Transmission electron microscopy of synthetic and natural Fünferketten and Siebenerketten pyroxenoids

A new type of fault, called a chain periodicity fault, has been observed in Fünferketten and Siebenerketten pyroxenoids. The faults are mainly parallel to (001) and are due to irregularities in the periodicity along c, the direction of the silicate chains. For example, pyroxmangite (Siebenerketten) contains slabs of rhodonite (Fünferketten) one unit cell thick in the c direction. A periodic arrangement of chain periodictiy faults in synthetic iron rhodonite gives rise to a superstructure, where eight Fünferketten units along a chain are followed by one Siebenerketten unit. When different pyroxenoids are intergrown, they have a sublattice exactly or nearly in common. Synthesis of pyroxferroite and iron rhodonite (all Mn replaced by Fe) was carried out at low pressure.     

Transmission electron microscopy on meteoritic troilite

Phase transitions and associated domains of meteoritic troilite (FeS) have been studied by means of transmission electron microscopy (TEM). Three polymorphs have been found, two of which can be described by superstructures of the NiAs-type structure (A, C subcell). The P \(\overline 6\) 2c (√3A, 2C) polymorph, stable at room temperature, displays antiphase domains with the displacement vector 1/3< \(\overline {\text{1}}\) 10>. In situ heating experiments showed that the P \(\overline 6\) 2c polymorph changes at temperatures of 115°–150° C into an orthorhombic pseudohexagonal transitional phase with the probable space group Pmcn (A,√3A, C). It contains antiphase domains with the displacement vector 1/2 [110] and twins with a threefold twin-axis parallel c. When heated above 210° C the transitional phase transforms into the high-temperature modification with NiAs structure (P6 ₃/mmc). All observed phase transitions are reversible. The occurrence of antiphase and twin domains, respectively, agrees with the symmetry reductions involved in the subsolidus phase transitions. This is demonstrated by group-subgroup relationships among the space groups P6 ₃/mmc, Pmcn, and P \(\overline 6\) 2c.     

Crystal-chemistry of natural and heated aluminous orthopyroxenes

X-ray single crystal diffraction data of natural and heated Al-rich orthopyroxenes were used to study the cation ordering and the geometrical changes induced by Si+R ²⁺=Al^IV+R ³⁺ substitution. The calculated site populations and the observed bond distances in tetrahedral and octahedral sites suggest a total ordering of Al^IV in the TB tetrahedron and of R ³⁺ cations in the M1 octahedron, even in samples heated at 1000° C. The mismatch between the tetrahedral and octahedral layers along the c axis seems to play a crucial role in determining the limits of Si/Al^IV substitution.     

Characterization of natural pyrolusite by electron microscopy

A manganese-bearing mineral characterized by a black hair-like surface crystal growth, and somewhat unique to the Socorro County, New Mexico Area, has been referred to as psilomelane or pseudo-pyrolusite. X-ray diffraction measurements indicated the structure to be the tetragonal (a=4.42 Å, c=2.87Å) MnO₂ (pyrolusite) structure; with α-Mn enrichment. Detailed examinations of the mineral specimens made in the scanning and transmission electron microscopes showed the fiber crystals to be pseudo-fluted as a result of an apparent stacking of long needles to form continuous single-crystral bundles oriented along the x-axis These crystals were shown by selected-area electron diffraction to be composed of extended superstructure cells, and these to be commposed of as many as 10 MnO₂ unit cells stacked along the x-axis; interrupted by a stacking fault shear of the basic MnO₂ lattice resulting in stacking faults. Individual whisker crystals were observed to be terminated by crystallographic facets which is indicative of solution growth expected on considering their geological and mineralogical environment.     

Transmission electron microscopy applied to fluid inclusion investigations

The transmission electron microscope (TEM) allows a detailed characterization of textural and chemical features of fluid inclusions (shape, inner compositions and inner textures), at a resolution higher than that attainable with an optical microscope (OM). TEM investigation indicates that most fluid inclusions appear as perfectly euhedral negative crystals, with variable shape (from prismatic to equant) and size (typically from <0.02 to 0.15 μm). Inner texture (fluid phase/melt distribution) and composition are variable as well. Different kinds of negative crystals may coexist in the same trail of inclusions, possibly indicating locally variable trapping conditions.

