directly adjacent to the same oxygen, the central oxygen site is bonded to four cations: this situation is found to be energetically unfavourable.     

Computer simulation of defect structure in sillimanite and mullites

 Defect structure and the defect formation in mullites and sillimanites have been investigated using computer simulation techniques. From point defect chemistry and computer simulations, oxygen vacancies are identified as the majority defect responsible for oxygen transport in mullite. The defect formation energies are between 3 and 4 eV. Using supercell calculation methods, the random structure is identified to be stable in mullites, whereas the ordered structure can be confirmed to be more stable in sillimanite. An energy of 0.7–1.0 eV for the association of oxygen vacancies with cations is estimated. Received: 11 May 2001 / Accepted: 12 December 2001     

Computer modelling of Al/Si ordering in sillimanite

Computer simulation is used to investigate the effect of Al/Si disordering over the tetrahedral sites on the lattice energy and the lattice constants of the mineral sillimanite Al₂SiO₅. A methodology for an atomistic assessment of the energy of the reaction 2(Si-O-Al)→(Si-O-Si)+(Al-O-Al) and its various contributions is established. This ordering energy is 0.97 eV for nearest neighbour sites in the ab-plane and 0.56 eV for those separated in the c-direction. The large difference is due to a greater constraint on the atomic relaxation in the ab-plane and shows the structural dependence of the ordering energy. Its magnitude appears to be determined by a complicated balance between Coulomb and short-range repulsive energy involving strain over many bonds, both in the ordered and disordered structures. There is also a significant interaction between second neighbour sites whereas the contribution of more distant neighbours is negligible. The lattice energies of most of the 154 configurations studied show a linear behaviour as a function of short-range order, specified by the number of Al-Al pairs. The ordering temperature T_c, estimated on the basis of a statistical mechanical model of disordering, and the calculated ordering energies are in semi-quantitative agreement with experimental values.     

The relationship of elasticity and crystal structure in andalusite and sillimanite

The nine elastic constants of andalusite and sillimanite have been determined, using the technique of Brillouin scattering. They are, in megabars, for andalusite: c ₁₁=2.334, c ₂₂=2.890, c ₃₃=3.801, c ₄₄=0.995, c ₅₅=0.878, c ₆₆=1.123, c ₂₃=0.977, c ₁₃=1.162, c ₁₂=0.814; for sillimanite: c ₁₁=2.873, c ₂₂=2.319, c ₃₃=3.884, c ₄₄=1.224, c ₅₅=0.807, c ₆₆=0.893, c ₂₃=1.586, c ₁₃=0.834, c ₁₂=0.947. Both structures are characterized by chains of edge-linked coordination octahedra extending parallel to the crystallographic c direction, cross-linked by polyhedra of lower coordination. In each structure the stiffness measured parallel to c is greater than that measured normal to c. The shear moduli can be directly correlated with the relative rigidity of the cross-linking structures.     

Deformation-induced polymorphic transformation: experimental deformation of kyanite, andalusite, and sillimanite

Torsion experiments were performed on the Al₂SiO₅ polymorphs in the sillimanite stability field to determine basic rheological characteristics and the effect of deformation on polymorphic transformation. The experiments resulted in extensive transformation of andalusite and kyanite to sillimanite. No transformation occurred during the hot-press (no deformation) stage of sample preparation, which was carried out at similar P–T conditions and duration as the torsion experiments. Experiments were conducted on fine-grained (< 15 µm) aggregates of natural andalusite, kyanite and sillimanite at 1250 °C, 300 MPa, and a constant shear strain rate of 2 × 10^− 4/s to a maximum shear strain of 400%. Electron back-scattered diffraction (EBSD) analysis of the experiments revealed development of lattice-preferred orientations, with alignment of sillimanite and andalusite [001] slightly oblique to the shear plane. The kyanite experiment could not be analyzed using EBSD because of near complete transformation to sillimanite. Very little strain ( 30%) is required to produce widespread transformation in kyanite and andalusite. Polymorphic transformation in andalusite and kyanite experiments occurred primarily along 500 µm wide shear bands oriented slightly oblique and antithetic to the shear plane and dominated by sub-µm (100–150 nm) fibrolitic sillimanite. Shear bands are observed across the entire strain field preserved in the torsion samples. Scanning transmission electron microscope imaging shows evidence for transformation away from shear bands; e.g. fibrolitic rims on relict andalusite or kyanite. Relict grains typically have an asymmetry that is consistent with shear direction. These experimental results show that sillimanite is by far the weakest of the polymorphs, but no distinction can yet be made on the relative strengths of kyanite and andalusite. These observations also suggest that attaining high bulk strain energy in strong materials such as the Al₂SiO₅ polymorphs is not necessary for triggering transformation. Strain energy is concentrated along grain boundaries, and transformation occurs by a dynamic recrystallization type process. These experiments also illustrate the importance of grain-size sensitive creep at high strains in a system with simultaneous reaction and deformation.     

