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Sample records for calcite crystal orientation

  1. The grinding tip of the sea urchin tooth exhibits exquisite control over calcite crystal orientation and Mg distribution.

    Science.gov (United States)

    Ma, Yurong; Aichmayer, Barbara; Paris, Oskar; Fratzl, Peter; Meibom, Anders; Metzler, Rebecca A; Politi, Yael; Addadi, Lia; Gilbert, P U P A; Weiner, Steve

    2009-04-14

    The sea urchin tooth is a remarkable grinding tool. Even though the tooth is composed almost entirely of calcite, it is used to grind holes into a rocky substrate itself often composed of calcite. Here, we use 3 complementary high-resolution tools to probe aspects of the structure of the grinding tip: X-ray photoelectron emission spectromicroscopy (X-PEEM), X-ray microdiffraction, and NanoSIMS. We confirm that the needles and plates are aligned and show here that even the high Mg polycrystalline matrix constituents are aligned with the other 2 structural elements when imaged at 20-nm resolution. Furthermore, we show that the entire tooth is composed of 2 cooriented polycrystalline blocks that differ in their orientations by only a few degrees. A unique feature of the grinding tip is that the structural elements from each coaligned block interdigitate. This interdigitation may influence the fracture process by creating a corrugated grinding surface. We also show that the overall Mg content of the tooth structural elements increases toward the grinding tip. This probably contributes to the increasing hardness of the tooth from the periphery to the tip. Clearly the formation of the tooth, and the tooth tip in particular, is amazingly well controlled. The improved understanding of these structural features could lead to the design of better mechanical grinding and cutting tools.

  2. Calcite crystal growth rate inhibition by polycarboxylic acids

    Science.gov (United States)

    Reddy, M.M.; Hoch, A.R.

    2001-01-01

    Calcite crystal growth rates measured in the presence of several polycarboxyclic acids show that tetrahydrofurantetracarboxylic acid (THFTCA) and cyclopentanetetracarboxylic acid (CPTCA) are effective growth rate inhibitors at low solution concentrations (0.01 to 1 mg/L). In contrast, linear polycarbocylic acids (citric acid and tricarballylic acid) had no inhibiting effect on calcite growth rates at concentrations up to 10 mg/L. Calcite crystal growth rate inhibition by cyclic polycarboxyclic acids appears to involve blockage of crystal growth sites on the mineral surface by several carboxylate groups. Growth morphology varied for growth in the absence and in the presence of both THFTCA and CPTCA. More effective growth rate reduction by CPTCA relative to THFTCA suggests that inhibitor carboxylate stereochemical orientation controls calcite surface interaction with carboxylate inhibitors. ?? 20O1 Academic Press.

  3. Mechanism of Calcite Co-Orientation in the Sea Urchin Tooth

    Energy Technology Data Exchange (ETDEWEB)

    Killian, Christopher; Metzler, Rebecca; Gong, Y. U. T.; Olson, Ian; Aizenberg, Joanna; Politi, Yael; Wilt, Fred; Scholl, Andreas; Young, Anthony; Doran, Andrew; Kunz, Martin; Tamura, Nobumichi; Coppersmith, Susan; Gilbert, P. U. P. A.

    2009-12-01

    Sea urchin teeth are remarkable and complex calcite structures, continuously growing at the forming end and self-sharpening at the mature grinding tip. The calcite (CaCO{sub 3}) crystals of tooth components, plates, fibers, and a high-Mg polycrystalline matrix, have highly co-oriented crystallographic axes. This ability to co-orient calcite in a mineralized structure is shared by all echinoderms. However, the physico-chemical mechanism by which calcite crystals become co-oriented in echinoderms remains enigmatic. Here, we show differences in calcite c-axis orientations in the tooth of the purple sea urchin (Strongylocentrotus purpuratus), using high-resolution X-ray photoelectron emission spectromicroscopy (X-PEEM) and microbeam X-ray diffraction ({mu}XRD). All plates share one crystal orientation, propagated through pillar bridges, while fibers and polycrystalline matrix share another orientation. Furthermore, in the forming end of the tooth, we observe that CaCO{sub 3} is present as amorphous calcium carbonate (ACC). We demonstrate that co-orientation of the nanoparticles in the polycrystalline matrix occurs via solid-state secondary nucleation, propagating out from the previously formed fibers and plates, into the amorphous precursor nanoparticles. Because amorphous precursors were observed in diverse biominerals, solid-state secondary nucleation is likely to be a general mechanism for the co-orientation of biomineral components in organisms from different phyla.

  4. Calcite biomineralization in coccoliths: Evidence from atomic force microscopy (AFM)

    DEFF Research Database (Denmark)

    Henriksen, Karen; Stipp, S.L.S.

    2002-01-01

    geochemistry, crystal orientation, coccolith function, biomineralization, biological calcite, atomic force microscopy......geochemistry, crystal orientation, coccolith function, biomineralization, biological calcite, atomic force microscopy...

  5. Interactions of salicylic acid derivatives with calcite crystals.

    Science.gov (United States)

    Ukrainczyk, Marko; Gredičak, Matija; Jerić, Ivanka; Kralj, Damir

    2012-01-01

    Investigation of basic interactions between the active pharmaceutical compounds and calcium carbonates is of great importance because of the possibility to use the carbonates as a mineral carrier in drug delivery systems. In this study the mode and extent of interactions of salicylic acid and its amino acid derivates, chosen as pharmaceutically relevant model compounds, with calcite crystals are described. Therefore, the crystal growth kinetics of well defined rhombohedral calcite seed crystals in the systems containing salicylic acid (SA), 5-amino salicylic acid (5-ASA), N-salicyloil-l-aspartic acid (N-Sal-Asp) or N-salicyloil-l-glutamic acid (N-Sal-Glu), were investigated. The precipitation systems were of relatively low initial supersaturation and of apparently neutral pH. The data on the crystal growth rate reductions in the presence of the applied salicylate molecules were analyzed by means of Cabrera & Vermileya's, and Kubota & Mullin's models of interactions of the dissolved additives and crystal surfaces. The crystal growth kinetic experiments were additionally supported with the appropriate electrokinetic, spectroscopic and adsorption measurements. The Langmuir adsorption constants were determined and they were found to be in a good correlation with values obtained from crystal growth kinetic analyses. The results indicated that salicylate molecules preferentially adsorb along the steps on the growing calcite surfaces. The values of average spacing between the adjacent salicylate adsorption active sites and the average distance between the neighboring adsorbed salicylate molecules were also estimated.

  6. Transformation of amorphous calcium carbonate to rod-like single crystal calcite via "copying" collagen template.

    Science.gov (United States)

    Xue, Zhonghui; Hu, Binbin; Dai, Shuxi; Du, Zuliang

    2015-10-01

    Collagen Langmuir films were prepared by spreading the solution of collagen over deionized water, CaCl2 solution and Ca(HCO3)2 solution. Resultant collagen Langmuir monolayers were then compressed to a lateral pressure of 10 mN/m and held there for different duration, allowing the crystallization of CaCO3. The effect of crystallization time on the phase composition and microstructure of CaCO3 was investigated. It was found that amorphous calcium carbonate (ACC) was obtained at a crystallization time of 6 h. The amorphous CaCO3 was transformed to rod-like single crystal calcite crystals at an extended crystallization time of 12 h and 24 h, via "copying" the symmetry and dimensionalities of collagen fibers. Resultant calcite crystallites were well oriented along the longitudinal axis of collagen fibers. The ordered surface structure of collagen fibers and electrostatic interactions played key roles in tuning the oriented nucleation and growth of the calcite crystallites. The mineralized collagen possessing both desired mechanical properties of collagen fiber and good biocompatibility of calcium carbonate may be assembled into an ideal biomaterial for bone implants.

  7. Monoclinic deformation of calcite crystals at ambient conditions

    Science.gov (United States)

    Przeniosło, R.; Fabrykiewicz, P.; Sosnowska, I.

    2016-09-01

    High resolution synchrotron radiation powder diffraction shows that the average crystal structure of calcite at ambient conditions is described with the trigonal space group R 3 bar c but there is a systematic hkl-dependent Bragg peak broadening. A modelling of this anisotropic peak broadening with the microstrain model from Stephens (1999) [15] is presented. The observed lattice parameters' correlations can be described by assuming a monoclinic-type deformation of calcite crystallites. A quantitative model of this monoclinic deformation observed at ambient conditions is described with the space group C 2 / c . The monoclinic unit cell suggested at ambient conditions is related with the monoclinic unit cell reported in calcite at high pressure (Merrill and Bassett (1975) [10]).

  8. Morphology of calcite crystals in clast coatings from four soils in the Mojave desert region

    Science.gov (United States)

    Chadwick, Oliver A.; Sowers, Janet M.; Amundson, Ronald G.

    1989-01-01

    Pedogenic calcite-crystal coatings on clasts were examined in four soils along an altitudinal gradient on Kyle Canyon alluvium in southern Nevada. Clast coatings were studied rather than matrix carbonate to avoid the effects of soil matrix on crystallization. Six crystal sizes and shapes were recognized and distinguished. Equant micrite was the dominant crystal form with similar abundance at all elevations. The distributions of five categories of spar and microspar appear to be influenced by altitudinally induced changes in effective moisture. In the drier, lower elevation soils, crystals were equant or parallel prismatic with irregular, interlocking boundaries while in the more moist, higher elevation soils they were randomly oriented, euhedral, prismatic, and fibrous. There was little support for the supposition that Mg(+2) substitution or increased (Mg + Ca)/HCO3 ratios in the precipitating solution produced crystal elongation.

  9. Functionalization of biomineral reinforcement in crustacean cuticle: Calcite orientation in the partes incisivae of the mandibles of Porcellio scaber and the supralittoral species Tylos europaeus (Oniscidea, Isopoda).

    Science.gov (United States)

    Huber, Julia; Griesshaber, Erika; Nindiyasari, Fitriana; Schmahl, Wolfgang W; Ziegler, Andreas

    2015-05-01

    In arthropods the cuticle forms an exoskeleton with its physical and chemical properties adapted to functions of distinct skeletal elements. The cuticle of the partes incisivae (PI) in mandibles of terrestrial isopods is a composite of chitin-protein fibrils/fibres and minerals. It consists of an unmineralized tip, a middle region with organic fibrils reinforced mainly with amorphous calcium phosphate and a base region mineralized with amorphous calcium carbonate and calcite. In this study we extend our work on the structure and material properties of the incisive cuticle employing electron backscatter diffraction (EBSD), and investigate calcite orientation patterns in the PI of two terrestrial isopod species from different habitats. We trace small-scale differences in texture sharpness and calcite microstructure, and compare calcite organization and orientation patterns in the PI with those in the tergites of the same isopod species. We observe that in the PI calcite orientation, the degree of crystal alignment, and mode of crystalline domain assemblage is highly varied within short length scales. This contrasts to calcite organization in the tergite cuticle, where calcite has only one specific texture pattern. Such a large range in the variation of calcite organization has not been observed in other carbonate biological hard tissues, such as shells and teeth, where one specific texture and microstructure prevails. Thus, the investigated isopod species are able to control crystallization of the amorphous carbonate precursor in a differential way, most probably related to the function of the individual skeletal element and the animals' behavior.

  10. Functionalizing single crystals: incorporation of nanoparticles inside gel-grown calcite crystals.

    Science.gov (United States)

    Liu, Yujing; Yuan, Wentao; Shi, Ye; Chen, Xiaoqiang; Wang, Yong; Chen, Hongzheng; Li, Hanying

    2014-04-14

    Synthetic single crystals are usually homogeneous solids. Biogenic single crystals, however, can incorporate biomacromolecules and become inhomogeneous solids so that their properties are also extrinsically regulated by the incorporated materials. The discrepancy between the properties of synthetic and biogenic single crystals leads to the idea to modify the internal structure of synthetic crystals to achieve nonintrinsic properties by incorporation of foreign material. Intrinsically colorless and diamagnetic calcite single crystals are turned into colored and paramagnetic solids, through incorporation of Au and Fe3O4 nanoparticles without significantly disrupting the crystalline lattice of calcite. The crystals incorporate the nanoparticles and gel fibers when grown in agarose gel media containing the nanoparticles, whereas the solution-grown crystals do not. As such, our work extends the long-history gel method for crystallization into a platform to functionalize single-crystalline materials.

  11. Magnesium-Calcite Crystal Formation Mediated by the Thermophilic Bacterium Geobacillus thermoglucosidasius Requires Calcium and Endospores.

    Science.gov (United States)

    Murai, Rie; Yoshida, Naoto

    2016-11-01

    Fresh Geobacillus thermoglucosidasius cells grown on soybean-casein digest nutrient agar were inoculated as a parent colony 1 cm in diameter on the surface of an agar gel containing acetate and calcium ions (calcite-promoting hydrogel) and incubated at 60 °C for 4 days, after which magnesium-calcite single crystals of 50-130 µm in size formed within the parent colony. Addition of EDTA, polyacrylic acid or N,N-dicyclohexylcarbodiimide to the calcite-forming hydrogel inhibited the parent colony from forming magnesium-calcite crystals. Inoculation of G. thermoglucosidasius on calcite-forming hydrogel containing 5 µM cadmium and 20 µM zinc resulted in a decrease in the sporulation rate from 55 to 7-8 %. Magnesium-calcite synthesis decreased relative to the sporulation rate. G. thermoglucosidasius exhibited higher adsorption/absorbance of calcium than other Geobacillus sp. that do not mediate calcite formation and higher levels of magnesium accumulation. Calcium ions contained in the calcite-promoting hydrogel and magnesium ions concentrated in G. thermoglucosidasius cells serve as the elements for magnesium-calcite synthesis. The observed decreases in sporulation rate and magnesium-calcite formation support the hypothesis that endospores act as nuclei for the synthesis of magnesium-calcite single crystals.

  12. An assessment of calcite crystal growth mechanisms based on crystal size distributions

    Science.gov (United States)

    Kile, D.E.; Eberl, D.D.; Hoch, A.R.; Reddy, M.M.

    2000-01-01

    Calcite crystal growth experiments were undertaken to test a recently proposed model that relates crystal growth mechanisms to the shapes of crystal size distributions (CSDs). According to this approach, CSDs for minerals have three basic shapes: (1) asymptotic, which is related to a crystal growth mechanism having constant-rate nucleation accompanied by surface-controlled growth; (2) lognormal, which results from decaying-rate nucleation accompanied by surface-controlled growth; and (3) a theoretical, universal, steady-state curve attributed to Ostwald ripening. In addition, there is a fourth crystal growth mechanism that does not have a specific CSD shape, but which preserves the relative shapes of previously formed CSDs. This mechanism is attributed to supply-controlled growth. All three shapes were produced experimentally in the calcite growth experiments by modifying nucleation conditions and solution concentrations. The asymptotic CSD formed when additional reactants were added stepwise to the surface of solutions that were supersaturated with respect to calcite (initial Ω = 20, where Ω = 1 represents saturation), thereby leading to the continuous nucleation and growth of calcite crystals. Lognormal CSDs resulted when reactants were added continuously below the solution surface, via a submerged tube, to similarly supersaturated solutions (initial Ω = 22 to 41), thereby leading to a single nucleation event followed by surface-controlled growth. The Ostwald CSD resulted when concentrated reactants were rapidly mixed, leading initially to high levels of supersaturation (Ω >100), and to the formation and subsequent dissolution of very small nuclei, thereby yielding CSDs having small crystal size variances. The three CSD shapes likely were produced early in the crystallization process, in the nanometer crystal size range, and preserved during subsequent growth. Preservation of the relative shapes of the CSDs indicates that a supply-controlled growth mechanism

  13. Morphological changes of calcite single crystals induced by graphene-biomolecule adducts

    Science.gov (United States)

    Calvaresi, Matteo; Di Giosia, Matteo; Ianiro, Alessandro; Valle, Francesco; Fermani, Simona; Polishchuk, Iryna; Pokroy, Boaz; Falini, Giuseppe

    2017-01-01

    Calcite has the capability to interact with a wide variety of molecules. This usually induces changes in shape and morphology of crystals. Here, this process was investigated using sheets of graphene-biomolecule adducts. They were prepared and made dispersible in water through the exfoliation of graphite by tip sonication in the presence tryptophan or N-acetyl-D-glucosamine. The crystallization of calcium carbonate in the presence of these additives was obtained by the vapor diffusion method and only calcite formed. The analysis of the microscopic observations showed that the graphene-biomolecule adducts affected shape and morphology of rhombohedral {10.4} faced calcite crystals, due to their stabilization of additional {hk.0} faces. The only presence of the biomolecule affected minimally shape and morphology of calcite crystals, highlighting the key role of the graphene sheets as 2D support for the adsorption of the biomolecules.

  14. Orientation with a Viking sun-compass, a shadow-stick, and two calcite sunstones under various weather conditions.

    Science.gov (United States)

    Bernáth, Balázs; Blahó, Miklós; Egri, Adám; Barta, András; Kriska, György; Horváth, Gábor

    2013-09-01

    It is widely accepted that Vikings used sun-compasses to derive true directions from the cast shadow of a gnomon. It has been hypothesized that when a cast shadow was not formed, Viking navigators relied on crude skylight polarimetry with the aid of dichroic or birefringent crystals, called "sunstones." We demonstrate here that a simple tool, that we call "shadow-stick," could have allowed orientation by a sun-compass with satisfying accuracy when shadows were not formed, but the sun position could have reliably been estimated. In field tests, we performed orientation trials with a set composed of a sun-compass, two calcite sunstones, and a shadow-stick. We show here that such a set could have been an effective orientation tool for Vikings only when clear, blue patches of the sky were visible.

  15. Accurate measurement of the main refractive indices and thermo-optical coefficients of the calcite crystal

    Institute of Scientific and Technical Information of China (English)

    Shuang Zhao; Fuquan Wu; Haifeng Wang; Weigang Zhong; Xiuzhen Li; Hengjing Tang; Meng Shi; Hongyan Deng

    2007-01-01

    The main refractive indices of calcite crystal are measured by the means of auto-collimation, and the thermo-optical coefficients are calculated. The coefficient expression of Sellmeier equation is obtained by solving Sellmeier equation strictly and the refractive indices of different wavelengths are calculated, which accord with experimental esultsery well. The measured main refractive indices of calcite at 488-nm wavelength are identical with the values obtained by Sellmeier equation.

  16. Capillarity creates single-crystal calcite nanowires from amorphous calcium carbonate.

    Science.gov (United States)

    Kim, Yi-Yeoun; Hetherington, Nicola B J; Noel, Elizabeth H; Kröger, Roland; Charnock, John M; Christenson, Hugo K; Meldrum, Fiona C

    2011-12-23

    Single-crystal calcite nanowires are formed by crystallization of morphologically equivalent amorphous calcium carbonate (ACC) particles within the pores of track etch membranes. The polyaspartic acid stabilized ACC is drawn into the membrane pores by capillary action, and the single-crystal nature of the nanowires is attributed to the limited contact of the intramembrane ACC particle with the bulk solution. The reaction environment then supports transformation to a single-crystal product.

  17. Morphological and mechanical characterization of composite calcite/SWCNT-COOH single crystals.

    Science.gov (United States)

    Calvaresi, Matteo; Falini, Giuseppe; Pasquini, Luca; Reggi, Michela; Fermani, Simona; Gazzadi, Gian Carlo; Frabboni, Stefano; Zerbetto, Francesco

    2013-08-01

    A growing number of classes of organic (macro)molecular materials have been trapped into inorganic crystalline hosts, such as calcite single crystals, without significantly disrupting their crystalline lattices. Inclusion of an organic phase plays a key role in enhancing the mechanical properties of the crystals, which are believed to share structural features with biogenic minerals. Here we report the synthesis and mechanical characterization of composite calcite/SWCNT-COOH single crystals. Once entrapped into the crystals SWCNT-COOH appeared both as aggregates of entangled bundles and nanoropes. Their observation was possible only after crystal etching, fracture or FIB (focused ion beam) cross-sectioning. SWCNT-COOHs occupied a small volume fraction and were randomly distributed into the host crystal. They did not strongly affect the crystal morphology. However, although the Young's modulus of composite calcite/SWCNT-COOH single crystals was similar to that of pure calcite their hardness increased by about 20%. Thus, SWCNT-COOHs provide an obstacle against the dislocation-mediated propagation of plastic deformation in the crystalline slip systems, in analogy with the well-known hardness increase in fiber-reinforced composites.

  18. The kinetics and mechanisms of amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite.

    Science.gov (United States)

    Rodriguez-Blanco, Juan Diego; Shaw, Samuel; Benning, Liane G

    2011-01-01

    The kinetics and mechanisms of nanoparticulate amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite, were studied at a range of environmentally relevant temperatures (7.5-25 °C) using synchrotron-based in situ time-resolved Energy Dispersive X-ray Diffraction (ED-XRD) in conjunction with high-resolution electron microscopy, ex situ X-ray diffraction and infrared spectroscopy. The crystallization process occurs in two stages; firstly, the particles of ACC rapidly dehydrate and crystallize to form individual particles of vaterite; secondly, the vaterite transforms to calcite via a dissolution and reprecipitation mechanism with the reaction rate controlled by the surface area of calcite. The second stage of the reaction is approximately 10 times slower than the first. Activation energies of calcite nucleation and crystallization are 73±10 and 66±2 kJ mol(-1), respectively. A model to calculate the degree of calcite crystallization from ACC at environmentally relevant temperatures (7.5-40 °C) is also presented.

  19. Strain-relief by single dislocation loops in calcite crystals grown on self-assembled monolayers

    Science.gov (United States)

    Ihli, Johannes; Clark, Jesse N.; Côté, Alexander S.; Kim, Yi-Yeoun; Schenk, Anna S.; Kulak, Alexander N.; Comyn, Timothy P.; Chammas, Oliver; Harder, Ross J.; Duffy, Dorothy M.; Robinson, Ian K.; Meldrum, Fiona C.

    2016-06-01

    Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. Here we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generated in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. This work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates.

  20. Study on vibrational modes by group theory and infrared spectra by D FT for calcite crystal

    Institute of Scientific and Technical Information of China (English)

    Danhua Lou; Fengjiu Sun; Lijuan Li

    2007-01-01

    The factor group symmetry analysis (FSA) method and position symmetry analysis (PSA) method are used to analyze the vibrational modes of calcite (CaCO3) crystal, respectively. With the activated results of infrared and Raman spectra presented, strong points of each method are concluded. The infrared spectra are studied by using dynamics calculations based on density-functional theory (DFT) with the supercell model of calcite crystal. The frequencies of 27 normal modes are achieved, which are consistent with that by the group symmetry analysis very well, and fit with the experimental results better than the lattice dynamical methods.

  1. Nanobacteria-like calcite single crystals at the surface of the Tataouine meteorite.

    Science.gov (United States)

    Benzerara, Karim; Menguy, Nicolas; Guyot, Francois; Dominici, Christian; Gillet, Philippe

    2003-06-24

    Nanobacteria-like objects evidenced at the surface of the orthopyroxenes of the Tataouine meteorite in South Tunisia have been studied by scanning and transmission electron microscopies. A method of micromanipulation has been developed to ensure that exactly the same objects were studied by both methods. We have shown that the nanobacteria-like objects are spatially correlated with filaments of microorganisms that colonized the surface of the meteoritic pyroxene during its 70 years of residence in the aridic Tataouine soil. Depressions of a few micrometers in depth are observed in the pyroxene below the carbonates, indicating preferential dissolution of the pyroxene and calcite precipitation at these locations. The nanobacteria-like small rods that constitute calcium carbonate rosettes are well crystallized calcite single crystals surrounded by a thin amorphous layer of carbonate composition that smoothes the crystal edges and induces rounded shapes. Those morphologies are unusual for calcite single crystals observed in natural samples. A survey of recent literature suggests that the intervention of organic compounds derived from biological activity is likely in their formation.

  2. Calcite crystal growth inhibition by humic substances with emphasis on hydrophobic acids from the Florida Everglades

    Science.gov (United States)

    Hoch, A.R.; Reddy, M.M.; Aiken, G.R.

    2000-01-01

    The crystallization of calcium carbonate minerals plays an integral role in the water chemistry of terrestrial ecosystems. Humic substances, which are ubiquitous in natural waters, have been shown to reduce or inhibit calcite crystal growth in experiments. The purpose of this study is to quantify and understand the kinetic effects of hydrophobic organic acids isolated from the Florida Everglades and a fulvic acid from Lake Fryxell, Antarctica, on the crystal growth of calcite (CaCO3). Highly reproducible calcite growth experiments were performed in a sealed reactor at constant pH, temperature, supersaturation (?? = 4.5), P(CO2) (10-3.5atm), and ionic strength (0.1 M) with various concentrations of organic acids. Higher plant-derived aquatic hydrophobic acids from the Everglades were more effective growth inhibitors than microbially derived fulvic acid from Lake Fryxell. Organic acid aromaticity correlated strongly with growth inhibition. Molecular weight and heteroatom content correlated well with growth inhibition, whereas carboxyl content and aliphatic nature did not. Copyright (C) 1999 Elsevier Science Ltd.

  3. Morphogenetic control of calcite crystal growth in sulfonic acid based hydrogels.

    Science.gov (United States)

    Grassmann, Olaf; Löbmann, Peer

    2003-03-17

    In this paper the mineralization of CaCO(3) in various hydrogel matrices is presented. Sulfonic acid based hydrogels were prepared by introduction of sulfonate-containing monomers into a polyacrylamide network. The sulfonate content of polyacrylamide-co-vinylsulfonate and polyacrylamide-co-allylsulfonate decreases during elution of the copolymers in demineralized water, indicating insufficient linking of the sulfonate-bearing monomers within the hydrogel. In contrast to this, acrylamidomethylpropanesulfonate (AMPS) effectively copolymerizes with acrylamide (AAm) monomers. To study the influence of spatial arrangement of ionic functional groups within hydrogel networks on the mineralization of CaCO(3), AMPS copolymers with different degrees of AMPS cross-linking were synthesized. For the mineralization experiments the copolymers were placed into a double-diffusion arrangement. Calcite as the thermodynamically stable modification of CaCO(3) was obtained with a particular morphology. The pseudocubic habitus resembles aggregates obtained by mineralization in pure polyacrylamide. However, closer examination of the aggregates by scanning electron microscopy (SEM) shows that the crystal growth in the AMPS copolymers is different from that observed in polyacrylamide. Whereas the morphology of the calcite aggregates could be fine-tuned by using copolymers with different sulfonate content, the spatial distribution of the ionic functional groups alters the course of crystallization. Calcium ions are locally accumulated due to the heterogeneous distribution of functional sulfonate groups within the copolymer network. Thereby the nucleation of calcite is triggered, resulting in enhanced mineralization.

  4. Biogenic and synthetic high magnesium calcite - a review.

    Science.gov (United States)

    Long, Xia; Ma, Yurong; Qi, Limin

    2014-01-01

    Systematic studies on the Mg distributions, the crystal orientations, the formation mechanisms and the mechanical properties of biogenic high-Mg calcites in different marine organisms were summarized in detail in this review. The high-Mg calcites in the hard tissues of marine organisms mentioned generally own a few common features as follows. Firstly, the Mg distribution is not uniform in most of the minerals. Secondly, high-Mg calcite biominerals are usually composed of nanoparticles that own almost the same crystallographic orientations and thus they behave like single crystals or mesocrystals. Thirdly, the formation of thermodynamically unstable high-Mg calcites in marine organisms under mild conditions is affected by three key factors, that is, the formation of amorphous calcium (magnesium) carbonate precursor, the control of polymorph via biomolecules and the high Mg/Ca ratios in modern sea. Lastly, the existence of Mg ions in the Mg-containing calcite may improve the mechanical properties of biogenic minerals. Furthermore, the key progress in the synthesis of high-Mg calcites in the laboratory based on the formation mechanisms of the biogenic high-Mg calcites was reviewed. Many researchers have realized the synthesis of high-Mg calcites in the laboratory under ambient conditions with the help of intermediate amorphous phase, mixed solvents, organic/inorganic surfaces and soluble additives. Studies on the structural analysis and formation mechanisms of thermodynamically unstable biogenic high-Mg calcite minerals may shed light on the preparation of functional materials with enhanced mechanical properties.

  5. Semiconductor monolayer assemblies with oriented crystal faces

    KAUST Repository

    Ma, Guijun

    2012-01-01

    Fabrication of two-dimensional monolayers of crystalline oxide and oxynitride particles was attempted on glass plate substrates. X-Ray diffraction patterns of the assemblies show only specific crystal facets, indicative of the uniform orientation of the particles on the substrate. The selectivity afforded by this immobilization technique enables the organization of randomly distributed polycrystalline powders in a controlled manner.

  6. Characteristic crystal orientation of folia in oyster shell, Crassostrea gigas

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Seung Woo [Department of Chemical and Biomolecular Engineering, Sogang University, Seoul (Korea, Republic of); Kim, Gyeung Ho [Nano-Materials Reserch Center, Korea Institute of Science and Technology, Seoul (Korea, Republic of); Choi, Cheong Song [Department of Chemical and Biomolecular Engineering, Sogang University, Seoul (Korea, Republic of)], E-mail: cschoi@sogang.ac.kr

    2008-03-10

    The thin sheets of calcite, termed folia, that make up much of the shell of an oyster are composed of foliated lath. Folia of the giant Pacific oyster (Crassostrea gigas) were examined using TEM (transmission electron microscopy) and tested using microindentation and nanoindentation techniques. Analysis of the Kikuchi patterns obtained from the folia showed that there are two types (type I and type II) of preferred orientation, with an angle of around 70{sup o} between them. Nanoindentation tests showed that the folia exhibit a hardness of about 3 GPa and elastic modulus of about 73 GPa. Microcracks were generated using a microindenter in order to study the fracture mechanisms of the folia. Following on from these investigations, fracture mechanisms are discussed in conjunction with the correlation between preferred orientation and structural characteristics during cracking of the folia. Comparing the morphology and the polymorphism with nacre (also known as mother of pearl), the advantages of the relatively fast crystal growth and less amount of organic matrix in folia may have interesting implications for the development of sophisticated synthetic materials.

  7. Birefringence measurements in single crystal sapphire and calcite shocked along the a axis

    Science.gov (United States)

    Tear, Gareth R.; Chapman, David J.; Eakins, Daniel E.; Proud, William G.

    2017-01-01

    Calcite and sapphire were shock compressed along the direction (a axis) in a plate impact configuration. Polarimetery and Photonic Doppler Velocimetery (PDV) were used to measure the change in birefringence with particle velocity in the shock direction. Results for sapphire agree well with linear photoelastic theory and current literature showing a linear relationship between birefringence and particle velocity up to 310 m s-1. A maximum change in birefringence of 5% was observed. Calcite however showed anomolous behaviour with no detectable change in birefringence (less than 0.1%) over the range of particle velocities studied (up to 75 m s-1).

  8. A novel acidic matrix protein, PfN44, stabilizes magnesium calcite to inhibit the crystallization of aragonite.

    Science.gov (United States)

    Pan, Cong; Fang, Dong; Xu, Guangrui; Liang, Jian; Zhang, Guiyou; Wang, Hongzhong; Xie, Liping; Zhang, Rongqing

    2014-01-31

    Magnesium is widely used to control calcium carbonate deposition in the shell of pearl oysters. Matrix proteins in the shell are responsible for nucleation and growth of calcium carbonate crystals. However, there is no direct evidence supporting a connection between matrix proteins and magnesium. Here, we identified a novel acidic matrix protein named PfN44 that affected aragonite formation in the shell of the pearl oyster Pinctada fucata. Using immunogold labeling assays, we found PfN44 in both the nacreous and prismatic layers. In shell repair, PfN44 was repressed, whereas other matrix proteins were up-regulated. Disturbing the function of PfN44 by RNAi led to the deposition of porous nacreous tablets with overgrowth of crystals in the nacreous layer. By in vitro circular dichroism spectra and fluorescence quenching, we found that PfN44 bound to both calcium and magnesium with a stronger affinity for magnesium. During in vitro calcium carbonate crystallization and calcification of amorphous calcium carbonate, PfN44 regulated the magnesium content of crystalline carbonate polymorphs and stabilized magnesium calcite to inhibit aragonite deposition. Taken together, our results suggested that by stabilizing magnesium calcite to inhibit aragonite deposition, PfN44 participated in P. fucata shell formation. These observations extend our understanding of the connections between matrix proteins and magnesium.

  9. Magnetostriction of Fe81Ga19 oriented crystals

    Institute of Scientific and Technical Information of China (English)

    Wang Zhi-Bin; Liu Jing-Hua; Jiang Cheng-Bao

    2010-01-01

    The effect of the orientation on the magnetostrietion in Fe81Ga19 alloy has been investigated experimentally and theoretically. The Fe81Ga19[001]and[110]oriented crystals were prepared and the magnetostriction was measured under different pre-stress. The saturation magnetostriction of the[001]oriented crystal increases from 170x10-6 to 330x 10-6 under the pre-stress from O to 50 Mpa. The[110]oriented crystal has a saturation magnetostriction from 20x10-6 to 140x10-6 with the compressive pre-stress from O to 40 Mpa. The magnetostriction of[001]and[110]oriented crystals has been simulated based on the phenomenological theory. The domain rotation path has been determined and the resultant magnetostrietion calculated under different pre-stress. The experimental and simulated results both show that the[001]oriented crystal exhibits better magnetostriction than[110]oriented crystal. The enhancement of the saturation magnetostriction by the compressive pre-stress in the[110]oriented crystal is higher than that in the[001]oriented crystal.

  10. Evolution and the Calcite Eye Lens

    CERN Document Server

    Williams, Vernon L

    2013-01-01

    Calcite is a uniaxial, birefringent crystal, which in its optically transparent form, has been used for animal eye lenses, the trilobite being one such animal. Because of the calcite birefringence there is a difficulty in using calcite as a lens. When the propagation direction of incoming light is not exactly on the c-axis, the mages blur. In this paper, calcite blurring is evaluated, and the non-blurring by a crystallin eye lens is compared to a calcite one.

  11. Stability of orientationally disordered crystal structures of colloidal hard dumbbells.

    Science.gov (United States)

    Marechal, Matthieu; Dijkstra, Marjolein

    2008-06-01

    We study the stability of orientationally disordered crystal phases in a suspension of colloidal hard dumbbells using Monte Carlo simulations. For dumbbell bond length L/sigmafcc structure for a large part of the stable plastic crystal regime. In addition, we study the stability of an orientationally disordered aperiodic crystal structure in which the spheres of the dumbbells are on a random-hexagonal-close-packed lattice, and the dumbbells are formed by taking random pairs of neighboring spheres. Using free-energy calculations, we determine the fluid-aperiodic crystal and periodic-aperiodic crystal coexistence regions for L/sigma>0.88 .

  12. Investigation on the Orientation Transition of Oriented Magnetostrictive TbDyFe Crystals

    Institute of Scientific and Technical Information of China (English)

    LIU Wei; JIANG Cheng-bao

    2006-01-01

    and TbDyFe magnetostrictive oriented crystals were prepared by the zone-melting unidirectional solidification method at 240 mm/h and 720 mm/h respectively. oriented crystals were also obtained with oriented seeds with the same technique as for growing the oriented crystals. It is confirmed that this technique is stable for growing the oriented crystals in the TbDyFe alloys. Meanwhile, the variation of orientation, the solidification morphology and the magnetostriction were studied during the transition from oriented seeds to the oriented crystal growth. As the growth speeds up, the preferred orientation changed from to , and its morphology develops from of initial cellular to dendritic gradually. When an axial compressive pre-stress of 10 MPa is applied, the magnetostriction at the bottom, the middle and the top are 972×10-6, 918×10-6 and 900×10-6 at 100 mT respectively. The middle sections with mixed orientations have the same high magnetostriction performance as those with a single preferred orientation, which may be due to its celluar-dendritic morphology.

  13. Shear induced orientation of edible fat and chocolate crystals

    Science.gov (United States)

    Mazzanti, Gianfranco; Welch, Sarah E.; Marangoni, Alejandro G.; Sirota, Eric B.; Idziak, Stefan H. J.

    2003-03-01

    Shear-induced orientation of fat crystallites was observed during crystallization of cocoa butter, milk fat, stripped milk fat and palm oil. This universal effect was observed in systems crystallized under high shear. The minor polar components naturally present in milk fat were found to decrease the shear-induced orientation effect in this system. The competition between Brownian and shear forces, described by the Peclet number, determines the crystallite orientation. The critical radius size, from the Gibbs-Thomson equation, provides a tool to understand the effect of shear at the onset stages of crystallization.

  14. Sea urchin tooth mineralization: calcite present early in the aboral plumula.

    Science.gov (United States)

    Stock, Stuart R; Veis, Arthur; Xiao, Xianghui; Almer, Jonathan D; Dorvee, Jason R

    2012-11-01

    In both vertebrate bone, containing carbonated hydroxyapatite as the mineral phase, and in invertebrate hard tissue comprised of calcium carbonate, a popular view is that the mineral phase develops from a long-lived amorphous precursor which later transforms into crystal form. Important questions linked to this popular view are: when and where is the crystallized material formed, and is amorphous solid added subsequently to the crystalline substrate? Sea urchin teeth, in which the earliest mineral forms within isolated compartments, in a time and position dependent manner, allow direct investigation of the timing of crystallization of the calcite primary plates. Living teeth of the sea urchin Lytechinus variegatus, in their native coelomic fluid, were examined by high-energy synchrotron X-ray diffraction. The diffraction data show that calcite is present in the most aboral portions of the plumula, representing the very earliest stages of mineralization, and that this calcite has the same crystal orientation as in the more mature adoral portions of the same tooth. Raman spectroscopy of the aboral plumula confirms the initial primary plate mineral material is calcite and does not detect amorphous calcium carbonate; in the more mature adoral incisal flange, it does detect a broader calcite peak, consistent with two or more magnesium compositions. We hypothesize that some portion of each syncytial membrane in the plumula provides the information for nucleation of identically oriented calcite crystals that subsequently develop to form the complex geometry of the single crystal sea urchin tooth.

  15. Preparing polished crystal slices with high precision orientation

    DEFF Research Database (Denmark)

    Mathiesen, S. Ipsen; Gerward, Leif; Pedersen, O.