A critical feature, revealed by TEM, is that inclusions are often connected to structural defects (in particular, to dislocation arrays), which are undetected by optical microscopy. The identification of these hidden nanostructures should be taken into account for the correct petrological interpretation of microthermometric results, particularly when controversial data have been obtained. In fact, these nanostructures may represent a possible path for fluid phase leakage, thus modifying the original composition and/or density of the inclusions.     

Transmission electron microscopy of experimentally deformed chalcopyrite single crystals

Two crystals of natural chalcopyrite, CuFeS₂, experimentally deformed at 200° C have been studied by means of transmission electron microscopy (TEM). The activated glide planes are (001) and {112}. The dislocations in (001) have the Burgers vector [110] and a predominating edge character. They are split into two colinear partials b=1/2[110] and can cross split into {112}. The dislocations in {112} consist of straight segments along low index lattice lines. They are often arranged in dipoles generating trails of loops. Few dislocations with b=1/2[ \(\overline {11} \) 1] and [1 \(\bar 1\) 0] are present and dislocations with b=[0 \(\bar 2\) 1] occur in low angle subgrain boundaries. From weak beam contrasts it is presumed that most of the dislocations gliding in {112} have b=1/2〈3 \(\overline {11} \) 〉. They are dissociated into up to four partials. Microtwins and different types of stacking faults in {112} also occur. Models of the dissociation of dislocations are discussed.     

Transmission electron microscopy on iron monosulfide varieties from the Suizhou meteorite

Transmission electron microscopy on the iron monosulfide (FeS) varieties from the Suizhou meteorite (Hubei, China) reveals the intergrowth of primary hexagonal 2C troilite and minor monoclinic 4C pyrrhotite (SG: F2/d) phases as nanometer-scale domain microstructure. In addition, anti-phase domain boundaries are found to present in the 2C troilite superstructure with the displacement vector 1/4[001]_2C, which is expected to form during the translational symmetry breaking during cooling from higher symmetry, high-temperature modification of the NiAs-type (SG: P6₃/mmc) structure. Furthermore, 60° rotation twinning about the pseudo-hexagonal c-axis is observed in the 4C pyrrhotite superstructure, which may result from rotation symmetry reduction induced by the ordered arrangements of metal vacancies through solid-state transformation during further cooling. All the above microstructural characteristics are discussed with consideration to the thermal metamorphism history experienced by the Suizhou meteorite.     

Transmission electron microscopy of subsolidus oxidation and weathering of olivine

Olivine crystals in basaltic andesites which crop out in the Abert Rim, south-central Oregon have been studied by high-resolution and analytical transmission electron microscopy. The observations reveal three distinct assemblages of alteration products that seem to correspond to three episodes of olivine oxidation. The olivine crystals contain rare, dense arrays of coherently intergrown Ti-free magnetite and inclusions of a phase inferred to be amorphous silica. We interpret this first assemblage to be the product of an early subsolidus oxidation event in the lava. The second olivine alteration assemblage contains complex ordered intergrowths on (001) of forsterite-rich olivine and laihunite (distorted olivine structure with Fe³⁺ charge balanced by vacancies). Based on experimental results for laihunite synthesis (Kondoh et al. 1985), these intergrowths probably formed by olivine oxidation between 400 and 800°C. The third episode of alteration involves the destruction of olivine by low-temperature hydrothermal alteration and weathering. Elongate etch-pits and channels in the margins of fresh olivine crystals contain semi-oriented bands of smectite. Olivine weathers to smectite and hematite, and subsequently to arrays of oriented hematite crystals. The textures resemble those reported by Eggleton (1984) and Smith et al. (1987). We find no evidence for a metastable phase intermediate between olivine and smectite (M — Eggleton 1984). The presence of laihunite exerts a strong control on the geometry of olivine weathering. Single laihunite layers and laihunite-forsteritic olivine intergrowths increase the resistance of crystals to weathering. Preferential development of channels between laihunite layers occurs where growth of laihunite produced compositional variations in olivine, rather than where coherency-strain is associated with laihunite-olivine interfaces.     