The energetics of interaction between oxygen vacancies in sillimanite: A model for the mullite structure

A microscopic model is introduced to discuss the modulated structure of mullite. The oxygen vacancies of this aluminosilicate are known to play a central role. In particular, a single vacancy strongly orders its surrounding Al/Si tetrahedral sites. It is shown in this work that if two oxygen vacancies approach too closely to one another, their Al/Si dressing overlap. This situation results in repulsive interaction. The field of interaction between the vacancies is estimated with the use of an atomistic computer simulation. We use a Bragg-Williams type of theory to dicuss the ordering pattern of the vacancies. Due to frustration between the two dominant repulsive interactions, our model predicts a modulated phase transition in agreement with observation.     

Growth and concentration of fibrous sillimanite related to heterogeneous deformation in K-feldspar-sillimanite metapelites

Abstract In foliated K-feldspar-sillimanite metapelites, fibrous sillimanite is commonly concentrated in folia that anastomose between lenticular pods of coarser-grained aggregates rich in quartz, feldspar and biotite, with or without garnet, cordierite and residual andalusite. Many of the folia appear to be limbs of crenulation microfolds. The sillimanite concentrations may be due largely to the ability of fibrous sillimanite aggregates to undergo strong non-coaxial deformation by grain-boundary sliding ('fibre sliding';) without appreciable build-up of dislocations, whereas other minerals are unstable in these zones and so concentrate in lower-strain interfolial zones. Initiation, and especially concentration of the sillimanite in folia, may be assisted by fluid flow and local base-cation leaching, whereby minerals unstable in zones of strong non-coaxial strain are dissolved and removed from these zones.     

长英质高级片麻岩中夕线石的形成与变形-变质-深熔作用的关系 —— 以南极拉斯曼丘陵区为例

南极拉斯曼丘陵高级长英质片麻岩的夕线片麻岩中可有两类结构和变质矿物组合均有所不同的两种域,一种含夕线石部分对应于片理组合,另一种对应无夕线石的非片理化组合.岩石的变形尤其是破裂性裂隙的率先出现对于富夕线石部分的形成是必要的.在非破裂性片麻理岩石域中,中-低压/高温条件下黑云斜长片麻岩进变质发展的结果往往是形成Grt+Qtz±Opx组合.这两种不同的变质域的组合与应变分解造成的强应变带和弱应变域相一致.而且,夕线石的形成不是简单的变质早期矿物固相反应的结果,而是反应链上的一部分.其出现是由开放体系中组分的差异迁移造成的,这种差异迁移实际上是碱土金属迁出(淋滤)的过程,与变形相伴的流体活动使得SiO2发生强烈淋滤,残留组分中SiO2活度大为降低,并使长英质组分和镁铁质组分分凝,主要组分大都可以单独富集(集中)、形成复杂的矿物演化和分布.这种演化还可从MgO等碱(土)金属组分的外迁程度差异来理解.随着碱(土)金属丢失程度的减小,依次出现夕线石、石榴子石、斜方辉石和堇青石,或者说,不同的变质或分异阶段形成不同的矿物(组合):变形-变质起始阶段,碱(土)金属组分迁移初期残留形成夕线石,之后为镁(铁)质组分迁移,初期残留不透明钛铁氧化物,晚期残留组分形成堇青石.石榴子石-长英质组合为体系基本封闭情况下的结晶.此外,夕线石的形成往往标志着深熔作用的开始,一旦深熔作用发展完善,夕线石呈准稳定状态或趋于消失.拉斯曼丘陵与夕线石有关的长英质岩石经历了复杂的变形、变质和流体活动变化.     