    1974-01-01

    A polishing procedure is described which utilizes a high precision Laue technique for crystal orientation. Crystal slices with their final polished surfaces parallel to a crystallographic plane within 0.02° can be prepared. ©1974 The American Institute of Physics......A polishing procedure is described which utilizes a high precision Laue technique for crystal orientation. Crystal slices with their final polished surfaces parallel to a crystallographic plane within 0.02° can be prepared. ©1974 The American Institute of Physics...

  16. Calcite sealing in a fractured geothermal reservoir: Insights from combined EBSD and chemistry mapping

    Science.gov (United States)

    McNamara, David D.; Lister, Aaron; Prior, Dave J.

    2016-09-01

    Fractures play an important role as fluid flow pathways in geothermal resources hosted in indurated greywacke basement of the Taupo Volcanic Zone, New Zealand, including the Kawerau Geothermal Field. Over time, the permeability of such geothermal reservoirs can be degraded by fracture sealing as minerals deposit out of transported geothermal fluids. Calcite is one such fracture sealing mineral. This study, for the first time, utilises combined data from electron backscatter diffraction and chemical mapping to characterise calcite vein fill morphologies, and gain insight into the mechanisms of calcite fracture sealing in the Kawerau Geothermal Field. Two calcite sealing mechanisms are identified 1) asymmetrical syntaxial growth of calcite, inferred by the presence of single, twinned, calcite crystals spanning the entire fracture width, and 2) 3D, interlocking growth of bladed vein calcite into free space as determined from chemical and crystallographic orientation mapping. This study also identifies other potential uses of combined EBSD and chemical mapping to understand geothermal field evolution including, potentially informing on levels of fluid supersaturation from the study of calcite lattice distortion, and providing information on a reservoir's history of stress, strain, and deformation through investigation of calcite crystal deformation and twinning patterns.

  17. Defects in Calcite.

    Science.gov (United States)

    1991-05-13

    Interatomic Distances in Halides and Chalcogenides" Acta. Cryst. 32 (19-76) 751. 3 8 S.A. Marshall, J.A. McMillan, and R.A. Serway . "Electron Spin... Serway RA (1967) Electron Spin Resonance Absorption Spectrum of Y3 -Stabilized C0 3- Molecular-Ion in Single- Crystal Calcite. J. Chem. Phys. 48:5131-5137

  18. Unified rotational dynamics of molecular crystals with orientational phase transition

    NARCIS (Netherlands)

    Michel, K.H.; Raedt, H. De

    1976-01-01

    A unified theory for the rotational dynamics of molecular crystals with orientational phase transitions is given. As basic secular variables one takes symmetry adapted functions, which describe the molecular orientations, and the angular momenta of the molecules. Using Mori’s projection operator tec

  19. Application-oriented Crystallization of Pharmaceutical Products

    DEFF Research Database (Denmark)

    Bruun Hansen, Thomas

    2017-01-01

    crystallizations were performed at fixed cooling rates, but also using Supersaturation control SSC and direct nucleation control DNC, to determine the temperature set point of the reactor. The impacts on crystal size, especially from the DNC experiments were quite impressive and clearly showed the advantages...

  20. Theoretical modeling of orientational effects in liquid-crystal layers

    Science.gov (United States)

    Melnikova, E. A.

    2005-11-01

    In the work the approximate analytical relations describing the director distribution in depth of a plane-parallel layer of nematic liquid crystal are presented. The analytical expression determining the orientational effect of the periodic surface in a system "relief grating - liquid crystal" is derived. Its diffraction characteristics are studied theoretically. Relaxation kinetics of the director in a plane-parallel layer of nematic liquid crystal is considered taking account of the microscopic inertia moment.

  1. Crystal-Orientation Dependent Evolution of Edge Dislocations from a Void in Single Crystal Gu

    Institute of Scientific and Technical Information of China (English)

    SONG Zhen-Fei; ZHU Wen-Jun; DENG Xiao-Liang; HE Hong-Liang

    2006-01-01

    @@ The micro-void growth by dislocation emission under tensile loading is explored with focus on the influence of crystal orientations. Based on the elastic theory, a dislocation emission criterion is formulated. It is predicted that the preferential location of dislocation nucleation and its threshold stress are dependent on the crystal orientation.Large-scale molecular dynamics (MD) simulations are also performed for single crystal copper to illustrate the dislocation evolution pattern associated with a nano-void growth. The results are in line with those given by the theoretical prediction. As revealed by MD simulations, the characteristics of void growth at micro-scale depend greatly on the crystal-orientation.

  2. The Crystal Hotel: A Microfluidic Approach to Biomimetic Crystallization.

    Science.gov (United States)

    Gong, Xiuqing; Wang, Yun-Wei; Ihli, Johannes; Kim, Yi-Yeoun; Li, Shunbo; Walshaw, Richard; Chen, Li; Meldrum, Fiona C

    2015-12-02

    A "crystal hotel" microfluidic device that allows crystal growth in confined volumes to be studied in situ is used to produce large calcite single crystals with predefined crystallographic orientation, microstructure, and shape by control of the detailed physical environment, flow, and surface chemistry. This general approach can be extended to form technologically important, nanopatterned single crystals.

  3. PAM微球表面方解石晶体的制备与表征%Synthesis and characterization of calcite crystal on surface of PAM microgel

    Institute of Scientific and Technical Information of China (English)

    李红; 阮美茹

    2013-01-01

    The synthesis of calcium carbonate crystals (calcite) from aqueous solutions containing polyacrylamide(PAM) microgels was performed by the method of dipping of the solution of CaCl2 and Na2CO3 by turns.The formation of calcite in several laboratory experiments was discussed.The PAM-CaCO3 composite spheres were characterized by SEM,FFIR,EDX,TAG.It was demonstrated that rhombohedral calcite is produced on the surface of microgels.Increasing the concentration of dipping solution,reaction speed quickens,meanwhile rhombohedral calcite begins to cluster.But delaying alternation time and increasing microgels quantity,size of calcite particles and clusters change smaller.%将聚丙烯酰胺(PAM)微凝胶在CaCl2和Na2CO3溶液中交替浸渍,其表面发生碳酸钙沉积反应,研究不同实验条件对所形成碳酸钙晶体(方解石)形貌的影响.利用SEM、FFIR、EDX、TAG等分析手段对制备的PAM-CaCO3复合微球进行表征.结果表明,在PAM微凝胶表面形成了由菱形层状簇集的方解石形貌;随着浸渍的溶液浓度增大,反应速度加快,层数增加,堆积成串状;但浸渍交替时间的延长和PAM微凝胶量的加大,均会使所形成的方解石颗粒变大,簇集层数减少.

  4. Role of crystal orientation on chemical mechanical polishing of single crystal copper

    Science.gov (United States)

    Zhu, Aibin; He, Dayong; Luo, Wencheng; Liu, Yangyang

    2016-11-01

    The material removal mechanism of single crystal copper in chemical mechanical polishing (CMP) has not been intensively investigated. And the role of crystal orientation in CMP of single crystal cooper is not quite clear yet. Quasi-continuum method was adopted in this paper to simulate the process of nano-particles grinding on single crystal copper in CMP process. Three different crystal orientations, i.e. x[100]y[001], x[001]y[110] and x[-211]y[111], were chosen for analysis. The atom displacement diagrams, stress distribution diagrams and load-displacement curves were obtained. After analyzing the deformation mechanism, residual stress of the work piece material and cutting force, results showed that, the crystal orientation of work piece has great influence on the deformation characteristics and surface quality of work piece during polishing. In the A(001)[100] orientation, the residual stress distribution after polishing is deeper, and the stress is larger than that in the B(110)[001] and C(111)[-211] orientations. And the average tangential cutting force in the A(001)[100] orientation is much larger than those in the other two crystal orientation. This research is helpful to revealing the material removal mechanism of CMP process.

  5. Oriented hydroxyapatite single crystals produced by the electrodeposition method

    Energy Technology Data Exchange (ETDEWEB)

    Santos, E.A. dos, E-mail: euler@ufs.br [INSA - Groupe Ingenierie des Surfaces, 24, Bld de la Victoire, 67084 Strasbourg (France); IPCMS - Departement de Surfaces et Interfaces, 23, rue du Loess, BP 43, 67034 Strasbourg (France); Moldovan, M.S. [INSA - Groupe Ingenierie des Surfaces, 24, Bld de la Victoire, 67084 Strasbourg (France); IPCMS - Departement de Surfaces et Interfaces, 23, rue du Loess, BP 43, 67034 Strasbourg (France); Jacomine, L. [INSA - Groupe Ingenierie des Surfaces, 24, Bld de la Victoire, 67084 Strasbourg (France); Mateescu, M. [IS2M - Equipe Interaction Surface-Matiere Vivant, 15, rue Jean Starcky, BP 2488, 68057 Mulhouse (France); Werckmann, J. [IPCMS - Departement de Surfaces et Interfaces, 23, rue du Loess, BP 43, 67034 Strasbourg (France); Anselme, K. [IS2M - Equipe Interaction Surface-Matiere Vivant, 15, rue Jean Starcky, BP 2488, 68057 Mulhouse (France); Mille, P.; Pelletier, H. [INSA - Groupe Ingenierie des Surfaces, 24, Bld de la Victoire, 67084 Strasbourg (France)

    2010-05-25

    We propose here the use of cathodic electrodeposition as tool to fabricate implant coatings consisting in nano/micro single crystals of hydroxyapatite (HA), preferentially orientated along the c-axis. Coating characterization is the base of this work, where we discuss the mechanisms related to the deposition of oriented hydroxyapatite thin films. It is shown that when deposited on titanium alloys, the HA coating is constituted by two distinct regions with different morphologies: at a distance of few microns from the substrate, large HA single crystals are oriented along the c-axis and appear to grow up from a base material, consisting in an amorphous HA. This organized system has a great importance for cell investigation once the variables involved in the cell/surface interaction are reduced. The use of such systems could give a new insight on the effect of particular HA orientation on the osteoblast cells.

  6. Crystal orientation dependent thermoelectric properties of highly oriented aluminum-doped zinc oxide thin films

    KAUST Repository

    Abutaha, Anas I.

    2013-02-06

    We demonstrate that the thermoelectric properties of highly oriented Al-doped zinc oxide (AZO) thin films can be improved by controlling their crystal orientation. The crystal orientation of the AZO films was changed by changing the temperature of the laser deposition process on LaAlO3 (100) substrates. The change in surface termination of the LaAlO3 substrate with temperature induces a change in AZO film orientation. The anisotropic nature of electrical conductivity and Seebeck coefficient of the AZO films showed a favored thermoelectric performance in c-axis oriented films. These films gave the highest power factor of 0.26 W m−1 K−1 at 740 K.

  7. Deformation microstructure and orientation of F.C.C. crystals

    DEFF Research Database (Denmark)

    Liu, Q.; Hansen, N.

    1995-01-01

    The effect of crystallographic orientation on the microstructural evolution in f.c.c. metals with medium to high stacking fault energy is analyzed. This analysis is based on a literature review of the behaviour of single crystals and polycrystals supplemented with an experimental study of cold...

  8. Crystal orientation effects on wurtzite quantum well electromechanical fields

    DEFF Research Database (Denmark)

    Duggen, Lars; Willatzen, Morten

    2010-01-01

    A one-dimensional continuum model for calculating strain and electric field in wurtzite semiconductor heterostructures with arbitrary crystal orientation is presented and applied to GaN/AlGaN and ZnO/MgZnO heterostructure combinations. The model is self-consistent involving feedback couplings of ...

  9. Orientational phase transition in cubic liquid crystals with positional order

    OpenAIRE

    Pokrovsky, V.L.; Saidachmetov, P.A.

    1988-01-01

    An electric field can give rise to a shear deformation of a cubic liquid crystal with long-range positional order fixed by two plates. The critical value of the field does not depend on the size of the system and depends crucially on the orientation.

  10. The Effect of Orientation Relaxation on Polymer Melt Crystallization Studied by Monte Carlo Simulations

    Institute of Scientific and Technical Information of China (English)

    WANG Mao-Xiang

    2009-01-01

    We use dynamic Monte Carlo simulations to study the athermal relaxation of bulk extended chains and the isothermal crystallization in intermediately relaxed melts. It is found that the memory of chain orientations in the melt can significantly enhance the crystallization rates. The crystal orientation and lamellar thickness essentially depend on the orientational relaxation. Moreover, there is a transition of the nucleation mechanism during the isothermal crystallization from the intermediately relaxed melts. These results explain the mechanism of the self-nucleation by orientation and suggest that in flow-induced polymer crystallization, the orientational relaxation of chains decides the crystal orientation.

  11. Direction-specific interactions control crystal growth by oriented attachment

    DEFF Research Database (Denmark)

    Li, Dongsheng; Nielsen, Michael H; Lee, Jonathan R.I.;

    2012-01-01

    The oriented attachment of molecular clusters and nanoparticles in solution is now recognized as an important mechanism of crystal growth in many materials, yet the alignment process and attachment mechanism have not been established. We performed high-resolution transmission electron microscopy...... using a fluid cell to directly observe oriented attachment of iron oxyhydroxide nanoparticles. The particles undergo continuous rotation and interaction until they find a perfect lattice match. A sudden jump to contact then occurs over less than 1 nanometer, followed by lateral atom-by-atom addition...... initiated at the contact point. Interface elimination proceeds at a rate consistent with the curvature dependence of the Gibbs free energy. Measured translational and rotational accelerations show that strong, highly direction-specific interactions drive crystal growth via oriented attachment....

  12. Uncertainty in Ice Crystal Orientation Distributions in Ice Sheets

    Science.gov (United States)

    Hay, Michael; Waddington, Edwin

    2016-04-01

    Crystal-orientation fabrics in polar ice sheets have a strong influence on ice flow due to the plastic anisotropy of ice. Crystal orientations evolve primarily in response to applied strain, but are also affected by temperature, impurities, interactions with neighbors, and other factors. While the evolution of each ice crystal is physically deterministic, in limited samples, such as those from ice-core thin sections, measured samples are stochastic due to sampling error. Even in continuum representations from models, crystal orientation distribution functions (ODFs) can be treated as stochastic due to uncertainties in how they developed. Here, we present results on the statistics of crystal orientation fabrics. We show a first-order estimate of the sampling distribution of fabric eigenvalues and fabric eigenvectors from ice-core thin sections. We also analyze uncertainty in electron backscatter diffraction measurements. In addition to sampling error, the strain histories of fabrics are generally poorly constrained, and may have varied in unknown ways through time. Nearby layers in ice sheets can also experience different strain histories due to inherent variabilities such as transient flow, or differences in impurities. This means that the continuum ODF itself can be treated as stochastic, because it depends on an effectively-stochastic unknown strain-history. To explore this, we analyze the effects of strain and vorticity variability on the evolution of the continuum ice-crystal ODF. We recast Jeffery's equation for the evolution of the ODF as a stochastic differential equation, with vorticity and strain perturbed by Gaussian processes. From this, we run a Monte-Carlo ensemble to determine likely bounds of true continuum ODF variability in response to random perturbations of strain and vorticity.

  13. Composite Magnetite and Protein Containing CaCO3 Crystals. External Manipulation and Vaterite → Calcite Recrystallization-Mediated Release Performance.

    Science.gov (United States)

    Sergeeva, Alena; Sergeev, Roman; Lengert, Ekaterina; Zakharevich, Andrey; Parakhonskiy, Bogdan; Gorin, Dmitry; Sergeev, Sergey; Volodkin, Dmitry

    2015-09-30

    Biocompatibility and high loading capacity of mesoporous CaCO3 vaterite crystals give an option to utilize the polycrystals for a wide range of (bio)applications. Formation and transformations of calcium carbonate polymorphs have been studied for decades, aimed at both basic and applied research interests. Here, composite multilayer-coated calcium carbonate polycrystals containing Fe3O4 magnetite nanoparticles and model protein lysozyme are fabricated. The structure of the composite polycrystals and vaterite → calcite recrystallization kinetics are studied. The recrystallization results in release of both loaded protein and Fe3O4 nanoparticles (magnetic manipulation is thus lost). Fe3O4 nanoparticles enhance the recrystallization that can be induced by reduction of the local pH with citric acid and reduction of the polycrystal crystallinity. Oppositely, the layer-by-layer assembled poly(allylamine hydrochloride)/poly(sodium styrenesulfonate) polyelectrolyte coating significantly inhibits the vaterite → calcite recrystallization (from hours to days) most likely due to suppression of the ion exchange giving an option to easily tune the release kinetics for a wide time scale, for example, for prolonged release. Moreover, the recrystallization of the coated crystals results in formulation of multilayer capsules keeping the feature of external manipulation. This study can help to design multifunctional microstructures with tailor-made characteristics for loading and controlled release as well as for external manipulation.

  14. Elastic constants of calcite

    Science.gov (United States)

    Peselnick, L.; Robie, R.A.

    1962-01-01

    The recent measurements of the elastic constants of calcite by Reddy and Subrahmanyam (1960) disagree with the values obtained independently by Voigt (1910) and Bhimasenachar (1945). The present authors, using an ultrasonic pulse technique at 3 Mc and 25??C, determined the elastic constants of calcite using the exact equations governing the wave velocities in the single crystal. The results are C11=13.7, C33=8.11, C44=3.50, C12=4.82, C13=5.68, and C14=-2.00, in units of 1011 dyncm2. Independent checks of several of the elastic constants were made employing other directions and polarizations of the wave velocities. With the exception of C13, these values substantially agree with the data of Voigt and Bhimasenachar. ?? 1962 The American Institute of Physics.

  15. Calcite growth kinetics: Modeling the effect of solution stoichiometry

    NARCIS (Netherlands)

    Wolthers, M.; Nehrke, G.; Gustafsson, J.P.; Van Cappellen, P.

    2012-01-01

    Until recently the influence of solution stoichiometry on calcite crystal growth kinetics has attracted little attention, despite the fact that in most aqueous environments calcite precipitates from non-stoichiometric solution. In order to account for the dependence of the calcite crystal growth rat

  16. Oriented growth and assembly of zeolite crystals on substrates

    Institute of Scientific and Technical Information of China (English)

    ZHOU Ming; ZHANG BaoQuan; LIU XiuFeng

    2008-01-01

    The aligned array and thin film of zeolites and molecular sieves possess a variety of potential applica-tions in membrane separation and catalysis, chemical sensors, and microelectronic devices. There are two main synthesis methods for manufacturing the aligned arrays and thin films of zeolites and mo-lecular sieves, i.e. in situ hydrothermal reaction and self-assembly of crystal grains on substrates. Both of them have attracted much attention in the scientific community worldwide. A series of significant progress has been made in recent years. By the in situ hydrothermal synthesis, the oriented nucleation and growth of zeolite and molecular sieve crystals can be achieved by modifying the surface properties of substrates or by changing the composition of synthesis solutions, leading to the formation of uni-formly oriented multicrystal-aligned arrays or thin films. On the other hand, the crystal grains of zeo-lites and molecular sieves can be assembled onto the substrate surface in required orientation using different bondages, for instance, the microstructure in the array or thin film can be controlled. This review is going to summarize and comment the significant results and progress reported recently in manufacturing highly covered and uniformly aligned arrays or thin films of zeolites and molecular sieves. It involves (1) in situ growth of highly aligned zeolite arrays and thin films via embedding func-tional groups on the substrate surface, modifying the surface microstructure of substrates, as well as varying the composition of synthesis solutions; (2) assembly of zeolite and molecular sieve crystals on various substrates to form aligned arrays and thin films with full coverage by covalent, ionic, and in-termolecular coupling interactions between crystals and substrates; (3) coupling surface assembly with microcontact printing or photoetching technique to produce patterned zeolite arrays and thin films. Finally, the functionality and applications of zeolite

  17. Automated determination of crystal orientations from electron backscattering patterns

    DEFF Research Database (Denmark)

    Lassen, Niels Christian Krieger

    1994-01-01

    determination of crystallographic orientations from EBSPs is accurate knowledge of three calibration parameters which describe the position of the point from which the patterns are emitted relative to the phosphor screen on which they are recorded. This thesis will describe a novel method by which...... of the position of the bands or the zone axes of EBSPs have existed for several years now. Until recently, however, the localization of either the bands or the zone axes of EBSPs has required the valuable time and attention of a human operator, thus obviously limiting the amounts of orientation data that can...... these calibration parameters can be estimated with high precision. The quality of EBSPs provides important information about the reliability of the measured crystal orientations and about the perfection of the lattice in which the pattern is generated. A measure which allows the quality of EBSPs to be evaluated...

  18. The calcite → aragonite transformation in low-Mg marble: Equilibrium relations, transformations mechanisms, and rates

    Science.gov (United States)

    Hacker, Bradley R.; Rubie, David C.; Kirby, Stephen H.; Bohlen, Steven R.

    2005-01-01

    Experimental transformation of a rather pure natural calcite marble to aragonite marble did not proceed via the expected straightforward polymorphic replacement. Instead, the small amount of Mg in the starting material (0.36 wt %) was excluded from the growing aragonite and diffused preferentially into the remaining calcite grains, producing Mg-rich calcite rods that persisted as relicts. Nucleation of aragonite occurred exclusively on grain boundaries, with aragonite [001] oriented subparallel to calcite [0001]. The aragonite crystals preferentially consumed the calcite crystal on which they nucleated, and the reaction fronts developed preferentially along the {010} and {110} planes of aragonite. Each aragonite neoblast that grew was nearly free of Mg (typically growth rates are approximately linear and range from ∼3 × 10−11 m s−1 at 600°C to ∼9 × 10−9 m s−1 at 850°C, with an apparent activation enthalpy of 166 ± 91 kJ mol−1. This reaction mechanism and the resultant texture are akin to cellular precipitation reactions in metals. Similar transformation textures have been reported from high-Mg marbles in Japan and China that disproportionated to low-Mg calcite and dolomite.

  19. Micromechanical Behavior of Single-Crystal Superalloy with Different Crystal Orientations by Microindentation

    Directory of Open Access Journals (Sweden)

    Jinghui Li

    2015-01-01

    Full Text Available In order to investigate the anisotropic micromechanical properties of single-crystal nickel-based superalloy DD99 of four crystallographic orientations, (001, (215, (405, and (605, microindentation test (MIT was conducted with different loads and loading velocities by a sharp Berkovich indenter. Some material parameters reflecting the micromechanical behavior of DD99, such as microhardness H, Young’s modulus E, yield stress σy, strain hardening component n, and tensile strength σb, can be obtained from load-displacement relations. H and E of four different crystal planes evidently decrease with the increase of h. The reduction of H is due to dislocation hardening while E is related to interplanar spacing and crystal variable. σy of (215 is the largest among four crystal planes, followed by (605, and (001 has the lowest value. n of (215 is the lowest, followed by (605, and that of (001 is the largest. Subsequently, a simplified elastic-plastic material model was employed for 3D microindentation simulation of DD99 with various crystal orientations. The simulation results agreed well with experimental, which confirmed the accuracy of the simplified material model.

  20. Driving voltage properties sensitive to microscale liquid crystal orientation pattern in twisted nematic liquid crystal cells

    Science.gov (United States)

    Honma, Michinori; Takahashi, Koki; Yamaguchi, Rumiko; Nose, Toshiaki

    2016-04-01

    We investigated the micropattern-sensitive driving voltage properties of twisted nematic liquid crystal (LC) cells and found that the threshold voltage for inducing the Fréedericksz transition strongly depends on the micropatterned LC molecular orientation state. We discuss the effects of various cell parameters such as the period of the micropattern Λ, the LC layer thickness d, and the twist angle Φ on the threshold voltage. By a computer simulation of the LC molecular orientation, we found that the threshold voltage V th varies in response to the deformation factor Δ (= d 2/Λ2 + Φ2/π2) of the spatially distributed LC molecular orientation. We confirm that V\\text{th}2 is proportional to 1 - Δ from both theoretical and experimental standpoints.

  1. Nanocrystalline calcitic lens arrays fabricated by self-assembly followed by amorphous-to-crystalline phase transformation.

    Science.gov (United States)

    Schmidt, Ingo; Lee, Kyubock; Zolotoyabko, Emil; Werner, Peter; Shim, Tae Soup; Oh, You-Kwan; Fratzl, Peter; Wagermaier, Wolfgang

    2014-09-23

    Natural calcium carbonate-based nanocomposites often have superior physical properties and provide a comprehensive source for bioinspired synthetic materials. Here we present thermodynamically stable, transparent CaCO3 microlens arrays (MLA) produced by transforming an amorphous CaCO3 phase into nanocrystalline calcite. We analyze the structure and properties of crystallized MLA by X-ray scattering, transmitted and polarized light microscopy, and electron microscopy and find that MLA are crystallized in spherulite-like patterns without changing the shape of the microlens. The key finding is that nanocrystallinity of the calcite formed diminishes structural anisotropy on the wavelength scale and results in greatly reduced birefringent effects. The remnant preferred orientation of the optical axes of calcite crystals in the plane of the microlens arrays leads to some directionality of optical properties, which may be beneficial for technical applications.

  2. Intracrystalline deformation of calcite

    NARCIS (Netherlands)

    de Bresser, Hans

    1991-01-01

    It is well established from observations on natural calcite tectonites that intracrystalline plastic mechanisms are important during the deformation of calcite rocks in nature. In this thesis, new data are presented on fundamental aspects of deformation behaviour of calcite under conditions where 'd

  3. Synthesis and characterization of spider silk calcite composite

    Directory of Open Access Journals (Sweden)

    Svetlana Dmitrović

    2016-03-01

    Full Text Available Spider silk poses excellent mechanical properties, tenacity and elasticity and it has been used as a template for calcite mineralization to improve load bearing strength of osteoconductive calcite. The samples were obtained by mimicking biomineralization for five days in order to follow formation and growth of calcite on the surface of spider silk. Crystal phase was detected by XRD and FTIR spectroscopy. Microstructure, crystal size and its morphology were studied by means of FESEM. After two days of processing, pure calcite phase was obtained, and a size of the formed crystals increased with prolongation of biomineralization.

  4. A generalized crystal-cutting method for modeling arbitrarily oriented crystals in 3D periodic simulation cells with applications to crystal-crystal interfaces

    Science.gov (United States)

    Kroonblawd, Matthew P.; Mathew, Nithin; Jiang, Shan; Sewell, Thomas D.

    2016-10-01

    A Generalized Crystal-Cutting Method (GCCM) is developed that automates construction of three-dimensionally periodic simulation cells containing arbitrarily oriented single crystals and thin films, two-dimensionally (2D) infinite crystal-crystal homophase and heterophase interfaces, and nanostructures with intrinsic N-fold interfaces. The GCCM is based on a simple mathematical formalism that facilitates easy definition of constraints on cut crystal geometries. The method preserves the translational symmetry of all Bravais lattices and thus can be applied to any crystal described by such a lattice including complicated, low-symmetry molecular crystals. Implementations are presented with carefully articulated combinations of loop searches and constraints that drastically reduce computational complexity compared to simple loop searches. Orthorhombic representations of monoclinic and triclinic crystals found using the GCCM overcome some limitations in standard distributions of popular molecular dynamics software packages. Stability of grain boundaries in β-HMX was investigated using molecular dynamics and molecular statics simulations with 2D infinite crystal-crystal homophase interfaces created using the GCCM. The order of stabilities for the four grain boundaries studied is predicted to correlate with the relative prominence of particular crystal faces in lab-grown β-HMX crystals. We demonstrate how nanostructures can be constructed through simple constraints applied in the GCCM framework. Example GCCM constructions are shown that are relevant to some current problems in materials science, including shock sensitivity of explosives, layered electronic devices, and pharmaceuticals.

  5. Effect of crystal orientation on low flux helium and hydrogen ion irradiation in polycrystalline tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Fangshu [Department of Physics, Beihang University, Beijing 100191 (China); School of Material Engineering, Panzhihua University, Panzhihua 617000 (China); Ren, Haitao; Peng, Shixiang [State Key Laboratory of Nuclear Physics and Technology, Institute of Heavy Ion Physics, Peking University, Beijing 100871 (China); Zhu, Kaigui, E-mail: kgzhu@buaa.edu.cn [Department of Physics, Beihang University, Beijing 100191 (China)

    2014-08-15

    Blistering behavior in polycrystalline tungsten is investigated under low flux helium and hydrogen ion irradiation. Subsequent to irradiation, the grain orientations near (0 1 1), (1 0 1) and (1 1 1) planes on the surface are analyzed by SEM and EBSD. It is found that blister density is the greatest on the grain orientation near (1 1 1) plane, and the smallest on the grain orientation near (0 0 1) plane. Experiments suggest that blistering degree highly depends upon the grain orientation, blisters are easily formed on the grain orientation near (1 1 1) plane, and medium on the grain orientation near (1 0 1) plane, and the most rare on the grain orientation near (0 1 1) plane. The surface resistant orientation of tungsten is orientation near (0 0 1) plane. The atom binding energy in the crystal plane in combination with the channeling effect of adjacent crystal planes may play an important role for the difference of the surface morphology.

  6. Room-Temperature Tensile Behavior of Oriented Tungsten Single Crystals with Rhenium in Dilute Solid Solution

    Science.gov (United States)

    1966-01-01

    SINGLE CRYSTALS WITH RHENIUM IN DILUTE SOLID SOLUTION Sby M. Garfinkle Lewis Research Center Cleveland, Ohio 20060516196 NATIONAL AERONAUTICS AND...WITH RHENIUM IN DILUTE SOLID SOLUTION By M. Garfinkle Lewis Research Center Cleveland, Ohio NATIONAL AERONAUTICS AND SPACE ADMINISTRATION For sale by...ORIENTED TUNGSTEN SINGLE CRYSTALS WITH RHENIUM IN DILUTE SOLID SOLUTION * by M. Garfinkle Lewis Research Center SUMMARY Tungsten single crystals

  7. Microstructural analysis of calcite-filled fractures inherited from basement structures, southern Ontario, Canada: long term instability of the craton?

    Science.gov (United States)

    Spalding, Jennifer; Schneider, David

    2016-04-01

    Intra-cratonic regions are generally characterized by tectonic stability and low seismicity. In southern Ontario, Canada, moderate levels of seismicity have been recorded over the last few decades reaching magnitudes of 5 MN, indicating that the geosphere is not as stable as predicted. The stratigraphy of the region consists of Ordovician limestone with a thickness of ~200 m that unconformably overlays the Mesoproterozoic crystalline Grenville Province. Subsequent tectonism including repeated Paleozoic orogenies and rifting along the east coast of North America has reactivated Proterozoic structures that have propagated into the overlying carbonate platform forming mesoscopic-scale brittle structures. Exposed along the shores of Lake Ontario are decameter-scale fracture zones, with a fracture spacing of 0.5 to 10 meters. The dominant fracture set trends E-W, and often forms conjugate sets with less prominent NNE-oriented fractures. More locally, an older NW-oriented fracture set is cross cut by the E-W and NNE oriented fractures. Regionally, there have been six directions of maximum horizontal stress in southern Ontario since the Precambrian, with the current orientation of maximum stress oriented ENE as a consequence of far field Atlantic ridge-push forces generated at distant plate boundaries. Calcite mineralization along fractured surfaces locally form sub-horizontal slickenside fabrics which are covered by a layer of euhedral calcite crystals, suggesting that fracture dilation (and fluid flow) occurred after fracture slip to allow the growth of calcite crystals. Due to the proximity of the carbonate units to the crystalline basement, we expect the calcitic veins to be enriched in rare earth elements and are presently conducting geochemical analyses. The calcite veins and surfaces vary from 2.5 cm to 1 mm thicknesses, often with larger calcite crystals in the center of the vein and smaller crystals at the vein boundaries, likely representing nucleation on small

  8. Influence of surfactant tail branching and organization on the orientation of liquid crystals at aqueous-liquid crystal interfaces.

    Science.gov (United States)

    Lockwood, Nathan A; de Pablo, Juan J; Abbott, Nicholas L

    2005-07-19

    We have examined the influence of two aspects of surfactant structure--tail branching and tail organization--on the orientational ordering (so-called anchoring) of water-immiscible, thermotropic liquid crystals in contact with aqueous surfactant solutions. First, we evaluated the influence of branches in surfactant tails on the anchoring of nematic liquid crystals at water-liquid crystal interfaces. We compared interfaces that were laden with one of three linear surfactants (sodium dodecyl sulfate, sodium dodecanesulfonate, and isomerically pure linear sodium dodecylbenzenesulfonate) to interfaces laden with branched sodium dodecylbenzenesulfonate. We carried out these experiments at 60 degrees C, above the Krafft temperatures of all the surfactants studied, and used the liquid crystal TL205 (a mixture of cyclohexane-fluorinated biphenyls and fluorinated terphenyls), which forms a nematic phase at 60 degrees C. Linear surfactants caused TL205 to assume a perpendicular orientation (homeotropic anchoring) above a threshold concentration of surfactant and parallel orientation (planar anchoring) at lower concentrations. In contrast, branched sodium dodecylbenzenesulfonate caused planar anchoring of TL205 at all concentrations up to the critical micelle concentration of the surfactant. Second, we used sodium dodecanesulfonate and a commercial linear sodium dodecylbenzenesulfonate to probe the influence of surfactant tail organization on the orientations of liquid crystals at water-liquid crystal interfaces. Commercial linear sodium dodecylbenzenesulfonate, which comprises a mixture of ortho and para isomers, has been previously characterized to form less ordered monolayers than sodium dodecanesulfonate at oil-water interfaces at room temperature. We found sodium dodecanesulfonate to cause homeotropic anchoring of both TL205 and 4'-pentyl-4-cyanobiphenyl (5CB, nematic at room temperature), whereas commercial linear sodium dodecylbenzenesulfonate caused predominantly

  9. Two-stage magnetic orientation of uric acid crystals as gout initiators

    Science.gov (United States)

    Takeuchi, Y.; Miyashita, Y.; Mizukawa, Y.; Iwasaka, M.

    2014-01-01

    The present study focuses on the magnetic behavior of uric acid crystals, which are responsible for gout. Under a sub-Tesla (T)-level magnetic field, rotational motion of the crystals, which were caused by diamagnetic torque, was observed. We used horizontal magnetic fields with a maximum magnitude of 500 mT generated by an electromagnet to observe the magnetic orientation of the uric acid microcrystals by a microscope. The uric acid crystals showed a perpendicular magnetic field orientation with a minimum threshold of 130 mT. We speculate that the distinct diamagnetic anisotropy in the uric acid crystals resulted in their rotational responses.

  10. Modeling of Crystal Orientations in Laser Powder Deposition of Single Crystal Material

    Science.gov (United States)

    Qi, Huan; Liu, Zhaoyang

    This paper presents a numerical model which simulates the dynamic molten pool formation and the crystal orientations of solidified SX alloy in a multi-layer laser powder deposition process. Based on the mathematical model of coaxial laser direct deposition, the effect of parameters (laser power, scanning speed, powder feed rate) on the tendency to form [001] direction expitaxial grains during solidification was evaluated. In the transient three- dimensional model, physical phenomena including heat transfer, melting, grain formation during solidification, mass addition, and fluid flow in the melt pool, were modeled in a self-consistent manner. The temperature fields, fluid flow velocity, clad geometry (width, height and melt pool depth) and grain formation in melting pool of single layer are predicted.

  11. Crystal orientation mapping via ion channeling: An alternative to EBSD

    Energy Technology Data Exchange (ETDEWEB)

    Langlois, C.; Douillard, T.; Yuan, H. [University of Lyon – INSA de Lyon – CNRS, MATEIS, UMR 5510, Bât. Blaise Pascal, 20 Avenue Albert Einstein, 69621 Villeurbanne (France); Blanchard, N.P. [University of Lyon – CNRS, ILM, UMR 5306, Université Lyon I, Bât. A. Kastler, 10 rue A. Byron, 69622 Villeurbanne (France); Descamps-Mandine, A. [University of Lyon – CNRS, INL, UMR 5510, Bât. B. Pascal, INSA de Lyon/Université Lyon I, 69621 Villeurbanne (France); Van de Moortèle, B. [Ecole Normale Supérieure de Lyon – CNRS, LGL, 46 allée d’Italie, 69364 Lyon (France); Rigotti, C. [University of Lyon – INSA de Lyon – CNRS, LIRIS, UMR 5205, INRIA, Bât. Blaise Pascal, 20 Avenue Albert Einstein, 69621 Villeurbanne (France); Epicier, T. [University of Lyon – INSA de Lyon – CNRS, MATEIS, UMR 5510, Bât. Blaise Pascal, 20 Avenue Albert Einstein, 69621 Villeurbanne (France)

    2015-10-15

    A new method, which we name ion CHanneling ORientation Determination (iCHORD), is proposed to obtain orientation maps on polycrystals via ion channeling. The iChord method exploits the dependence between grain orientation and ion beam induced secondary electron image contrast. At each position of the region of interest, intensity profiles are obtained from a series of images acquired with different orientations with respect to the ion beam. The profiles are then compared to a database of theoretical profiles of known orientation. The Euler triplet associated to the most similar theoretical profile gives the orientation at that position. The proof-of-concept is obtained on a titanium nitride sample. The potentialities of iCHORD as an alternative to EBSD are then discussed. - Highlights: • A new method is proposed to obtain orientation maps via ion channeling. • This method exploits the dependence between grain orientation and SE image contrast. • Intensity profiles are obtained from images acquired with different orientations. • The profiles are then compared to a database of theoretical profiles of known orientation. • The potentialities of this method as an alternative to EBSD are discussed.

  12. Inducing uniform single-crystal like orientation in natural rubber with constrained uniaxial stretch.

    Science.gov (United States)

    Zhou, Weiming; Meng, Lingpu; Lu, Jie; Wang, Zhen; Zhang, Wenhua; Huang, Ningdong; Chen, Liang; Li, Liangbin

    2015-07-07

    The effect of flow on crystallization is commonly attributed to entropic reduction, which is caused by stretch and orientation of polymer chains but overlooks the role of flow on final-state free energy. With the aid of in situ synchrotron radiation wide-angle X-ray diffraction (WAXD) and a homemade constrained uniaxial tensile testing machine, polycrystals possessing single-crystal-like orientation rather than uniaxial orientation are found during the constrained stretch of natural rubber, whereas the c-axis and a-axis align in the stretch direction (SD) and constrained direction (CD), respectively. Molecular dynamics simulation shows that aligning the a-axis of crystal nuclei in CD leads to the lowest free energy increase and favors crystal nucleation. This indicates that the nomenclature of strain-induced crystallization may not fully account for the nature of flow-induced crystallization (FIC) as strain mainly emphasizes the entropic reduction of initial melt, whereas stress rather than strain plays the dominant role in crystal deformation. The current work not only contributes to a comprehensive understanding of the mechanism of flow-induced crystallization but also demonstrates the potential application of constrained uniaxial tensile stretch for the creation of functional materials containing polycrystals that possess single-crystal-like orientation.

