The nature of ordering and ordering defects in dolomite

The apparent lack of transformation-induced domains and stacking disorder defects in natural dolomites is considered in light of the different types of order in the dolomite structure. Experimentally produced twin domain boundaries and basal stacking defects are documented in a dolomite using high-resolution electron microscopy and electron diffraction techniques. Results reveal that upon cation ordering to form the dolomite structure, a twin domain is favored over an antiphase domain. The twin domain boundaries closely resemble antiphase boundaries (APB's) and are in contrast for superlattice reflections. However, background contrast within domains is shown to be different when imaged using certain fundamental reflections. The results allow speculation about the nature of ordering at low temperatures. Observations of twin domain boundaries in samples annealed at different temperatures allow estimation of the critical ordering temperature at 1,100°–1,150° C in stoichiometric dolomite.     

Mechanisms of exsolution in sodic pyroxenes

The free energy curves for simple binary solid solutions with limited miscibility or atomic ordering have been combined to predict the phase relations and exsolution mechanisms for a system in which both ordering and exsolution are possible. The nature of the ordering process affects which exsolution mechanisms may be used. If the ordering is second (or higher) order in character then continuous mechanisms predominate and a ‘conditional spinodal’ (Alien and Cahn, 1976) can be described which operates between ordered and disordered end members. For a first order case, the ordered phase can only precipitate a disordered phase by nucleation and growth. Microstructures in omphacites observed by transmission electron microscopy include exsolution lamellae and antiphase domains and the relations between them in selected specimens have been used to interpret the exsolution mechanisms which operated under geological conditions. It appears that most omphacites undergo cation ordering, and then remain homogeneous or exsolve a disordered pyroxene by spinodal decomposition. The predominance of continuous mechanisms has been used to indicate that the C2/c→P2/n transformation may be second (or higher) order in character. A possible phase diagram for jadeite-augite is presented. It is based on the idea that there should be limited miscibility between the disordered end members at low temperatures and that the cation ordering at intermediate compositions (omphacite) is superimposed on a solvus. It is adequate to explain many of the observed microstructures and fits with petrographic evidence of broad two phase fields between impure jadeite and omphacite and between omphacite and sodic augite. The effect of adding acmite is analogous to increasing temperature so that the phase relations for jadeite-acmite-augite can also be predicted.     

有序绿辉石空间群类型的群论研究

本文根据畴结构的群论原理,对有序绿辉石的空间群归属问题(P2还是P2/n)进行了讨论。通过把无序绿辉石的空间群C2/c分别相对于P2和P2/n的陪集展开可以得知,C2/c→P2相变将产生■的反相畴及■(001/2)和(■1/2 1/2 1/2)两种倒反孪晶,而C2/c→P2/n相变则仅产生■/2的反相畴,显然后者与有序绿辉石畴结构的透射电境观察结果一致。因此可以断定,有序绿辉石的空间群为P2/n,而非P2。     

Kinetic control of ordering and exsolution in omphacite

Omphacites with a range of compositions from the blueschist rocks of Syros, Greece and from included blocks in serpentinite from the Motagua fault zone, Guatemala, have been examined by transmission electron microscopy. The complex microstructures observed are all on a fine scale and are composed of exsolution and antiphase features. At least three different assemblages have been identified: (a) a single ordered phase with antiphase domains, (b) two exsolved phases, one ordered and the other disordered and (c) two exsolved phases, both apparently ordered. Selected area electron diffraction patterns provide evidence for P2/n, P2/c, and P2 space groups in different parts of the ordered crystals.The microstructures cannot all be readily explained in terms of a simple equilibrium phase diagram and some are attributed to alternative and metastable transformations. It is suggested that under the low temperature conditions of blueschist metamorphism, omphacite crystallised metastably below its ordering temperature with imperfect cation order. Subsequent development by cation ordering and exsolution was controlled by kinetics, the fastest available transformation being used to give reductions in free energy. Ordering preceded exsolution and may have occurred in a series of steps as predicted by the Ostwald step rule. Slight differences in composition and initial state of order locally influenced which reaction pathway was embarked upon and many of the products may be metastable. Such behaviour is apparently sensitive to thermal history.     