Shock metamorphism in sillimanite from the Haughton impact structure,Devon Island,Canada

Clasts of shocked garnet-sillimanite gneisses comprise a minor fraction of the allochthonous breccia at the Haughton impact structure. Refractive indices of the diaplectic and fused components of the gneisses, and reduced specific gravity indicate shock pressures from 35 to 55±5 GPa and effective post-shock temperatures from 500° to 1,000° C in a suite of selected samples.Sillimanites remain birefringent but display several effects of shock metamorphism. Shock-produced planar features and planar fractures are highly developed; optic axial angle (2V _y ) increases from near normal (26°) to over 80° within a sample; there is a reduction in optical relief and a development of a pale brown colouring which generally deepens in shade as shock level increases. There is no unambiguous evidence, optically or from X-ray investigation, of a high-pressure Al₂SiO₅ polymorph or breakdown to mullite and silica. The highly shocked sillimanites have anomalous K₂O contents from 0.11% to 0.92%. Potassium appears to substitute for aluminum and, to a lesser degree, for iron while retaining sillimanite stoichiometry, and the amount of substitution generally reflects increased shock level. The source of the contributed potassium is the coexisting shock-fused feldspar glass. The glass of each sample is derived primarily from melted alkali feldspar with a minor and varied admixture from the breakdown of mafic minerals. The glasses are depleted in K₂O, although Na₂O is unaffected, and the extent of depletion can be correlated with the increased K₂O content of the associated sillimanite. The incorporation of potassium in shocked sillimanites is a function of both degree of shock deformation and availability of potassium from other coexisting shocked phases. It is speculated that the brown colouration is a function of ferrous iron content and may reflect post-crater thermal history rather than shock level.Contribution from the Earth Physics Branch No. 951     

Correlation of spectroscopic properties and substitutional sites of Cr3+ in aluminosilicates: II. Andalusite and sillimanite

This paper is an extension of the earlier one dealing with kyanite in which the best fitting value of the oxygen ligand distance for Cr³⁺ is adopted to study the spectroscopic properties of Cr³⁺ ions doped at the two possible Al sites in the other two polymorphs of the aluminosilicate group (Al₂O₃ · SiO₂), namely, andalusite and sillimanite. The superposition model and the crystal field analysis package recently developed for 3d ions doped at arbitrary low symmetry sites in crystals are used to predict energy levels and statevectors within the whole 3d ³ configuration. Then the values of the ground state zerofield splitting for Cr³⁺ ions at each Al sites in the two crystals are obtained. The splittings of the lower excited states ² E and ⁴ T ₂ as well as the admixture of ⁴ T ₂ into ² E have also been predicted. Comparison of our results with the available experimental data enable us to correlate the optical and EPR Spectroscopic properties with the substitutional Cr³⁺ sites. The conclusion is that in andalusite and sillimanite only the Al sites with nearly-octahedral six-fold coordination seem to be occupied by Cr³⁺ ions.     

Formation of late sillimanite by hydrogen metasomatism (base-leaching) in some high-grade gneisses

Microstructural evidence indicates that fibrolitic sillimanite partly replaced of the highest-grade metamorphic assemblage in the high-grade metapelitic gneisses, migmatites and granodiorite of the Cooma Complex, southeastern Australia. The sillimanite is interpreted as having formed by the action of mobile hydrogen ions on pre-existing minerals, base cations being released and removed from the sites of reaction. The hydrogen ions may have been liberated during widespread hydration of cordierite. The general base-leaching process may be applicable to the formation of late sillimanite in high-grade, migmatitic gneisses in other areas.     

关于东南极拉斯曼丘陵夕线片麻岩类原岩恢复问题的讨论

南极拉斯曼丘陵及其邻区的(含)夕线片麻岩类的原岩可以是杂砂岩、亚杂砂岩、石英砂岩、泥质岩或页岩等。粘土岩或页岩之类的富铝沉积岩与富夕线片麻岩并没有直接对应关系。没有一种泥质岩的化学组成可以与富夕线片麻岩相对应。研究区内夕线石片麻岩的形成主要与黑云斜长片麻岩有关,影响夕线石出现的决定性因素是特定温压条件下的变形变质改造过程,而不是原岩成分。夕线石片麻岩在很大程度上是黑云斜长片麻岩经长英质组分迁移之后的滞留-残留体。夕线石化过程中岩石组分发生了改造,相关变质作用已经明显偏离等化学过程,基本上属于开放体系。原岩中Al2O3的含量也不能控制夕线石的出现与否,含夕线石的岩石未必富铝,反之亦然,岩石富铝也可以不出现夕线石;但是夕线石化过程往往是Al2O3相对增加的过程,这些认识对于夕线石片麻岩成岩环境的确定和原岩建造的重建都具有重要意义。     