  13. Pure crystal orientation and anisotropic charge transport in large-area hybrid perovskite films.

    OpenAIRE

    Cho, N; Li, F; Turedi, B; Sinatra, L; Sarmah, SP; Parida,, B.; Saidaminov, MI; Murali, B; Burlakov, VM; Goriely, Alain; Mohammed, OF; Wu, T; Bakr, OM

    2016-01-01

    Controlling crystal orientations and macroscopic morphology is vital to develop the electronic properties of hybrid perovskites. Here we show that a large-area, orientationally pure crystalline (OPC) methylammonium lead iodide (MAPbI3) hybrid perovskite film can be fabricated using a thermal-gradient-assisted directional crystallization method that relies on the sharp liquid-to-solid transition of MAPbI3 from ionic liquid solution. We find that the OPC films spontaneously form periodic microa...

  14. Pure crystal orientation and anisotropic charge transport in large-area hybrid perovskite films

    OpenAIRE

    Cho, Namchul; LI Feng; Turedi, Bekir; Sinatra, Lutfan; Sarmah, Smritakshi P.; Parida, Manas R.; Saidaminov, Makhsud I.; Murali, Banavoth; Burlakov, Victor M.; Goriely, Alain; Mohammed, Omar F; Wu, Tom; Bakr, Osman M.

    2016-01-01

    Controlling crystal orientations and macroscopic morphology is vital to develop the electronic properties of hybrid perovskites. Here we show that a large-area, orientationally pure crystalline (OPC) methylammonium lead iodide (MAPbI3) hybrid perovskite film can be fabricated using a thermal-gradient-assisted directional crystallization method that relies on the sharp liquid-to-solid transition of MAPbI3 from ionic liquid solution. We find that the OPC films spontaneously form periodic microa...

  15. Disentangling the secondary relaxations in the orientationally disordered mixed crystals: cycloheptanol + cyclooctanol two-component system

    OpenAIRE

    2010-01-01

    The dynamics of the pure compounds and mixed crystals formed between cycloheptanol (cC7-ol) and cyclooctanol (cC8-ol) has been studied by means of broadband dielectric spectroscopy at temperatures near and above the orientational glass transition temperature. Both compounds are known to display at least one orientationally disordered (OD) phase of simple cubic symmetry, and within this phase, a continuous formation of mixed crystals was demonstrated in the past (Rute, M. A. et al. J. Phys. Ch...

  16. Orientation dependence of the stress rupture properties of Nickel-base superalloy single crystals

    Science.gov (United States)

    Mackay, R. A.

    1981-05-01

    The influence of orientation of the stress rupture behavior of Mar-M247 single crystals was studied. Stress rupture tests were performed at 724 MPa and 774 C where the effect of anisotropy is prominent. The mechanical behavior of the single crystals was rationalized on the basis of the Schmid factors for the operative slip systems and the lattice rotations which the crystals underwent during deformation. The stress rupture lives were found to be greatly influenced by the lattice rotations required to produce intersecting slip, because steady-state creep does not begin until after the onset of intersecting slip. Crystals which required large rotations to become oriented for intersecting slip exhibited a large primary creep strain, a large effective stress level at the onset of steady-state creep, and consequently a short stress rupture life. A unified analysis was attained for the stress rupture behavior of the Mar-M247 single crystals tested in this study at 774 C and that of the Mar-M200 single crystals tested in a prior study at 760 C. In this analysis, the standard 001-011-111 stereographic triangle was divided into several regions of crystallographic orientation which were rank ordered according to stress rupture life for this temperature regime. This plot indicates that those crystals having orientations within about 25 deg of the 001 exhibited significantly longer lives when their orientations were closer to the 001-011 boundary of the stereographic triangle than to the 001-111 boundary.

  17. Results on the Coherent Interaction of High Energy Electrons and Photons in Oriented Single Crystals

    CERN Document Server

    Apyan, A; Badelek, B; Ballestrero, S; Biino, C; Birol, I; Cenci, P; Connell, S H; Eichblatt, S; Fonseca, T; Freund, A; Gorini, B; Groess, R; Ispirian, K; Ketel, T; Kononets, Y V; López, A; Mangiarotti, A; Van Rens, B; Sellschop, J P Friedel; Shieh, M; Sona, P; Strakhovenko, V M; Uggerhøj, Erik; Uggerhøj, U; Ünel, G; Velasco, M; Vilakazi, Z Z; Wessely, O; Kononets, Yu.V.

    2005-01-01

    The CERN-NA-59 experiment examined a wide range of electromagnetic processes for multi-GeV electrons and photons interacting with oriented single crystals. The various types of crystals and their orientations were used for producing photon beams and for converting and measuring their polarisation. The radiation emitted by 178 GeV unpolarised electrons incident on a 1.5 cm thick Si crystal oriented in the Coherent Bremsstrahlung (CB) and the String-of-Strings (SOS) modes was used to obtain multi-GeV linearly polarised photon beams. A new crystal polarimetry technique was established for measuring the linear polarisation of the photon beam. The polarimeter is based on the dependence of the Coherent Pair Production (CPP) cross section in oriented single crystals on the direction of the photon polarisation with respect to the crystal plane. Both a 1 mm thick single crystal of Germanium and a 4 mm thick multi-tile set of synthetic Diamond crystals were used as analyzers of the linear polarisation. A birefringence ...

  18. ORIENTATIONAL MICRO-RAMAN SPECTROSCOPY ON HYDROXYAPATITE SINGLE-CRYSTALS AND HUMAN ENAMEL CRYSTALLITES

    NARCIS (Netherlands)

    TSUDA, H; ARENDS, J

    1994-01-01

    Single crystals of synthetic hydroxyapatite have been examined by orientational micro-Raman spectroscopy. The observed Raman bands include the PO43-/OH- internal and external. modes over the spectral range from 180 to 3600 cm(-1). The Raman-active symmetry tensors (A, E(1), and E(2)) of crystal-clas

  19. Plasmonic Photopatterning of Complex Molecular Orientations in Liquid Crystals

    Science.gov (United States)

    Guo, Yubing; Jiang, Miao; Peng, Chenhui; Sun, Kai; Yaroshchuk, Oleg; Lavrentovich, Oleg; Wei, Qi-Huo

    Aligning liquid crystal (LC) molecules in spatially non-uniform patterns are highly demanded for applications such as programmable origami and liquid crystal enabled nonlinear electrokinetics. We developed a high resolution projection photoalignment technique for patterning arbitrary LC alignment fields. The photoalignment is based on carefully engineered metasurfaces, or dubbed as plasmonic metamasks (PMMs). When illuminated by light, the PMMs generate patterns of both light intensity and polarization. By projecting the light transmitted through the PMMs onto liquid crystal cells coated with photosensitive materials, alignment patterns predesigned in polarization patterns of the PMMs can be imposed in liquid crystals. This technique makes the liquid crystal alignment a repeatable and scalable process similar to conventional photolithography, promising various applications. National Science Foundation CMMI-1436565.

  20. Modeling the evolution of complex conductivity during calcite precipitation on glass beads

    Science.gov (United States)

    Leroy, Philippe; Li, Shuai; Jougnot, Damien; Revil, André; Wu, Yuxin

    2017-01-01

    SUMMARYWhen pH and alkalinity increase, calcite frequently precipitates and hence modifies the petrophysical properties of porous media. The complex conductivity method can be used to directly monitor calcite precipitation in porous media because it is sensitive to the evolution of the mineralogy, pore structure and its connectivity. We have developed a mechanistic grain polarization model considering the electrochemical polarization of the Stern and diffuse layer surrounding calcite particles. Our complex conductivity model depends on the surface charge density of the Stern layer and on the electrical potential at the onset of the diffuse layer, which are computed using a basic Stern model of the calcite/water interface. The complex conductivity measurements of Wu et al. (2010) on a column packed with glass beads where calcite precipitation occurs are reproduced by our surface complexation and complex conductivity models. The evolution of the size and shape of calcite particles during the calcite precipitation experiment is estimated by our complex conductivity model. At the early stage of the calcite precipitation experiment, modeled particles sizes increase and calcite particles flatten with time because calcite crystals nucleate at the surface of glass beads and grow into larger calcite grains around glass beads. At the later stage of the calcite precipitation experiment, modeled sizes and cementation exponents of calcite particles decrease with time because large calcite grains aggregate over multiple glass beads, a percolation threshold is achieved, and small and discrete calcite crystals polarize.

  1. Crystal orientation dependence of femtosecond laser-induced periodic surface structure on (100) silicon.

    Science.gov (United States)

    Jiang, Lan; Han, Weina; Li, Xiaowei; Wang, Qingsong; Meng, Fantong; Lu, Yongfeng

    2014-06-01

    It is widely believed that laser-induced periodic surface structures (LIPSS) are independent of material crystal structures. This Letter reports an abnormal phenomenon of strong dependence of the anisotropic formation of periodic ripples on crystal orientation, when Si (100) is processed by a linearly polarized femtosecond laser (800 nm, 50 fs, 1 kHz). LIPSS formation sensitivity with a π/2 modulation is found along different crystal orientations with a quasi-cosinusoid function when the angle between the crystal orientation and polarization direction is changed from 0° to 180°. Our experiments indicate that it is much easier (or more difficult) to form ripple structures when the polarization direction is aligned with the lattice axis [011]/[011¯] (or [001]). The modulated nonlinear ionization rate along different crystal orientations, which arises from the direction dependence of the effective mass of the electron is proposed to interpret the unexpected anisotropic LIPSS formation phenomenon. Also, we demonstrate that the abnormal phenomenon can be applied to control the continuity of scanned ripple lines along different crystal orientations.

  2. Diffusion of Ca and Mg in Calcite

    Energy Technology Data Exchange (ETDEWEB)

    Cygan, R.T.; Fisler, D.K.

    1999-02-10

    The self-diffusion of Ca and the tracer diffusion of Mg in calcite have been experimentally measured using isotopic tracers of {sup 25}Mg and {sup 44}Ca. Natural single crystals of calcite were coated with a thermally-sputtered oxide thin film and then annealed in a CO{sub 2} gas at one atmosphere total pressure and temperatures from 550 to 800 C. Diffusion coefficient values were derived from the depth profiles obtained by ion microprobe analysis. The resultant activation energies for Mg tracer diffusion and Ca self-diffusion are respectively: E{sub a}(Mg) = 284 {+-} 74 kJ/mol and E{sub a}(Ca) = 271 {+-} 80 kJ/mol. For the temperature ranges in these experiments, the diffusion of Mg is faster than Ca. The results are generally consistent in magnitude with divalent cation diffusion rates obtained in previous studies and provide a means of interpreting the thermal histories of carbonate minerals, the mechanism of dolomitization, and other diffusion-controlled processes. The results indicate that cation diffusion in calcite is relatively slow and cations are the rate-limiting diffusing species for the deformation of calcite and carbonate rocks. Application of the calcite-dolomite geothermometer to metamorphic assemblages will be constrained by cation diffusion and cooling rates. The direct measurement of Mg tracer diffusion in calcite indicates that dolomitization is unlikely to be accomplished by Mg diffusion in the solid state but by a recrystallization process.

  3. Correlation of the crystal orientation and electrical properties of silicon thin films on glass crystallized by line focus diode laser

    Energy Technology Data Exchange (ETDEWEB)

    Yun, J., E-mail: j.yun@unsw.edu.au [School of Photovoltaic and Renewable Energy Engineering, University of New South Wales, Sydney, NSW 2052 (Australia); Huang, J.; Teal, A. [School of Photovoltaic and Renewable Energy Engineering, University of New South Wales, Sydney, NSW 2052 (Australia); Kim, K. [School of Photovoltaic and Renewable Energy Engineering, University of New South Wales, Sydney, NSW 2052 (Australia); Suntech R& D Australia, Botany, NSW 2019 (Australia); Varlamov, S.; Green, M.A. [School of Photovoltaic and Renewable Energy Engineering, University of New South Wales, Sydney, NSW 2052 (Australia)

    2016-06-30

    In this work, crystallographic orientation of polycrystalline silicon films on glass formed by continuous wave diode laser crystallization was studied. Most of the grain boundaries were coincidence lattice Σ3 twin boundaries and other types of boundaries such as, Σ6, Σ9, and Σ21 were also frequently observed. The highest photoluminescence signal and mobility were observed for a grain with (100) orientation in the normal direction. X-ray diffraction results showed the highest occupancies between 41 and 70% along the (110) orientation. However, the highest occupancies changed to (100) orientation when a 100 nm thick SiO{sub x} capping layer was applied. Suns-Voc measurement and photoluminescence showed that higher solar cell performance is obtained from the cell crystallized with the capping layer, which is suspected from increased occupancies of (100) orientation. - Highlights: • Linear grains parallel to the scan direction formed with high density. • Σ3 coincidence lattice (CSL) boundaries found inside a grain • Grain boundaries exhibit various CSL boundaries such as Σ9, Σ18, and Σ27. • Grain with < 100 > orientation in normal direction showed highest electrical properties. • Improved voltage observed when percentage of < 100 > normal orientation is increased.

  4. Pure crystal orientation and anisotropic charge transport in large-area hybrid perovskite films

    Science.gov (United States)

    Cho, Namchul; Li, Feng; Turedi, Bekir; Sinatra, Lutfan; Sarmah, Smritakshi P.; Parida, Manas R.; Saidaminov, Makhsud I.; Murali, Banavoth; Burlakov, Victor M.; Goriely, Alain; Mohammed, Omar F.; Wu, Tom; Bakr, Osman M.

    2016-11-01

    Controlling crystal orientations and macroscopic morphology is vital to develop the electronic properties of hybrid perovskites. Here we show that a large-area, orientationally pure crystalline (OPC) methylammonium lead iodide (MAPbI3) hybrid perovskite film can be fabricated using a thermal-gradient-assisted directional crystallization method that relies on the sharp liquid-to-solid transition of MAPbI3 from ionic liquid solution. We find that the OPC films spontaneously form periodic microarrays that are distinguishable from general polycrystalline perovskite materials in terms of their crystal orientation, film morphology and electronic properties. X-ray diffraction patterns reveal that the film is strongly oriented in the (112) and (200) planes parallel to the substrate. This film is structurally confined by directional crystal growth, inducing intense anisotropy in charge transport. In addition, the low trap-state density (7.9 × 1013 cm-3) leads to strong amplified stimulated emission. This ability to control crystal orientation and morphology could be widely adopted in optoelectronic devices.

  5. Pure crystal orientation and anisotropic charge transport in large-area hybrid perovskite films

    KAUST Repository

    Cho, Nam Chul

    2016-11-10

    Controlling crystal orientations and macroscopic morphology is vital to develop the electronic properties of hybrid perovskites. Here we show that a large-area, orientationally pure crystalline (OPC) methylammonium lead iodide (MAPbI3) hybrid perovskite film can be fabricated using a thermal-gradient-assisted directional crystallization method that relies on the sharp liquid-to-solid transition of MAPbI3 from ionic liquid solution. We find that the OPC films spontaneously form periodic microarrays that are distinguishable from general polycrystalline perovskite materials in terms of their crystal orientation, film morphology and electronic properties. X-ray diffraction patterns reveal that the film is strongly oriented in the (112) and (200) planes parallel to the substrate. This film is structurally confined by directional crystal growth, inducing intense anisotropy in charge transport. In addition, the low trap-state density (7.9 × 1013 cm−3) leads to strong amplified stimulated emission. This ability to control crystal orientation and morphology could be widely adopted in optoelectronic devices.

  6. Electromechanical characterization of [Formula: see text] crystals as a function of crystallographic orientation and temperature.

    Science.gov (United States)

    Zhang, Shujun; Luo, Jun; Hackenberger, Wesley; Sherlock, Nevin P; Meyer, Richard J; Shrout, Thomas R

    2009-05-15

    Relaxor based [Formula: see text] ternary single crystals (PIN-PMN-PT) were reported to have broader temperature usage range [Formula: see text] and comparable piezoelectric properties to [Formula: see text] (PMNT) crystals. In this work, the orientation dependent dielectric, piezoelectric and electromechanical properties for PIN-PMN-PT crystals were investigated along [Formula: see text] and [Formula: see text] directions. The electromechanical couplings [Formula: see text] and [Formula: see text] for [Formula: see text] poled crystals were found to be 0.91 and 0.91, respectively, with piezoelectric coefficients [Formula: see text] and [Formula: see text] on the order of 925 and -1420 pC/N. Of particular significance was the mechanical quality factor [Formula: see text] for [Formula: see text] oriented crystals, which was found to be [Formula: see text], much higher than the [Formula: see text] values of [Formula: see text] oriented relaxor-PT crystals [Formula: see text]. The temperature dependence of the piezoelectric properties exhibited good temperature stability up to their ferroelectric phase transition [Formula: see text], indicating [Formula: see text] and [Formula: see text] oriented PIN-PMN-PT are promising materials for transducer applications, with the latter for high power resonant devices where low loss (high [Formula: see text]) was required.

  7. The influence of orientation on the stress rupture properties of nickel-base superalloy single crystals

    Science.gov (United States)

    Mackay, Rebecca A.; Maier, Ralph D.

    1982-10-01

    The influence of orientation on the stress rapture properties of MAR-M247 single crystals was studied. Stress rupture tests were performed at 724 MPa and 774 °C where the effect of anisotropy is prominent. The mechanical behavior of the single crystals was rationalized on the basis of the Schmid factors for the operative slip systems and the lattice rotations which the crystals underwent during deformation. The stress rupture lives at 774 °C were found to be greatly influenced by the lattice rotations required to produce intersecting slip, because second-stage creep does not begin until after the onset of intersecting slip. Crystals which required large rotations to become oriented for intersecting slip exhibited a large primary creep strain, a large effective stress level at the onset of steady-state creep, and consequently, a short stress rupture life. Those crystals having orientations within about 25° of the [001] exhibited significantly longer lives when their orientations were closer to the [001]-[011] boundary of the stereographic triangle than to the [001]-[1l 1] boundary, because they required smaller rotations to produce intersecting slip and the onset of second-stage creep. Thus, the direction off the [001], as well as the number of degrees off the [001], has a major influence on the stress rapture lives of single crystals in this temperature regime.

  8. Orientational Phase Transition Around 274 K in C60 Single Crystal

    Institute of Scientific and Technical Information of China (English)

    徐亚伯; 何丕模; 杨宏顺; 郑萍; 余朝文; 陈兆甲; 张宣嘉; 李文铸

    1994-01-01

    The electrical conductivity of a C60 single crystal around 274 K and the specific heat of C60 crystals from 150 to 340 K have been measured.The delta-like specific heat peak at about 251 K related to the first-order phase transition has been reported.The activation energy change around 274 K and the lambda-like specific heat peak beginning at 270 K and ending at 310 K show that there is an orientational phase transition in fcc C60 crystals above 251 K.By taking the symmetry into consideration and further analyzing lambda-like specific heat peak and the activation energy change around 274 K,the conclusion has been reached that this new phase transition is an orientational structure transition from the merohedral twinning fcc to the orientationally disordered fcc.The temperature of free rotation of C60 molecules is about 281 K.

  9. Crystal orientation mapping applied to the Y-TZP/WC composite

    CERN Document Server

    Faryna, M; Sztwiertnia, K

    2002-01-01

    Crystal orientation measurements made by electron backscattered diffraction (EBSD) in the scanning electron microscope (SEM) and microscopic observations provided the basis for a quantitative investigation of microstructure in an yttria stabilized, tetragonal zirconia-based (Y-TZP) composite. Automatic crystal orientation mapping (ACOM) in a SEM can be preferable to transmission electron microscopy (TEM) for microstructural characterization, since no sample thinning is required, extensive crystal data is already available, and the analysis area is greatly increased. A composite with a 20 vol.% tungsten carbide (WC) content was chosen since it revealed crystal relationships between the matrix and carbide phase already established by TEM analysis. However, this composite was difficult to investigate in the EBSD/ SEM since it is non-conductive, the Y-TZP grain size is of the order of the system resolution, and the sample surface, though carefully prepared, reveals a distinctive microtopography. In this paper, so...

  10. Interaction of alcohols with the calcite surface

    DEFF Research Database (Denmark)

    Bovet, Nicolas Emile; Yang, Mingjun; Javadi, Meshkat Sadat

    2015-01-01

    . Controlling their growth requires complex polysaccharides. Polysaccharide activity depends on the functionality of OH groups, so to simplify the system in order to get closer to a molecular level understanding, we investigated the interaction of OH from a suite of alcohols with clean, freshly cleaved calcite......A clearer understanding of calcite interactions with organic molecules would contribute to a range of fields including harnessing the secrets of biomineralisation where organisms produce hard parts, increasing oil production from spent reservoirs, remediating contaminated soils and drinking water...... with the calcite surface through the OH group, with their carbon chains sticking away in a standing-up orientation. Alcohol molecules are closely packed and form a well-ordered monolayer on the surface....

  11. Faraday rotator based on TSAG crystal with orientation.

    Science.gov (United States)

    Yasuhara, Ryo; Snetkov, Ilya; Starobor, Aleksey; Mironov, Evgeniy; Palashov, Oleg

    2016-07-11

    A Faraday isolator (FI) for high-power lasers with kilowatt-level average power and 1-µm wavelength was demonstrated using a terbium scandium aluminum garnet (TSAG) with its crystal axis aligned in the direction. Furthermore, no compensation scheme for thermally induced depolarization in a magnetic field was used. An isolation ratio of 35.4 dB (depolarization ratio γ of 2.9 × 10-4) was experimentally observed at a maximum laser power of 1470 W. This result for room-temperature FIs is the best reported, and provides a simple, practical solution for achieving optical isolation in high-power laser systems.

  12. Aluminum induced crystallization of strongly (111) oriented polycrystalline silicon thin film and nucleation analysis

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A polycrystalline silicon thin film was fabricated on glass substrate by means of aluminum induced crystallization (AIC). Al and α-Si layers were deposited by magnetron sputtering respectively and annealed at 480°C for 1 h to realize layer exchange. The polycrystalline silicon thin film was continuous and strongly (111) oriented. By analyzing the structure variation of the oxidation membrane and lattice mismatch between γ-Al2O3 and Si, it was concluded that aluminum promoted the formation of (111) oriented silicon nucleus by controlling the orientation of γ-Al2O3, which was formed at the early stage of annealing.

  13. Cyclic growth and branching phenomena of calcite grown in Mg(2+) containing solutions and in natural systems

    Science.gov (United States)

    Wiethoff, Felix; Richter, Detlef K.; Neuser, Rolf D.; Immenhauser, Adrian; Gies, Hermann; Schreuer, Jürgen

    2016-04-01

    Undulosity in calcites (radiaxial fibrous calcite (RFC) and fascicular-optic fibrous calcite (FOFC)) is a common phenomenon in paleozoic and mesozoic limestones. Despite their importance as archives for climate reconstruction the underlying mechanisms and processes of their formation are still poorly understood [1]. To improve the application of such archives for climate reconstruction a better knowledge of their formation and possible alteration scenarios is necessary. In Mg2+ containing gel based growth experiments calcite crystals develop pathological morphologies. The morphology can be described as a product of a geometrical selective branching process at the rhombohedral crystal faces. Multiple sheet like building blocks evolve at the branching crystal face; each slightly tilted in respect to their substrate. The product is a crystal aggregate consisting out of several misoriented sub domains. In polarized light thin section microscopy the extinction behaviour of these sub units resemble the optical undulosity of radiaxial fibrous cements. In a multi method approach the local Mg2+ concentration was measured using EMPA and compared with maps of the local crystal orientation (via electron backscatter diffraction (EBSD)) and thin section microscopy. We found that Mg2+ is enriched at the sub-domain boundaries and deduced that lattice misfit as a consequence of impurity incorporation causes the crystal branching. We propose that this process is cyclic and each new misoriented sheet represents a growth period after a phase of inhibited growth caused by crystal faces covered by Mg2+-ions. In comparison to natural systems we found that radiaxial-fibrous cave cements show a pathological morphology based on the same formation principles. [1] Richter et al. (2011) Sediment. Geol. 239, 23-36 [2] Reeder & Paquette (1989) Sediment. Geol. 65, 239-247 [3] Davis et al. (2004) Am. Min. 89, 714-720

  14. The Influence of Crystal Annealing on Orientation Dependence of Nuclear Quadrupole Resonance in InSe

    Directory of Open Access Journals (Sweden)

    V.O. Khandozhko

    2013-10-01

    Full Text Available The dependence of the spectrum intensity on the orientation of crystallographic axes of anisotropic crystal with respect to the magnetic component vector of high-frequency field was studied using NQR method. The existence of residual intensity of the resonance spectrum while Н1c indicates the presence of defects in single crystal – blocks with small angle boundaries or other violations of atomic layers. Crystal annealing at the temperature of 550C is accompanied by improvment of quality of NQR resonance spectra and diffraction maxima at topograms.

  15. Crystal Orientation Controlled Photovoltaic Properties of Multilayer GaAs Nanowire Arrays.

    Science.gov (United States)

    Han, Ning; Yang, Zai-Xing; Wang, Fengyun; Yip, SenPo; Li, Dapan; Hung, Tak Fu; Chen, Yunfa; Ho, Johnny C

    2016-06-28

    In recent years, despite significant progress in the synthesis, characterization, and integration of various nanowire (NW) material systems, crystal orientation controlled NW growth as well as real-time assessment of their growth-structure-property relationships still presents one of the major challenges in deploying NWs for practical large-scale applications. In this study, we propose, design, and develop a multilayer NW printing scheme for the determination of crystal orientation controlled photovoltaic properties of parallel GaAs NW arrays. By tuning the catalyst thickness and nucleation and growth temperatures in the two-step chemical vapor deposition, crystalline GaAs NWs with uniform, pure ⟨110⟩ and ⟨111⟩ orientations and other mixture ratios can be successfully prepared. Employing lift-off resists, three-layer NW parallel arrays can be easily attained for X-ray diffraction in order to evaluate their growth orientation along with the fabrication of NW parallel array based Schottky photovoltaic devices for the subsequent performance assessment. Notably, the open-circuit voltage of purely ⟨111⟩-oriented NW arrayed cells is far higher than that of ⟨110⟩-oriented NW arrayed counterparts, which can be interpreted by the different surface Fermi level pinning that exists on various NW crystal surface planes due to the different As dangling bond densities. All this indicates the profound effect of NW crystal orientation on physical and chemical properties of GaAs NWs, suggesting the careful NW design considerations for achieving optimal photovoltaic performances. The approach presented here could also serve as a versatile and powerful platform for in situ characterization of other NW materials.

  16. A Rate-Dependent Crystal Plasticity Analysis of Orientation Stability in Biaxial Tension of Magnesium

    Institute of Scientific and Technical Information of China (English)

    Donghong Zhang; Saiyi Li

    2011-01-01

    The development of texture during plastic deformation plays an important role in determining the stretch formability of magnesium alloy sheets. In this study, the orientation stability during equibiaxial tension of magnesium was analyzed based on three dimensional lattice rotations calculated by using a rate-dependent crystal plasticity model and assuming five different combinations of slip modes. The results show that no orientations can satisfy the stability criteria with both zero rotation velocity and convergent orientation flow in all dimensions. However, relatively stable orientations with zero rotation velocity and an overall convergence are found. They are featured by characteristic alignments of specific crystallographic directions in the macroscopic axis of contraction, depending on the slip modes involved in the deformation. It is also shown that the orientation stability varies significantly with the deviation of deformation mode from equibiaxial tension. The simulation results are briefly discussed in comparison with pre-existing experiments.

  17. Observations of defect propagation in [100]-oriented opal-type photonic crystals

    Institute of Scientific and Technical Information of China (English)

    Jin Chong-Jun; Richard M. De La Rue; Nigel P. Johnson

    2008-01-01

    Charged colloidal suspensions have been used as experimental models for the study of crystal nucleation. Here we propose that the technique of template-assisted colloidal self-assembly can be used to visualize the effects of defect propagation in atomic crystal films produced using epitaxial growth. Templates with periodic line defects were used to grow [100]-oriented three-dimeusional photonic crystals by means of the template-assisted colloidal self-assembly method,aided by capillary and gravitational forces. The defect propagation in the [100J-oriented photonie crystal was observed using scanning electron microscopy, both at the surface of the crystal and on cleaved facets. This method is useful in the understanding of defect propagation in the growth of colloidal films on templates - and the same approach may also prove useful for the understanding of atomic crystal growth on substrates with defects. Additionally, the deliberate incorporation of line defects may prove valuable as a way of introducing waveguide channels into three-dimensional photonic crystals.

  18. Preferential {100} grain orientation in 10 micrometer-thick laser crystallized multicrystalline silicon on glass

    Energy Technology Data Exchange (ETDEWEB)

    Kühnapfel, S., E-mail: sven.kuehnapfel@helmholtz-berlin.de [Helmholtz-Zentrum Berlin für Materialien und Energie, Institut für Silizium-Photovoltaik, Kekuléstr. 5, 12489 Berlin (Germany); Nickel, N.H.; Gall, S. [Helmholtz-Zentrum Berlin für Materialien und Energie, Institut für Silizium-Photovoltaik, Kekuléstr. 5, 12489 Berlin (Germany); Klaus, M.; Genzel, C. [Helmholtz-Zentrum Berlin für Material und Energie, Abteilung Mikrostruktur- und Eigenspannungsanalyse, Albert-Einstein-Str. 15, 12489 Berlin (Germany); Rech, B.; Amkreutz, D. [Helmholtz-Zentrum Berlin für Materialien und Energie, Institut für Silizium-Photovoltaik, Kekuléstr. 5, 12489 Berlin (Germany)

    2015-02-02

    Liquid phase crystallization of 10 μm thin silicon layers on glass substrates was performed with a line-shaped continuous wave laser beam. The process window was investigated in terms of the scanning velocity of the laser, the pre-heating of the specimens and the applied laser intensity. We have identified the entire process window, in which large-scale crystallization without deformation or destruction of the substrate and cracking of the silicon layer can be obtained. The grain orientations of the resulting Si layers were analyzed using both electron backscatter diffraction (EBSD) and X-ray diffraction (XRD). The influence of the critical crystallization parameters on the grain orientation of the silicon film was examined. EBSD and XRD measurements show that a preferential {100} surface texture and {100} and {101} orientations in scanning direction of the laser can be achieved if appropriate crystallization parameters are used. This texture formation is accompanied with a substantial decrease of high angle grain boundaries. - Highlights: • Zone melting of thin silicon films (10 μm) directly on glass substrates. • The process window was examined in dependence of all process parameters. • A preferential {100} orientation was obtained within a specific parameter range. • A reduction of high angle boundaries is accompanied with the texture formation.

  19. Acousto-optical phonon excitation in cubic piezoelectric slabs and crystal growth orientation effects

    DEFF Research Database (Denmark)

    Duggen, Lars; Willatzen, Morten

    2017-01-01

    In this paper we investigate theoretically the influence of piezoelectric coupling on phonon dispersion relations. Specifically we solve dispersion relations for a fully coupled zinc-blende freestanding quantum well for different orientations of the crystal unit cell. It is shown that the phonon ...

  20. Influence of Substrate on Crystal Orientation of Large-Grained Si Thin Films Formed by Metal-Induced Crystallization

    Directory of Open Access Journals (Sweden)

    Kaoru Toko

    2015-01-01

    Full Text Available Producing large-grained polycrystalline Si (poly-Si film on glass substrates coated with conducting layers is essential for fabricating Si thin-film solar cells with high efficiency and low cost. We investigated how the choice of conducting underlayer affected the poly-Si layer formed on it by low-temperature (500°C Al-induced crystallization (AIC. The crystal orientation of the resulting poly-Si layer strongly depended on the underlayer material: (100 was preferred for Al-doped-ZnO (AZO and indium-tin-oxide (ITO; (111 was preferred for TiN. This result suggests Si heterogeneously nucleated on the underlayer. The average grain size of the poly-Si layer reached nearly 20 µm for the AZO and ITO samples and no less than 60 µm for the TiN sample. Thus, properly electing the underlayer material is essential in AIC and allows large-grained Si films to be formed at low temperatures with a set crystal orientation. These highly oriented Si layers with large grains appear promising for use as seed layers for Si light-absorption layers as well as for advanced functional materials.

  1. Heat-labile enterotoxin crystal forms with variable A/B5 orientation. Analysis of conformational flexibility

    NARCIS (Netherlands)

    Sixma, Titia K.; Aguirre, Angel; Terwisscha van Scheltinga, Anke C.; Wartna, Ellen S.; Kalk, Kor H.; Hol, Wim G.J.

    1992-01-01

    A new native crystal form of heat-labile enterotoxin (LT) has two AB5 complexes in the asymmetric unit with different orientations of the A subunit with respect to the B pentamer. Comparison with other crystal forms of LT shows that there is considerable conformational freedom for orientating the A

  2. Heat-labile enterotoxin crystal forms with variable A/B5 orientation. Analysis of conformational flexibility

    NARCIS (Netherlands)

    Sixma, Titia K.; Aguirre, Angel; Terwisscha van Scheltinga, Anke C.; Wartna, Ellen S.; Kalk, Kor H.; Hol, Wim G.J.

    1992-01-01

    A new native crystal form of heat-labile enterotoxin (LT) has two AB, complexes in the asymmetric unit with different orientations of the A subunit with respect to the B pentamer. Comparison with other crystal forms of LT shows that there is considerable conformational freedom for orientating the A

  3. Influence of the orientation of methylammonium lead iodide perovskite crystals on solar cell performance

    Directory of Open Access Journals (Sweden)

    Pablo Docampo

    2014-08-01

    Full Text Available Perovskite solar cells are emerging as serious candidates for thin film photovoltaics with power conversion efficiencies already exceeding 16%. Devices based on a planar heterojunction architecture, where the MAPbI3 perovskite film is simply sandwiched between two charge selective extraction contacts, can be processed at low temperatures (<150 °C, making them particularly attractive for tandem and flexible applications. However, in this configuration, the perovskite crystals formed are more or less randomly oriented on the surface. Our results show that by increasing the conversion step temperature from room temperature to 60 °C, the perovskite crystal orientation on the substrate can be controlled. We find that films with a preferential orientation of the long axis of the tetragonal unit cell parallel to the substrate achieve the highest short circuit currents and correspondingly the highest photovoltaic performance.

  4. Critical CuI buffer layer surface density for organic molecular crystal orientation change

    Science.gov (United States)

    Ahn, Kwangseok; Kim, Jong Beom; Kim, Hyo Jung; Lee, Hyun Hwi; Lee, Dong Ryeol

    2015-01-01

    We have determined the critical surface density of the CuI buffer layer inserted to change the preferred orientation of copper phthalocyanine (CuPc) crystals grown on the buffer layer. X-ray reflectivity measurements were performed to obtain the density profiles of the buffer layers and out-of-plane and 2D grazing-incidence X-ray diffraction measurements were performed to determine the preferred orientations of the molecular crystals. Remarkably, it was found that the preferred orientation of the CuPc film is completely changed from edge-on (1 0 0) to face-on (1 1 -2) by a CuI buffer layer with a very low surface density, so low that a large proportion of the substrate surface is bare.

  5. Influence of crystal orientation on damages of tungsten exposed to helium plasma

    Energy Technology Data Exchange (ETDEWEB)

    Ohno, Noriyasu, E-mail: ohno@ees.nagoya-u.ac.jp [Graduate School of Engineering, Nagoya University, Furo-Cho, Chikusa-Ku, Nagoya 464-8603 (Japan); Hirahata, Yuki; Yamagiwa, Masato [Graduate School of Engineering, Nagoya University, Furo-Cho, Chikusa-Ku, Nagoya 464-8603 (Japan); Kajita, Shin [EcoTopia Science Institute, Nagoya University, Furo-Cho, Chikusa-Ku, Nagoya 464-8603 (Japan); Takagi, Makoto [Graduate School of Engineering, Nagoya University, Furo-Cho, Chikusa-Ku, Nagoya 464-8603 (Japan); Yoshida, Naoaki; Yoshihara, Reiko [Research Institute for Applied Mechanics, Kyushu University, Kasuga, Fukuoka 816-8580 (Japan); Tokunaga, Tomonori [Interdisciplinary Graduate School of Eng. Sci., Kyushu University, Kasuga, Fukuoka 816-8580 (Japan); Tokitani, Masayuki [NIFS, 322-6 Oroshi-cho, Toki, Gifu 509-5292 (Japan)

    2013-07-15

    The effect of crystallographic orientation on the morphology change of tungsten (W) has been investigated in the linear plasma device, NAGDIS-I by exposing high density helium plasma to ITER grade W. After helium plasma exposure, the surface of specimens was analyzed by scanning electron microscope and orientation imaging microscope. The internal structure was analyzed with transmission electron microscope after the sample was milled by focused ion beam procedure. A clear difference in the surface morphology was observed on different crystal grains. Regular wavy structure were observed on crystal grains of {0 0 1}, {1 1 2}, {1 0 1}, and {1 1 1} surface, but there were no clear wavy structure on the crystal grains of {1 0 3}, {1 0 2}, {4 0 7} and {2 0 3}. The experimental results indicate that the angle between a slip face and face of each grains are important to determine the helium induced surface morphology change of tungsten.

  6. In vitro regulation of CaCO(3) crystal growth by the highly acidic proteins of calcitic sclerites in soft coral, Sinularia Polydactyla.

    Science.gov (United States)

    Rahman, M Azizur; Oomori, Tamotsu

    2009-01-01

    Acidic proteins are generally thought to control mineral formation and growth in biocalcification. Analysis of proteinaceous components in the soluble and insoluble matrix fractions of sclerites in Sinularia polydactyla indicates that aspartic acid composes about 60% of the insoluble and 29% of the soluble matrix fractions. We previously analyzed aspartic acids in the matrix fractions (insoluble = 17 mol%; soluble = 38 mol%) of sclerites from a different type of soft coral, Lobophytum crassum, which showed comparatively lower aspartic acid-rich proteins than S. polydactyla. Thus, characterization of highly acidic proteins in the organic matrix of present species is an important first step toward linking function to individual proteins in soft coral. Here, we show that aspartic-acid rich proteins can control the CaCO(3) polymorph in vitro. The CaCO(3) precipitates in vitro in the presence of aspartic acid-rich proteins and 50 mM Mg(2+) was verified by Raman microprobe analysis. The matrix proteins of sclerites demonstrated that the aspartic-acid rich domain is crucial for the calcite precipitation in soft corals. The crystalline form of CaCO(3) in the presence of aspartic acid-rich proteins in vitro was identified by X-ray diffraction and, revealed calcitic polymorphisms with a strong (104) reflection. The structure of soft coral organic matrices containing aspartate-rich proteins and polysaccharides was assessed by Fourier transform infrared spectroscopy. These results strongly suggest that the aspartic acid-rich proteins within the organic matrix of soft corals play a key role in biomineralization regulation.