Microtextures and crystal chemistry in P21/c pigeonites

Summary ?A single-crystal X-ray investigation was performed on crystals of P2₁/c natural pigeonite with varying Ca and Fe^* ( = Fe²⁺ + Mn²⁺) contents, in order to verify the effect of microtextural disorder on structure refinements and to constrain the crystal chemistry of pigeonite. Antiphase domains and exsolution lamellae affect differently the refinement results. In a crystal free of exsolution the structure obtained after refinement with all reflections is an average of that of the antiphase domains and of their boundaries, whereas in an exsolved crystal it represents only the structure of the prevailing pigeonite lamellae. The refinement using only h + k odd reflections seems to give the structure of the Ca-free pigeonite characteristic of the antiphase domains rather than that of Ca-rich domain walls. The ratio of the scale factors in refinements with all reflections and with only h + k odd reflections allows the ratios of the exsolved augite and pigeonite phases to be estimated. The crystal chemistry of the investigated samples follows the trends outlined by data on Ca-free and Fe-free synthetic samples. In particular, it is shown that Ca and Fe^* substitution for Mg induce similar changes in the average structure, i.e. both induce an expansion in the M1 polyhedron and decrease the difference between the M2–O3 distances. Received October 18, 2001; revised version accepted February 15, 2002     

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.     

Structure,formation, and decomposition of APB's in calcic plagioclase

In calcic plagioclase (Ca, Na) [(Al, Si) AlSi₂O₈] Al-Si ordering produces superstructures with periodic and non periodic antiphase boundaries (APB's). Crystals growing at high temperature close to the melting point and cooling fairly rapidly order by nucleation of ordered domains which grow, resulting in an irregular pattern of curved APB's (b plagioclase). A modulated structure with periodic APB's forms by continuous ordering at large undercooling below the critical ordering temperature (e plagioclase). During annealing APB's are eliminated by pairwise recombination of adjacent APB's to reduce strain energy along the boundaries thereby transforming nonstable e plagioclase into stable b plagioclase without change in chemical composition. This process is often accompanied by a chemical phase separation with APB's providing favorable surfaces for diffusion. Transformations are documented by transmission electron microscopy (TEM) micrographs illustrating the variation in morphology of APB patterns in igneous and metamorphic plagioclase. They are in agreement with Korekawa et al.'s (1978) model of intermediate plagioclase which relies on periodic stacking of basic units rather than wavelike modulations. The paper includes observations of a new type of satellite in Stillwater bytownite (‘h’ satellites) which are due to fine lamellar exsolution.     

Omphacite microstructures as time-temperature indicators of blueschist- and eclogite-facies metamorphism

Omphacites from a wide range of geological environments have been examined by transmission electron-microscopy. Their microstructures are sufficiently variable as to be potential indicators of thermal history for blueschist and eclogite metamorphism. In particular, the average size of equiaxed antiphase domains (APD's) arising from cation ordering appears to be a characteristic feature of each environment and increases in the sequence: Franciscan, blueschist (1) ≈ Turkey, blueschist (2) < Guatemala, jadeitic blocks in serpentinite (3) < Syros, blueschist (9) ≈ Red Wine Complex, Canada, amphibolite (1) < Maksyutov Complex, Urals, blueschist (3) ≈ Zermatt-Saas, blueschist (5) ≈ Allalin, metagabbro (4) < Tauern, eclogite (1) ≈ Franciscan, eclogite (5) < Nybö, Norway, eclogite (2) (numbers in brackets indicate the number of hand specimens for which omphacite microstuctures are known). A relationship between APD size, annealing time and temperature has been derived by analogy with the known APD coarsening behaviour in other systems where: (APD size)ⁿ $$({\text{APD size)}}^{\text{n}} \propto {\text{e}}^{{\text{(}} - {\text{Q/RT)}}} \cdot {\text{ }}time{\text{.}}$$ . Most omphacites fit into a self-consistent scheme with n=8±2 if the activation energy (Q) is assumed to be that of cation disordering (75 kcal mole^?1), available estimates of peak metamorphic temperature (T) are used, and a reasonable geological time-scale is taken as 10⁴–10⁸ years. According to this model, APD sizes are set in a relatively short interval of the total history of a rock when its temperature is close to its peak value. APD sizes are much more sensitive to temperature than to time and may be used as a geothermometer which has the advantage of not being reset by re-equilibration at low temperatures. Petrological implications arising from the model are that Allalin metagabbros were metamorphosed at a similar peak temperature to Zermatt-Saas blueschists, Franciscan eclogites reached higher temperatures than has been previously supposed and that the microstructures in some Sesia-Lanzo omphacites are consistent with a high temperature, pre-blueschist origin. Deviation from an ideal coarsening law with n=2 implies that the APD's are not simply stacking mistakes but have some associated structural or compositional modification locally. Excess titanium concentrated at APD's in Red Wine Complex omphacites may account for their anomalously low observed APD size.     

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.     