Compositional restraints on the sillimanite paragenesis in metapelites from Kuanthal,district Udaipur,India

The rocks exposed in the area around Kuanthal represent one of the oldest Precambrian formations of India and constitute the Banded Gneissic Complex (B.G.C.) of Heron (1953). The main rock types are staurolite-sillimanite schists/gneisses, sillimanite gneisses with or without K-feldspar, migmatites and amphibolites, often intimately and inextricably mixed up with one another. The petrochemical studies of the metapelitic rocks show that the formation of sillimanite is controlled by parent rock chemistry. The critical controlling parameters area: alumina, alkalies (Na₂O + K₂O) and oxidation ratio of rocks. These criteria are equally valid for other well-known areas of high-grade metamorphism. The validity of this proposition has been tested by statistical methods such as multivariate analysis and Mahalonbis's generalized distance D². The linear discriminant function controlling sillimanite paragenesis in metapelites has been worked out and an equation has been evolved to delineate the ‘SB’ (sillimanite-bearing) and ‘SF’ (sillimanite-free) rocks.     

Sapphirine-bearing orthopyroxene-kyanite/sillimanite granulites from South Harris, NW Scotland: evidence for Proterozoic UHT metamorphism in the Lewisian

Sapphirine-bearing orthopyroxene-kyanite (Opx-Ky) and -sillimanite (Opx-Sil) granulites have been found in the Lewisian complex of South Harris in northwest Scotland. In the Opx-Ky granulites, orthopyroxene and kyanite are intergrown in a stable mineral assemblage, which indicates metamorphic condition at 800–900 °C >12 kbar. Sillimanite inclusions within orthopyroxene suggest that sillimanite formed earlier; conditions are estimated at 950 ± 30 °C at 10 kbar from orthopyroxene isopleths for aluminous orthopyroxene (<9.7 wt%). In the Opx-Sil granulite, the orthopyroxene + sillimanite + garnet + sapphirine assemblage is stable at the peak metamorphic stages, indicating P-T condition of 930–950 °C, >8 kbar according to the FMAS petrogenetic grid, and similar conditions were obtained by using orthopyroxene-garnet geothermobarometers. The two types of orthopyroxene-aluminosilicate granulites indicate that the peak metamorphic conditions were over 900 °C, compatible with ultra-high temperature metamorphism. As accessory sapphirine occurs in several assemblages and with different compositions; it is interpreted to be formed at different stages of the metamorphism. These granulites were formed during Early Proterozoic high-grade metamorphism due to the emplacement of the South Harris Igneous Complex at c. 2170–1870 Ma, and are not related to the major metamorphic episode of the Badcallian/Inverian metamorphism at c. 2700–2500 Ma in the mainland Lewisian. Received: 17 July 1998 / Accepted 8 March 1999     

南极拉斯曼丘陵长英质片麻岩中夕线石的出溶现象

南极拉斯曼丘陵长英质片麻岩中的粗粒夕线石可能有内部出溶现象,出溶形成的矿物有磁铁矿、钛铁矿-赤铁矿和石英出溶矿物条纹,并有少量的斜方辉石.电子探针成分分析表明,本区夕线石高温结晶时不仅有Fe3 ,可能还有Fe2 、Mg2 和Ti4 的替换,铁氧化物质量分数可高达2.9%;随着温度的不断降低,固溶体互溶度也不断减小,大部分微量组分从夕线石中析出形成出溶结构,而且低温变体中稳定的替换元素以Fd3 为主.铁组分的类质同像替换对物理化学计算和夕线石矿化环境均有所影响,对夕线石晶胞参数a的影响很小,而对b,尤其对c的影响较大,与前人的结论有所不同.     