  7. Near-Field Orientation Sensitive Terahertz Micro-Spectroscopy of Single Crystals

    Science.gov (United States)

    Acbas, Gheorghe; Singh, Rohit; Snell, Edward; Markelz, Andrea

    2012-02-01

    We present spectroscopic imaging studies of molecular crystals. These measurements examine the anisotropy of the intra and inter-molecular vibrational modes of single crystals at terahertz frequencies. The method is based on the technique developed in [1-2] for sub-wavelength resolution time domain terahertz spectroscopy (THz TDS), with added polarization orientation dependent measurements and hydration control. This method allows us to study the spectroscopic properties of small single crystals with sizes down to 20 micrometers. In addition, mapping the spectroscopic information at such small spatial scales allows us to reduce the water absorption and interference artifacts that usually affect protein THz TDS measurements. We show the polarization sensitive terahertz absorption spectra in the (0.3-3THz) range of sucrose, oxalic acid and lysozyme protein crystals. *M. A. Seo, et. al., Opt. Express, 15(19):11781--11789, 09 (2007) *J. R Knab, et. al., App. Phys. Lett.,97, 031115 (2010)

  8. Single-contact pressure solution creep on calcite monocrystals

    CERN Document Server

    Zubtsov, Sergei; Gratier, Jean-Pierre; Dysthe, Dag; Traskine, Vladimir

    2005-01-01

    Pressure solution creep rates and interface structures have been measured by two methods on calcite single crystals. In the first kind of experiments, calcite monocrystals were indented at 40 degrees C for six weeks using ceramic indenters under stresses in the 50-200 MPa range in a saturated solution of calcite and in a calcite-saturated aqueous solution of NH4Cl. The deformation (depth of the hole below the indenter) is measured ex-situ at the end of the experiment. In the second type of experiment, calcite monocrystals were indented by spherical glass indenters for 200 hours under stresses in the 0-100 MPa range at room temperature in a saturated aqueous solution of calcite. The displacement of the indenter was continuously recorded using a specially constructed differential dilatometer. The experiments conducted in a calcite-saturated aqueous solution of NH4Cl show an enhanced indentation rate owing to the fairly high solubility of calcite in this solution. In contrast, the experiments conducted in a calc...

  9. Singular orientations and faceted motion of dislocations in body-centered cubic crystals.

    Science.gov (United States)

    Kang, Keonwook; Bulatov, Vasily V; Cai, Wei

    2012-09-18

    Dislocation mobility is a fundamental material property that controls strength and ductility of crystals. An important measure of dislocation mobility is its Peierls stress, i.e., the minimal stress required to move a dislocation at zero temperature. Here we report that, in the body-centered cubic metal tantalum, the Peierls stress as a function of dislocation orientation exhibits fine structure with several singular orientations of high Peierls stress-stress spikes-surrounded by vicinal plateau regions. While the classical Peierls-Nabarro model captures the high Peierls stress of singular orientations, an extension that allows dislocations to bend is necessary to account for the plateau regions. Our results clarify the notion of dislocation kinks as meaningful only for orientations within the plateau regions vicinal to the Peierls stress spikes. These observations lead us to propose a Read-Shockley type classification of dislocation orientations into three distinct classes-special, vicinal, and general-with respect to their Peierls stress and motion mechanisms. We predict that dislocation loops expanding under stress at sufficiently low temperatures, should develop well defined facets corresponding to two special orientations of highest Peierls stress, the screw and the M111 orientations, both moving by kink mechanism. We propose that both the screw and the M111 dislocations are jointly responsible for the yield behavior of BCC metals at low temperatures.

  10. Comparison between AlN thin films with different crystal orientations for MEMS applications

    Science.gov (United States)

    Ababneh, A.; Marchand, G.; Seidel, H.; Hernando, J.; Sánchez-Rojas, J. L.; Sökmen, Ü.; Peiner, E.; Schmid, U.

    2009-05-01

    Aluminium nitride (AlN) reactively sputter deposited from an aluminium target is an interesting compound material due to its CMOS compatible fabrication process and its piezoelectric properties. The crystal structure obtained during sputtering is a very importance criterion to obtain a good piezoelectric performance. To demonstrate this, we focused our investigations on two types of films. The first type shows a good c- axis orientation with round grain geometry. The second type is (101) oriented having a triangular grain shape. For measuring the out-of-plane displacements for dij determination, a MSV 400 Polytec scanning laser Doppler vibrometer was used. To obtain the piezoelectric constants d33 and d31 a fitting procedure between experimental and theoretical predicted results is used. Effective values for d33 and d31 in c-axis oriented films are about 3.0 pm/V and -1.0 pm/V, respectively. By contrast, films with (101) orientation show a lower effective longitudinal piezoelectric coefficients, consistent with this different orientation. Finally, both types of AlN layers were deposited on 640 μm long micro-cantilevers. The average displacement of the first mode on the vertical axis was about 12 nm for the film with good c -axis orientation and 0.3 nm for that with (101)- orientation when applying the same excitation.

  11. Orientation dependence of the plastic slip near notches in ductile FCC single crystals

    Science.gov (United States)

    Crone, W. C.; Shield, T. W.; Creuziger, A.; Henneman, B.

    2004-01-01

    Results from experiments conducted on copper FCC single crystals are reported. Two symmetric crystallographic orientations and four nonsymmetric crystallographic orientations were tested. The slip line fields that form near a pre-existing notch in these specimens were observed. The changes in these patterns as the orientation of the notch in the crystal is rotated in an {101} plane are discussed. Sectors of similar slip line patterns are identified and the type of boundaries between these sectors are discussed. A type of sector boundary called mixed kink is identified. Specimen orientations that differ by 90° are found to have different slip line patterns, contrary to the predictions of perfectly plastic slip line theory. The locations of the first slip lines to form are compared to the predictions obtained using anisotropic linear elastic stress field solutions and the initial plane-strain yield surfaces. It is found that comparison of these surface slip line fields to plane strain crack tip solutions in the annular region between 350 and 750 μm is justified. The differences in anisotropic elastic solutions for orientations that are 90° apart explain the lack of agreement with perfectly plastic slip line theory.

  12. Determination of crystal grain orientations by optical microscopy at textured surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Lausch, D.; Gläser, M.; Hagendorf, C. [Team Mikrostrukturdiagnostik und Analytik, Fraunhofer-Center für Silizium-Photovoltaik CSP, Walter-Hülse-Straße 1 Halle (Saale), Sachsen-Anhalt D-06120 (Germany)

    2013-11-21

    In this contribution, a new method to determine the crystal orientation with the example of chemical treated silicon wafers by means of optical microscopy has been demonstrated. The introduced procedure represents an easy method to obtain all relevant parameters to describe the crystal structure of the investigated material, i.e., the crystal grain orientation and the grain boundary character. The chemical treatment is a standard mono-texture for solar cells, well known in the solar industry. In general, this concept can also be applied to other crystalline materials, i.e., GaAs, SiC, etc., the only thing that needs to be adjusted is the texturing method to reveal specific crystal planes and the calculation model. In conclusion, an application of this method is shown with the example of the defect classification of recombination active defects in mc-Si solar cell. The introduced method demonstrates a simple and quick opportunity to improve the crystallization process and the quality of electronic devices by means of an optical microscope and a chemical treatment of the material.

  13. Disentangling the secondary relaxations in the orientationally disordered mixed crystals: cycloheptanol + cyclooctanol two-component system.

    Science.gov (United States)

    Martínez-García, Julio C; Tamarit, Josep Ll; Pardo, Luis C; Barrio, María; Rzoska, Sylwester J; Droz-Rzoska, Aleksandra

    2010-05-13

    The dynamics of the pure compounds and mixed crystals formed between cycloheptanol (cC7-ol) and cyclooctanol (cC8-ol) has been studied by means of broadband dielectric spectroscopy at temperatures near and above the orientational glass transition temperature. Both compounds are known to display at least one orientationally disordered (OD) phase of simple cubic symmetry, and within this phase, a continuous formation of mixed crystals was demonstrated in the past (Rute, M. A. et al. J. Phys. Chem. B 2003, 107, 5914). The dielectric loss spectra of cC7-ol and cC8-ol show, in addition to the well-pronounced alpha-relaxation peaks with a continuous temperature shift (characteristic of the freezing of the molecular dynamics), secondary relaxations (beta and gamma for cC8-ol and gamma for cC7-ol) which are intramolecular in nature. The dynamics of several OD mixed crystals was recently studied (Singh, L. P.; Murthy, S. S. N. J. Phys. Chem. B 2008, 112, 2606), and surprisingly enough one of the secondary relaxations was not evidenced. We show here by means of a careful set of measurements for several mixed crystals and of a detailed analysis procedure the existence of the secondary relaxations for the mixed crystals. The results, moreover, doubtless reinforce the physical origin of each of the secondary relaxations.

  14. Optical properties of planar nematic liquid crystals samples which are parallel oriented by nanofibers

    Science.gov (United States)

    Yusuf, Yusril; Kusumasari, Ervanggis Minggar; Ula, Nur Mufidatul; Jahidah, Khannah; Triyana, Kuwat; Sosiati, Harini; Harsojo

    2016-04-01

    Optical properties of two nematic liquid crystals, i.e., 4-methoxybenzylidene-4-butylaniline (MBBA) and 4-cyano-4'-pentylbiphenyl (5 CB) which are parallel oriented by nanofibers has been successfully performed. Planar samples of liquid crystals were made using polyvinyl alcohol (PVA) nanofiber from electrospinning process. Electrospinning method was modified using copper (Cu) as gap collector. These planar samples area are 15 mm x 25 mm. Optical characteristic of these samples were studied by using optical polarizing microscope. The optical intensity changes by a rotationof crossed polarizers is observed. The sinusoidal intensity change was observedin these samples as such as in the planar sample prepared by the rubbing method.

  15. Oxygen and hydrogen evolution reaction on oriented single crystals of ruthenium dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Berger, L I; Pollak, F H; Canivez, Y; O& #x27; Grady, W

    1979-01-01

    A novel design for water electrolysis using a solid polymer electrolyte is being developed by General Electric. Ruthenium is one of the best electrocatalysts for the oxygen evolution reaction. There are problems connected with the significant loss in electrocatalytic activity with time. This performance degradation is presumably due to the gradual formation of an RuO/sub 2/ film. We have performed electrochemical measurements on (100), (110) and (111) oriented single crystals of RuO/sub 2/ in order to elucidate the mechanism of the electrocatalytic process. Large single crystals were grown by the vapor transport method. Our investigation has revealed several interesting differences for the various orientations. This study indicates that RuO/sub 3/ may be an important intermediate species prior to oxygen evolution and that the formation of the RuO/sub 3/ is the rate limiting process. Similar results were previously obtained for IrO/sub 2/.

  16. Solvent minimization induces preferential orientation and crystal clustering in serial micro-crystallography on micro-meshes, in situ plates and on a movable crystal conveyor belt

    Energy Technology Data Exchange (ETDEWEB)

    Soares, Alexei S., E-mail: soares@bnl.gov [Brookhaven National Laboratory, Upton, NY 11973 (United States); Mullen, Jeffrey D. [Brookhaven National Laboratory, Upton, NY 11973 (United States); University of Oregon, Eugene, OR 97403-1274 (United States); Parekh, Ruchi M. [Brookhaven National Laboratory, Upton, NY 11973 (United States); Suffolk County Community College, Selden, NY 11784 (United States); McCarthy, Grace S.; Roessler, Christian G.; Jackimowicz, Rick; Skinner, John M. [Brookhaven National Laboratory, Upton, NY 11973 (United States); Orville, Allen M. [Brookhaven National Laboratory, Upton, NY 11973 (United States); Brookhaven National Laboratory, Upton, NY 11973 (United States); Allaire, Marc [Brookhaven National Laboratory, Upton, NY 11973 (United States); Sweet, Robert M. [Brookhaven National Laboratory, Upton, NY 11973 (United States); Brookhaven National Laboratory, Upton, NY 11973 (United States)

    2014-10-09

    Strategies are described for optimizing the signal-to-noise of diffraction data, and for combining data from multiple crystals. One challenge that must be overcome is the non-random orientation of crystals with respect to one another and with respect to the surface that supports them. X-ray diffraction data were obtained at the National Synchrotron Light Source from insulin and lysozyme crystals that were densely deposited on three types of surfaces suitable for serial micro-crystallography: MiTeGen MicroMeshes™, Greiner Bio-One Ltd in situ micro-plates, and a moving kapton crystal conveyor belt that is used to deliver crystals directly into the X-ray beam. 6° wedges of data were taken from ∼100 crystals mounted on each material, and these individual data sets were merged to form nine complete data sets (six from insulin crystals and three from lysozyme crystals). Insulin crystals have a parallelepiped habit with an extended flat face that preferentially aligned with the mounting surfaces, impacting the data collection strategy and the design of the serial crystallography apparatus. Lysozyme crystals had a cuboidal habit and showed no preferential orientation. Preferential orientation occluded regions of reciprocal space when the X-ray beam was incident normal to the data-collection medium surface, requiring a second pass of data collection with the apparatus inclined away from the orthogonal. In addition, crystals measuring less than 20 µm were observed to clump together into clusters of crystals. Clustering required that the X-ray beam be adjusted to match the crystal size to prevent overlapping diffraction patterns. No additional problems were encountered with the serial crystallography strategy of combining small randomly oriented wedges of data from a large number of specimens. High-quality data able to support a realistic molecular replacement solution were readily obtained from both crystal types using all three serial crystallography strategies.

  17. Direct evidence for radar reflector originating from changes in crystal-orientation fabric

    Directory of Open Access Journals (Sweden)

    O. Eisen

    2007-06-01

    Full Text Available The origin of a strong continuous radar reflector observed with airborne radio-echo sounding (RES at the EPICA deep-drilling site in Dronning Maud Land, Antarctica, is identified as a transition in crystal fabric orientation from a vertical girdle- to increased single-pole orientation seen along the ice core. The reflector is observed with a 60 ns and 600 ns long pulse at a frequency of 150 MHz, spans one pulse length, is continuous over 5 km, and occurs at a depth of about 2020–2030 m at the drill site. Changes in conductivity as reflector origin are excluded by investigating the ice-core profile and synthetic RES data. Our observations allow to extrapolate the crystal orientation feature along the reflector in space, with implications for ice-sheet dynamics. As the conductivity profile of the EPICA shows no distinctive peak at this depths, we exclude changes in conductivity as the reflector origin. This is supported by application of numerical forward modelling of electromagnetic wave propagation, based on the conductivity profile, which is able to reproduce nearby reflections, but fails to reproduce this one. Because of background noise, the permittivity profile based on dielectric does not show prominent signals at these depths. We therefore interpret the observed reflector to originate from this change in crystal fabric.

  18. Orientational dynamics and energy landscape features of thermotropic liquid crystals: An analogy with supercooled liquids

    Indian Academy of Sciences (India)

    Biman Jana; Biman Bagchi

    2007-09-01

    Recent optical kerr effect (OKE) studies have revealed that orientational relaxation of rodlike nematogens near the isotropic-nematic (I-N) phase boundary and also in the nematic phase exhibit temporal power law decay at intermediate times. Such behaviour has drawn an intriguing analogy with supercooled liquids. Here, we have investigated the single-particle and collective orientational dynamics of a family of model system of thermotropic liquid crystals using extensive computer simulations. Several remarkable features of glassy dynamics are on display including non-exponential relaxation, dynamical heterogeneity, and non-Arrhenius temperature dependence of the orientational relaxation time. Over a temperature range near the I-N phase boundary, the system behaves like a fragile glass-forming liquid. Using proper scaling, we construct the usual relaxation time versus inverse temperature plot and explicitly demonstrate that one can successfully define a density dependent fragility of liquid crystals. The fragility of liquid crystals shows a temperature and density dependence which is remarkably similar to the fragility of glass forming supercooled liquids. Energy landscape analysis of inherent structures shows that the breakdown of the Arrhenius temperature dependence of relaxation rate occurs at a temperature that marks the onset of the growth of the depth of the potential energy minima explored by the system.

  19. Crystal orientation dependence of ion-irradiation hardening in pure tungsten

    Science.gov (United States)

    Hasenhuetl, Eva; Zhang, Zhexian; Yabuuchi, Kiyohiro; Song, Peng; Kimura, Akihiko

    2017-04-01

    Pure tungsten (W) single crystals of {0 0 1} and {0 1 1} surface orientations were irradiated with 6.4 MeV Fe3+ ions up to 1 dpa at 573 K. The TEM examination revealed that there was a very small orientation dependence in the radiation damaged microstructure, showing that both W{0 0 1} and W{0 1 1} exhibited a double black band structure with high number density of dislocation loop rafts in the black bands. However, the depth profile of ion-irradiation hardening evaluated by nanoindentation (NI) technique turned out to show a clear orientation dependence, namely, W{0 0 1} showed a deeper NI hardness profile than W{0 1 1}.

  20. Direct evidence for continuous radar reflector originating from changes in crystal-orientation fabric

    Directory of Open Access Journals (Sweden)

    O. Eisen

    2007-10-01

    Full Text Available The origin of a strong continuous radar reflector observed with airborne radio-echo sounding (RES at the EPICA deep-drilling site in Dronning Maud Land, Antarctica, is identified as a transition in crystal fabric orientation from a vertical girdle to an increased single-pole orientation seen along the ice core. The reflector is observed with a 60 ns and 600 ns long pulse at a frequency of 150 MHz, spans one pulse length, is continuous over 5 km, and occurs at a depth of about 2025–2045 m at the drill site. Changes in conductivity as reflector origin are excluded by investigating the ice-core profile, synthetic RES data, and a RES profile with different electromagnetic polarisation azimuths. The reflector's magnitude shows maximum values for polarisation parallel to the nearby ice divide and disappears for polarisation perpendicular to it, identifying the orientation of the girdle to lie in the vertical plane parallel to the ice divide. Observations allow us to extrapolate the crystal orientation feature along the reflector in space, with implications for ice-sheet dynamics and modeling.

  1. Calculation of inelastic scattering processes of relativistic electrons in oriented crystals

    Energy Technology Data Exchange (ETDEWEB)

    Hinderks, Dieter; Kohl, Helmut

    2015-04-15

    The inelastic scattering of electrons in oriented crystals has been used to determine the positions of atoms within a crystal, to obtain site-dependent electron energy loss spectra and, more recently, to obtain an energy loss signal corresponding to the circular dichroism in X-ray absorption spectroscopy. The theoretical approaches currently used for the description of these processes are based on the nonrelativistic Schrödinger equation. Nowadays many experiments, however, are conducted with incident energies of 200 or 300 keV. Therefore it is indispensable to use a relativistic description for such processes based on the Dirac equation. Using the Coulomb gauge it is shown, that the fully relativistic cross sections for plane wave scattering are given by the modulus square of a sum of two terms: one describing the electrostatic interactions similar to the nonrelativistic theory plus one additional term describing the interaction of the specimen with the magnetic field produced by the incident electron. In crystals both terms can interfere leading to large deviations from nonrelativistic theory. - Highlights: • Inelastic scattering of relativistic electrons in oriented crystals is described. • We have derived equations for relativistic Bloch waves. • Strong deviations from nonrelativistic theory have been demonstrated.

  2. Offset-free Measurement of Dipolar Couplings in a Single Crystal and Determination of Molecular Orientation

    CERN Document Server

    Jayanthi, S

    2010-01-01

    Dipolar couplings are an important source of structure as they provide site specific dipolar splittings for aligned samples and hence are extensively used for the study of membrane proteins in lipid bilayers, liquid crystals and single crystals. Of the many Separated Local Field (SLF) techniques existing to avail this information for static oriented systems, PISEMA (Polarization Inversion Spin Exchange at Magic Angle) has found to have wide application due to its many favorable characteristics. However the pulse sequence suffers from its inherent sensitivity to proton resonance frequency offset. We have recently proposed a sequence named DAPT (Dipolar Assisted Polarization Transfer: S. Jayanthi et al. Chem. Phys. Lett. 439, 407, 2007.) for dipolar coupling measurement which is found to be insensitive to proton offsets over wide range. In this presentation, we report the first implementation of the sequence on rigid systems. Experiments were done on a single crystal of N-Acetyl DL-Valine (NAV). Dipolar couplin...

  3. Studies on Crystal Orientation of ZnO Film on Sapphire Using High-throughout X-ray Diffraction

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The orientation of the nano-columnar ZnO films grown on sapphire using the technique of metal-organic chemical vapor deposition (MOCVD) exhibits deviation because of the mismatch between the crystal lattices of the films and the sapphire substrate. A high-throughout X-ray diffraction method was employed to determine the crystal orientation of the ZnO films at a time scale of the order of minutes based on the general area detection diffraction system (GADDS). This rapid, effective, and ready method, adapted for characterizing the orientation of the nano-columnar crystals is used to directly explain the results of observation of the X-ray diffraction images, by the measurements of the orientations of the crystal columns of the ZnO films along c-axis and in parallel to ab plane.

  4. Prevalence for the universal distribution of relaxation times near the glass transitions in experimental model systems: Rodlike liquid crystals and orientationally disordered crystals

    OpenAIRE

    2011-01-01

    Recently, Nielsen et al. [J. Chem. Phys. 130, 154508 (2009); Philos. Mag. 88, 4101 (2008)] demonstrated a universal pattern for the high frequency wing of the loss curve for primary relaxation time on approaching the glass transition for organic liquids. In this contribution it is presented that a similar universality occurs for glass-forming liquid crystals and orientationally disordered crystals (plastic crystals). Empirical correlations of the found behavior are also briefly di...

  5. Orientation and Optical Polarized Spectra (380–900 nm of Methylene Blue Crystals on a Glass Surface

    Directory of Open Access Journals (Sweden)

    Maja D. Milošević

    2013-01-01

    Full Text Available The crystallographic directions of the crystal toward the vector of polarized light can accurately be positioned, so the information that we gain from polarized spectra can be consistently interpreted according to known crystal structure. The orientation and optical properties of the methylene blue (MB crystals were analyzed by XRD, XRPD, and polarized VIS-NIR spectroscopy. Cationic dye, MB, was polymerized into crystals on a glass slate. The blue color crystals showed pronounced dichroism, twin lamellar structure and bladed to fibrous habit. According to XRD data, [010] direction lies perpendicular to the crystal surface, so we recognized it as (0k0 face, while [100] and [001] directions coincide with crystal elongation and crystal thickness respectively. In this paper, the polarized spectra of MB crystal are presented, measured with the aim of acquisition of referent values, which could be helpful for the identification of MB molecular aggregation.

  6. NMR of bicelles: orientation and mosaic spread of the liquid-crystal director under sample rotation

    Energy Technology Data Exchange (ETDEWEB)

    Zandomeneghi, Giorgia; Tomaselli, Marco; Williamson, Philip T.F.; Meier, Beat H. [Physical Chemistry, ETH Zurich, ETH-Hoenggerberg (Switzerland)], E-mail: beme@ethz.ch

    2003-02-15

    Model-membrane systems composed of liquid-crystalline bicellar phases can be uniaxially oriented with respect to a magnetic field, thereby facilitating structural and dynamics studies of membrane-associated proteins. Here we quantitatively characterize a method that allows the manipulation of the direction of this uniaxial orientation. Bicelles formed from DMPC/DHPC are examined by {sup 31}P NMR under variable-angle sample-spinning (VAS) conditions, confirming that the orientation of the liquid-crystalline director can be influenced by sample spinning. The director is perpendicular to the rotation axis when {theta} (the angle between the sample-spinning axis and the magnetic field direction) is smaller than the magic angle, and is parallel to the rotation axis when {theta} is larger than the magic angle. The new {sup 31}P NMR VAS data presented are considerably more sensitive to the orientation of the bicelle than earlier {sup 2}H studies and the analysis of the sideband pattern allows the determination of the orientation of the liquid-crystal director and its variation over the sample, i.e., the mosaic spread. Under VAS, the mosaic spread is small if {theta} deviates significantly from the magic angle but becomes very large at the magic angle.

  7. Estimation of diffusion anisotropy in microporous crystalline materials and optimization of crystal orientation in membranes.

    Science.gov (United States)

    Gounaris, Chrysanthos E; First, Eric L; Floudas, Christodoulos A

    2013-09-28

    The complex nature of the porous networks in microporous materials is primarily responsible for a high degree of intracrystalline diffusion anisotropy. Although this is a well-understood phenomenon, little attention has been paid in the literature with regards to classifying such anisotropy and elucidating its effect on the performance of membrane-based separation systems. In this paper, we develop a novel methodology to estimate full diffusion tensors based on the detailed description of the porous network geometry through our recent advances for the characterization of such networks. The proposed approach explicitly accounts for the tortuosity and complex connectivity of the porous framework, as well as for the variety of diffusion regimes that may be experienced by a guest molecule while it travels through the different localities of the crystal. Results on the diffusion of light gases in silicalite demonstrate good agreement with results from experiments and other computational techniques that have been reported in the literature. A comprehensive computational study involving 183 zeolite frameworks classifies these structures in terms of a number of anisotropy metrics. Finally, we utilize the computed diffusion tensors in a membrane optimization model that determines optimal crystal orientations. Application of the model in the context of separating carbon dioxide from nitrogen demonstrates that optimizing crystal orientation can offer significant benefit to membrane-based separation processes.

  8. Grain coarsening of calcite: Fundamental mechanisms and biogenic inhibition

    DEFF Research Database (Denmark)

    Schultz, Logan Nicholas

    In a saturated solution, submicrometer calcite (CaCO3) crystals recrystallize and coarsen to minimize surface area. The thermodynamic driving force is described by the Gibbs-Thomson equation, but the rates and mechanism are poorly understood. Calcite grain coarsening has many implications...... in industry and nature, but the specific focus of this research project was to understand how small, biogenic calcite particles in chalk have resisted grain coarsening for over 60 million years in saturated reservoir fluids. A new method was developed to produce pure calcite powder that has submicrometer...... coarsening – small grains coarsen by aggregation at high temperatures, followed by Ostwald ripening. Alginate, a model for the acidic polysaccharides produced by coccolithiphores, inhibited coarsening at a steady rate. A Pseudomonas aeruginosa biofilm preserved particles for at least 60 days before...

  9. Beta tricalcium phosphate ceramics with controlled crystal orientation fabricated by application of external magnetic field during the slip casting process.

    Science.gov (United States)

    Hagio, Takeshi; Yamauchi, Kazushige; Kohama, Takenori; Matsuzaki, Toshiya; Iwai, Kazuhiko

    2013-07-01

    Beta tricalcium phosphate (β-TCP) is a resorbable bioceramic that has hitherto been utilized in the medical field. Since it crystallizes in the anisotropic hexagonal system, properties such as chemical and physical ones are expected to depend on its crystal axis direction and/or on its crystal plane (anisotropy). Control of crystal orientation is thus important when used in polycrystalline form. Meanwhile, application of a strong magnetic field has been found to be a promising technique to control crystal orientation of anisotropic shape or structured crystals. In this work, we attempted to fabricate β-TCP ceramics with controlled crystal orientation by applying an external magnetic field during the slip casting process and subsequently sintering them at 1050°C, below the β-α transition temperature. Application of a vertical magnetic field increased intensities of planes perpendicular to c-plane on the top surface, while a horizontal one with simultaneous mechanical mold rotation decreased it. These results indicated that crystal orientation of β-TCP ceramics were successfully controlled by the external magnetic field and together that the magnetic susceptibility of β-TCP is χ(c[perpendicular])>χ(c//).

  10. Unusual calcite stromatolites and pisoids from a landfill leachate collection system

    Science.gov (United States)

    Maliva, Robert G.; Missimer, Thomas M.; Leo, Kevin C.; Statom, Richard A.; Dupraz, Christophe; Lynn, Matthew; Dickson, J. A. D.

    2000-10-01

    Low-magnesium calcite stromatolites and pisoids were found to have precipitated within the leachate collection system piping of a Palm Beach County, Florida, landfill. The stromatolites and pisoids formed in an aphotic and anoxic environment that was at times greatly supersaturated with calcite. The stromatolites are composed of branching cylindrical bundles of concentrically laminated radial fibrous crystals. The pisoids consist of concentric layers of radial fibrous and microcrystalline calcite. Bacteria, likely sulfate reducing, appear to have acted as catalysts for calcite crystal nucleation, and thus the formation of the stromatolites and pisoids. The leachate system stromatolites provide a recent example of stromatolites that formed largely by cement precipitation. By acting as catalysts for calcite nucleation, bacteria may cause more rapid cementation than would have occurred under purely abiotic conditions. Rapid calcite precipitation catalyzed by bacteria has interfered with the operation of the Palm Beach County landfill leachate collection by obstructing pipes and may be an unrecognized problem at other landfill sites.

  11. Solvent minimization induces preferential orientation and crystal clustering in serial micro-crystallography on micro-meshes, in situ plates and on a movable crystal conveyor belt.

    Science.gov (United States)

    Soares, Alexei S; Mullen, Jeffrey D; Parekh, Ruchi M; McCarthy, Grace S; Roessler, Christian G; Jackimowicz, Rick; Skinner, John M; Orville, Allen M; Allaire, Marc; Sweet, Robert M

    2014-11-01

    X-ray diffraction data were obtained at the National Synchrotron Light Source from insulin and lysozyme crystals that were densely deposited on three types of surfaces suitable for serial micro-crystallography: MiTeGen MicroMeshes™, Greiner Bio-One Ltd in situ micro-plates, and a moving kapton crystal conveyor belt that is used to deliver crystals directly into the X-ray beam. 6° wedges of data were taken from ∼100 crystals mounted on each material, and these individual data sets were merged to form nine complete data sets (six from insulin crystals and three from lysozyme crystals). Insulin crystals have a parallelepiped habit with an extended flat face that preferentially aligned with the mounting surfaces, impacting the data collection strategy and the design of the serial crystallography apparatus. Lysozyme crystals had a cuboidal habit and showed no preferential orientation. Preferential orientation occluded regions of reciprocal space when the X-ray beam was incident normal to the data-collection medium surface, requiring a second pass of data collection with the apparatus inclined away from the orthogonal. In addition, crystals measuring less than 20 µm were observed to clump together into clusters of crystals. Clustering required that the X-ray beam be adjusted to match the crystal size to prevent overlapping diffraction patterns. No additional problems were encountered with the serial crystallography strategy of combining small randomly oriented wedges of data from a large number of specimens. High-quality data able to support a realistic molecular replacement solution were readily obtained from both crystal types using all three serial crystallography strategies.

  12. The Crystallization of Poly (3-dodecylthiophene) in an Oriented Solidification Environment

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The crystallization behaviors of poly (3-dodecylthiophene) (P3DDT) under two different oriented solidification conditions, I.e., two different relative relations (90° and 180°) between the directions of gravity and solidification, were investigated. X-ray diffraction results reveal that although similar layered structures are formed, under the condition of the relative relation 180°, temperature gradient has greater effects on the perfect degree of the layered structures of P3DDT. It also can be concluded that after recrystallization, the layered structures of P3DDT can be improved at relative relation 90o, but the orderly degree of the arrangements of alkyl side chains are not improved yet, even is reduced for both of the oriented solidification conditions.

  13. The effect of crystal orientation on the cryogenic strength of hydroxide catalysis bonded sapphire

    Science.gov (United States)

    Haughian, K.; Douglas, R.; van Veggel, A. A.; Hough, J.; Khalaidovski, A.; Rowan, S.; Suzuki, T.; Yamamoto, K.

    2015-04-01

    Hydroxide catalysis bonding has been used in gravitational wave detectors to precisely and securely join components of quasi-monolithic silica suspensions. Plans to operate future detectors at cryogenic temperatures has created the need for a change in the test mass and suspension material. Mono-crystalline sapphire is one candidate material for use at cryogenic temperatures and is being investigated for use in the KAGRA detector. The crystalline structure of sapphire may influence the properties of the hydroxide catalysis bond formed. Here, results are presented of studies of the potential influence of the crystal orientation of sapphire on the shear strength of the hydroxide catalysis bonds formed between sapphire samples. The strength was tested at approximately 8 K; this is the first measurement of the strength of such bonds between sapphire at such reduced temperatures. Our results suggest that all orientation combinations investigated produce bonds of sufficient strength for use in typical mirror suspension designs, with average strengths >23 MPa.

  14. Influence of crystal orientation on the formation of femtosecond laser-induced periodic surface structures and lattice defects accumulation

    Science.gov (United States)

    Sedao, Xxx; Maurice, Claire; Garrelie, Florence; Colombier, Jean-Philippe; Reynaud, Stéphanie; Quey, Romain; Pigeon, Florent

    2014-04-01

    The influence of crystal orientation on the formation of femtosecond laser-induced periodic surface structures (LIPSS) has been investigated on a polycrystalline nickel sample. Electron Backscatter Diffraction characterization has been exploited to provide structural information within the laser spot on irradiated samples to determine the dependence of LIPSS formation and lattice defects (stacking faults, twins, dislocations) upon the crystal orientation. Significant differences are observed at low-to-medium number of laser pulses, outstandingly for (111)-oriented surface which favors lattice defects formation rather than LIPSS formation.

  15. Influence of crystal orientation on the formation of femtosecond laser-induced periodic surface structures and lattice defects accumulation

    Energy Technology Data Exchange (ETDEWEB)

    Sedao, Xxx; Garrelie, Florence, E-mail: florence.garrelie@univ-st-etienne.fr; Colombier, Jean-Philippe; Reynaud, Stéphanie; Pigeon, Florent [Université de Lyon, CNRS, UMR5516, Laboratoire Hubert Curien, Université de Saint Etienne, Jean Monnet, F-42023 Saint-Etienne (France); Maurice, Claire; Quey, Romain [Ecole Nationale Supérieure des Mines de Saint-Etienne, CNRS, UMR5307, Laboratoire Georges Friedel, F-42023 Saint-Etienne (France)

    2014-04-28

    The influence of crystal orientation on the formation of femtosecond laser-induced periodic surface structures (LIPSS) has been investigated on a polycrystalline nickel sample. Electron Backscatter Diffraction characterization has been exploited to provide structural information within the laser spot on irradiated samples to determine the dependence of LIPSS formation and lattice defects (stacking faults, twins, dislocations) upon the crystal orientation. Significant differences are observed at low-to-medium number of laser pulses, outstandingly for (111)-oriented surface which favors lattice defects formation rather than LIPSS formation.

  16. Formation of oriented nickel aggregates in rutile single crystals by Ni implantation

    Energy Technology Data Exchange (ETDEWEB)

    Cruz, M.M., E-mail: mmcruz@fc.ul.pt [CFMC, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa (Portugal); Dep. Física, Fac. Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa (Portugal); Silva, R.C. da [IST/ITN, Instituto Superior Técnico, Universidade de Lisboa, Campus Tecnológico e Nuclear, E.N.10, 2686-953 Sacavém (Portugal); CFNUL, Av. Prof. Gama Pinto 2, 1649-003 Lisboa (Portugal); Pinto, J.V. [CFMC, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa (Portugal); CFNUL, Av. Prof. Gama Pinto 2, 1649-003 Lisboa (Portugal); Borges, R.P. [CFMC, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa (Portugal); Franco, N. [IST/ITN, Instituto Superior Técnico, Universidade de Lisboa, Campus Tecnológico e Nuclear, E.N.10, 2686-953 Sacavém (Portugal); CFNUL, Av. Prof. Gama Pinto 2, 1649-003 Lisboa (Portugal); Casaca, A. [CFMC, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa (Portugal); Instituto Superior de Engenharia de Lisboa—ISEL, R. Cons. Emídio Navarro 1, 1959-007 Lisboa (Portugal); Alves, E. [IST/ITN, Instituto Superior Técnico, Universidade de Lisboa, Campus Tecnológico e Nuclear, E.N.10, 2686-953 Sacavém (Portugal); CFNUL, Av. Prof. Gama Pinto 2, 1649-003 Lisboa (Portugal); Godinho, M. [CFMC, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa (Portugal); Dep. Física, Fac. Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa (Portugal)

    2013-08-15

    The magnetic and electrical properties of Ni implanted single crystalline TiO{sub 2} rutile were studied for nominal implanted fluences between 0.5×10{sup 17} cm{sup −2} and 2.0×10{sup 17} cm{sup −2} with 150 keV energy, corresponding to maximum atomic concentrations between 9 at% and 27 at% at 65 nm depth, in order to study the formation of metallic oriented aggregates. The results indicate that the as implanted crystals exhibit superparamagnetic behavior for the two higher fluences, which is attributed to the formation of nanosized nickel clusters with an average size related with the implanted concentration, while only paramagnetic behavior is observed for the lowest fluence. Annealing at 1073 K induces the aggregation of the implanted nickel and enhances the magnetization in all samples. The associated anisotropic behavior indicates preferred orientations of the nickel aggregates in the rutile lattice consistent with Rutherford backscattering spectrometry—channelling results. Electrical conductivity displays anisotropic behavior but no magnetoresistive effects were detected. - Author-Highlights: • Ni nano-aggregates were grown on TiO{sub 2} using Ni implantation with different fluences. • In the as implanted state, the aggregates size is a function of the implanted fluence. • Ni aggregates are oriented within the rutile structure-2 orientations are proposed.

  17. A positron source using an axially oriented crystal associated to a granular amorphous converter

    Institute of Scientific and Technical Information of China (English)

    XU Cheng-Hai; Robert Chehab; Peter Sievers; Xavier Artru; Michel Chevallier; Olivier Dadoun; PEI Guo-Xi; Vladimir M. Strakhovenko; Alessandro Variola

    2012-01-01

    A non-conventional positron source using the intense γ radiation from an axially oriented monocrystal which materializes into e+e- pairs in a granular amorphous converter is described.The enhancement of photon radiation by multi-GeV electrons crossing a tungsten crystal along its 〈111〉 axis is reported.The resulting enhancement of pair production in an amorphous converter placed 2 meters downstream,is also reported.Sweeping off the charged particles from the crystal by a bending magnet upstream of the converter allows a significant reduction of the deposited energy density.Substituting a granular target made of small spheres for the usual compact one,makes the energy dissipation easier.The deposited energy and corresponding heating are analyzed and solutions for cooling are proposed.The configurations studied here for this kind of positron source allow its consideration for unpolarized positrons for the ILC.