Exsolution and coarsening in iron-free clinopyroxene during isothermal annealing

Exsolution and coarsening in Fe-free clinopyroxene of composition En_45.1Di_54.9 was studied at temperatures of 1300, 1200, and 1100°C, and annealing times between 10 min and 4320 h. Based on the wavelength of the exsolution lamellae, the exsolution process can be divided into exsolution sensu stricto and coarsening. During exsolution sensu stricto, the average wavelength of the “001” and “100” lamellae remains constant in contrast to the subsequent coarsening process. A progressive development of the microstructure is observed before coarsening which includes formation of island-like regions of dark contrast without phase separation, occurrence of pigeonite and diopside domains predominantly elongated along (100), formation of “100” exsolution lamellae, dissolution of the “100” lamellae, and predominant occurrence of “001” exsolution lamellae. All observations are in accordance with the exsolution mechanism of spinodal decomposition. After termination of the exsolution process, coarsening of the exsolution lamellae is observed. The “001” lamellae coarsen according to the rate law

     

Cation ordering in omphacite and effect on deformation mechanism and lattice preferred orientation (LPO)

We present microstructural data and lattice preferred orientations (LPOs) of omphacites from a suite of eclogites, from the Adula/Cima Lunga nappe (Central Alps). Our work shows a surprisingly strong correlation between the measured LPO and the ordering state of cations in omphacite. Estimates of deformation temperature from metamorphic petrology, together with measured omphacite compositions and LPOs, determine the field (ordering state), on the omphacite phase diagram, into which each sample falls. LPOs dominated by L-type and S-type signatures are developed in samples that fall in the P2/n field (ordered structure) and C2/c field (disordered structure), respectively.Dislocations with b=1/2−110 or b=[001] are observed in the transmission electron microscope (TEM) in all samples. The former change from a perfect dislocation in the C2/c structure to a partial in P2/n. Any movement of a partial dislocation requires the formation or growth of a stacking fault. Furthermore, in order to pass an obstacle a partial dislocation has to constrict to a unit dislocation. The energy to form a constriction is high in omphacite due to the large separation width. Thus, the activity of the b=1/2−110 dislocation is hindered in the P2/n structure relative to the C2/c structure, which change the balance between the two and might give rise to the different LPOs.     

Time evolution of twin domains in cordierite: a computer simulation study

The time and temperature evolution of twinning in cordierite is simulated using three computer models. The orientation of walls between twin domains in natural cordierite follows mainly the ferroelastic pattern which minimises the strain energy of the walls between twin-related domains. Such ferroelastic twinning is simulated in an elastic three-states Potts model in which each structural six-membered ring is represented by a three state pseudo-spin. The resulting twin pattern in a sample with 3169 structural rings shows sector trilling and fine scale ferroelastic wall patterns which coarsen with increasing annealing time. The poorly defined wall directions observed in cordierite were found to be related to twin walls which do not minimise the strain energy. Instead, these walls are located along the corners of pseudo-hexagonal rings and appear as the consequence of local rather than global interatomic interactions. Simulations using two-dimensional (38028 atoms) and three-dimensional (408 228 atoms) structural models show a predominance of these topological walls over the strain walls at early stages in the ordering process. The domain structure in the simulation is patchy rather than corresponding to repeated stripe structures found in other ferroelastic and co-elastic materials. In all models, a strong tendency for sector trilling is observed. In kinetic tweed patterns a novel 60o tweed is found at atomic length scales while the usual strain-mediated 90o tweed appears at mesoscopic length scales. An unusual surface tension effect in domain formation and ’writhing’, fluid-like motion was found in the three-dimensional structural model. This motion, along with the existence of non strain-mediated walls may contribute to cordierite’s poorly defined domain wall directions at the early stages of domain coarsening. Received: 11 March 1998 / Revised, accepted: 28 August 1998     

Investigation of superstructures in mullite by high resolution electron microscopy and electron diffraction

Superstructures in synthetic mullite, Al_4+2x Si_2?2x O_10?x , prepared using the zone melting technique, are studied by high resolution electron microscopy (HREM), electron diffraction, and in situ energy dispersive X-ray spectroscopy. For x=0.40 composition HREM images indicate only short-range order. Near x=0.5 composition mullite has an antiphase domain structure with antiphase boundaries (APB's) oriented parallel to (100). For higher Al-content the APB's run in non-rational orientations which are slightly inclined against the {601}-planes. We propose models for the superstructures in which oxygen vacancies are arranged in channels parallel to the crystal b-axis. The models are supported by a one-to-one match between observed and computer-simulated images. An Al-rich limit of x=2/3 for mullite is deduced on the basis of stereochemical considerations. Different ordering schemes for the tetrahedral cations are believed to result in the orientation change of the APB's near x=0.5 composition.     