利用高铝粉煤灰制备莫来石微晶玻璃的实验研究

以高铝粉煤灰为主要原料,采用粉末烧结法制备出莫来石微晶玻璃。X射线衍射分析显示,经1350~1550℃热处理后,制得的微晶玻璃的主晶相均为莫来石。扫描电镜分析表明,较高的温度下热处理有利于晶体的生长。微晶玻璃的理化性能如吸水率、气孔率、体积密度、抗折强度和化学稳定性,随热处理温度的不同而发生相应的变化。1500℃热处理2 h制得的微晶玻璃具有优良的理化性能,在工程和结构领域具有潜在的应用前景。     

Kinetic study of the kaolinite-mullite reaction sequence. Part II: Mullite formation

The present work is a follow-up of the investigation on the decomposition reaction of kaolinite as a function of the defectivity of the starting material and the temperature of reaction. In the present work we study the high temperature reaction of mullite synthesis from kaolinite, from the starting point of the results obtained in the first part.Time resolved energy-dispersive powder diffraction patterns have been measured using synchrotron radiation in isothermal conditions. The apparent activation energy for mullite nucleation and growth is found to be related to the defective structure of the starting kaolinite, which thus must have an influence on the chemical homogeneity of the amorphous intermediate phase.     

Carbon isotopic thermometry and geobarometry of sillimanite isograd in thermal aureoles: the depth of emplacement of upper crustal granitic bodies

Carbon isotope fractionation between coexisting calcite and graphite (C ) has been studied in metamorphosed limestones from three thermal aureoles around Cretaceous granitic bodies (i.e., Tanohata, Tono, and Senmaya aureoles) in the Kitakami Mountains, Northeast Japan. C in each aureole decreases toward the granitic bodies, and becomes virtually uniform near the sillimanite isograd for metapelites, although calcite has variable isotopic ratios reflecting the original sedimentary compositions. The relationships indicate that isotopic equilibrium has been attained in metamorphosed limestone of sillimanite grade. Estimated C at the sillimanite isograd is similar in the Tanohata and Tono aureoles, but different in the Senmaya aureole with smaller carbon isotopic fractionations. From the temperature dependence of C and the negative dP/dT of andalusite–sillimanite equilibrium, we conclude that the sillimanite isograd in the Senmaya aureole was under higher temperature and lower pressure than in the other two localities. Temperatures at the sillimanite isograd are estimated by using existing calibrations of carbon isotopic exchange between calcite and graphite, whereas pressures are estimated from carbon isotopic temperatures and the andalusite–sillimanite equilibrium (Holdaway and Mukhopadhyay 1993a). Consistency of the P–T estimates is examined in the light of phase equilibria in the pelitic system. The estimated pressures at the sillimanite isograd are at about 2.1–2.7(±0.2) kbar for the Tanohata and Tono aureoles and less than 1 kbar for the Senmaya aureole, respectively. Geobarometry of sillimanite isograd in thermal aureoles indicates a marked difference in the depth of solidification of upper crustal granitoids: the Senmaya pluton has intruded and solidified at a very shallow level of less than 4 km whereas the Tanohata and Tono plutons are more deep-seated (ca. 8–10 km). The method can also be an effective tool in studying low-pressure type metamorphism in which geothermobarometry using garnet is not always applicable.Editorial responsibility: J. Hoefs     

The nature and significance of the mechanism of sillimanite growth in the Connemara schists,Ireland

During prograde metamorphism of the Connemara pelites, sillimanite first develops in biotite immediately adjacent to, or replacing, garnet. In some rocks, breakdown of garnet+muscovite and staurolite +muscovite+quartz leads to the development of fibrolite pseudomorphs after garnet. The textures indicate a constant volume replacement of garnet with movement of Al from staurolite and muscovite in the matrix towards the few, widely scattered, garnet sites. The complex ionic reaction patterns are the result of the strong preference of sillimanite to grow on biotite that is replacing garnet, and this pattern of preferred nucleations is taken to indicate that the equilibrium conditions for the reaction were only overstepped by the minimum required for initial sillimanite nucleation. Chemical movements were controlled by the heterogeneous nucleation pattern, not by intrinsic properties of the moving species. In order for extensive reaction to occur under near-equilibrium conditions, the rate at which the total thermal reaction proceeded must have been controlled by the supply of heat to the rocks rather than by diffusion or local reaction steps.