  18. The method and equipment for the investigation of ions orienting transmission through thin single crystals

    CERN Document Server

    Soroka, V Y; Maznij, Y O

    2003-01-01

    A new approach is proposed to solve the task of angular distribution measurement of intensity strongly differentiated ions fluxes. Channeling effect makes this problem a regular feature of experimental study of ions orientating transmission through thin single crystals. The approach is based on the use of ions additional scattering by an amorphous (polycrystalline) target after passing through single crystal. The additional target manipulator is joined with the principal target chamber equipment with three-axis goniometer. The manipulator allows to move an additional target in the vicinity of the accelerator beam within the limits of +- 3 sup 0 in all directions and allows to measure the angular distribution of scattered ions with the accuracy of 1 min. The method and equipment were tested at the single ended electrostatic accelerator (EG-5) using a proton beam. At present the measurements have been resumed at the tandem accelerator (EG-10) of the Institute for Nuclear Research of the Academy of Sciences of U...

  19. A positron source using an axially oriented crystal associated to a granular amorphous converter

    CERN Document Server

    Xu, Cheng-Hai; Sievers, Peter; Artru, Xavier; Chevallier, Michel; Dadoun, Olivier; Pei, Guo-Xi; Strakhovenko, Vladimir M; Variola, Alessandro

    2012-01-01

    A non-conventional positron source using the intense l radiation from an axially oriented monocrystal which materializes into e(+)e(-') pairs in a granular amorphous converter is described. The enhancement of photon radiation by multi-GeV electrons crossing a tungsten crystal along its axis is reported. The resulting enhancement of pair production in an amorphous converter placed 2 meters downstream, is also reported. Sweeping off the charged particles from the crystal by a bending magnet upstream of the converter allows a significant reduction of the deposited energy density. Substituting a granular target made of small spheres for the usual compact one, makes the energy dissipation easier. The deposited energy and corresponding heating are analyzed and solutions for cooling are proposed. The configurations studied here for this kind of positron source allow its consideration for unpolarized positrons for the ILC.

  20. Orientation of growing crystals of Co- or Gd-containing L-threonine dehydrogenase by magnetic fields

    Science.gov (United States)

    Maki, Syou; Ishikawa, Kazuhiko; Ataka, Mitsuo

    2009-12-01

    L-Threonine dehydrogenase from Pyrococcus horikoshii (TDH) is a water-soluble metalloenzyme, the molecular structure of which has been unknown until recently. The Zn 2+ ion in the native TDH, prepared as a recombinant protein, is replaced artificially with Co 2+, Ni 2+ or Gd 3+. These samples are crystallized in homogeneous magnetic fields of 2-10 T. Half of the Co- or Gd-substituted crystals show magnetic orientation in a field of 2 T at 278 K whereas the crystals of the native TDH require a 4 T magnetic field for half orientation. The sensitivity to magnetic orientation can thus be increased by metal substitution. On the other hand, we cannot assign clear changes in the size, number, and quality of the native and metal-substituted crystals with and without the presence of the magnetic field.

  1. Optical properties of the cirrus cloud ice crystals with preferred azimuthal orientation for polarization lidars with azimuthal scanning

    Science.gov (United States)

    Konoshonkin, Alexander V.; Kustova, Natalia V.; Nasonov, Sergey V.; Bryukhanov, Ilia D.; Shishko, Viktor A.; Timofeev, Dmitriy N.; Borovoi, Anatoly G.

    2016-10-01

    Optical properties of the cirrus cloud ice crystals with preferred azimuthal orientation are required for current numerical models of the Earth's radiation balance. Retrieving the orientation distributions function of the crystals from a vertically pointing polarization lidar measuring the full Mueller matrix is a very complicated problem because of lake of information. Lidars with zenith scanning can be used only to retrieve the properties of horizontally oriented particles. The paper shows that if the particles have preferred azimuthal orientation, the polarization lidars with azimuthal scanning should be used. It is also shown that all the elements of the Mueller matrix give no extra information compare to the depolarization ratio. Optical properties of preferred azimuthal oriented hexagonal ice columns with size from 10 to 1000 μm for wavelengths of 0.355, 0.532 and 1.064 μm were collected as a data bank.

  2. Orientations of Chromonic Liquid Crystals by Imprinted or Rubbed Polymer Films

    Science.gov (United States)

    Yi, Youngwoo; McGuire, Aya; Clark, Noel

    2014-03-01

    A variety of novel alignment effects of chromonic liquid crystal phases of sunset yellow (SSY)/water, disodium cromoglycate (DSCG)/water, and their mixtures by thiol-ene polymer films topographically imprinted with linear channels are observed using polarizing optical microscopy. Nematic DSCG and SSY at low concentration and their nematic mixtures orient with the long axes of stacked chromonic aggregates on average parallel to the channels, that is, with the molecular planes normal to the channel axis. On the contrary, nematic SSY in contact with the rubbed polyimide films orients with the long axes on average in-plane perpendicular to the rubbing direction, arguably, due to a tongue-groove interaction between SSY and the stretched PI chains. Furthermore, multi-stable alignments are observed in SSY solutions of sufficiently high concentration, including preferential in-plane orientation of the long axes of the aggregates parallel to, perpendicular to, and 45° rotated from the channels. This work was supported by NSF grant DMR 1207606, NSF MRSEC grant DMR 0820579, and NSF Research Experience for Undergraduate programs.

  3. Attempt to detect diamagnetic anisotropy of dust-sized crystal orientated to investigate the origin of interstellar dust alignment

    Science.gov (United States)

    Takeuchi, T.; Hisayoshi, K.; Uyeda, C.

    2013-03-01

    Diamagnetic anisotropy Δ χ dia was detected on a submillimeter-sized calcite crystal by observing the rotational oscillation of its magnetically stable axis with respect to the magnetic field direction. The crystal was released in an area of microgravity generated by a 1.5-m-long drop shaft. When the oscillations are observable, the present method can measure Δ χ dia of crystal grains irrespective of how small they are without measuring the sample mass. In conventional Δ χ measurements, the background signal from the sample holder and the difficulty in measuring the sample mass prevent measurement of Δ χ dia for small samples. The present technique of observing Δ χ dia of a submillimeter-sized single crystal is a step toward realizing Δ χ dia measurements of micron-sized grains. The Δ χ dia values of single micron-sized grains can be used to assess the validity of a dust alignment model based on magnetic torque that originates from the Δ χ dia of individual dust particles.

  4. Interactions between cadmium and calcite

    OpenAIRE

    Van der Weijden, R.D.

    1995-01-01

    The thesis is composed of five chapters, some of which have been published or have been accepted for publication. The contents in some of the chapters may therefore slightly overlap, also because the subjects are closely related. The first two chapters focus mostly on the sorption of Cd on calcite, whereas the next two chapters are devoted to calcite growth and Cd incorporation during growth. In the fifth and final chapter, Cd sorption and incorporation is studied in an environment where calc...

  5. Small scale shear zone in calcite: AMS and microstructure

    Science.gov (United States)

    Roxerová, Zuzana; Machek, Matěj; Kusbach, Vladimír; Racek, Martin; Silva, Pedro F.

    2016-04-01

    Two structural profiles across thin shear zone in calcite from quarry in Estremoz (Portugal) were studied to find a relationship between AMS and strain in natural rocks. The mesoscopic fabric is characterized by the change from the subhorizontal coarse-grained foliation towards the ~2cm-wide shear zone center with subvertical fine-grained foliation. In microstructure, the shear zone records dynamic recrystallization of calcite aggregate which resulted in development of porphyroclastic microstructure with increasing proportion of fine-grained recrystallized matrix towards the shear zone center. Two distinct crystallographic preferred orientations of calcite were recorded. One related with porphyroclasts, characterized by subvertical orientation of calcite axes and another associated with recrystallized matrix showing subhorizontal calcite axes orientation. The magnetic susceptibility ranges from -8e-6SI to 9e-6SI, with the average -4e-6SI. The majority of the rock mass is diamagnetic, corresponding well with the thermomagnetic curves, with local paramagnetic accumulations in form of thin bands. The AMS of the both profiles exhibits stable subvertical foliation bearing vertical lineation which is locally alternated by the medium-angle foliation. We interpret the AMS fabric pattern which is perpendicular to the mineral one as a type of inverse AMS fabric, due to high iron content in major part of calcite grains The magnetic and microstructural description of the shear zone is accompanied by numerical modeling of AMS based on CPO and different proportion of porphyroclasts, matrix and mica for purposes of deciphering the influence of present microstructural features on AMS.

  6. Control of Spin Helix Symmetry in Semiconductor Quantum Wells by Crystal Orientation

    Science.gov (United States)

    Kammermeier, Michael; Wenk, Paul; Schliemann, John

    2016-12-01

    We investigate the possibility of spin-preserving symmetries due to the interplay of Rashba and Dresselhaus spin-orbit coupling in n -doped zinc-blende semiconductor quantum wells of general crystal orientation. It is shown that a conserved spin operator can be realized if and only if at least two growth direction Miller indices agree in modulus. The according spin-orbit field has in general both in-plane and out-of-plane components and is always perpendicular to the shift vector of the corresponding persistent spin helix. We also analyze higher-order effects arising from the Dresselhaus term, and the impact of our results on weak (anti)localization corrections.

  7. Optical Dispersion Parameters with Different Orientations for SrLaAlO4 Single Crystals

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The different optical dispersion parameters of SrLaAlO4 single crystals have been studied by the transmission andreflection measurements at normal incidence for the three orientations 001, 100 and 101 in the spectral range400 nm~2500 nm.The optical absorption data revealed the existance of allowed indirect and direct transition. Therefractive index has abnormal behaviour in the spectral region 400~900 nm, but has a normal one in the higherwavelength region. The optical dispersion parameters, the single oscillator energy Eo and the dispersion energy Edwere determined and indicated the ionic structure of the material. The high-frequency dielectric constant, the latticedielectric constant and the electronic polarizability were determined by the free carriers and the lattice vibrationmodes. The real dielectric constant e1, the dielectric loss tangent (tanδ), the volume (VELF) and the surface energyloss function (SELF) have also been discussed.

  8. Shape Memory Behavior of [111]-Oriented NiTi Single Crystals After Stress-Assisted Aging

    Institute of Scientific and Technical Information of China (English)

    Irfan Kaya; Hirobumi Tobe; Haluk Ersin Karaca; Emre Acar; Yuriy Chumlyakov

    2016-01-01

    The shape memory behavior of [111]-oriented NistTi49 (at.%) single crystals was investigated after stressassisted aging at 500 ℃ for 1.5 h under a compressive stress of-150 MPa.It was found that a single family of Ni4Ti3 precipitates with two crystallographically equivalent variants was formed after aging under compressive stress.Stressassisted aging resulted in tensile two-way shape memory effect strain of 1.56% under-5 MPa.Thermal cycling under -600 MPa resulted in a transformation strain of-2.15%,while the subsequent thermal cycling under-5 MPa resulted in a tensile two-way shape memory effect strain of 2.2%.

  9. Ultrafast infrared observation of exciton equilibration from oriented single crystals of photosystem II

    Science.gov (United States)

    Kaucikas, Marius; Maghlaoui, Karim; Barber, Jim; Renger, Thomas; van Thor, Jasper J.

    2016-12-01

    In oxygenic photosynthesis, two photosystems work in series. Each of them contains a reaction centre that is surrounded by light-harvesting antennae, which absorb the light and transfer the excitation energy to the reaction centre where electron transfer reactions are driven. Here we report a critical test for two contrasting models of light harvesting by photosystem II cores, known as the trap-limited and the transfer-to-the trap-limited model. Oriented single crystals of photosystem II core complexes of Synechococcus elongatus are excited by polarized visible light and the transient absorption is probed with polarized light in the infrared. The dichroic amplitudes resulting from photoselection are maintained on the 60 ps timescale that corresponds to the dominant energy transfer process providing compelling evidence for the transfer-to-the-trap limitation of the overall light-harvesting process. This finding has functional implications for the quenching of excited states allowing plants to survive under high light intensities.

  10. Biotic control of skeletal growth by scleractinian corals in aragonite-calcite seas.

    Directory of Open Access Journals (Sweden)

    Tomihiko Higuchi

    Full Text Available Modern scleractinian coral skeletons are commonly composed of aragonite, the orthorhombic form of CaCO3. Under certain conditions, modern corals produce calcite as a secondary precipitate to fill pore space. However, coral construction of primary skeletons from calcite has yet to be demonstrated. We report a calcitic primary skeleton produced by the modern scleractinian coral Acropora tenuis. When uncalcified juveniles were incubated from the larval stage in seawater with low mMg/Ca levels, the juveniles constructed calcitic crystals in parts of the primary skeleton such as the septa; the deposits were observable under Raman microscopy. Using scanning electron microscopy, we observed different crystal morphologies of aragonite and calcite in a single juvenile skeleton. Quantitative analysis using X-ray diffraction showed that the majority of the skeleton was composed of aragonite even though we had exposed the juveniles to manipulated seawater before their initial crystal nucleation and growth processes. Our results indicate that the modern scleractinian coral Acropora mainly produces aragonite skeletons in both aragonite and calcite seas, but also has the ability to use calcite for part of its skeletal growth when incubated in calcite seas.

  11. Effect of (1010) crystal orientation on electronic properties of wurtzite GaN/AlGaN quantum-well

    CERN Document Server

    Park, S H

    2000-01-01

    The electronic properties of a (1010)-oriented wurtzite (WZ) GaN/AlGaN quantum well (QW) are investigated using the multiband effective-mass theory. These results are compared with those of a (0001)-oriented WZ GaN/AlGaN QW with the piezoelectric (PZ) effect taken into account. For the (0001)-oriented structure, the optical matrix element is significantly reduced with increasing the well thickness due to the PZ electric field. This means that, in the (0001)-oriented structure, a QW structure with a thinner well thickness is desirable to obtain better laser characteristics. For the (1010)-oriented structure, it is found that the average hole effective masses are largely reduced compared to those for the (0001)-oriented structure. Also, the (1010)-oriented structure shows a much larger optical matrix element for g'-polarization due to the crystal orientation effect. These results suggest that the (1010)-oriented QW structures show improved characteristic compared to the (0001)-oriented QW structure with the PZ ...

  12. Characterization of the crystal orientation in mono-oriented films of HDPE/LLDPE blends by IR dichroism

    Science.gov (United States)

    Canevarolo, Sebastião V.; Elias, Marcelo; Ravazzi, Camila; Silva, Jorge

    2016-03-01

    Polyethylene films are a common packaging material. The level and type of chain orientation in these films are a very important property which is of great care and concern of the converter personnel during the conformation process. Usually bi-orientation is the conventional procedure but when easy tear in one direction is needed mono-orientation is sought. This paper deal with the characterization of the crystalline orientation in films of polyethylene blends (HDPE/LLDPE) which have being oriented in two steps: initially the polymer was bi-oriented via extrusion-blown, cooled, and then in a second process hot stretched along the machine direction in order to produce mono-oriented films. In order to evaluate the orientation of the film, the polarization of the FT-IR beam was rotated 360° in steps of 5° by rotating the polarizer. In each step the absorbance spectrum was recorded and the corresponding dichroic ratio (DR) calculated after subtracting the baseline. With differential scanning calorimetry (DSC) was possible to infer about the changes in the morphology caused by the stretching.

  13. Robustness of the periodic and chaotic orientational behavior of tumbling nematic liquid crystals.

    Science.gov (United States)

    Heidenreich, Sebastian; Ilg, Patrick; Hess, Siegfried

    2006-06-01

    The dynamical behavior of molecular alignment strongly affects physical properties of nematic liquid crystals. A theoretical description can be made by a nonlinear relaxation equation of the order parameter and leads to the prediction that rather complex even chaotic orientational behavior occur. Here the influence of fluctuating shear rates on the orientational dynamics especially on chaotic solutions is discussed. With the help of phase portraits and time evolution diagrams, we investigated the influence of different fluctuation strengths on the flow aligned, isotropic, and periodic solutions. To explore the effect of fluctuations on the chaotic behavior, we calculated the largest Lyapunov exponent for different fluctuation strengths. We found in all cases that small fluctuations of the shear rate do not affect the basic features of the dynamics of tumbling nematics. Furthermore, we present an amended potential modeling the isotropic to nematic transition and discuss the equivalence and difference to the commonly used Landau-de Gennes potential. In contrast to the Landau-de Gennes potential, our potential has the advantage to restrict the order parameter to physically admissible values. In the case of extensional flow, we show that the amended potential leads for increasing extensional rate to a better agreement with experimental results.

  14. Young's Modulus, Residual Stress, and Crystal Orientation of Doubly Clamped Silicon Nanowire Beams.

    Science.gov (United States)

    Calahorra, Y; Shtempluck, O; Kotchetkov, V; Yaish, Y E

    2015-05-13

    Initial or residual stress plays an important role in nanoelectronics. Valley degeneracy in silicon nanowires (SiNWs) is partially lifted due to built-in stresses, and consequently, electron-phonon scattering rate is reduced and device mobility and performance are improved. In this study we use a nonlinear model describing the force-deflection relationship to extract the Young's modulus, the residual stress, and the crystallographic growth orientation of SiNW beams. Measurements were performed on suspended doubly clamped SiNWs subjected to atomic force microscopy (AFM) three-point bending constraints. The nanowires comprised different growth directions and two SiO2 sheath thicknesses, and underwent different rapid thermal annealing processes. Analysis showed that rapid thermal annealing introduces compressive strains into the SiNWs and may result in buckling of the SiNWs. Furthermore, the core-shell model together with the residual stress analysis accurately describe the Young's modulus of oxide covered SiNWs and the crystal orientation of the measured nanowires.

  15. Orientational order controls crystalline and amorphous thermal transport in superatomic crystals

    Science.gov (United States)

    Ong, Wee-Liat; O'Brien, Evan S.; Dougherty, Patrick S. M.; Paley, Daniel W.; Fred Higgs, C., III; McGaughey, Alan J. H.; Malen, Jonathan A.; Roy, Xavier

    2017-01-01

    In the search for rationally assembled functional materials, superatomic crystals (SACs) have recently emerged as a unique class of compounds that combine programmable nanoscale building blocks and atomic precision. As such, they bridge traditional semiconductors, molecular solids, and nanocrystal arrays by combining their most attractive features. Here, we report the first study of thermal transport in SACs, a critical step towards their deployment as electronic, thermoelectric, and phononic materials. Using frequency domain thermoreflectance (FDTR), we measure thermal conductivity in two series of SACs: the unary compounds Co6E8(PEt3)6 (E = S, Se, Te) and the binary compounds [Co6E8(PEt3)6][C60]2. We find that phonons that emerge from the periodicity of the superstructures contribute to thermal transport. We also demonstrate a transformation from amorphous to crystalline thermal transport behaviour through manipulation of the vibrational landscape and orientational order of the superatoms. The structural control of orientational order enabled by the atomic precision of SACs expands the conceptual design space for thermal science.

  16. Elasticity, viscosity, and orientational fluctuations of a lyotropic chromonic nematic liquid crystal disodium cromoglycate.

    Science.gov (United States)

    Zhou, Shuang; Neupane, Krishna; Nastishin, Yuriy A; Baldwin, Alan R; Shiyanovskii, Sergij V; Lavrentovich, Oleg D; Sprunt, Samuel

    2014-09-14

    Using dynamic light scattering, we study orientational fluctuation modes in the nematic phase of a self-assembled lyotropic chromonic liquid crystal (LCLC) disodium cromoglycate and measure the Frank elastic moduli and viscosity coefficients. The elastic moduli of splay (K1) and bend (K3) are in the order of 10 pN while the twist modulus (K2) is an order of magnitude smaller. The splay constant K1 and the ratio K1/K3 both increase substantially as the temperature T decreases, which we attribute to the elongation of the chromonic aggregates at lower temperatures. The bend viscosity is comparable to that of thermotropic liquid crystals, while the splay and twist viscosities are several orders of magnitude larger. The temperature dependence of bend viscosity is weak. The splay and twist viscosities change exponentially with the temperature. In addition to the director modes, the fluctuation spectrum reveals an additional mode that is attributed to diffusion of structural defects in the column-like aggregates.

  17. Effect of crystal plane orientation on tribochemical removal of monocrystalline silicon

    Science.gov (United States)

    Xiao, Chen; Guo, Jian; Zhang, Peng; Chen, Cheng; Chen, Lei; Qian, Linmao

    2017-01-01

    The effect of crystal plane orientation on tribochemical removal of monocrystalline silicon was investigated using an atomic force microscope. Experimental results indicated that the tribochemical removal of silicon by SiO2 microsphere presented strong crystallography-induced anisotropy. Further analysis suggested that such anisotropic tribochemical removal of silicon was not dependent on the crystallography-dependent surface mechanical properties (i.e., hardness and elastic modulus), but was mainly attributed to various atomic planar density and interplanar spacing in different crystal planes. Phenomenological results speculated that higher density of silicon atom could promote the formation of Si-O-Si bonds between the SiO2 microsphere and silicon substrate, resulting in more severe tribochemical material removal. Larger interplanar spacing with smaller energy barrier facilitated the rupture of the Si-Si network with the help of mechanical shearing stress, which caused more serious wear of the silicon surface. The results may help understand the material removal mechanism of silicon and provide useful knowledge for chemical mechanical polishing. PMID:28084433

  18. Crystal preferred orientation of amphibole and implications for seismic anisotropy in the crust

    Science.gov (United States)

    Jung, Haemyeong

    2016-04-01

    Strong seismic anisotropy is often observed in the middle to lower crust and it has been considered to be originated from the crystal preferred orientation (CPO) of anisotropic minerals such as amphibole. Amphibolite is one of the dominant rocks in the middle to lower crust. In this study, crystal preferred orientations of hornblende in amphibolites at Yeoncheon and Chuncheon areas in South Korea were determined by using the electron backscattered diffraction (EBSD)/SEM with HKL Channel 5 software. In Yeoncheon area, hornblende showed two types of CPOs. Type-I CPO is characterized as (100) poles of hornblende aligned subnormal to foliation and [001] axes aligned subparallel to lineation. Type-II CPO is characterized as (100) poles of hornblende aligned subnormal to foliation and (010) poles aligned subparallel to lineation (refer to Ko and Jung, 2015, Nature Communications). In Chuncheon area, three types of CPOs of hornblende were observed. In addition to the type-I and -II CPOs described above, type-III CPO of hornblende was observed in Chuncheon area and it is characterized as (100) poles of hornblende aligned subnormal to foliation and both [001] axes and (010) poles aligned as a girdle subparallel to foliation. Using the observed CPO and the single crystal elastic constant of hornblende, seismic anisotropy of hornblende was calculated. Seismic anisotropy of P-wave was strong in the range of 10.2 - 13.5 %. Seismic anisotropy of S-wave was also strong in the range of 6.9 - 11.2 %. These results show that hornblende deformed in nature can produce a strong CPO, resulting in a strong seismic anisotropy in the middle to lower crust. Taking into account of the CPO of plagioclase in the rock, seismic anisotropies of whole rock turned out to be maximum P-wave anisotropy (Vp) of 9.8% and maximum S-wave anisotropy (Vs) of 8.2%. Therefore, strong seismic anisotropy found in the middle to lower crust in nature can be attributed to the CPO of hornblende in amphibolite.

  19. Peculiar orientational disorder in 4-bromo-4'-nitrobiphenyl (BNBP) and 4-bromo-4'-cyanobiphenyl (BCNBP) leading to bipolar crystals.

    Science.gov (United States)

    Burgener, Matthias; Aboulfadl, Hanane; Labat, Gaël Charles; Bonin, Michel; Sommer, Martin; Sankolli, Ravish; Wübbenhorst, Michael; Hulliger, Jürg

    2016-05-01

    180° orientational disorder of molecular building blocks can lead to a peculiar spatial distribution of polar properties in molecular crystals. Here we present two examples [4-bromo-4'-nitrobiphenyl (BNBP) and 4-bromo-4'-cyanobiphenyl (BCNBP)] which develop into a bipolar final growth state. This means orientational disorder taking place at the crystal/nutrient interface produces domains of opposite average polarity for as-grown crystals. The spatial inhomogeneous distribution of polarity was investigated by scanning pyroelectric microscopy (SPEM), phase-sensitive second harmonic microscopy (PS-SHM) and selected volume X-ray diffraction (SVXD). As a result, the acceptor groups (NO2 or CN) are predominantly present at crystal surfaces. However, the stochastic process of polarity formation can be influenced by adding a symmetrical biphenyl to a growing system. For this case, Monte Carlo simulations predict an inverted net polarity compared with the growth of pure BNBP and BCNBP. SPEM results clearly demonstrate that 4,4'-dibromobiphenyl (DBBP) can invert the polarity for both crystals. Phenomena reported in this paper belong to the most striking processes seen for molecular crystals, demonstrated by a stochastic process giving rise to symmetry breaking. We encounter here further examples supporting the general thesis that monodomain polar molecular crystals for fundamental reasons cannot exist.

  20. Precise Characterisation of Molecular Orientation in a Single Crystal Field-Effect Transistor Using Polarised Raman Spectroscopy

    Science.gov (United States)

    Wood, Sebastian; Rigas, Grigorios-Panagiotis; Zoladek-Lemanczyk, Alina; Blakesley, James C.; Georgakopoulos, Stamatis; Mas-Torrent, Marta; Shkunov, Maxim; Castro, Fernando A.

    2016-09-01

    Charge transport in organic semiconductors is strongly dependent on the molecular orientation and packing, such that manipulation of this molecular packing is a proven technique for enhancing the charge mobility in organic transistors. However, quantitative measurements of molecular orientation in micrometre-scale structures are experimentally challenging. Several research groups have suggested polarised Raman spectroscopy as a suitable technique for these measurements and have been able to partially characterise molecular orientations using one or two orientation parameters. Here we demonstrate a new approach that allows quantitative measurements of molecular orientations in terms of three parameters, offering the complete characterisation of a three-dimensional orientation. We apply this new method to organic semiconductor molecules in a single crystal field-effect transistor in order to correlate the measured orientation with charge carrier mobility measurements. This approach offers the opportunity for micrometre resolution (diffraction limited) spatial mapping of molecular orientation using bench-top apparatus, enabling a rational approach towards controlling this orientation to achieve optimum device performance.

  1. EFFECT OF AUSTENITIC CRYSTAL ORIENTATION IN A MULTIPHASE STEEL ANALYZED BY A DISCRETE DISLOCATION-TRANSFORMATION MODEL

    NARCIS (Netherlands)

    Shi, J.; Turteltaub, S.; Van der Giessen, E.

    2009-01-01

    A discrete dislocation-transformation model is used to analyze the response of an aggregate of ferritic and austenitic grains that can transform into martensite. In particular, the influence of the crystal orientation of the austenitic grains on the plastic and transformation behavior is studied. It

  2. Roles of Oxygen and Hydrogen in Crystal Orientation Transition of Copper Foils for High-Quality Graphene Growth

    Science.gov (United States)

    Hu, Junxiong; Xu, Jianbao; Zhao, Yanfei; Shi, Lin; Li, Qi; Liu, Fengkui; Ullah, Zaka; Li, Weiwei; Guo, Yufen; Liu, Liwei

    2017-01-01

    The high-quality graphene film can be grown on single-crystal Cu substrate by seamlessly stitching the aligned graphene domains. The roles of O2 and H2 have been intensively studied in the graphene growth kinetics, including lowering the nucleation sites and tailoring the domain structures. However, how the O2 and H2 influence Cu orientations during recrystallization prior to growing graphene, still remains unclear. Here we report that the oxidation of Cu surface tends to stabilize the Cu(001) orientation while impedes the evolution of Cu(111) single domain during annealing process. The crystal orientation-controlled synthesis of aligned graphene seeds is further realized on the long-range ordered Cu(111) substrate. With decreasing the thickness of oxide layer on Cu surface by introducing H2, the Cu(001) orientation changes into Cu(111) orientation. Meanwhile, the average domain size of Cu foils is increased from 50 μm to larger than 1000 μm. The density functional theory calculations reveal that the oxygen increases the energy barrier for Cu(111) surface and makes O/Cu(001) more stable than O/Cu(111) structure. Our work can be helpful for revealing the roles of O2 and H2 in controlling the formation of Cu single-crystal substrate as well as in growing high-quality graphene films. PMID:28367988

  3. Tuning hardness in calcite by incorporation of amino acids

    Science.gov (United States)

    Kim, Yi-Yeoun; Carloni, Joseph D.; Demarchi, Beatrice; Sparks, David; Reid, David G.; Kunitake, Miki E.; Tang, Chiu C.; Duer, Melinda J.; Freeman, Colin L.; Pokroy, Boaz; Penkman, Kirsty; Harding, John H.; Estroff, Lara A.; Baker, Shefford P.; Meldrum, Fiona C.

    2016-08-01

    Structural biominerals are inorganic/organic composites that exhibit remarkable mechanical properties. However, the structure-property relationships of even the simplest building unit--mineral single crystals containing embedded macromolecules--remain poorly understood. Here, by means of a model biomineral made from calcite single crystals containing glycine (0-7 mol%) or aspartic acid (0-4 mol%), we elucidate the origin of the superior hardness of biogenic calcite. We analysed lattice distortions in these model crystals by using X-ray diffraction and molecular dynamics simulations, and by means of solid-state nuclear magnetic resonance show that the amino acids are incorporated as individual molecules. We also demonstrate that nanoindentation hardness increased with amino acid content, reaching values equivalent to their biogenic counterparts. A dislocation pinning model reveals that the enhanced hardness is determined by the force required to cut covalent bonds in the molecules.

  4. Nanometer-Scale Chemistry of a Calcite Biomineralization Template: Implications for Skeletal Composition and Nucleation

    Energy Technology Data Exchange (ETDEWEB)

    Branson, Oscar; Bonnin, Elisa A.; Perea, Daniel E.; Spero, Howard J.; Zhu, Zihua; Winters, Maria; Hönisch, Bärbel; Russell, Ann D.; Fehrenbacher, Jennifer S.; Gagnon, Alexander C.

    2016-10-28

    Biomineralizing organisms exhibit exquisite control over skeletal morphology and composition. The promise of understanding and harnessing this feat of natural engineering has motivated an intense search for the mechanisms that direct in vivo mineral self-assembly. We used atom probe tomography, a sub-nanometer 3D chemical mapping technique, to examine the chemistry of a buried organic-mineral interface in biomineral calcite from a marine foraminifer. The chemical patterns at this interface capture the processes of early biomineralization, when the shape, mineralogy, and orientation of skeletal growth are initially established. Sodium is enriched by a factor of nine on the organic side of the interface. Based on this pattern, we suggest that sodium plays an integral role in early biomineralization, potentially altering interfacial energy to promote crystal nucleation, and that interactions between organic surfaces and electrolytes other than calcium or carbonate could be a crucial aspect of CaCO3 biomineralization.

  5. Influence of crystal-orientation effects on pulse-shape-based identification of heavy-ions stopped in silicon detectors

    Science.gov (United States)

    Bardelli, L.; Bini, M.; Casini, G.; Pasquali, G.; Poggi, G.; Barlini, S.; Becla, A.; Berjillos, R.; Borderie, B.; Bougault, R.; Bruno, M.; Cinausero, M.; D'Agostino, M.; de Sanctis, J.; Dueñas, J. A.; Edelbruck, P.; Geraci, E.; Gramegna, F.; Kordyasz, A.; Kozik, T.; Kravchuk, V. L.; Lavergne, L.; Marini, P.; Nannini, A.; Negoita, F.; Olmi, A.; Ordine, A.; Piantelli, S.; Rauly, E.; Rivet, M. F.; Rosato, E.; Scian, C.; Stefanini, A. A.; Vannini, G.; Velica, S.; Vigilante, M.; Fazia Collaboration

    2009-07-01

    Current and charge signals have been collected for Se ions at 408 MeV, S at 160 MeV and Ni at 703 MeV, all stopped in silicon detectors. Some detectors were cut 0∘ off the axis and some off the axis. Important effects on the shape of the silicon current and charge signals have been observed, depending on the orientation of the impinging ion relative to the crystal axes and planes. A degradation of the energy and risetime resolution of about a factor ˜3 with respect to the measured optimal values (for example 7∘ off-axis orientation) is observed for ion impinging directions close to crystal axes and/or planes, i.e. the common scenario for normal incidence on 0∘ cut detectors. For Pulse Shape Analysis applications, the necessity of using such "random" oriented silicon detectors is demonstrated.

  6. Influence of crystal-orientation effects on pulse-shape-based identification of heavy-ions stopped in silicon detectors

    Energy Technology Data Exchange (ETDEWEB)

    Bardelli, L. [University of Florence (Italy); I.N.F.N. Sezione di Firenze (Italy)], E-mail: bardelli@fi.infn.it; Bini, M. [University of Florence (Italy); I.N.F.N. Sezione di Firenze (Italy); Casini, G. [I.N.F.N. Sezione di Firenze (Italy); Pasquali, G.; Poggi, G. [University of Florence (Italy); I.N.F.N. Sezione di Firenze (Italy); Barlini, S. [LPC Caen, ENSICAEN, Universite de Caen, CNRS/IN2P3, Caen (France); Institut de Physique Nucleaire, CNRS/IN2P3, Universite Paris-Sud 11, F-91406 Orsay cedex (France); Becla, A. [Jagiellonian University, Institute of Physics, Reymonta 4, 30-059 Krakow (Poland); Berjillos, R. [Departamento de Fisica Aplicada, Universidad de Huelva, E-21071 Huelva (Spain); Borderie, B. [Institut de Physique Nucleaire, CNRS/IN2P3, Universite Paris-Sud 11, F-91406 Orsay cedex (France); Bougault, R. [LPC Caen, ENSICAEN, Universite de Caen, CNRS/IN2P3, Caen (France); Bruno, M. [University of Bologna (Italy); I.N.F.N. Sezione di Bologna (Italy); Cinausero, M. [I.N.F.N. Laboratori Nazionali di Legnaro (Italy); D' Agostino, M.; De Sanctis, J. [University of Bologna (Italy); I.N.F.N. Sezione di Bologna (Italy); Duenas, J.A. [Departamento de Fisica Aplicada, Universidad de Huelva, E-21071 Huelva (Spain); Edelbruck, P. [Institut de Physique Nucleaire, CNRS/IN2P3, Universite Paris-Sud 11, F-91406 Orsay cedex (France); Geraci, E. [University of Bologna (Italy); I.N.F.N. Sezione di Bologna (Italy); Gramegna, F. [I.N.F.N. Laboratori Nazionali di Legnaro (Italy); Kordyasz, A. [Heavy Ion Laboratory, Warsaw University, Pasteura 5a, 02-093 Warsaw (Poland); Kozik, T. [Jagiellonian University, Institute of Physics, Reymonta 4, 30-059 Krakow (Poland)] (and others)

    2009-07-01

    Current and charge signals have been collected for Se ions at 408 MeV, S at 160 MeV and Ni at 703 MeV, all stopped in silicon detectors. Some detectors were cut 0 deg. off the <111> axis and some off the <100> axis. Important effects on the shape of the silicon current and charge signals have been observed, depending on the orientation of the impinging ion relative to the crystal axes and planes. A degradation of the energy and risetime resolution of about a factor {approx}3 with respect to the measured optimal values (for example 7 deg. off-axis orientation) is observed for ion impinging directions close to crystal axes and/or planes, i.e. the common scenario for normal incidence on 0 deg. cut detectors. For Pulse Shape Analysis applications, the necessity of using such 'random' oriented silicon detectors is demonstrated.

  7. Preferred orientation of n-hexane crystallized in silicon nanochannels: A combined x-ray diffraction and sorption isotherm study

    CERN Document Server

    Henschel, Anke; Hofmann, Tommy; Knorr, Klaus; Huber, Patrick; 10.1103/PhysRevE.79.032601

    2009-01-01

    We present an x-ray diffraction study on n-hexane in tubular silicon channels of approximately 10 nm diameter both as a function of the filling fraction f of the channels and as a function of temperature. Upon cooling, confined n-hexane crystallizes in a triclinic phase typical of the bulk crystalline state. However, the anisotropic spatial confinement leads to a preferred orientation of the confined crystallites, where the crystallographic direction coincides with the long axis of the channels. The magnitude of this preferred orientation increases with the filling fraction, which corroborates the assumption of a Bridgman-type crystallization process being responsible for the peculiar crystalline texture. This growth process predicts for a channel-like confinement an alignment of the fastest crystallization direction parallel to the long channel axis. It is expected to be increasingly effective with the length of solidifying liquid parcels and thus with increasing f. In fact, the fastest solidification front...

  8. Influence of external constraint and rolling geometry on deformation banding of copper single crystals with {123} orientation

    Institute of Scientific and Technical Information of China (English)

    Yanping Zeng; Jianxin Dong; Maicang Zhang; Xishan Xie; Weimin Mao; Zhensheng Li

    2003-01-01

    In order to further understand the similarity and difference between deformation mechanisms of single crystals and poly-crystalline materials, the influence of external constraint and rolling geometry on the deformation behaviour of copper single crystalswith {123} orientation was investigated by embedding them into metal frames of different strengths. The metal frames weremade of aluminum and mild steel, respectively. The results show that the deformation banding degree of the crystal increases withthe strength of metal frame and shear strain. For the crystals rolled under lower γg (γg is the ratio of the geometrical redundant shearstrain to the normal rolling strain), the deformation is homogeneous. For the crystals rolled under higher γg, the deformation is ex-tremely inhomogeneous. The deformation is more homogeneous in the crystals rolled in steel frames than that rolled in aluminumframes. The S-orientation is more stable in the crystals rolled under lower γg than that rolled under higher γg.