Phase transition and mixing behaviour of the cummingtonite–grunerite solid solution

 Natural amphiboles with composition close to the binary join cummingtonite–grunerite and crystals of the same samples annealed at 700 °C for 55.5 h, in order to obtain different degrees of non-convergent cation order, have been characterised by means of X-ray single-crystal diffraction and IR spectroscopy. Long-range order parameters describing the non-convergent order of Mg/Fe among the different octahedral sites have been calculated from the site occupancies of the investigated samples. Values of the O6-O5-O6 angles and of the 〈M4-O〉 mean bond distances depend on the C2/m → P2₁/m phase transition for a given degree of order. In the IR spectra, only two phonon lines dominated by the bending of the tetrahedral chains are sensitive to the displacive phase transition and to the different degree of cation order; all the other wavenumber shifts are correlated with compositional changes only. The local strains arising from the cation substitution, ordering and phase transition have been quantified by means of the autocorrelation function. Very small local heterogeneities are associated with the Mg/Fe substitution and disordering in samples at intermediate composition. The displacive phase transition seems to occur in order to reduce local distortions and the P2₁/m samples are as homogeneous as orthorhombic anthophyllites. The orthorhombic structure, however, appears less flexible than the monoclinic in accommodating cations larger than Mg at the octahedral sites. Received: 9 February 2000 / Accepted: 30 September 2000     

The influence of multiple diffraction on the space group determination of orthopyroxene,spodumene, low omphacite and pigeonite

Forbidden reflections of some pyroxenes described as having a lower symmetry than Pbca or C2/c have been examined, mainly using the detailed ψ-scanning method of the four-circle automated diffractometer. All reflections violating the systematic absences of Pbca orthopyroxene, C2/c spodumene, P2/n omphacite and P2₁/c pigeonite were found to be due to the Umweganregung process of multiple diffraction; the Umweganregung peaks observed for the ψ azimuth were indexed in terms of a four-circle geometry. Thus, the space groups of orthopyroxene, α spodumene, low omphacite and low pigeonite were confirmed to be Pbca, C2/c, P2/n and P2₁/c, respectively.     

Electron microscopy study of domain structure due to phase transitions in natural perovskite

Transmission electron microscopy on natural calcium metatitanate perovskite (dysanalyte) reveals the following twin laws in the orthorhombic (space group Pbnm) phase: reflection twins on the {110} and {112} planes, and 90° rotation twins about the [001] axis (referred to as [001]_90° twin). Single crystals that were heattreated and quenched from above 1585 K exhibit a dramatic change in domain structure compared with the starting material and specimens quenched from T < 1470=" k.=" mutually=" perpendicular=" {110}=" and=">_90° twins are observed throughout the crystal, forming a cross-hatched domain texture. 1/2[001] antiphase domains, which are very rarely observed in the starting material, also become dominant in the crystal. This change in domain structure is interpreted as due to a structural phase transition in perovskite at a temperature below 1585 K. From the point symmetry elements that describe the twin laws and the translational elements that relate the antiphase domains, the most likely phase near 1585 K is tetragonal with space group P4/mbm. These results are consistent with high-temperature powder X-ray diffraction study. On the other hand, density of the {112} twins is increased significantly in the crystal quenched from 1673 K. Twin domains are either bound by mutually perpendicular {110} and (001) walls, or by {112} walls with {110} twin domains within the polygonal {112} domains. Both twin density variation and domain morphology suggest that the crystal may be cubic at this temperature. Microstructure of a single crystal deformed at 1273 K and 3.5 GPa (within the orthorhombic stability field) is morphologically quite distinct from that of the heat-treated specimens. Dislocations dominate the microstructure and often interact with twin domain boundaries.A National Science Foundation Science and Technology Center     

Mechanisms of exsolution in omphacites from high temperature,type B,eclogites

The microstructural development during the transformation of omphacite into pyroxene-plagioclase symplectites has been studied in some eclogites from the Seve nappe, Central Scandinavian Caledonides. The omphacite transformation can be described as a discontinuous precipitation reaction that occurred in two clearly defined stages to produce a coarser type A, followed by a finer, type B symplectite. Each type has its distinctive chemistry. The combination of microstructural and chemical characteristics of the transformation is used to reconstruct the early stages of the cooling history of the eclogites. In addition, based on a classification of phase transformations according to growth processes, the continuous exsolution reaction reported in high-temperature omphacites is combined with the discontinuous reaction in a time-temperature transformation (TTT) diagram to produce a more unified view of the exsolution in the omphacites.     

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.     

Transmission electron microscopic study of antiphase domains in CaAl2Ge2O8-Feldspar

Transmission electron microscopic study of synthetic CaAl₂Ge₂O₈-feldspar revealed two types of antiphase domains: type “b”-antiphase domains with the displacement vector 1/2 [110] and type “c”-antiphase domains with the displacement vector 1/2 [111]. The “b”-domains were on the order of 0.1 μm in size, while the “c”-domains displayed wall to wall distances mostly between 0.1 and 1 μm. The formation of the two types of antiphase domains is due to reductions in translational symmetry associated with the phase transitions \(C\bar 1 \to I\bar 1 \to P\bar 1\) . The antiphase domain textures of CaAl₂Ge₂O₈-feldspar are very similar to the textures found in natural and synthetic anorthite, CaAl₂Si₂O₈.