Analytical electron microscopy study of the plessite structure in four IIICD iron meteorites

Electron optical techniques were employed to investigate the plessite structure and composition of four IIICD fine octahedrites. These meteorites have a similar thermal history and differences in plessite structure can be ascribed to varying bulk Ni content and/or localized differences in carbon content. Microdiffraction patterns from regions as small as 20 nm dia. were obtained for the first time from plessite structures. It was established that transformation twins in clear taenite I have the conventional fcc twin relationship, individual kamacite and taenite cells in the cloudy zone have the Kurdjumov-Sachs orientation and fine γ rods in the decomposed martensite zone display both the Nishiyama and Kurdjumov-Sachs relation with the matrix-α. All the IIICD irons contain cloudy zone and martensitic plessite. Except for Dayton, martensitic plessite shows further decomposition into α + λ at low temperatures. Using STEM X-ray microanalysis with a spatial resolution of ~ 50 nm, Ni composition profiles in taenite from all the IIICD irons showed a maximum of ~48 wt% Ni. The structural and compositional data indicate that plessite formation occurs at quite low temperatures (~ 200–300°C) during the cooling history of the IIICD irons.     

An investigation by transmission electron microscopy of planar deformation features in naturally shocked quartz

We have investigated by Transmission Electron Microscopy (TEM) the planar deformation features(PDF) in quartz from various sites where shock metamorphism has been detected optically: impact sites; the Vredefort complex (South Africa) and the K/T boundary at Raton Basin (Colorado). PDFs are straight narrow bands of glass or microtwins or huge densities of dislocations. Such contrasting microstructures must reflect different shock scenarios. In the Vredefort complex the post-shock thermal history has strongly overprinted the shock-induced defects. In the Raton Basin samples very tiny bubbles have precipitated on the dislocations, strongly suggesting a lengthy annealing at moderate pressure and temperature. This new information should be taken into account in any model of the origin of the K/T transition. In any case, observation of PDFs by optical microscopy alone is not sufficient to unambiguously conclude on their origin.     

基于扫描电镜和CT成像技术的碳酸盐岩溶蚀作用微观结构和变化规律研究

为研究溶蚀作用下碳酸盐岩孔隙的演变规律及控制作用,文章选取三峡地区4种类型碳酸盐岩开展溶蚀实验。同时结合扫描电镜、CT成像对实验前后岩石的溶蚀特征及孔隙结构进行测试。结果表明：溶蚀总发生在低晶格能的矿物处且沿矿物晶体的菱形解理面以及薄弱部位发育,表现为对矿物和孔隙等结构的选择性溶解;碳酸盐岩的孔隙度对溶蚀过程影响较小,岩石的孔径大小是影响碳酸盐岩溶蚀速率的重要因素;小孔径岩石的溶蚀多在样品表面发育小型溶孔,大孔径岩石的溶蚀主要发生在孔隙隙壁且有向岩石内部溶蚀的痕迹;经溶蚀改造,孔喉半径和连通性均呈现出增长趋势。本研究对碳酸盐岩差异性岩溶作用机理及岩溶发育规律的认识有一定指导意义。     

Environmental scanning electron microscopy (ESEM) and nanoindentation investigation of the crack tip process zone in marble

This study explores the interaction between crack initiation and nanomechanical properties in the crack-tip fracture process zone of Carrara marble. Specimens with preexisting cracks were loaded in a uniaxial testing machine until the process zone appeared at the tips of the preexisting cracks. ESEM analysis reveals an increase in microcrack density in the process zone with increased loading of the specimen. Nanoindentation testing comprised of lines and grids of single nanoindentations located both near and far from the process zone shows a decrease in both indentation modulus and indentation hardness near grain boundaries in intact material, and with closeness to the process zone. Ultimately, the study confirms that the crack-tip process zone manifests itself as an area of reduced indentation hardness and indentation modulus in marble.     

Experimental deformation of a synthetic dunite at high temperature and pressure. II. Transmission electron microscopy

We have performed detailed transmission electron microscope on most of the deformed synthetic dunite specimens prepared in the study by Zeuch and Green (1984). We have identified three basic types of sub-boundaries, simple tilt walls in (100) and (001). composed by b = [100] and b = [001] edge dislocations, respectively, and twist boundaries in (010) composed of b = [100] and b = [001] screws. We have also observed more complex, asymmetric lilt boundaries in (100) and (001). Like the (010) twist boundaries, these asymmetric tilt walls are common only at the highest temperatures and lowest strain rates. Subgrain development is extensive at the higher temperatures and lower strain rates, and subgrains are composed of the above-mentioned three types of sub-boundaries; edge components in (100) and (001) ire “knitted” to screw components in (010) as described by Kirby and Wegner (1978) for naturally deformed olivine. In many areas of the samples which we studied, subgrain development is not observed, but parallel arrays of tilt boundaries of one type or the other are present. At higher temperatures and lower strain rates. “(100) organization” (Durham et al., 1977) is common; this structure consists of parallel arrays of (100) tilt boundaries with b = [100] screws connecting the sub-boundaries. At lower temperatures we have observed an analogous arrangement of (001) sub-boundaries and b = [001] screws, which we refer to as “(001) organization”. Under all experimental conditions, dislocations with b = [100] and b = [001] are present in approximately equal numbers. However, the two types of dislocations also have distinctly different geometries under all test conditions. We suggest that the transition from slip parallel to [001] to slip parallel to [100] with increasing temperature, which has been reported in earlier studies may also depend upon water content. The substructures which we observe are virtually identical to those seen in many naturally deformed peridolites. and we conclude that the mechanisms involved in both natural and laboratory deformation of olivine polycrystals are similar. On the other hand, the substructures reported here are very different from those observed in experimentally deformed olivine single crystals. It seems likely that these substructural differences reflect fundamental differences in the behavior oh single crystals and polycrystals. which are in turn reflected in different measured creep strengths.     