  9. Enhancing mechanical properties of calcite by Mg substitutions: An ab initio study

    Science.gov (United States)

    Elstnerova, Pavlina; Friak, Martin; Hickel, Tilmann; Fabritius, Helge Otto; Lymperakis, Liverios; Petrov, Michal; Raabe, Dierk; Neugebauer, Joerg; Nikolov, Svetoslav; Zigler, Andreas; Hild, Sabine

    2011-03-01

    Arthropoda representing a majority of all known animal species are protected by an exoskeleton formed by their cuticle. The cuticle represents a hierarchically structured multifunctional bio-composite based on chitin and proteins. Some groups like Crustacea reinforce the load-bearing parts of their cuticle with calcite. As the calcite sometimes contains Mg it was speculated that Mg may have a stiffening impact on the mechanical properties of the cuticle. We present a theoretical parameter-free quantum-mechanical study of thermodynamic, structural and elastic properties of Mg-substituted calcite. Our results show that substituting Ca by Mg causes an almost linear decrease in the crystal volume with Mg concentration and of substituted crystals. As a consequence the calcite crystals become stiffer giving rise e.g. to substantially increased bulk moduli.

  10. Inversion of calcite twin data for stress (2) : EBSD as a tool for data measurements

    Science.gov (United States)

    Parlangeau, Camille; Lacombe, Olivier; Brisset, Francois; Kohler, Eric; Daniel, Jean-Marc; Schueller, Sylvie

    2015-04-01

    Inversion of calcite twin data are known to be a powerful tool to reconstruct the past state(s) of stress in carbonate rocks of the crust, especially in fold-and-thrust belts and sedimentary basins. Twin data measurements have been for long carried out optically using a Universal-Stage. This data collection is time-consuming and suffers from limitations and bias related to measurements of twin planes oblique at low angle or parallel to the thin section, or the unambiguous evaluation of the twinned/untwinned character of collected twin data. EBSD (electron backscatter diffraction) is a well-known technique applied to characterize textures and microstructures of metals or deformed fine-grained rocks. The challenge is to define a strategy for measuring calcite-twin orientations that should be fast, without any loss of information, and which must reconcile (1) the need for a large amount of calcite twin data (3 mutually perpendicular thin sections and at least 30 crystals per thin section), (2) the spacing between EBSD spots, that should take into account (3) the small width of twin lamellae within grains deformed at low pressure and temperature and (4) the large size (usually several hundreds of microns) of twinned calcite grains used for stress analysis. To date, these multiple requirements preclude any (classical) automatic twin data acquisition but instead imply a preliminary definition of the areas of the thin section to be scanned by the EBSD spots, including grain boundaries, because the stress inversion technique requires to know for each grain the orientations of the C axis and of the 3 potential e twin planes. In order to reconcile a perfectly polished surface as required by EBSD and the recognition of grain boundaries, we adopted the double etching technique (Herwegh, 2000) to first reveal grain and twin boundaries. Then, with a SEM and a very fine coating sample, the section is scanned using secondary electrons bin; each spot of interest is visually defined

  11. Processing of X-ray snapshots from crystals in random orientations

    Energy Technology Data Exchange (ETDEWEB)

    Kabsch, Wolfgang, E-mail: kabsch@mpimf-heidelberg.mpg.de [Max-Planck-Institut für medizinische Forschung, Jahnstrasse 29, D-69120 Heidelberg (Germany)

    2014-08-01

    A new method for the treatment of partial reflections from X-ray snapshots is implemented in the program package nXDS, which yields intensity data of almost the same quality as those obtained by the classical rotation method. A functional expression is introduced that relates scattered X-ray intensities from a still or a rotation snapshot to the corresponding structure-factor amplitudes. The new approach was implemented in the program nXDS for processing monochromatic diffraction images recorded by a multi-segment detector where each exposure could come from a different crystal. For images containing indexable spots, the intensities of the expected reflections and their variances are obtained by profile fitting after mapping the contributing pixel contents to the Ewald sphere. The varying intensity decline owing to the angular distance of the reflection from the surface of the Ewald sphere is estimated using a Gaussian rocking curve. This decline is dubbed ‘Ewald offset correction’, which is well defined even for still images. Together with an image-scaling factor and other corrections, an explicit expression is defined that predicts each recorded intensity from its corresponding structure-factor amplitude. All diffraction parameters, scaling and correction factors are improved by post-refinement. The ambiguous case of a lower point group than the lattice symmetry is resolved by a method reminiscent of the technique of ‘selective breeding’. It selects the indexing alternative for each image that yields, on average, the highest correlation with intensities from all other images. Processing a test set of rotation images by XDS and treating the same images by nXDS as snapshots of crystals in random orientations yields data of comparable quality, clearly indicating an anomalous signal from Se atoms.

  12. Interactions between cadmium and calcite

    NARCIS (Netherlands)

    van der Weijden, R.D.

    1995-01-01

    The thesis is composed of five chapters, some of which have been published or have been accepted for publication. The contents in some of the chapters may therefore slightly overlap, also because the subjects are closely related. The first two chapters focus mostly on the sorption of Cd on calcite,

  13. Praseodymium Cuprate Thin Film Cathodes for Intermediate Temperature Solid Oxide Fuel Cells: Roles of Doping, Orientation, and Crystal Structure.

    Science.gov (United States)

    Mukherjee, Kunal; Hayamizu, Yoshiaki; Kim, Chang Sub; Kolchina, Liudmila M; Mazo, Galina N; Istomin, Sergey Ya; Bishop, Sean R; Tuller, Harry L

    2016-12-21

    Highly textured thin films of undoped, Ce-doped, and Sr-doped Pr2CuO4 were synthesized on single crystal YSZ substrates using pulsed laser deposition to investigate their area-specific resistance (ASR) as cathodes in solid-oxide fuel cells (SOFCs). The effects of T' and T* crystal structures, donor and acceptor doping, and a-axis and c-axis orientation on ASR were systematically studied using electrochemical impedance spectroscopy on half cells. The addition of both Ce and Sr dopants resulted in improvements in ASR in c-axis oriented films, as did the T* crystal structure with the a-axis orientation. Pr1.6Sr0.4CuO4 is identified as a potential cathode material with nearly an order of magnitude faster oxygen reduction reaction kinetics at 600 °C compared to thin films of the commonly studied cathode material La0.6Sr0.4Co0.8Fe0.2O3-δ. Orientation control of the cuprate films on YSZ was achieved using seed layers, and the anisotropy in the ASR was found to be less than an order of magnitude. The rare-earth doped cuprate was found to be a versatile system for study of relationships between bulk properties and the oxygen reduction reaction, critical for improving SOFC performance.

  14. Calcite Formation in Soft Coral Sclerites Is Determined by a Single Reactive Extracellular Protein*

    Science.gov (United States)

    Rahman, M. Azizur; Oomori, Tamotsu; Wörheide, Gert

    2011-01-01

    Calcium carbonate exists in two main forms, calcite and aragonite, in the skeletons of marine organisms. The primary mineralogy of marine carbonates has changed over the history of the earth depending on the magnesium/calcium ratio in seawater during the periods of the so-called “calcite and aragonite seas.” Organisms that prefer certain mineralogy appear to flourish when their preferred mineralogy is favored by seawater chemistry. However, this rule is not without exceptions. For example, some octocorals produce calcite despite living in an aragonite sea. Here, we address the unresolved question of how organisms such as soft corals are able to form calcitic skeletal elements in an aragonite sea. We show that an extracellular protein called ECMP-67 isolated from soft coral sclerites induces calcite formation in vitro even when the composition of the calcifying solution favors aragonite precipitation. Structural details of both the surface and the interior of single crystals generated upon interaction with ECMP-67 were analyzed with an apertureless-type near-field IR microscope with high spatial resolution. The results show that this protein is the main determining factor for driving the production of calcite instead of aragonite in the biocalcification process and that –OH, secondary structures (e.g. α-helices and amides), and other necessary chemical groups are distributed over the center of the calcite crystals. Using an atomic force microscope, we also explored how this extracellular protein significantly affects the molecular-scale kinetics of crystal formation. We anticipate that a more thorough investigation of the proteinaceous skeleton content of different calcite-producing marine organisms will reveal similar components that determine the mineralogy of the organisms. These findings have significant implications for future models of the crystal structure of calcite in nature. PMID:21768106

  15. Calcite formation in soft coral sclerites is determined by a single reactive extracellular protein.

    Science.gov (United States)

    Rahman, M Azizur; Oomori, Tamotsu; Wörheide, Gert

    2011-09-09

    Calcium carbonate exists in two main forms, calcite and aragonite, in the skeletons of marine organisms. The primary mineralogy of marine carbonates has changed over the history of the earth depending on the magnesium/calcium ratio in seawater during the periods of the so-called "calcite and aragonite seas." Organisms that prefer certain mineralogy appear to flourish when their preferred mineralogy is favored by seawater chemistry. However, this rule is not without exceptions. For example, some octocorals produce calcite despite living in an aragonite sea. Here, we address the unresolved question of how organisms such as soft corals are able to form calcitic skeletal elements in an aragonite sea. We show that an extracellular protein called ECMP-67 isolated from soft coral sclerites induces calcite formation in vitro even when the composition of the calcifying solution favors aragonite precipitation. Structural details of both the surface and the interior of single crystals generated upon interaction with ECMP-67 were analyzed with an apertureless-type near-field IR microscope with high spatial resolution. The results show that this protein is the main determining factor for driving the production of calcite instead of aragonite in the biocalcification process and that -OH, secondary structures (e.g. α-helices and amides), and other necessary chemical groups are distributed over the center of the calcite crystals. Using an atomic force microscope, we also explored how this extracellular protein significantly affects the molecular-scale kinetics of crystal formation. We anticipate that a more thorough investigation of the proteinaceous skeleton content of different calcite-producing marine organisms will reveal similar components that determine the mineralogy of the organisms. These findings have significant implications for future models of the crystal structure of calcite in nature.

  16. Utilization of oriented crystal growth for screening of aromatic carboxylic acids cocrystallization with urea

    Science.gov (United States)

    Przybyłek, Maciej; Ziółkowska, Dorota; Kobierski, Mirosław; Mroczyńska, Karina; Cysewski, Piotr

    2016-01-01

    The possibility of molecular complex formation in the solid state of urea with benzoic acid analogues was measured directly on the crystallite films deposited on the glass surface using powder X-ray diffractometry (PXRD). Obtained solid mixtures were also analyzed using Fourier transform infrared spectroscopy (FTIR). The simple droplet evaporation method was found to be efficient, robust, fast and cost-preserving approach for first stage cocrystal screening. Additionally, the application of orientation effect to cocrystal screening simplifies the analysis due to damping of majority of diffraction signals coming from coformers. During validation phase the proposed approach successfully reproduced both positive cases of cocrystallization (urea:salicylic acid and urea:4-hydroxy benzoic acid) as well as pairs of co-formers immiscible in the solid state (urea:benzoic acid and urea:acetylsalicylic acids). Based on validated approach new cocrystals of urea were identified in complexes with 3-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid and 3,5-dihydroxybenzoic acid. In all cases formation of multicomponent crystal phase was confirmed by the appearance of new reflexes on the diffraction patterns and FTIR absorption band shifts of O-H and N-H groups.

  17. Near-Field Birefringence Response of Liquid Crystal Molecules in Thickness Direction of Liquid Crystal Thin Film Orientated by Shear Force

    Institute of Scientific and Technical Information of China (English)

    Jing QIN; Norihiro UMEDA

    2007-01-01

    Information of molecular orientation in nematic liquid crystal (LC) is attractive and important for applications in the field of display devices. We demonstrate a novel method using a birefringence scanning near-field optical microscope (Bi-SNOM) with a probe which is inserted into the LC thin film to detect the molecular orientation from its birefringence responses in the thickness direction of the LC thin film. The probe is laterally vibrated when going forward into the LC thin film, and the retardation and azimuth angle are recorded as the probe going down. Firstly, the thickness of the LC thin film is measured by the shear force detection. Since the shear force acts as a stimulation to reorientate the LC molecules above the substrate surface, we can detect the molecular orientation caused by a polyimide alignment substrate and the effect to molecular orientation caused by vibration of fibre probe. As a result, the orientation profiling of the LC film in depth direction is obtained in both the cases that the direction of probe vibrating is vertical/parallel to the rubbing direction of the alignment film.Furthermore, the thickness of completely orientated layers just above the substrate surface can also be obtained by either vibrating probe or no-vibrating probe. Ultimately, the LC thin film can be modelled in thickness direction from all the results using this method.

  18. Influence of the crystal orientation on the electrical properties of AlN thin films on LTCC substrates

    Energy Technology Data Exchange (ETDEWEB)

    Bittner, A., E-mail: achim.bittner@tuwien.ac.at [Micromechanics, Microfluidics/Microactuators, Faculty of Natural Sciences and Technology II, Saarland University, D-66123 Saarbruecken (Germany); Ababneh, A.; Seidel, H. [Micromechanics, Microfluidics/Microactuators, Faculty of Natural Sciences and Technology II, Saarland University, D-66123 Saarbruecken (Germany); Schmid, U. [Department for Microsystems Technology, Institute of Sensor and Actuator Systems, Vienna University of Technology, Floragasse 7, A-1040 Vienna (Austria)

    2010-11-15

    In this study, the influence of the crystal orientation on the electrical properties of sputter deposited aluminium nitride (AlN) thin films on low temperature co-fired ceramics (LTCC) substrates is investigated. The degree of c-axis orientation can be tailored by the deposition conditions such as plasma power, gas pressure and gas composition in the deposition chamber. Due to the large surface roughness of LTCC substrates (R{sub a} = {approx}0.4 {mu}m) the quality of thin films is lower compared to silicon. Between areas of columnar grains arranged perpendicular to the LTCC surface, defects like voids are generated due to the wavy surface characteristics. The impact of crystal orientation and temperature up to 400 deg. C on the electrical performance is evaluated, as these layers are targeted as potential candidates for dielectric heat spreaders on multilayered ceramic substrates for high frequency applications. These AlN thin films having a good c-axis orientation exhibit lower leakage current levels over the complete temperature range compared to those with a poor alignment with respect to this crystallographic plane. The leakage current behaviour, however, is dominated according to the Pool-Frenkel electron emission independent of the degree of c-axis orientation.

  19. Analysis of the variation in nanohardness of pearlitic steel: Influence of the interplay between ferrite crystal orientation and cementite morphology

    Energy Technology Data Exchange (ETDEWEB)

    Debehets, Jolien, E-mail: jolien.debehets@mtm.kuleuven.be [Department of Materials Engineering, KU Leuven, University of Leuven, Kasteelpark Arenberg 44 bus 2450, B-3001 Leuven (Belgium); Tacq, Jeroen [Department of Materials Engineering, KU Leuven, University of Leuven, Kasteelpark Arenberg 44 bus 2450, B-3001 Leuven (Belgium); Favache, Audrey; Jacques, Pascal [Institute of Mechanics, Materials and Civil Engineering, Université catholique de Louvain, Place Sainte Barbe 2 L5.02.02, 1348 Louvain-la-Neuve (Belgium); Seo, Jin Won; Verlinden, Bert; Seefeldt, Marc [Department of Materials Engineering, KU Leuven, University of Leuven, Kasteelpark Arenberg 44 bus 2450, B-3001 Leuven (Belgium)

    2014-10-20

    The influence of the relative orientation of the ferrite crystallite lattice and the cementite lamellae on the hardness of pearlitic steel has been investigated by a combination of nanoindentation and electron microscopy (electron back scatter diffraction (EBSD) and scanning electron microscopy (SEM)). Three pearlitic samples, each with a different interlamellar spacing, and one ferritic sample were nanoindented. Although the hardness of the ferritic sample is very similar at different spots on the sample, a large variation in hardness is obtained on each of the pearlitic samples. It has been found that this variation cannot be accounted for solely by the variation in interlamellar spacing and is related to differences in ferrite crystal orientation. As to explain the observed large variation in hardness, the ferrite crystal orientation was considered relative to the cementite lamellae orientation by calculation of the distance dislocations can glide between adjacent lamellae in the slip direction. However, no clear correlation was found for a scaling of this orientation factor with the hardness. Possible interpretations of this discrepancy are suggested.

  20. In situ crystallization of b-oriented MFI films on plane and curved substrates coated with a mesoporous silica layer

    KAUST Repository

    Deng, Zhiyong

    2013-05-01

    A simple and reproducible method is presented for preparing b-oriented MFI films on plane (disc) and curved (hollow fiber) supports by in situ hydrothermal synthesis. A mesoporous silica (sub-)layer was pre-coated on the supports by dip coating followed by a rapid thermal calcination step (973 K during 1 min) to reduce the number of grain boundaries while keeping the hydrophilic behavior of silica. The role of the silica sub-layer is not only to smoothen the substrate surface, but also to provide a silica source to promote the nucleation and growth of zeolite crystals via a heterogeneous nucleation mechanism (zeolitization), and adsorb zeolite moieties generated in the synthesis solution via a homogeneous nucleation mechanism. A monolayer of b-oriented MFI crystals was obtained on both supports after 3 h synthesis time with a moderate degree of twinning on the surface. © 2013 Elsevier Ltd.

  1. Calcite growth-rate inhibition by fulvic acids isolated from Big Soda Lake, Nevada, USA, The Suwannee River, Georgia, USA and by polycarboxylic acids

    Science.gov (United States)

    Reddy, Michael M.; Leenheer, Jerry

    2011-01-01

    Calcite crystallization rates are characterized using a constant solution composition at 25°C, pH=8.5, and calcite supersaturation (Ω) of 4.5 in the absence and presence of fulvic acids isolated from Big Soda Lake, Nevada (BSLFA), and a fulvic acid from the Suwannee River, Georgia (SRFA). Rates are also measured in the presence and absence of low-molar mass, aliphatic-alicyclic polycarboxylic acids (PCA). BSLFA inhibits calcite crystal-growth rates with increasing BSLFA concentration, suggesting that BSLFA adsorbs at growth sites on the calcite crystal surface. Calcite growth morphology in the presence of BSLFA differed from growth in its absence, supporting an adsorption mechanism of calcite-growth inhibition by BSLFA. Calcite growth-rate inhibition by BSLFA is consistent with a model indicating that polycarboxylic acid molecules present in BSLFA adsorb at growth sites on the calcite crystal surface. In contrast to published results for an unfractionated SRFA, there is dramatic calcite growth inhibition (at a concentration of 1 mg/L) by a SRFA fraction eluted by pH 5 solution from XAD-8 resin, indicating that calcite growth-rate inhibition is related to specific SRFA component fractions. A cyclic PCA, 1, 2, 3, 4, 5, 6-cyclohexane hexacarboxylic acid (CHXHCA) is a strong calcite growth-rate inhibitor at concentrations less than 0.1 mg/L. Two other cyclic PCAs, 1, 1 cyclopentanedicarboxylic acid (CPDCA) and 1, 1 cyclobutanedicarboxylic acid (CBDCA) with the carboxylic acid groups attached to the same ring carbon atom, have no effect on calcite growth rates up to concentrations of 10 mg/L. Organic matter ad-sorbed from the air onto the seed crystals has no effect on the measured calcite crystal-growth rates.

  2. Effects of crystal orientation and ferroelastic domain structure on the photochemical reactivity of BiVO4 and related compounds

    Science.gov (United States)

    Munprom, Ratiporn

    Bismuth vanadate, BiVO4, has been recognized for its high efficiency as a photoanode for water splitting. However, its performance is limited by photogenerated electron--hole recombination. Thus, researchers have attempted to modify BiVO4 to improve its performance. One strategy to improve charge separation is to utilize an internal field arising from surface termination differences. Previous studies concentrated on polygonal single crystals of BiVO4, providing limited information about the orientation-reactivity relationship. The current research focuses on polycrystalline BiVO4, which makes it possible to study the photochemical reactivity of all possible orientations and determine the complete orientation dependence of the photochemical reactivity of BiVO4. (Abstract shortened by UMI.).

  3. Binding of ethanol on calcite: the role of the OH bond and its relevance to biomineralization

    DEFF Research Database (Denmark)

    Sand, K K; Yang, M; Makovicky, E;

    2010-01-01

    adsorption on calcite relative to OH from water and the consequences of the differences in interaction on crystal growth and dissolution. A combination of atomic force microscopy (AFM) and molecular dynamics (MD) simulations showed that EtOH attachment on calcite is stronger than HOH binding...... to the surface. The strong influence of calcite in structuring ethanol extends further into the liquid than expected from electrical double-layer theory. This suggests that in fluids where water activity is low, such as in biological systems optimized for biomineralization, organic molecules can control ion...

  4. Preparation of zirconium phenylphosphonate films with different crystallite orientations on polystyrene substrates by in situ hydrothermal crystallization

    Energy Technology Data Exchange (ETDEWEB)

    Lei Xiaodong; Wang Lei; Cui Zhaohui; Xu Sailong; Zhang Fazhi, E-mail: zhangfz@mail.buct.edu.c

    2011-03-31

    Zirconium phenylphosphonate (ZrPP) films with different crystallite orientations have been fabricated on unmodified and surface-sulfonated polystyrene (PS) substrates by an in situ hydrothermal crystallization method. On the unmodified PS substrate, a monolayer film with the hexagonal ab planes of the ZrPP crystallites parallel to the PS can be obtained by restricting the crystallization time. After a longer crystallization time, the ZrPP films adopt a bilayer arrangement, with the ab planes of the ZrPP crystallites in the lower layer being parallel to the substrate, and the ab planes of the ZrPP crystallites in the upper layer being perpendicular to the substrate. On the surface-sulfonated PS, however, the ZrPP crystallites form a monolayer film with their ab planes perpendicular to the substrate irrespective of the crystallization time. We suggest that the different interactions between the ZrPP crystallites and the two substrates, namely the {pi}-{pi} interactions between the phenyl groups in the ZrPP surface and those in the unmodified PS substrate, and the coordinate interactions between the lone pairs of electrons on oxygen atoms in the sulfonate groups on the sulfonated PS and vacant coordination sites on Zr atoms on the edges of ZrPP crystallites, are responsible for the different morphologies of the monolayer films on the unmodified and sulfonated substrates. Two distinct growth mechanisms are proposed which can satisfactorily account for the different crystallite orientations in the two ZrPP films.

  5. Pressure-Induced Oriented Attachment Growth of Large-Size Crystals for Constructing 3D Ordered Superstructures.

    Science.gov (United States)

    Wang, Jun; Lian, Gang; Si, Haibin; Wang, Qilong; Cui, Deliang; Wong, Ching-Ping

    2016-01-26

    Oriented attachment (OA), a nonclassical crystal growth mechanism, provides a powerful bottom-up approach to obtain ordered superstructures, which also demonstrate exciting charge transmission characteristic. However, there is little work observably pronouncing the achievement of 3D OA growth of crystallites with large size (e.g., submicrometer crystals). Here, we report that SnO2 3D ordered superstructures can be synthesized by means of a self-limited assembly assisted by OA in a designed high-pressure solvothermal system. The size of primary building blocks is 200-250 nm, which is significantly larger than that in previous results (normally pressure plays the key role in the formation of 3D configuration and fusion of adjacent crystals. Furthermore, this high-pressure strategy can be readily expanded to additional materials. We anticipate that the welded structures will constitute an ideal system with relevance to applications in optical responses, lithium ion battery, solar cells, and chemical sensing.

  6. Incorporation of Eu(III) into Calcite under Recrystallization conditions.

    Science.gov (United States)

    Hellebrandt, S E; Hofmann, S; Jordan, N; Barkleit, A; Schmidt, M

    2016-09-13

    The interaction of calcite with trivalent europium under recrystallization conditions was studied on the molecular level using site-selective time-resolved laser fluorescence spectroscopy (TRLFS). We conducted batch studies with a reaction time from seven days up to three years with three calcite powders, which differed in their specific surface area, recrystallization rates and impurities content. With increase of the recrystallization rate incorporation of Eu(3+) occurs faster and its speciation comes to be dominated by one species with its excitation maximum at 578.8 nm, so far not identified during previous investigations of this process under growth and phase transformation conditions. A long lifetime of 3750 μs demonstrates complete loss of hydration, consequently Eu must have been incorporated into the bulk crystal. The results show a strong dependence of the incorporation kinetics on the recrystallization rate of the different calcites. Furthermore the investigation of the effect of different background electrolytes (NaCl and KCl) demonstrate that the incorporation process under recrystallization conditions strongly depends on the availability of Na(+). These findings emphasize the different retention potential of calcite as a primary and secondary mineral e.g. in a nuclear waste disposal site.

  7. Incorporation of Eu(III) into Calcite under Recrystallization conditions

    Science.gov (United States)

    Hellebrandt, S. E.; Hofmann, S.; Jordan, N.; Barkleit, A.; Schmidt, M.

    2016-09-01

    The interaction of calcite with trivalent europium under recrystallization conditions was studied on the molecular level using site-selective time-resolved laser fluorescence spectroscopy (TRLFS). We conducted batch studies with a reaction time from seven days up to three years with three calcite powders, which differed in their specific surface area, recrystallization rates and impurities content. With increase of the recrystallization rate incorporation of Eu3+ occurs faster and its speciation comes to be dominated by one species with its excitation maximum at 578.8 nm, so far not identified during previous investigations of this process under growth and phase transformation conditions. A long lifetime of 3750 μs demonstrates complete loss of hydration, consequently Eu must have been incorporated into the bulk crystal. The results show a strong dependence of the incorporation kinetics on the recrystallization rate of the different calcites. Furthermore the investigation of the effect of different background electrolytes (NaCl and KCl) demonstrate that the incorporation process under recrystallization conditions strongly depends on the availability of Na+. These findings emphasize the different retention potential of calcite as a primary and secondary mineral e.g. in a nuclear waste disposal site.

  8. Polarized fluorescent emission in uniaxial liquid crystals. The effect of intramolecular energy transfer and rotational Brownian motion on measurements of the orientational distribution function

    DEFF Research Database (Denmark)

    Chapoy, Larry Lawrence; DuPré, Donald B.

    1978-01-01

    An expression is derived for the anisotropic fluorescent emission in uniaxial liquid crystals where fluorescent sites governed by an initial nonrandom distribution of orientations are subject to rotational Brownian motion. The possibility of nonparallelism of absorption and emission oscillators...

  9. Surface chemistry of the preferred (111) and (220) crystal oriented microcrystalline Si films by radio-frequency plasma-enhanced chemical vapor deposition

    Energy Technology Data Exchange (ETDEWEB)

    Ohba, Daisuke; Koshino, Hideto; Tang, Zeguo; Shirai, Hajime [Graduate School of Science and Engineering, Saitama University, Sakura (Japan)

    2011-10-15

    The surface chemistry of the preferentially (111) and (220) crystal orientated chlorinated hydrogenated microcrystalline silicon ({mu}c-Si:H:Cl) films was studied using a rf PE-CVD of a dichlorosilane (SiH{sub 2}Cl{sub 2}) and H{sub 2} mixture. The growing surface for the preferentially (220) crystal oriented {mu}c-Si:H:Cl films included much voids and dangling bonds, whereas the growing surface with the preferential (111) crystal orientation was chemically stable relatively. These findings suggest that the sticking process of deposition precursors and/or the reconstruction of Si clusters within the sub-surface determine the preferential crystal orientation. (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  10. Fracture-aperture alteration induced by calcite precipitation

    Science.gov (United States)

    Jones, T.; Detwiler, R. L.

    2013-12-01

    Mineral precipitation significantly alters the transport properties of fractured rock. Chemical solubility gradients that favor precipitation induce mineral growth, which decreases the local aperture and alters preferential flow paths. Understanding the resulting development of spatial heterogeneities is necessary to predict the evolution of transport properties in the subsurface. We present experimental results that quantify the relationship between mineral precipitation and aperture alteration in a transparent analog fracture, 7.62cm x 7.62cm, with a uniform aperture of ~200 μm. Prior to flow experiments, a pump circulated a super-saturated calcite solution over the bottom glass, coating the glass surface with calcite. This method of seeding resulted in clusters of calcite crystals with large reactive surface area and provided micro-scale variability in the aperture field. A continuous flow syringe pump injected a reactive fluid into the fracture at 0.5 ml/min. The fluid was a mixture of sodium bicarbonate (NaHCO3, 0.02M) and calcium chloride (CaCl2 0.0004M) with a saturation index, Ω, of 8.51 with respect to calcite. A strobed LED panel backlit the fracture and a high-resolution CCD camera monitored changes in transmitted light intensity. Light transmission techniques provided a quantitative measurement of fracture aperture over the flow field. Results from these preliminary experiments showed growth near the inlet of the fracture, with decreasing precipitation rates in the flow direction. Over a period of two weeks, the fracture aperture decreased by 17% within the first 4mm of the inlet. Newly precipitated calcite bridged individual crystal clusters and smoothed the reacting surface. This observation is an interesting contradiction to the expectation of surface roughening induced by mineral growth. Additionally, the aperture decreased uniformly across the width of the fracture due to the initial aperture distribution. Future experiments of precipitation

  11. High orientation Al films growth on LiNbO3 single crystal and its adhesion

    Institute of Scientific and Technical Information of China (English)

    LI Dong-mei; CHEN Jing-jing; PAN Feng

    2004-01-01

    High orientation Al films were deposited on 64°Y-XLiNbO3 substrate by DC magnetron sputtering and the influence of deposition temperature on microstructure and adhesion properties of Al films were investigated. The results show that crystallographic orientation of films varies with substrate temperature and the adhesion strength between LiNbO3 and Al films strongly depends on crystallographic orientation of Al films. The (111) orientated Al films shows stronger adhesion strength to LiNbO3 substrate than (100) orientated films. There is an optimum substrate temperature of 60 ℃ and hardening temperature of 200 ℃ for obtaining high (111) orientated Al films with good surface structure and adhesion property. Using this Al film, we have successfully fabricated the SAW filters with high frequency of about 1.89 GHz.

  12. Shock-induced devolatilization of calcite

    Science.gov (United States)

    Boslough, M. B.; Ahrens, T. J.; Vizgirda, J.; Becker, R. H.; Epstein, S.

    1982-01-01

    Experimental measurements of the release adiabats by Vizgirda (1981) indicate that substantial vaporization takes place upon release from shock pressures of 37 GPa for calcite and 14 GPa for aragonite. The present investigation includes the first controlled partial vaporization experiments on calcite. The experiments were conducted to test the predictions of the release adiabat experiments. The quantities of the gaseous species produced from shocked calcite and their carbon and oxygen isotopic compositions were determined, and the shock-induced effect on the Mn(2+) electron spin resonance spectrum in the shock-recovered calcite was observed. On the basis of the obtained results, it is concluded that shock stresses at the 17-18 GPa level give rise to volatilization of 0.03-0.3 (mole) percent of calcite to CO2 and CO. The devolatilization of calcite occurs at low pressure at significantly lower entropy densities than predicted on the basis of thermodynamic continuum models.

  13. Oriented crystallization and mechanical properties of polypropylene nucleated on fibrillated polytetrafluoroethylene scaffolds

    NARCIS (Netherlands)

    Meer, van der Douwe W.; Milazzo, Daniel; Sanguineti, Aldo; Vancso, G. Julius

    2005-01-01

    It is known that friction deposited polytetrafluoroethylene (PTFE) layers are able to nucleate crystallization of thin films of isotactic polypropylene (iPP). In order to investigate the influence of PTFE on the crystallization behavior and morphology of iPP in bulk, PTFE-particles of two different

  14. Direct nanoscale observations of the coupled dissolution of calcite and dolomite and the precipitation of gypsum.

    Science.gov (United States)

    Offeddu, Francesco Giancarlo; Cama, Jordi; Soler, Josep Maria; Putnis, Christine V

    2014-01-01

    In-situ atomic force microscopy (AFM) experiments were performed to study the overall process of dissolution of common carbonate minerals (calcite and dolomite) and precipitation of gypsum in Na2SO4 and CaSO4 solutions with pH values ranging from 2 to 6 at room temperature (23 ± 1 °C). The dissolution of the carbonate minerals took place at the (104) cleavage surfaces in sulfate-rich solutions undersaturated with respect to gypsum, by the formation of characteristic rhombohedral-shaped etch pits. Rounding of the etch pit corners was observed as solutions approached close-to-equilibrium conditions with respect to calcite. The calculated dissolution rates of calcite at pH 4.8 and 5.6 agreed with the values reported in the literature. When using solutions previously equilibrated with respect to gypsum, gypsum precipitation coupled with calcite dissolution showed short gypsum nucleation induction times. The gypsum precipitate quickly coated the calcite surface, forming arrow-like forms parallel to the crystallographic orientations of the calcite etch pits. Gypsum precipitation coupled with dolomite dissolution was slower than that of calcite, indicating the dissolution rate to be the rate-controlling step. The resulting gypsum coating partially covered the surface during the experimental duration of a few hours.

  15. Influence of surface conductivity on the apparent zeta potential of calcite.

    Science.gov (United States)

    Li, Shuai; Leroy, Philippe; Heberling, Frank; Devau, Nicolas; Jougnot, Damien; Chiaberge, Christophe

    2016-04-15

    Zeta potential is a physicochemical parameter of particular importance in describing the surface electrical properties of charged porous media. However, the zeta potential of calcite is still poorly known because of the difficulty to interpret streaming potential experiments. The Helmholtz-Smoluchowski (HS) equation is widely used to estimate the apparent zeta potential from these experiments. However, this equation neglects the influence of surface conductivity on streaming potential. We present streaming potential and electrical conductivity measurements on a calcite powder in contact with an aqueous NaCl electrolyte. Our streaming potential model corrects the apparent zeta potential of calcite by accounting for the influence of surface conductivity and flow regime. We show that the HS equation seriously underestimates the zeta potential of calcite, particularly when the electrolyte is diluted (ionic strength ⩽ 0.01 M) because of calcite surface conductivity. The basic Stern model successfully predicted the corrected zeta potential by assuming that the zeta potential is located at the outer Helmholtz plane, i.e. without considering a stagnant diffuse layer at the calcite-water interface. The surface conductivity of calcite crystals was inferred from electrical conductivity measurements and computed using our basic Stern model. Surface conductivity was also successfully predicted by our surface complexation model.

  16. Birefringence imaging and orientation of laser patterned β-BaB{sub 2}O{sub 4} crystals with bending and curved shapes in glass

    Energy Technology Data Exchange (ETDEWEB)

    Ogawa, Kazuki; Honma, Tsuyoshi; Komatsu, Takayuki, E-mail: komatsu@mst.nagaokaut.ac.jp

    2013-11-15

    Nonlinear optical β-BaB{sub 2}O{sub 4} crystals (β-BBO) with bending and curved shapes were patterned at the surface of 8Sm{sub 2}O{sub 3}–42BaO–50B{sub 2}O{sub 3} glass by laser irradiations (Yb:YVO{sub 4} laser with a wavelength of 1080 nm, power of 0.8 W, and scanning speed of 4 μm/s), and the orientation state of β-BBO crystals was examined from the birefringence imaging obtained by polarization optical microscope (POM) observations. The formation (crystallization) of β-BBO crystals follows along laser scanning direction even if the laser scanning direction changes at a certain point within the bending angle of 60°. The birefringence images indicate that the formation of highly c-axis oriented β-BBO crystals follows along laser scanning direction even if the laser scanning direction changes, and in particular the direction of the c-axis of β-BBO crystals changes gradually at the bending point. The model for the orientation of the c-axis of β-BBO near the bending point is proposed. The present study proposes that the laser-induced crystallization opens a new door for the science and technology in crystal growth engineering. - Graphical abstract: This figure shows the birefringence images obtained by the Abrio IM imaging system (λ=546 nm) for the laser-patterned β-BaB{sub 2}O{sub 4} crystal line with the bending angle of 45° in the glass. The relation between the direction of slow axis and color is also shown. It is demonstrated that the formation (crystallization) of highly c-axis oriented β-BaB{sub 2}O{sub 4} crystals follows along laser scanning direction even if the laser scanning direction changes. Display Omitted - Highlights: • β-BaB{sub 2}O{sub 4} crystals with bending and curved shapes were patterned by laser irradiations. • The orientation was examined from the birefringence imaging. • Highly c-axis oriented crystals follows along laser scanning direction. • The c-axis direction changes gradually at the bending point. • The

  17. Adsorption and hydrogenation of simple alkenes at Pt-group metal electrodes studied by DEMS: influence of the crystal orientation

    Science.gov (United States)

    Müller, Ulrich; Schmiemann, Udo; Dülberg, Andreas; Baltruschat, Helmut

    1995-07-01

    The adsorption of ethene and cyclohexene on mono-and polycrystalline Pt and on polycrystalline Pd electrodes was studied using differential electrochemical mass spectrometry (DEMS). Both molecules are partially hydrated to an oxygen containing species upon adsorption on Pt. In the case of ethene, this species dissociated to methane and adsorbed CO at negative potentials. Another part of the adsorbed ethene can be cathodically desorbed as ethane and butane. The ratio of the various species formed strongly depends on crystal orientation and adsorption potential. Contrary to heterogenous gas phase hydrogenation (and also contrary to some earlier reports on electrochemical hydrogenation), the rate of the Faradaic hydrogenation reaction is also strongly dependent on the crystallographic orientation, being faster on Pt(110) or roughened surfaces. During hydrogenation, H/D exchange occurs to an appreciable degree, suggesting the participation of adsorbed intermediates.

  18. Thermotropic orientational order of discotic liquid crystals in nanochannels: an optical polarimetry study and a Landau-de Gennes analysis.

    Science.gov (United States)

    Kityk, Andriy V; Busch, Mark; Rau, Daniel; Calus, Sylwia; Cerclier, Carole V; Lefort, Ronan; Morineau, Denis; Grelet, Eric; Krause, Christina; Schönhals, Andreas; Frick, Bernhard; Huber, Patrick

    2014-07-07

    Optical polarimetry measurements of the orientational order of a discotic liquid crystal based on a pyrene derivative confined in parallelly aligned nanochannels of monolithic, mesoporous alumina, silica, and silicon as a function of temperature, channel radius (3-22 nm) and surface chemistry reveal a competition of radial and axial columnar orders. The evolution of the orientational order parameter of the confined systems is continuous, in contrast to the discontinuous transition in the bulk. For channel radii larger than 10 nm we suggest several, alternative defect structures, which are compatible both with the optical experiments on the collective molecular orientation presented here and with a translational, radial columnar order reported in previous diffraction studies. For smaller channel radii our observations can semi-quantitatively be described by a Landau-de Gennes model with a nematic shell of radially ordered columns (affected by elastic splay deformations) that coexists with an orientationally disordered, isotropic core. For these structures, the cylindrical phase boundaries are predicted to move from the channel walls to the channel centres upon cooling, and vice-versa upon heating, in accord with the pronounced cooling/heating hystereses observed and the scaling behavior of the transition temperatures with the channel diameter. The absence of experimental hints of a paranematic state is consistent with a biquadratic coupling of the splay deformations to the order parameter.

  19. Boosting Photon Harvesting in Organic Solar Cells with Highly Oriented Molecular Crystals via Graphene-Organic Heterointerface.

    Science.gov (United States)

    Jo, Sae Byeok; Kim, Hyun Ho; Lee, Hansol; Kang, Boseok; Lee, Seongkyu; Sim, Myungsun; Kim, Min; Lee, Wi Hyoung; Cho, Kilwon

    2015-08-25

    Photon harvesting in organic solar cells is highly dependent on the anisotropic nature of the optoelectronic properties of photoactive materials. Here, we demonstrate an efficient approach to dramatically enhance photon harvesting in planar heterojunction solar cells by using a graphene-organic heterointerface. A large area, residue-free monolayer graphene is inserted at anode interface to serve as an atomically thin epitaxial template for growing highly orientated pentacene crystals with lying-down orientation. This anisotropic orientation enhances the overall optoelectronic properties, including light absorption, charge carrier lifetime, interfacial energetics, and especially the exciton diffusion length. Spectroscopic and crystallographic analysis reveal that the lying-down orientation persists until a thickness of 110 nm, which, along with increased exciton diffusion length up to nearly 100 nm, allows the device optimum thickness to be doubled to yield significantly enhanced light absorption within the photoactive layers. The resultant photovoltaic performance shows simultaneous increment in Voc, Jsc, and FF, and consequently a 5 times increment in the maximum power conversion efficiency than the equivalent devices without a graphene layer. The present findings indicate that controlling organic-graphene heterointerface could provide a design strategy of organic solar cell architecture for boosting photon harvesting.

  20. Magnetocrystalline Anisotropy and Magnetoelasticity of Preferentially Oriented Martensitic Variants in Ni52Mn24Ga24 Single Crystals

    Institute of Scientific and Technical Information of China (English)

    曲静萍; 王文洪; 孟凡斌; 刘宝丹; 柳祝红; 陈京兰; 李养贤; 吴光恒

    2002-01-01

    The magnetocrystalline anisotropy and magnetoelasticity of preferentially oriented martensitic variants in an off-stoichiometric Nis2Mn24Ga24 single crystal have been investigated. We found that the easy magnetization direction of the martensite phase is the [110] direction, and the hard magnetization exhibited in [001], the growth direction of single crystals. The temperature dependence of the anisotropy fields and constants of Ni52Mn24 Ga24 have been determined. It was found that, at the martensite phase, the anisotropy field increases monotonically with decreasing temperature, but the anisotropy constant first increases rapidly and then the increasing rate becomes smaller and smaller. Based on a previous model, the present results suggest that the competition between the Zeeman energy and the magnetocrystalline anisotropy energy is mainly responsible for the magnitude of magnetic-field-induced strain in this material.

  1. Orientational instabilities in nematic liquid crystals with weak anchoring under combined action of steady flow and external fields.

    Science.gov (United States)

    Nasibullayev, I Sh; Tarasov, O S; Krekhov, A P; Kramer, L

    2005-11-01

    We study the homogeneous and the spatially periodic instabilities in a nematic liquid crystal layer subjected to steady plane Couette or Poiseuille flow. The initial director orientation is perpendicular to the flow plane. Weak anchoring at the confining plates and the influence of the external electric and/or magnetic field are taken into account. Approximate expressions for the critical shear rate are presented and compared with semianalytical solutions in case of Couette flow and numerical solutions of the full set of nematodynamic equations for Poiseuille flow. In particular the dependence of the type of instability and the threshold on the azimuthal and the polar anchoring strength and external fields is analyzed.

  2. Microcracking in calcite and dolomite marble: microstructural influences and effects on properties

    OpenAIRE

    Shushakova, Victoria; Fuller, Edwin; Siegesmund, Siegfried

    2012-01-01

    Microstructure‐based finite-element analysis with a microcracking algorithm was used to simulate an actual degradation phenomenon of marble structures, i.e., microcracking. Both microcrack initiation and crack propagation were characterized, as were their dependence on lattice preferred orientation (LPO), grain shape preferred orientation (SPO), grain size, marble composition (calcite and dolomite) and grain‐boundary fracture toughness. Two LPOs were analyzed: a random orientation distributio...

  3. Study of Ice Crystal Orientation in Cirrus Clouds based on Satellite Polarized Radiance Measurements

    OpenAIRE

    Noel, Vincent; Chepfer, Hélène

    2004-01-01

    International audience; The goal of this paper is to retrieve information about ice particle orientation in cirrus clouds. This is achieved by comparing simulations of sunlight reflection on a cirrus cloud with measurements of polarized radiances from the spaceborne instrument Polarization and Directionality of the Earth's Reflectance (POLDER-1) on Advanced Earth Observing Satellite-1 (ADEOS-1). Results show that horizontal orientation of cr ystals can be spotted by the presence of a local ma...

  4. Cryogenic and non-cryogenic pool calcites reflect alternating permafrost and interglacial periods (Breitscheid-Erdbach Cave, Germany

    Directory of Open Access Journals (Sweden)

    D. K. Richter

    2010-07-01

    Full Text Available Weichselian cryogenic calcites collected in what is referred to as the "Rätselhalle" of the Breitscheid-Erdbach Cave were structurally classified as rhombohedral crystal and spherulitic crystal sinters. The carbon and oxygen isotopic composition of these precipitates corresponds to those of known cryogenic calcites of slow genesis of Central European caves (δ13C=+0.6 and −7.3‰; δ18O=−6.9 to −18.0‰. The variant carbon and oxygen isotope pattern differing between different caves is attributed to cave specific ventilation. Particularly, Breitscheid cryogenic calcites reflect mean levels of cave ventilation. By petrographic and geochemical comparisons of Weichselian cryogenic calcite with recent to sub-recent precipitates as well as Weichselian non-cryogenic calcites of the same locality, a model for the precipitation of these calcites is proposed. While the recent and sub-recent pool-calcites isotopically match the geochemistry of interglacial speleothems (stalagmites, etc., isotope ratios of Weichselian non-cryogenic pool-calcites reflect cooler conditions. Weichselian cryogenic calcites show a trend towards 18O-depleted values with higher carbon isotope ratios reflecting slow freezing of the precipitating solution. In essence, the isotope geochemistry of the Weichselian calcites reflects the climate history changing from overall initial permafrost (glacial conditions to an interglacial and subsequently to renewed permafrost conditions. The last stage then grades into the present-day warm period. Judging from the data compiled here, the last permafrost stage is followed by only one interglacial. During this interglacial, the cave ice melted and non-cryogenic Weichselian calcite precipitates were deposited on the cave ground or on fallen blocks, respectively.

  5. Large Area Single Crystal (0001) Oriented MoS2 Thin Films

    OpenAIRE

    Laskar, Masihhur R.; Ma, Lu; K, ShanthaKumar; Park, Pil Sung; Krishnamoorthy, Sriram; Nath, Digbijoy N.; Lu, Wu; Wu, Yiying; Rajan, Siddharth

    2013-01-01

    Layered metal dichalcogenide materials are a family of semiconductors with a wide range of energy band gaps and properties, and potential to open up new areas of physics and technology applications. However, obtaining high crystal quality thin films over a large area remains a challenge. Here we show that chemical vapor deposition (CVD) can be used to achieve large area electronic grade single crystal Molybdenum Disulfide (MoS2) thin films with the highest mobility reported in CVD grown films...

  6. The potential for phosphorus pollution remediation by calcite precipitation in UK freshwaters

    Directory of Open Access Journals (Sweden)

    C. Neal

    2001-01-01

    Full Text Available This paper examines the potential for calcium carbonate to reduce phosphate pollution in freshwaters by co-precipitation, a process known as a "self cleansing mechanism". Calcium carbonate saturation levels and phosphate concentrations (SRP - soluble reactive phosphate across the major eastern UK river basins are examined to test for solubility controls. The study shows that calcite saturation varies for each catchment as a function of flow and biological activity rather than by direct regulation by SRP. Indeed, there is no evidence, for any of the rivers studied, that calcite solubility controls hold. However, for groundwater and groundwater-fed springs in the Chalk of the Thames basin, calcite saturation is observed with associated low SRP levels. A self-cleansing mechanism may well be operative within the Chalk due to two factors. Firstly, there is a high potential for nucleation on the calcite micro-crystals in the aquifer. Secondly, there are within aquifer reactions that remove the calcite nucleating inhibitors (SRP and dissolved organic carbon, DOC to levels lower than those occurring within the rivers do. These inhibitors enter the catchment at very high concentrations in association with agricultural pollution (fertilizer application and animal slurry and household contamination (e.g. sewage sources from septic tanks. Under low flow conditions, when the saturation index for calcite is at its highest, so too is the concentration of the nucleation inhibitor SRP. Companion work shows that calcite precipitation can occur at the water-sediment interface of the river and this may involve SRP removal. The data, as a whole, define an apparent bound for calcite solubility control where in the presence of nucleating centres, SRP must be less than 4 mM-P l-1 and DOC must be less than 150 mM-C l-1: a condition that does not seem to pertain within most UK rivers. Keywords: calcite, calcium carbonate, phosphate, soluble reactive phosphate, dissolved

  7. Investigation of design parameters and choice of substrate resistivity and crystal orientation for the CMS silicon microstrip detector

    CERN Document Server

    Braibant, S

    2000-01-01

    The electrical characteristics ( interstrip and backplane capacitance, leakage current, depletion and breakdown voltage) of silicon microstrip detectors were measured for strip pitches between 60 um and 240 um and various strip implant and metal widths on multi-geometry devices. Both AC and DC coupled devices wereinvestigated. Measurements on detectors were performed before and after irradiation with 24 GeV/c protons up to a fluence of 4.1x10E14 cm-2. We found that the total strip capacitance can be parametrized as a linear function of the ratio of the implant width over the read-out pitch only. We found a significant increase in the interstrip capacitance after radiation on detectors with standard <111> crystal orientation but not on sensors with <100> crystal orientation. We analyzed the measured depletion voltages as a function of the detector geometrical parameters ( read-out pitch, strip width and substrate thickness) found in the literature and we found a linear dependence in...

  8. ARTICLES: Orientation in Nematic Liquid Crystals Doped with Orange Dyes and Effect of Carbon Nanoparticles

    Science.gov (United States)

    Alicilar, Ahmet; Akkurt, Fatih; Kaya, Nihan

    2010-06-01

    Some properties of nematic liquid crystal E7 doped with two disperse orange dyes used together and effect of addition of carbon nanoparticles (single walled carbon nanotube or fullerene C60) on them were studied. Two dyes (disperse orange 11 and 13) having high solubility and order parameter were used as co-dopants. A notable increase in order parameter was obtained comparing to that of liquid crystal doped with single dye. When carbon nanoparticles were used as dopant, a decrease in order parameter was observed at low temperatures while it increased at high temperatures. When applied voltage changed, the order parameter abruptly increased in its threshold value and saturated in higher voltages as expected. An appreciable change in textures was not observed with addition of dopants. This addition gave rise to an increase in nematic-isotropic phase transition temperatures compared with that of pure liquid crystal.

  9. Heterogeneous growth of cadmium and cobalt carbonate phases at the (101¯4) calcite surface

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Man; Ilton, Eugene S.; Engelhard, Mark H.; Qafoku, Odeta; Felmy, Andrew R.; Rosso, Kevin M.; Kerisit, Sebastien N.

    2015-03-01

    The ability of surface precipitates to form heteroepitaxially is an important factor that controls the extent of heterogeneous growth. In this work, the growth of cadmium and cobalt carbonate phases on (10-14) calcite surfaces is compared for a range of initial saturation states with respect to otavite (CdCO3) and sphaerocobaltite (CoCO3), two isostructural metal carbonates that exhibit different lattice misfits with respect to calcite. Calcite single crystals were reacted in static conditions for 16 hours with CdCl2 and CoCl2 aqueous solutions with initial concentrations 0.3 ≤ [Cd2+]0 ≤ 100 μM and 25 ≤ [Co2+]0 ≤ 200 μM. The reacted crystals were imaged in situ with atomic force microscopy (AFM) and analyzed ex situ with X-ray photoelectron spectroscopy (XPS). AFM images of Cd-reacted crystals showed the formation of large islands elongated along the direction, clear evidence of heteroepitaxial growth, whereas surface precipitates on Co-reacted crystals were small round islands. Deformation of calcite etch pits in both cases indicated the incorporation of Cd and Co at step edges. XPS analysis pointed to the formation of a Cd-rich (Ca,Cd)CO3 solid solution coating atop the calcite substrate. In contrast, XPS measurements of the Co-reacted crystals provided evidence for the formation of a mixed hydroxy-carbonate cobalt phase. The combined AFM and XPS results suggest that the lattice misfit between CoCO3 and CaCO3 ( 15% based on surface areas) is too large to allow for heteroepitaxial growth of a pure cobalt carbonate phase on calcite surfaces in aqueous solutions and at ambient conditions. The use of the satellite structure of the Co 2p3/2 photoelectron line as a tool for determining the nature of cobalt surface precipitates is also discussed.

  10. Pyroelectric and electrocaloric effect of <1 1 1>-oriented 0.9PMN-0.1PT single crystal

    Energy Technology Data Exchange (ETDEWEB)

    Luo Laihui, E-mail: llhsic@126.com [Department of Physics, Ningbo University, Ningbo 315211 (China); Chen Hongbing [Institute of Materials Science and Engineering, Ningbo University, Ningbo 315211 (China); Zhu Yuejin; Li Weiping [Department of Physics, Ningbo University, Ningbo 315211 (China); Luo Haosu [Shanghai Institute of ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Zhang Yuepin [Department of Physics, Ningbo University, Ningbo 315211 (China)

    2011-08-11

    Highlights: > Here, we use indirect method to measure pyroelectric and electrocaloric effect. > The largest temperature change achieves {approx}1 deg. C with a small field change. > The mechanism of electrocaloric effect of PMN-PT is explained. > The largest ({partial_derivative}P/{partial_derivative}T){sub E} value achieves -0.5 {mu}C/cm{sup 2} K. > PMN-PT has excellent pyroelectric effect. - Abstract: In this paper, the polarization vs. electric field hysteresis loops of <1 1 1>-oriented 0.9PbMg{sub 1/3}Nb{sub 2/3}O{sub 3}-0.1PbTiO{sub 3} (0.9PMN-0.1PT) single crystal at different temperatures (20-110 deg. C) were measured. The adiabatic temperature change {Delta}T of <1 1 1>-oriented 0.9PMN-0.1PT single crystal due to the application or withdraw of electric field were calculated through the thermodynamic relation. The largest temperature change {Delta}T achieves {approx}1 K with only a change of 40 kV/cm electric field, the mechanism of the electrocaloric effect (ECE) is discussed for 0.9PMN-0.1PT crystal. The pyroelectric coefficient of 0.9PMN-0.1PT under bias field was calculated according to the data of hysteresis loop. The result shows that 0.9PMN-0.1PT have large pyroelectric coefficient under bias field, the largest ({partial_derivative}P/{partial_derivative}T){sub E} value achieves -0.5 {mu}C/cm{sup 2} K.

  11. Crystal structure of importin-{alpha} complexed with a classic nuclear localization sequence obtained by oriented peptide library screening

    Energy Technology Data Exchange (ETDEWEB)

    Takeda, A.A.S.; Fontes, M.R.M. [UNESP, Universidade Estadual Paulista, Botucatu, SP (Brazil); Yang, S.N.Y. [University of Melbourne, Melbourne (Australia); Harris, J.M. [Queensland University of Technology, Brisbane (Australia); Jans, D.A. [Monash University, Clayton (Australia); Kobe, B. [University of Queensland, Brisbane, QU (Australia)

    2012-07-01

    Full text: Importin-{alpha} (Imp{alpha}) plays a role in the classical nuclear import pathway, binding to cargo proteins with activities in the nucleus. Different Imp{alpha} paralogs responsible for specific cargos can be found in a single organism. The cargos contain nuclear localization sequences (NLSs), which are characterized by one or two clusters of basic amino acids (monopartite and bipartite NLSs, respectively). In this work we present the crystal structure of Imp{alpha} from M. musculus (residues 70-529, lacking the auto inhibitory domain) bound to a NLS peptide (pepTM). The peptide corresponds to the optimal sequence obtained by an oriented peptide library experiment designed to probe the specificity of the major NLS binding site. The peptide library used five degenerate positions and identified the sequence KKKRR as the optimal sequence for binding to this site for mouse Imp{alpha} (70-529). The protein was obtained using an E. coli expression system and purified by affinity chromatography followed by an ion exchange chromatography. A single crystal of Imp{alpha} -pepTM complex was grown by the hanging drop method. The data were collected using the Synchrotron Radiation Source LNLS, Brazil and processed to 2.3. Molecular replacement techniques were used to determine the crystal structure. Electron density corresponding to the peptide was present in both major and minor binding sites The peptide is bound to Imp{alpha} similar as the simian virus 40 (SV40) large tumour (T)-antigen NLS. Binding assays confirmed that the peptide bound to Imp{alpha} with low nM affinities. This is the first time that structural information has been linked to an oriented peptide library screening approach for importin-{alpha}; the results will contribute to understanding of the sequence determinants of classical NLSs, and may help identify as yet unidentified classical NLSs in novel proteins. (author)

  12. Coupled Crystal Plasticity-Phase Field Fracture Simulation Study on Damage Evolution Around a Void: Pore Shape Versus Crystallographic Orientation

    Science.gov (United States)

    Diehl, Martin; Wicke, Marcel; Shanthraj, Pratheek; Roters, Franz; Brueckner-Foit, Angelika; Raabe, Dierk

    2017-03-01

    Various mechanisms such as anisotropic plastic flow, damage nucleation, and crack propagation govern the overall mechanical response of structural materials. Understanding how these mechanisms interact, i.e. if they amplify mutually or compete with each other, is an essential prerequisite for the design of improved alloys. This study shows—by using the free and open source software DAMASK (the Düsseldorf Advanced Material Simulation Kit)—how the coupling of crystal plasticity and phase field fracture methods can increase the understanding of the complex interplay between crystallographic orientation and the geometry of a void. To this end, crack initiation and propagation around an experimentally obtained pore with complex shape is investigated and compared to the situation of a simplified spherical void. Three different crystallographic orientations of the aluminum matrix hosting the defects are considered. It is shown that crack initiation and propagation depend in a non-trivial way on crystallographic orientation and its associated plastic behavior as well as on the shape of the pore.

  13. Crystal orientation dependence of Young’s modulus in Ti-Nb-based β-titanium alloy

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The paper investigated the texture evolution of a biomedical β-titanium alloy (Ti-28Nb-13Zr-2Fe) under 15%-85% cold rolling reduction and 700°C-900°C recrystallization annealing treatment,and clarified the effects of crystal orientation on Young’s modulus of the alloy.Orientation distribution function (ODF) maps and electron backscatter diffraction (EBSD) analysis revealed that the rolling texture type changed with the increase of reduction according to the sequence:α-fiber texture→γ-fiber texture→α-rotated cubic texture.Young’s modulus exhibited the lowest value 54 GPa under 15% reduction.Strong {111}<112> γ-fiber texture was developed after rolling 85% reduction and annealing at 700°C,which was favorable to decreasing Young’s modulus in comparison with randomly orientated microstructure.Cyclic loading-unloading tensile test proved that the gradual rotation of {110} slip plane during plastic deformation promoted the development of {001}<110> texture component,leading to the marked decrease of Young’s modulus.

  14. X-ray and Raman scattering study of orientational order in nematic and heliconical nematic liquid crystals

    Science.gov (United States)

    Singh, Gautam; Fu, Jinxin; Agra-Kooijman, Dena M.; Song, Jang-Kun; Vengatesan, M. R.; Srinivasarao, Mohan; Fisch, Michael R.; Kumar, Satyendra

    2016-12-01

    The temperature dependence of the orientational order parameters cos β ) > and cos β ) > in the nematic (N ) and twist-bend nematic (Ntb) phases of the liquid crystal dimer CB7CB have been measured using x-ray and polarized Raman scattering. The cos β ) > obtained from both techniques are the same, while cos β ) > , determined by Raman scattering is, as expected, systematically larger than its x-ray value. Both order parameters increase in the N phase with decreasing temperature, drop across the N -Ntb transition, and continue to decrease. In the Ntb phase, the x-ray value of cos β ) > eventually becomes negative, providing a direct and independent confirmation of a conical molecular orientational distribution. The heliconical tilt angle α, determined from orientational distribution functions in the Ntb phase, increases to ˜24∘ at ˜15 K below the transition. In the Ntb phase, α (T ) ∝(T*-T)λ , with λ =0.19 ±0.03 . The transition supercools by 1.7 K, consistent with its weakly first-order nature. The value of λ is close to 0.25 indicating close proximity to a tricritical point.

  15. Growth and Crystal Orientation of ZnTe on m-Plane Sapphire with Nanofaceted Structure

    Science.gov (United States)

    Nakasu, Taizo; Sun, Wei-Che; Kobayashi, Masakazu; Asahi, Toshiaki

    2016-11-01

    ZnTe thin films on sapphire substrate with nanofaceted structure have been studied. The nanofaceted structure of the m-plane (10-10) sapphire was obtained by heating the substrate at above 1100°C in air, and the r-plane (10-12) and S-plane (1-101) were confirmed. ZnTe layers were prepared on the nanofaceted m-plane sapphire substrates by molecular beam epitaxy (MBE). The effect of the nanofaceted structure on the orientation of the thin films was examined based on x-ray diffraction (XRD) pole figures. Transmission electron microscopy (TEM) was also employed to characterize the interface structures. The ZnTe layer on the nanofaceted m-plane sapphire substrate exhibited (331)-plane orientation, compared with (211)-plane without the nanofaceted structure. After thermal treatment, the m-plane surface vanished and (211) layer could not be formed because of the lack of surface lattice matching. On the other hand, (331)-plane thin film was formed on the nanofaceted m-plane sapphire substrate, since the (111) ZnTe domains were oriented on the S-facet. The orientation of the ZnTe epilayer depended on the atomic ordering on the surface and the influence of the S-plane.

  16. Crystal orientation effects on the piezoelectric field of strained zinc-blende quantum-well structures

    DEFF Research Database (Denmark)

    Duggen, Lars; Willatzen, Morten; Lassen, Benny

    2008-01-01

    A three-layered zinc-blende quantum-well structure is analyzed subject to both static and dynamic conditions for different crystal growth directions taking into account piezoelectric effects and lattice mismatch. It is found that the strain component Szz in the quantum-well region strongly depend...

  17. Effect of crystal orientation on the phase diagrams, dielectric and piezoelectric properties of epitaxial BaTiO{sub 3} thin films

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Huaping, E-mail: wuhuaping@gmail.com, E-mail: hpwu@zjut.edu.cn [Key Laboratory of E& M (Zhejiang University of Technology), Ministry of Education & Zhejiang Province, Hangzhou 310014 (China); State Key Laboratory of Structural Analysis for Industrial Equipment, Dalian University of Technology, Dalian 116024 (China); Ma, Xuefu; Zhang, Zheng; Zeng, Jun; Chai, Guozhong [Key Laboratory of E& M (Zhejiang University of Technology), Ministry of Education & Zhejiang Province, Hangzhou 310014 (China); Wang, Jie [Department of Engineering Mechanics, School of Aeronautics and Astronautics, Zhejiang University, Hangzhou 310027 (China)

    2016-01-15

    The influence of crystal orientations on the phase diagrams, dielectric and piezoelectric properties of epitaxial BaTiO{sub 3} thin films has been investigated using an expanded nonlinear thermodynamic theory. The calculations reveal that crystal orientation has significant influence on the phase stability and phase transitions in the misfit strain-temperature phase diagrams. In particular, the (110) orientation leads to a lower symmetry and more complicated phase transition than the (111) orientation in BaTiO{sub 3} films. The increase of compressive strain will dramatically enhance the Curie temperature T{sub C} of (110)-oriented BaTiO{sub 3} films, which matches well with previous experimental data. The polarization components experience a great change across the boundaries of different phases at room temperature in both (110)- and (111)-oriented films, which leads to the huge dielectric and piezoelectric responses. A good agreement is found between the present thermodynamics calculation and previous first-principles calculations. Our work provides an insight into how to use crystal orientation, epitaxial strain and temperature to tune the structure and properties of ferroelectrics.

  18. Effect of crystal orientation on the phase diagrams, dielectric and piezoelectric properties of epitaxial BaTiO3 thin films

    Directory of Open Access Journals (Sweden)

    Huaping Wu

    2016-01-01

    Full Text Available The influence of crystal orientations on the phase diagrams, dielectric and piezoelectric properties of epitaxial BaTiO3 thin films has been investigated using an expanded nonlinear thermodynamic theory. The calculations reveal that crystal orientation has significant influence on the phase stability and phase transitions in the misfit strain-temperature phase diagrams. In particular, the (110 orientation leads to a lower symmetry and more complicated phase transition than the (111 orientation in BaTiO3 films. The increase of compressive strain will dramatically enhance the Curie temperature TC of (110-oriented BaTiO3 films, which matches well with previous experimental data. The polarization components experience a great change across the boundaries of different phases at room temperature in both (110- and (111-oriented films, which leads to the huge dielectric and piezoelectric responses. A good agreement is found between the present thermodynamics calculation and previous first-principles calculations. Our work provides an insight into how to use crystal orientation, epitaxial strain and temperature to tune the structure and properties of ferroelectrics.

  19. Simulating Succinate-Promoted Dissolution at Calcite {104} Steps

    Science.gov (United States)

    Mkhonto, D.; Sahai, N.

    2008-12-01

    Organic molecules of a wide range of molecular weights from small organic acids, amino-acids, acidic peptides and acidic proteins to humic and fulvic acids play a key role in modulating nucleation, crystal growth and dissolution of calcium carbonate polymorphs. In general, these acidic molecules inhibit calcite growth and, promote dissolution preferentially along specific crystallographic directions, in the process, regulating crystal shape and size, and even whether a metastable polymorph (e.g., vaterite or aragonite) is nucleated first. For example, chiral faces of calcite are selected by chiral amino-acids and the unusual {hk0} faces are expressed in the presence of amino-acids [Orme et al., 2001], and unusual heptagonal dissolution etch-pit are seen in the presence of succinate compared to the normal rhombohedral pits in water alone [Teng et al., 2006]. Thus, the presence of unusual crystal morphologies may indicate organic-mediated growth, thus serving as a biosignature. We have conducted the Molecular Dynamics (MD) simulations using the Consistent Valence Force Field (CVFF) as implemented in the FORCITE© module of the Materials Studio © software package (Accelrys, Inc. TM) to model the adsorption of succinate, a dicarboxylic acid, and charge- balancing Na+ ions on dry and hydrated steps in different directions on the {104} cleavage face of calcite [Mkhonto and Sahai, in prep.]. At the site of succinate adsorption, we find elongation of the interatomic distances (Ca-OCO3,i) between surface Ca2+ cation and the oxygen of the underlying inorganic CO32- anion the first surface layer of calcite, compared to the corresponding distances in the presence of water alone, suggesting greater ease of surface Ca2+ detachment. This result is consistent with the empirically observed increase in overall dissolution rate with succinate [Teng et al., 2006]. Furthermore, succinate adsorption lowers the step energies, which explains the appearance of steps in the unsusual [42

  20. [Study on the orientation of liquid crystals presented on the glass substrates spin-coated and functionalized with copper ions].

    Science.gov (United States)

    Wang, Shiming; Xiong, Xingliang; Zhang, Yan; Li, Guang; Chen, Mengmeng

    2013-06-01

    A stable, uniform, easily implemented, LC-based chemical and biological sensor substrate for orientations of liquid crystals (LCs) for a long-term is urgently needed for medical applications of the sensors. We proposed a use of spin-coating of copper perchlorate (Cu(ClO4)2), with five different concentrations(0-100mmol/L), directly on glass slides for fabricating a layer of chemically-sensitive copper ions. Observing the transmitted light with a polarized microscope, we found the luminosity of the light propagated through sensors deposited with copper ions started to weaken gradually after a certain time. The higher was the concentration of copper ions covered on the glass substrates of the sensors, the faster the weakening occurred, and the less time was needed for transmitted light to turn completely dark. But there was no change in luminosity of the transmitted light for the sensors without Cu(ClO4)2 spin-coating even after stored at room temperature (25 degrees C) for a whole day. When the Cu(ClO4)2 deposited sensors were stored within a drying oven at room temperature (25 degrees C) for 2 months, it was found that there vas almost no change in luminosity of the transmitted lights. The results showed that all the thin films of LC on glass slides functionalized with Cu(ClO4)2 could keep homeotropic and stable orientation for a long time; the concentration of Cu (ClO4)2I has an influence on the orientation response speed of LC from planar to perpendicular orientation.

  1. Interface charge behaviors of BaTiO3 film heterostructures with various crystal orientations

    Science.gov (United States)

    Zhang, Wei; Ouyang, Jun; Cheng, Hongbo; Yang, Qian; Kang, Limin; Zhang, Hua; Hu, Fangren

    2017-02-01

    Heteroepitaxial BaTiO3 ferroelectric films with (001), (110), and (111) orientations were grown on SrRuO3-buffered SrTiO3 substrates by magnetron sputtering. The leakage current and interface charge behaviors were systematically investigated. Without a discernible orientation-dependence behavior, the leakage current behaviors were all well described by a modified Schottky-contact model. On the basis of this theory, the interface charge state parameters, including dynamic dielectric constant, potential barriers, depletion layer width, effective space-charge density and hole concentration, and their evolution behaviors were analyzed in detail. They all exhibited anisotropic characteristics and were proved to be essentially attributed to the macrophysical properties of BaTiO3 film heterostructures.

  2. New morphology, symmetry, orientation and perfection of lysozyme crystals grown in a magnetic field when paramagnetic salts (NiCl 2, CoCl 2 and MnCl 2) are used as crystallizing agents

    Science.gov (United States)

    Yin, D. C.; Oda, Y.; Wakayama, N. I.; Ataka, M.

    2003-05-01

    Chlorides with different paramagnetic cations such as Ni 2+, Co 2+ and Mn 2+ were used as crystallizing agents instead of NaCl to crystallize hen egg-white lysozyme. NiCl 2 was found to give two types of crystals with different morphologies: one (roof-like) is a new type of orthorhombic P2 12 12 1 crystal with lattice constants a=79.0 Å, b=80.8 Å, and c=37.5 Å; the second is an ordinary tetragonal crystal of its characteristic shape with a= b=80 Å and c=38 Å. The appearance of the roof-like shape became dominant in the presence of a magnetic field. In the case of using CoCl 2 and MnCl 2, ordinary tetragonal crystals were formed. A striking fact was that the a-axis of the crystals oriented along the magnetic field when CoCl 2 was used, as opposed to the usual c-axis orientation. Large and optically perfect lysozyme crystals can be obtained in a magnetic field when NiCl 2 or MnCl 2 is used as a crystallizing agent. These profound effects of the paramagnetic cations may be caused by the coordination of Ni 2+ and Co 2+ ions to a lysozyme molecule, which was found by X-ray crystallography.

  3. Relationship between crystal growth mode, preferred orientation and magnetostriction of (Tb0.3Dy0.7)Fe1.95 alloys

    Institute of Scientific and Technical Information of China (English)

    ZHANG Shirong; LI Kuoshe; YU Dunbo; LI Yongsheng; YANG Hongchuan; LI Hongwei; TU Ganfeng

    2008-01-01

    The relationship between crystal growth mode, preferred orientation and magnetostrictive properties of (Tb0.3Dy0.7)Fe1.95 alloys was investigated at different directional solidification rates. The results showed that preferred orientation had a strong influence on the characteristics of (Tb0.3Dy0.7)Fe1.95 alloys. At lower solidification rates, the sample with preferred orientation showed larger low-field magnetostriction and apparent compressive stress effect. The excessive solidification rate resulted in failure of preferred orientation and a poor magnetostrictive performance. With an increase in solidification rates, the crystal growth modes changed gradually from cellular and primary dendrite morphology to developed dendritic morphology. In addition, domain configurations were observed using magnetic force microscopy, and the change of magnetostrictive properties was interpreted in terms of revealing the domain configurations.

  4. Experimental observation of the strong influence of crystal orientation on Electron Rutherford Backscattering Spectra

    Science.gov (United States)

    Vos, Maarten; Aizel, Koceila; Winkelmann, Aimo

    2010-06-01

    In Electron Rutherford Backscattering Spectroscopy (ERBS) energetic electrons (in our case up to 40 keV) impinge on a target and one measures the energy of elastically scattered electrons. This energy depends on the mass of the scattering atom, due to the recoil effect. This technique thus provides information about the sample composition. For single crystals the interaction of the projectile electron with the crystal potential modifies the angular intensity distribution of the scattered electrons. This leads, for example, to the well-known Kikuchi patterns. Here we investigate if such modified angular distribution has any influence on the intensity ratio of the observed elastic peaks in ERBS. Dramatic effects are found. Implications of these observations for quantitative surface analysis using energetic electrons are discussed.

  5. Properties of boron-doped epitaxial diamond layers grown on (110) oriented single crystal substrates

    OpenAIRE

    Mortet, Vincent; Pernot, J.; Jomard, F.; Soltani, A; Remes, Zdenek; Barjon, Julien; D'Haen, J; Haenen, Ken

    2015-01-01

    Boron doped diamond layers have been grown on (110) single crystal diamond substrates with B/C ratios up to 20 ppm in the gas phase. The surface of the diamond layers observed by scanning electron microscopy consists of (100) and (113) micro-facets. Fourier Transform Photocurrent Spectroscopy indicates substitutional boron incorporation. Electrical properties were measured using Hall effect from 150 to 1000 K. Secondary ion mass spectrometry analyses are consistent with the high incorporation...

  6. Unravelling the enigmatic origin of calcitic nanofibres in soils and caves: purely physicochemical or biogenic processes?

    Directory of Open Access Journals (Sweden)

    S. Bindschedler

    2014-01-01

    Full Text Available Calcitic nanofibres are ubiquitous habits of secondary calcium carbonate (CaCO3 accumulations observed in calcareous vadose environments. Despite their widespread occurrence, the origin of these nanofeatures remains enigmatic. Three possible mechanisms fuel the debate: (i purely physicochemical processes, (ii mineralization of rod-shaped bacteria, and (iii crystal precipitation on organic templates. Nanofibres can be either mineral (calcitic or organic in nature. They are very often observed in association with Needle Fibre Calcite (NFC, another typical secondary CaCO3 habit in terrestrial environments. This association has contributed to some confusion between both habits, however they are truly two distinct calcitic features and their recurrent association is likely to be an important fact to help understanding the origin of nanofibres. In this manuscript the different hypotheses that currently exist to explain the origin of calcitic nanofibres are critically reviewed. In addition to this, a new hypothesis for the origin of nanofibres is proposed based on the fact that current knowledge attributes a fungal origin to NFC. As this feature and nanofibres are recurrently observed together, a possible fungal origin for nanofibres which are associated with NFC is investigated. Sequential enzymatic digestion of the fungal cell wall of selected fungal species demonstrates that the fungal cell wall can be a source of organic nanofibres. The obtained organic nanofibres show a striking morphological resemblance when compared to their natural counterparts, emphasizing a fungal origin for part of the organic nanofibres observed in association with NFC. It is further hypothesized that these organic nanofibres may act as templates for calcite nucleation in a biologically-influenced mineralization process, generating calcitic nanofibres. This highlights the possible involvement of Fungi in CaCO3 biomineralization processes, a role still poorly documented at

  7. Colloidal-crystal-assisted patterning of crystalline materials.

    Science.gov (United States)

    Li, Cheng; Qi, Limin

    2010-04-06

    Colloidal crystals have shown great potential as versatile templates for the fabrication of patterned micro- and nanostructures with complex architectures and novel properties. The patterning of functional crystalline materials in two and three dimensions is essential to the realization of their applications in many technologically important fields. This article highlights some recent progress in the fabrication of 2D and 3D patterned crystalline materials with the assistance of colloidal crystals. By combining a bioinspired synthetic strategy based on a transient amorphous phase with a colloidal-crystal templating method, unique 3D ordered macroporous (3DOM) calcite single crystals can be created. Moreover, patterned arrays of regular ZnO nanopillars with controlled size, shape, and orientation can be fabricated via a facile wet chemical approach by using masks derived from monolayer colloidal crystals (MCC).

  8. Domain Rotation Simulation of the Magnetostriction Jump Effect of 〈110〉 Oriented TbDyFe Crystals

    Institute of Scientific and Technical Information of China (English)

    ZHANG Chang-Sheng; MA Tian-Yu; PAN Xing-Wen; YAN Mi

    2012-01-01

    The compressive pre-stress induced magnetostriction jump effect of an [-110] oriented TbDyFe crystal is simulated by tracking the initial redistribution of magnetic domains and their volume fraction evolutions under external magnetic fields. Through searching for the free energy minima within both (-110) and (110) planes, it is found that the axial compressive pre-stress not only switches magnetizations of the 35° domains toward the perpendicular plane, but also switches magnetizations of the 90° domains approaching the [110] direction. When increasing the stress magnitude, the volume fraction for 35° domains decreases and the one for the [110] domain increases rapidly. However, the volume fraction for the four 90° domains within the perpendicular plane first increases to a maximum under a certain stress magnitude and further decreases. The stress-induced anisotropy thereafter changes the volume fraction evolutions during the magnetization process, which explains well the magnetostriction jump effect.%The compressive pre-stress induced magnetostriction jump effect of an [(-1) 10] oriented TbDyFe crystal is simulated by tracking the initial redistribution of magnetic domains and their volune fraction evolutions under external magnetic fields.Through searching for the free energy minima within both ((-1) 10) and (110) planes,it is found that the axial compressive pre-stress not only switches magnetizations of the 35° domains toward the perpendicular plane,but also switches magnetizations of the 90° domains approaching the [110] direction.When increasing the stress magnitude,the volume fraction for 35° domains decreases and the one for the [110] domain increases rapidly.However,the volume fraction for the four 90° domains within the perpendicular plane first increases to a maximum under a certain stress magnitude and further decreases.The stress-induced anisotropy thereafter changes the volume fraction evolutions during the magnetization process,which explains

  9. Formation Process and Thermodynamic Poperties of Calcite

    Institute of Scientific and Technical Information of China (English)

    NAN,Zhao-Dong; SHI,Zuo-Yi; QIN,Mei; HOU,Wan-Guo; TAN,Zhi-Cheng

    2007-01-01

    The fast mixing of aqueous solutions of calcium chloride and sodium carbonate resulted in crystalline forms of vaterite and calcite under vigorous stirring. Then, the vaterite was transformed to pure calcite within about 180 min.The crystalline forms all grew with experimental time increase. Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and X-ray diffraction spectroscopy (XRD) techniques were employed to characterize the as-prepared samples. The heat capacity of the stable as-synthesized calcite was determined by means of an adiabatic calorimeter from 80 to 390 K. The thermodynamic functions of the calcite were derived based on the relationships among the thermodynamic functions and the function of the measured heat capacity with respect to temperature.