An electron spin resonance spectrometric investigation of natural,extracted and thermally altered kerogenous materials

Core cuttings from three wells representing a 1000–7000-ft range of depths were examined by ESR spectroscopy. The spectral parameters of some of the series of samples follow trends, as suggested by the ESR kerogen method for paleotemperature estimation, while the spectral parameters of other series of samples do not. Samples extracted with mineral acids exhibit spectra parameters which follow the proposed trends somewhat better, but show large local variations which appear to be due to factors other than paleotemperature. Thermally treated samples show a general increase in free radical concentration, although there are several anomalies. While the ESR-kerogen method of paleotemperature estimation appears to have potential due to the large variations in some of the observed parameters, factors such as mineral acid extraction and sample lithology, among others, need further investigation to refine the technique.     

A comparison of electron staining agents for the transmission electron microscopy examination of coal

A systematic comparison was made using several different stains on ultrathin sections of coal. Two stains (uranyl acetate+lead citrate and potassium permanganate) stood out by enhancing contrast and bringing out additional detail during the electron microscopy of coal.     

High resolution electron microscopy of tourmaline crystals

Summary High resolution electron micrographs have been obtained from crystals of two types of tourmaline, aligned in a goniometer stage so that the electron beam is parallel to thec axis. Images having a resolution of about 3 Å taken out of focus show direct indications of the atomic arrangement; they suggest medium-range ordering of the metal atoms in buergerite and unexpectedh31l symmetry in elbaite-schorl solid solution. The appearance of ordering is tentatively explained in terms of electron-irradiation effects.

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Hochauflösende Elektronenmikroskopie von Turmalinkristallen

Zusammenfassung Hochauflösende Elektronen-Mikrographien wurden von zwei Typen von Turmalinkristallen, die auf einer Goniometereinrichtung so orientiert waren, daß der Elektronenstrahl parallel zurc-Achse verlief, erhalten. Bilder mit einer 3 Å-Auflösung, die entfokusiert aufgenommen wurden, geben direkte Hinweise auf die Atomanordnung; sie deuten auf Ordnung mittlerer Reichweite der Metallatome in Buergerit und zeigen unerwarteterweiseh31l-Symmetrie bei Elbait-Schörl-Mischkristallen. Das Auftreten von Ordnung wird als vermutlicher Elektronenbestrahlungseffekt gedeutet.

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With 3 Figures     

Some constraints on the thermodynamic mixing properties of Fe-Mg orthopyroxenes and olivines

Existing data on the temperature and composition dependence of the Fe²⁺-Mg²⁺ distribution between Fe-Mg olivine and orthopyroxene, the intra-crystalline distribution of Fe²⁺ and Mg²⁺ between M1 and M2 sites in orthopyroxene, and macroscopic activity-composition relations in olivine and orthopyroxene are shown to be inconsistent with generally accepted thermodynamic formulations which assume that the non-configurational Gibbs energy of orthopyroxene is independent of the degree of long-range ordering of Fe²⁺ and Mg⁺ between M1 and M2 sites. These data are interpreted in terms of the constraints they provide on the size of Bragg-Williams type energy, entropy, and volume terms for olivine and orthopyroxene. The apparent equilibrium constant for Fe-Mg exchange between olivine and orthopyroxene is shown to be a potentially useful ‘geothermometer’ for olivine-orthopyroxene assemblages with olivines with mole fraction of Fe₂SiO₄ component less than 0.2 or greater than 0.6. A provisional calibration of this ‘geothermometer’ is presented.