  10. Comparison of Dissolution and Surface Reactions Between Calcite and Aragonite in L-Glutamic and L-Aspartic Acid Solutions

    Directory of Open Access Journals (Sweden)

    Kwangsuk You

    2010-01-01

    Full Text Available We have investigated dissolution and surface reaction of calcite and aragonite in amino acid solutions of L-glutamic (L-glu and L-aspartic acid (L-asp at weak acidity of above pH 3. The surface reactions of calcite and aragonite were related with the dissolution. Calcite was dissolved in both solutions but the dissolution was limited by an adsorption of Ca-carboxylate salt. Aragonite was neither dissolved nor reacted in amino acid solutions because the crystal surface consisted of a hard to dissolve structure.

  11. Trace concentration - Huge impact: Nitrate in the calcite/Eu(III) system

    Science.gov (United States)

    Hofmann, Sascha; Voïtchovsky, Kislon; Schmidt, Moritz; Stumpf, Thorsten

    2014-01-01

    The interactions of trivalent lanthanides and actinides with secondary mineral phases such as calcite is of high importance for the safety assessment of deep geological repositories for high level nuclear waste (HLW). Due to similar ionic radii, calcium-bearing mineral phases are suitable host minerals for Ln(III) and An(III) ions. Especially calcite has been proven to retain these metal ions effectively by both surface complexation and bulk incorporation. Since anionic ligands (e.g., nitrate) are omnipresent in the geological environment and due to their coordinating properties, their influence on retentive processes should not be underestimated. Nitrate is a common contaminant in most HLW forms as a result of using nitric acid in fuel reprocessing. It is also formed by microbial activity under aerobic conditions. In this study, atomic force microscopy investigations revealed a major influence of nitrate upon the surface of calcite crystals. NaNO3 causes serious modifications even in trace amounts (surface layer of low crystallinity on top of the calcite crystal. Time-resolved laser fluorescence spectroscopy of Eu(III) showed that, within this layer, Eu(III) ions are incorporated, while losing most of their hydration shell. The results show that solid solution modelling for actinides in calcite must take into account the presence of nitrate in pore and ground waters.

  12. Hydrothermal replacement of calcite by Mg-carbonates

    Science.gov (United States)

    Jonas, Laura; Mueller, Thomas; Dohmen, Ralf

    2014-05-01

    The transport of heat and mass through the Earth's crust is coupled to mineral reactions and the exchange of isotopes and elements between different phases. Carbonate minerals are a major constituent of the Earth's crust and play an important role in different physical, chemical and even biological processes. In this experimental study, the element exchange reaction between calcite (CaCO3) and a Mg-rich fluid phase is investigated under hydrothermal conditions. Single crystals of calcite (2x2x2 mm) react with 1 ml of a 1 M MgCl2 solution at 200° C in a Teflon-lined steel autoclave for different times between one day and four weeks. The reaction leads to the formation of a porous reaction front and the pseudomorphic replacement of calcite by dolomite [CaMg(CO3)2] and magnesite (MgCO3). Scanning electron microscopy revealed that the reaction rim consists of small Mg-carbonate rhombs closely attached to each other, suggesting that the replacement reaction takes place by a dissolution-precipitation mechanism. Typically, the observed reaction front can be divided into two different domains. The outer part of the reaction rim, i.e. from the mineral surface in contact to the fluid inwards, consists of magnesite, whereas the inner part of the rim surrounding the unreacted calcite core consists of Ca-rich dolomite. The formation of a porous microstructure that varies in different parts of the reaction rim is a direct result of the large molar volume change induced by the replacement of calcite by magnesite and dolomite. The developing porosity therefore creates fluid pathways that promote the progress of the reaction front towards the unreacted core of the single crystal. Compositional profiles measured perpendicular to the mineral surface across the reactions rims using electron microprobe (EMPA) further revealed a compositional gradient within the reaction rim with regard to the structure-forming elements Mg and Ca. Here, the amount of Mg incorporated in both product

  13. Surface-Controlled Orientational Transitions in Elastically Strained Films of Liquid Crystal That Are Triggered by Vapors of Toluene.

    Science.gov (United States)

    Bedolla Pantoja, Marco A; Abbott, Nicholas L

    2016-05-25

    We report the fabrication of chemically patterned microwells that enable the rapid and facile preparation (by spin coating and patterned dewetting) of thin films of liquid crystals (LCs) that have precise thicknesses (0.7-30 μm), are supported on chemically defined substrates, and have free upper surfaces. We use these microwells to prepare elastically strained nematic LC films supported on silica glass, gold, or polystyrene substrates and thereby characterize the response of the strained LC films to vapors of toluene. We report that low concentrations of toluene vapor (LC to lower the anchoring energy of the LC on these substrates, thus allowing the elastic energy of the strained LC film to drive the LC films through an orientational transition. The central role of the toluene-induced change in surface anchoring energy is supported by additional experiments in which the response of the nematic LC to changes in film thickness and substrate identity are quantified. A simple thermodynamic model captures these trends and yielded estimates of anchoring energies (8-22 μJ/m(2)). Significantly, the orientational transitions observed in these strained LC thin films occur at concentrations of toluene vapor that are almost 1 order of magnitude below those which lead to bulk phase transitions, and they are not triggered by exposure to water vapor. Overall, these results hint at principles for the design of responsive LC-based materials that can be triggered by concentrations of aromatic, volatile organic compounds that are relevant to human health.

  14. Surface characterization and orientation interaction between diamond- like carbon layer structure and dimeric liquid crystals

    Science.gov (United States)

    Naradikian, H.; Petrov, M.; Katranchev, B.; Milenov, T.; Tinchev, S.

    2017-01-01

    Diamond-like carbon (DLC) and amorphous carbon films are very promising type of semiconductor materials. Depending on the hybridization sp2/sp3 ratio, the material’s band gap varies between 0.8 and 3 eV. Moreover carbon films possess different interesting for practice properties: comparable to the Silicon, Diamond like structure has 22-time better thermal conductivity etc. Here we present one type of implementation of such type nanostructure. That is one attempt for orientation of dimeric LC by using of pre-deposited DLC layer with different ratio of sp2/sp3 hybridized carbon content. It could be expected a pronounced π1-π2interaction between s and p orbital levels on the surface and the dimeric ring of LC. We present comparison of surface anchoring strengths of both orientation inter-surfaces DLC/dimeric LC and single wall carbon nanotubes (SWCNT)/dimeric LC. The mechanism of interaction of dimeric LC and activated surfaces with DLC or SWCNT will be discussed. In both cases we have π-π interaction, which in combination with hydrogen bonding, typical for the dimeric LCs, influence the LC alignment. The Raman spectroscopy data evidenced the presence of charge transfer between contacting hexagonal rings of DLC and the C = O groups of the LC molecules.

  15. Molecular Dynamics Simulation of the Crystal Orientation and Temperature Influences in the Hardness on Monocrystalline Silicon

    Directory of Open Access Journals (Sweden)

    Hongwei Zhao

    2014-01-01

    Full Text Available A nanoindentation simulation using molecular dynamic (MD method was carried out to investigate the hardness behavior of monocrystalline silicon with a spherical diamond indenter. In this study, Tersoff potential was used to model the interaction of silicon atoms in the specimen, and Morse potential was used to model the interaction between silicon atoms in the specimen and carbon atoms in the indenter. Simulation results indicate that the silicon in the indentation zone undergoes phase transformation from diamond cubic structure to body-centred tetragonal and amorphous structure upon loading of the diamond indenter. After the unloading of the indenter, the crystal lattice reconstructs, and the indented surface with a residual dimple forms due to unrecoverable plastic deformation. Comparison of the hardness of three different crystal surfaces of monocrystalline silicon shows that the (0 0 1 surface behaves the hardest, and the (1 1 1 surface behaves the softest. As for the influence of the indentation temperature, simulation results show that the silicon material softens and adhesiveness of silicon increases at higher indentation temperatures.

  16. Molecular simulation of oligomer inhibitors for calcite scale

    Institute of Scientific and Technical Information of China (English)

    Qiuyu Zhang; Hua Ren; Wenwen Wang; Junping Zhang; Hepeng Zhang

    2012-01-01

    Molecular simulation was performed to study the interaction between CaCO3 crystal and several oligomer inhibitors,by using the equilibrium morphology method to calculate the growth morphology of CaCO3 without inhibitors.The calculated morphology agreed well with SEM photographs.Then,a double-layer model was built to investigate the interaction between calcite crystal and oligomer inhibitors containing maleic anhydride (MA) and acrylic acid (AA).Interaction energy per gram of an oligomer inhibitor was introduced as a scale of inhibition efficiency of different monomers.The results indicated that,for calcite scale inhibition,acrylamide (AM) and vinyl phosphonic acid (VPA) were the most efficient monomers,while allylsulfonic acid (AS) was the poorest.Increasing proportion of AM in dimer inhibitor molecule would improve the inhibition efficiency of MA,though,for a trimer,such as MA-AA-AM,certain sequence of monomers in the inhibitor molecule was necessary besides higher proportion of AM.

  17. Acceleration of calcite kinetics by abalone nacre proteins

    Energy Technology Data Exchange (ETDEWEB)

    Fu, G; Qiu, S R; Orme, C A; Morse, D E; De Yoreo, J J

    2005-06-09

    The fascinating shapes and hierarchical designs of biomineralized structures have long been an inspiration to materials scientists because of the potential they suggest for biomolecular control over synthesis of crystalline materials. One prevailing view is that mineral-associated macromolecules are responsible for initiating and stabilizing non-equilibrium crystal polymorphs and morphologies through interactions between anionic moieties and cations in solution or at mineral surfaces. Indeed, numerous studies have demonstrated that bio-organic additives can dramatically alter crystal shapes and growth-rates in vitro. However, previous molecular-scale studies revealing mechanisms of growth modification focused on small molecules such as amino acids or peptides and always observed growth inhibition. In contrast, studies using full proteins were non-quantitative and underlying sources of growth modification were ill-defined. Here we investigate interactions between proteins isolated from abalone shell nacre and growing surfaces of calcite. We find that these proteins significantly accelerate the molecular-scale kinetics and, though much larger than atomic steps, alter growth morphology through step-specific interactions that lower their free energies. We propose that these proteins act as surfactants to promote ion attachment at calcite surfaces.

  18. Peculiar orientational disorder in 4-bromo-4′-nitrobiphenyl (BNBP and 4-bromo-4′-cyanobiphenyl (BCNBP leading to bipolar crystals

    Directory of Open Access Journals (Sweden)

    Matthias Burgener

    2016-05-01

    Full Text Available 180° orientational disorder of molecular building blocks can lead to a peculiar spatial distribution of polar properties in molecular crystals. Here we present two examples [4-bromo-4′-nitrobiphenyl (BNBP and 4-bromo-4′-cyanobiphenyl (BCNBP] which develop into a bipolar final growth state. This means orientational disorder taking place at the crystal/nutrient interface produces domains of opposite average polarity for as-grown crystals. The spatial inhomogeneous distribution of polarity was investigated by scanning pyroelectric microscopy (SPEM, phase-sensitive second harmonic microscopy (PS-SHM and selected volume X-ray diffraction (SVXD. As a result, the acceptor groups (NO2 or CN are predominantly present at crystal surfaces. However, the stochastic process of polarity formation can be influenced by adding a symmetrical biphenyl to a growing system. For this case, Monte Carlo simulations predict an inverted net polarity compared with the growth of pure BNBP and BCNBP. SPEM results clearly demonstrate that 4,4′-dibromobiphenyl (DBBP can invert the polarity for both crystals. Phenomena reported in this paper belong to the most striking processes seen for molecular crystals, demonstrated by a stochastic process giving rise to symmetry breaking. We encounter here further examples supporting the general thesis that monodomain polar molecular crystals for fundamental reasons cannot exist.

  19. Orientational order and translational dynamics of magnetic particle assemblies in liquid crystals.

    Science.gov (United States)

    Peroukidis, Stavros D; Klapp, Sabine H L

    2016-08-10

    Implementing extensive molecular dynamics simulations we explore the organization of magnetic particle assemblies (clusters) in a uniaxial liquid crystalline matrix comprised of rodlike particles. The magnetic particles are modelled as soft dipolar spheres with diameter significantly smaller than the width of the rods. Depending on the dipolar strength coupling the magnetic particles arrange into head-to-tail configurations forming various types of clusters including rings (closed loops) and chains. In turn, the liquid crystalline matrix induces long range orientational ordering to these structures and promotes their diffusion along the director of the phase. Different translational dynamics are exhibited as the liquid crystalline matrix transforms either from isotropic to nematic or from nematic to smectic state. This is caused due to different collective motion of the magnetic particles into various clusters in the anisotropic environments. Our results offer a physical insight for understanding both the structure and dynamics of magnetic particle assemblies in liquid crystalline matrices.

  20. The role of grain boundary structure and crystal orientation on crack growth asymmetry in aluminum

    Energy Technology Data Exchange (ETDEWEB)

    Adlakha, I. [School for Engineering of Matter, Transport, and Energy, Arizona State University, Tempe, AZ 85287 (United States); Tschopp, M.A. [U.S. Army Research Laboratory, Aberdeen Proving Ground, MD 21005 (United States); Solanki, K.N., E-mail: kiran.solanki@asu.edu [School for Engineering of Matter, Transport, and Energy, Arizona State University, Tempe, AZ 85287 (United States)

    2014-11-17

    Atomistic simulations have shown that the grain boundary (GB) structure affects a number of physical, mechanical, thermal, and chemical properties, which can have a profound effect on macroscopic properties of polycrystalline materials. The research objective herein is to use atomistic simulations to explore the role that GB structure and the adjacent crystallographic orientations have on the directional asymmetry of an intergranular crack (i.e. cleavage behavior is favored along one direction, while ductile behavior along the other direction of the interface) for aluminum grain boundaries. Simulation results from seven 〈110〉 symmetric tilt grain boundaries (STGBs) show that the GB structure and the associated free volume directly influence the stress–strain response, crack growth rate, and crack tip plasticity mechanisms for middle-tension (M(T)) crack propagation specimens. In particular, the structural units present within the GB promote whether a dislocation or twinning-based mechanism operates at the crack tip during intergranular fracture along certain GBs (e.g., the ‘E’ structural unit promotes twinning at the crack tip in Al). Furthermore, the crystallography of the adjacent grains, and therefore the available slip planes, can significantly affect the crack growth rates in both directions of the crack – this creates a strong directional asymmetry in the crack growth rate in the Σ11 (113) and the Σ27 (552) STGBs. Upon comparing these results with the theoretical Rice criterion, it was found that certain GBs in this study (Σ9 (221), Σ11 (332) and Σ33 (441)) show an absence of directional asymmetry in the observed crack growth behavior, in conflict with the Rice criterion. The significance of the present research is that it provides a physical basis for the role of GB character and crystallographic orientation on intergranular crack tip deformation behavior.

  1. Galacturonomannan and Golgi-derived membrane linked to growth and shaping of biogenic calcite

    Science.gov (United States)

    Marsh, M. E.; Ridall, A. L.; Azadi, P.; Duke, P. J.

    2002-01-01

    The coccolithophores are valuable models for the design and synthesis of composite materials, because the cellular machinery controlling the nucleation, growth, and patterning of their calcitic scales (coccoliths) can be examined genetically. The coccoliths are formed within the Golgi complex and are the major CaCO(3) component in limestone sediments-particularly those of the Cretaceous period. In this study, we describe mutants lacking a sulfated galacturonomannan and show that this polysaccharide in conjunction with the Golgi-derived membrane is directly linked to the growth and shaping of coccolith calcite but not to the initial orientated nucleation of the mineral phase.

  2. Higher Order Elastic Constants, Gruneisen Parameters and Lattice Thermal Expansion of Trigonal Calcite

    Directory of Open Access Journals (Sweden)

    Thresiamma Phlip

    2005-01-01

    Full Text Available The second- and third-order elastic constants of trigonal calcite have been obtained using the deformation theory. The strain energy density derived using the deformation theory is compared with the strain dependent lattice energy obtained from the elastic continuum model approximation to get the expressions for the second- and third-order elastic constants. Higher order elastic constants are a measure of the anharmonicity of a crystal lattice. The seven second-order elastic constants and the fourteen non-vanishing third-order elastic constants of trigonal calcite are obtained. The second-order elastic constants C11, which corresponds to the elastic stiffness along the basal plane of the crystal is greater than C33, which corresponds to the elastic stiffness tensor component along the c-axis of the crystal. First order pressure derivatives of the second-order elastic constants of calcite are evaluated. The higher order elastic constants are used to find the generalized Gruneisen parameters of the elastic waves propagating in different directions in calcite. The Brugger gammas are evaluated and the low temperature limit of the Gruneisen gamma is obtained. The results are compared with available reported values.

  3. Crystalline order of a water/glycine film coadsorbed on the (104) calcite surface.

    Science.gov (United States)

    Magdans, Uta; Torrelles, Xavier; Angermund, Klaus; Gies, Hermann; Rius, Jordi

    2007-04-24

    For biomineralization processes, the interaction of the surface of calcite crystals with organic molecules is of particular importance. Especially, biologically controlled biomineralization as in exoskeletons of mollusks and echinoderms, e.g., sea urchin with single-crystal-like spines and shells,1-3 requires molecular control of seed formation and growth process. So far, experiments showing the obvious influence of organic molecules on the morphology and habit of calcite crystals have demonstrated the molecular dimension of the interaction.4-7 Details of the kinetics of growth and dissolution of mineral surfaces influenced by additives are available,8,9 but other experimental data about the structure of the organic/inorganic interface on the atomic scale are rare. On the other hand, complicated organic macromolecules which are involved in biomineralization are numerous, with only a small fraction solved in structure and function so far.10-13 Therefore, model systems have to be designed to provide a basic understanding for the interaction process.14 Using grazing incidence X-ray diffraction combined with molecular modeling techniques, we show that glycine molecules order periodically on the calcite (104) face in competition with the solvent water when exposed to an aqueous solution of the most simple amino acid. In contrast to the general concept of the charge-matching fit of organic molecules on mineral surfaces,4,14 glycine is not attached to the calcite surface directly but substitutes for water molecules in the second hydration layer.

  4. Do organic ligands affect calcite dissolution rates?

    Science.gov (United States)

    Oelkers, Eric H.; Golubev, Sergey V.; Pokrovsky, Oleg S.; Bénézeth, Pascale

    2011-04-01

    Steady state Iceland-spar calcite dissolution rates were measured at 25 °C in aqueous solutions containing 0.1 M NaCl and up to 0.05 M dissolved bicarbonate at pH from 7.9 to 9.1 in the presence of 13 distinct dissolved organic ligands in mixed-flow reactors. The organic ligands considered in this study include those most likely to be present in either (1) aquifers at the conditions pertinent to CO 2 sequestration or (2) soil/early diagenetic environments: acetate, phthalate, citrate, EDTA 4-, succinate, D-glucosaminate, L-glutamate, D-gluconate, 2,4-dihydroxybenzoate, 3,4-dihydroxybenzoate, fumarate, malonate, and gallate. Results show that the presence of extract, humic acid, pectin, and gum xanthan. In no case did the presence of <100 ppm of these organics change calcite dissolution rates by more than a factor of 2.5. Results obtained in this study suggest that the presence of aqueous organic anions negligibly affects calcite forward dissolution rates in most natural environments. Some effect on calcite reactivity may be observed, however, by the presence of organic anions if they change substantially the chemical affinity of the fluid with respect to calcite.

  5. Magnetoelectric effect in FeCo/PMN-PT/FeCo trilayers prepared by electroless deposition of FeCo on PMN-PT crystals with various orientations

    Energy Technology Data Exchange (ETDEWEB)

    Shen, H.Q.; Wang, Y.G., E-mail: yingang.wang@nuaa.edu.cn; Xie, D.; Cheng, J.H.

    2014-10-15

    Highlights: • The composites FeCo/PMN-PT/FeCo were prepared by electroless deposition. • The influence of the crystal cut of PMN-PT on ME coupling is discussed. • Optimizing the crystal cut of the piezoelectric substrate, proper resonant frequency and ME effect could be obtained. - Abstract: The magnetoelectric (ME) effect was studied in the FeCo/PMN-PT/FeCo trilayer composites prepared by electroless deposition of the FeCo layers on the single crystal PMN-PT substrates with various crystal cuts. X-ray diffraction reveals that the orientation of PMN-PT substrate has no effect on the growth of FeCo layer. The structures with PMN-PT crystals of various orientations have different acoustic resonance frequencies. FeCo/PMN-PT/FeCo composites with PMN-PT of 〈0 0 1〉{sup L} × 〈01{sup ‾}1〉{sup W} × 〈0 1 1〉{sup T} crystal cut shows superior ME performance, which is due to the highest piezoelectric module of PMN-PT.

  6. Smaller calcite lattice deformation caused by occluded organic material in coccoliths than in mollusk shell

    DEFF Research Database (Denmark)

    Frølich, Simon; Sørensen, Henning Osholm; Hakim, Sepideh Sadat

    2015-01-01

    The growth and nucleation of biominerals are directed and affected by associated biological molecules. In this paper, we investigate the influence of occluded biomolecules on biogenic calcite from the coccolithophorid Pleurochrysis carterae and from chalk, a rock composed predominantly of fossil....... Two heating cycles allow us to differentiate the effects of thermal agitation and organic molecules. Single peak analysis and Rietveld refinement were combined to show significant differences resulting from the occluded biomolecules on the mineral phase in biogenic calcite in the mollusk shell....... This suggests that the interaction between biomolecules and calcite is not as tight in the coccoliths as in the shell. Although the shape of chalk has been preserved over millions of years, no major influence on the crystal lattice was observed in the chalk samples....

  7. Calcite Biohybrids as Microenvironment for Stem Cells

    Directory of Open Access Journals (Sweden)

    Razi Vago

    2012-04-01

    Full Text Available A new type of composite 3D biomaterial that provides extracellular cues that govern the differentiation processes of mesenchymal stem cells (MSCs has been developed. In the present study, we evaluated the chondrogenecity of a biohybrid composed of a calcium carbonate scaffold in its calcite polymorph and hyaluronic acid (HA. The source of the calcite scaffolding is an exoskeleton of a sea barnacle Tetraclita rifotincta (T. rifotincta, Pilsbry (1916. The combination of a calcium carbonate-based bioactive scaffold with a natural polymeric hydrogel is designed to mimic the organic-mineral composite of developing bone by providing a fine-tuned microenvironment. The results indicate that the calcite-HA interface creates a suitable microenvironment for the chondrogenic differentiation of MSCs, and therefore, the biohybrid may provide a tool for tissue-engineered cartilage.

  8. Selective adsorption of L- and D-amino acids on calcite: Implications for biochemical homochirality

    Science.gov (United States)

    Hazen, R. M.; Filley, T. R.; Goodfriend, G. A.

    2001-01-01

    The emergence of biochemical homochirality was a key step in the origin of life, yet prebiotic mechanisms for chiral separation are not well constrained. Here we demonstrate a geochemically plausible scenario for chiral separation of amino acids by adsorption on mineral surfaces. Crystals of the common rock-forming mineral calcite (CaCO(3)), when immersed in a racemic aspartic acid solution, display significant adsorption and chiral selectivity of d- and l-enantiomers on pairs of mirror-related crystal-growth surfaces. This selective adsorption is greater on crystals with terraced surface textures, which indicates that d- and l-aspartic acid concentrate along step-like linear growth features. Thus, selective adsorption of linear arrays of d- and l-amino acids on calcite, with subsequent condensation polymerization, represents a plausible geochemical mechanism for the production of homochiral polypeptides on the prebiotic Earth.

  9. Morphology and orientation of β-BaB{sub 2}O{sub 4} crystals patterned by laser in the inside of samarium barium borate glass

    Energy Technology Data Exchange (ETDEWEB)

    Nishii, Akihito; Shinozaki, Kenji; Honma, Tsuyoshi; Komatsu, Takayuki, E-mail: komatsu@mst.nagaokaut.ac.jp

    2015-01-15

    Nonlinear optical β-BaB{sub 2}O{sub 4} crystal lines (β-BBO) were patterned in the inside of 8Sm{sub 2}O{sub 3}–42BaO–50B{sub 2}O{sub 3} glass by irradiations of continuous-wave Yb:YVO{sub 4} lasers with a wavelength of 1080 nm (power: P=0.8–1.0 W, scanning speed: S=0.2–2.5 μm/s), in which the laser focal position was moved gradually from the surface to the inside. The morphology, size, and orientation of β-BBO crystals were examined from polarization optical microscope and birefringence imaging observations. It was demonstrated that c-axis oriented β-BBO crystals with long lengths (e.g., 20 mm) were patterned in the inside of the glass. The morphology of β-BBO in the cross-section of lines was a rectangular shape with rounded corners, and the volume of β-BBO formed increased with increasing laser power and with decreasing laser scanning speed. The maximum depth in the inside from the surface for β-BBO patterning increased with increasing laser power, e.g., D{sub max}∼100 μm at P=0.8 W, D{sub max}∼170 μm at P=0.9 W, and D{sub max}∼200 μm at P=1 W. The present study proposes that the laser-induced crystallization opens a new door for applied engineering in glassy solids. - Graphical abstract: This figure shows the POM photographs for β-BaB{sub 2}O{sub 4} crystal lines patterned by cw Yb:YVO{sub 4} fiber laser irradiations with a laser power of P=0.8 W and a laser scanning speed S=2 μm/s in the glass. The laser focal point was moved gradually from the surface into the inside. The results shown in Fig. 1 demonstrate that it is possible to pattern highly oriented β-BaB{sub 2}O{sub 4} crystals even in the inside of glasses. - Highlights: • β-BaB{sub 2}O{sub 4} crystal lines were patterned in the inside of a glass by lasers. • Laser focal position was moved gradually from the surface to the inside. • Birefringence imaging was observed. • Morphology, size, and orientation of crystals were clarified. • Crystal lines with long lengths

  10. The Influence of Hydrogen on Shape Memory Effect and Superelasticity in [001]-Oriented FeNiCoAlTi Single Crystals

    Science.gov (United States)

    Chumlyakov, Yu. I.; Kireeva, I. V.; Platonova, Yu. N.

    2016-04-01

    Using [001]-oriented single crystals of an iron-based alloy (Fe - 28% Ni - 17% Co - 11.5% Al - 2.5% Ti at.%), which were aged at 973 K for 7 h, the influence of hydrogen on the axial-stress temperature response σ0.1(T), the values of shape-memory effect (SME) and superelasticity (SE) is investigated during thermoelastic γ-α'-martensitic transformation (MT) (γ-FCC - face centered lattice, α'-BCT - body centered tetragonal lattice) under tensile conditions. It is found that saturation of [001]-oriented single crystals of the Fe - 28% Ni - 17% Co - 11.5% Al - 2.5% Ti alloy with hydrogen within 2 h at T = 300 K and current density j = 50 mA/cm2 results in lower starting temperature, Ms, of a forward MT during cooling and Md temperature, increased strength properties of the high-temperature phase at Md temperature and wider temperature range of SE observation compared to hydrogen-free crystals. It is shown that hydrogen affects but only slightly the SME and SE values, the temperature and stress hysteresis under the above saturation mode. In [001]-oriented crystals aged at 973 K for 7 h, which are saturated with hydrogen and hydrogen-free, the SME and SE values are found to be equal to 7.8-8 and 6.5-6.9%, respectively.

  11. Interaction of europium and nickel with calcite studied by Rutherford Backscattering Spectrometry and Time-Resolved Laser Fluorescence Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sabau, A. [Agence Nationale pour la gestion des Déchets RAdioactifs, 1-7 rue J. Monnet, Parc de la Croix Blanche, 92298 Châtenay-Malabry Cedex (France); Université de Nice Sophia Antipolis, Ecosystèmes Côtiers Marins et Réponses aux Stress (ECOMERS), 28 avenue Valrose, 06108 Nice Cedex 2 (France); Pipon, Y., E-mail: pipon@ipnl.in2p3.fr [Institut de Physique Nucléaire de Lyon (IPNL), Université Lyon 1, CNRS/IN2P3, 4 rue Enrico Fermi, 69 622 Villeurbanne Cedex (France); Institut Universitaire de Technologie (IUT) Lyon-1, Université Claude Bernard Lyon 1, 69 622 Villeurbanne Cedex (France); Toulhoat, N. [Institut de Physique Nucléaire de Lyon (IPNL), Université Lyon 1, CNRS/IN2P3, 4 rue Enrico Fermi, 69 622 Villeurbanne Cedex (France); CEA/DEN, Saclay, 91191 Gif sur Yvette (France); Lomenech, C. [Université de Nice Sophia Antipolis, Ecosystèmes Côtiers Marins et Réponses aux Stress (ECOMERS), 28 avenue Valrose, 06108 Nice Cedex 2 (France); Jordan, N. [Helmholtz Zentrum Dresden Rossendorf (HZDR), Institute of Resource Ecology (IRE) (Germany); Moncoffre, N. [Institut de Physique Nucléaire de Lyon (IPNL), Université Lyon 1, CNRS/IN2P3, 4 rue Enrico Fermi, 69 622 Villeurbanne Cedex (France); Barkleit, A. [Helmholtz Zentrum Dresden Rossendorf (HZDR), Institute of Resource Ecology (IRE) (Germany); and others

    2014-08-01

    This study aims at elucidating the mechanisms regulating the interaction of Eu and Ni with calcite (CaCO{sub 3}). Calcite powders or single crystals (some mm sized) were put into contact with Eu or Ni solutions at concentrations ranging from 10{sup −3} to 10{sup −5} mol L{sup −1} for Eu and 10{sup −3} mol L{sup −1} for Ni. The sorption durations ranged from 1 week to 1 month. Rutherford Backscattering Spectrometry (RBS) well adapted to discriminate incorporation processes such as: (i) adsorption or co precipitation at the mineral surfaces or, (ii) incorporation into the mineral structure (through diffusion for instance), has been carried out. Moreover, using the fluorescence properties of europium, the results have been compared to those obtained by Time-Resolved Laser Fluorescence Spectroscopy (TRLFS) on calcite powders. For the single crystals, complementary SEM observations of the mineral surfaces at low voltage were also performed. Results showed that Ni accumulates at the calcite surface whereas Eu is also incorporated at a greater depth. Eu seems therefore to be incorporated into two different states in calcite: (i) heterogeneous surface accumulation and (ii) incorporation at depth greater than 160 nm after 1 month of sorption. Ni was found to accumulate at the surface of calcite without incorporation.

  12. Discovery of room-temperature spin-glass behaviors in two-dimensional oriented attached single crystals

    Science.gov (United States)

    Ma, Ji; Chen, Kezheng

    2016-05-01

    In this study, room-temperature spin-glass behaviors were observed in flake-like oriented attached hematite (α-Fe2O3) and iron phosphate hydroxide hydrate (Fe5(PO4)4(OH)3·2H2O) single crystals. Remarkably, their coercivity (HC) values were found to be almost invariable at various given temperatures from 5 to 300 K. The spin topographic map in these flakes was assumed as superparamagnetic (SPM) "islands" isolated by spin glass (SG)-like "bridges". A spin-glass model was then proposed to demonstrate the spin frustration within these "bridges", which were formed by the staggered atomic planes in the uneven surfaces belonging to different attached nanoparticles. Under the spatial limitation and coupling shield of these "bridges", the SPM "islands" were found to be collectively frozen to form a superspin glass (SSG) state below 80 K in weak applied magnetic fields; whereas, when strong magnetic fields were applied, the magnetic coupling of these "islands" would become superferromagnetic (SFM) through tunneling superexchange, so that, these SFM spins could antiferromagnetically couple with the SG-like "bridges" to yield pronounced exchange bias (EB) effect.

  13. Adsorption of arsenic and phosphate onto the surface of calcite as revealed by batch experiments and surface complexation modelling

    DEFF Research Database (Denmark)

    Sø, Helle Ugilt

    The adsorption of phosphate, arsenate (As(V)) and arsenite (As(III)) onto synthetic calcite was studied in a series of batch experiments. The adsorption of the three ions was studied separately followed by studies of the competition between arsenate and phosphate. The experimental data was utilized...... is complete after 1 and 2-3 hours, respectively). Also desorption is fast and complete for both ions within 0.5 h. The reversibility of the sorption process indicates that neither arsenate nor phosphate is readily incorporated into the calcite crystal lattice under our experimental conditions. The phosphate....... This clearly shows the importance of competition studies in validating multicomponent models. Extrapolation of the experimental results to calcite bearing aquifers suggests a large variability in the mobility of arsenic. Under reduced conditions, arsenite, which does not adsorb onto calcite, will dominate and...

  14. A preliminary study of the calcite beef found in the Cretaceous Jinju Formation, Gyeongsang Basin, South Korea

    Science.gov (United States)

    Ha, S.; Chae, Y. U.; Son, M.; Jeong, G. Y.; Paik, I. S.; Lim, H. S.

    2015-12-01

    The term "beef" refers to fibrous minerals in bedding-parallel veins, where the fibers are approximately perpendicular to the vein margins (Cobbold et al., 2013). It mostly appears within organic-rich black shale layers in sedimentary basin. Although the veins can consist of white gangue minerals, such as calcite, gypsum, or quartz, the commonest mineral in the fibers is calcite. According to the worldwide localities of calcite beef compiled by Cobbold et al (2012), they concentrated in some areas, especially around the Atlantic Ocean. However, they have been rarely reported in the western Pacific margin, except Australia and New Zealand. Recently, calcite beefs have been found in the Cretaceous Jinju Formation, Gyeongsang Basin, Korea. As far as we know, this is the first report of calcite beef in Korea. The lacustrine Jinju Formation is about 1,200 m thick, and made up mainly of lacustrine dark grey to black mudstones. In the study area, calcite beefs were commonly found in the organic-rich black shale layers. The vein thickness is anywhere between a few millimeters to maximum 3 centimeters, and their length ranges from a few centimeters to several tens of meters. The interval between successive veins is from a few centimeters to about 1 meter. Most of them occur parallel to the bedding planes, although some of them are developed along fault planes or within deformed layers. In case of relatively thick beefs, the center of veins often shows a dark grey to black central median line, defined by fine-grained calcite grains, fluid inclusion lines, or wall rock particles. Based on the orientation of fibrous calcite, they can be divided into two types: straight and sigmoidal types. The fibrous calcites are thought to have been symmetrically grown from the median lines to top and bottom of wall rock. The formation mechanism of horizontal fractures, and the formation temperature of beefs in the study area remain as a matter to be studied further.

  15. Modelling how incorporation of divalent cations affects calcite wettability–implications for biomineralisation and oil recovery

    Science.gov (United States)

    Andersson, M. P.; Dideriksen, K.; Sakuma, H.; Stipp, S. L. S.

    2016-06-01

    Using density functional theory and geochemical speciation modelling, we predicted how solid-fluid interfacial energy is changed, when divalent cations substitute into a calcite surface. The effect on wettability can be dramatic. Trace metal uptake can impact organic compound adsorption, with effects for example, on the ability of organisms to control crystal growth and our ability to predict the wettability of pore surfaces. Wettability influences how easily an organic phase can be removed from a surface, either organic compounds from contaminated soil or crude oil from a reservoir. In our simulations, transition metals substituted exothermically into calcite and more favourably into sites at the surface than in the bulk, meaning that surface properties are more strongly affected than results from bulk experiments imply. As a result of divalent cation substitution, calcite-fluid interfacial energy is significantly altered, enough to change macroscopic contact angle by tens of degrees. Substitution of Sr, Ba and Pb makes surfaces more hydrophobic. With substitution of Mg and the transition metals, calcite becomes more hydrophilic, weakening organic compound adsorption. For biomineralisation, this provides a switch for turning on and off the activity of organic crystal growth inhibitors, thereby controlling the shape of the associated mineral phase.

  16. Cyclic Cratonic Carbonates and Phanerozoic Calcite Seas.

    Science.gov (United States)

    Wilkinson, Bruce H.

    1982-01-01

    Discusses causes of cyclicity in cratonic carbonate sequences and evidence for and potential significance of postulated primary calcite sediment components in past Paleozoic seas, outlining problems, focusing on models explaining existing data, and identifying background. Future sedimentary geologists will need to address these and related areas…

  17. Electro-optical response of polymer-dispersed liquid crystal single layers of large nematic droplets oriented by rubbed teflon nanolayers

    Science.gov (United States)

    Marinov, Y. G.; Hadjichristov, G. B.; Petrov, A. G.; Marino, S.; Versace, C.; Scaramuzza, N.

    2013-02-01

    The surface orienting effect of rubbed teflon nanolayers on the morphology and electro-optical (EO) response of polymer-dispersed liquid crystal (PDLC) single layers of large nematic droplets was studied experimentally. In PDLC composites of the nematic liquid crystal (LC) E7 and NOA65 polymer, single droplets of LC with diameters as larger as 10 μm were confined in layers with a thickness of 10 μm, and the nematic director field was efficiently modified by nanostructuring teflon rubbing of the glass plates of the PDLC cell. For layered PDLCs arranged and oriented in this way, the modulated EO response by the dielectric oscillations of the nematic director exhibits a selective amplitude-frequency modulation controllable by both temperature and voltage applied, and is simply related to the LC droplet size. That may be of practical interest for PDLC-based modulators operating in the infrasound frequency range.

  18. Fluid inclusion studies of calcite veins from Yucca Mountain, Nevada, Tuffs: Environment of formation

    Energy Technology Data Exchange (ETDEWEB)

    Roedder, E. [Harvard Univ., Cambridge, MA (United States); Whelan, J.F. [Geological Survey, Denver, CO (United States); Vaniman, D.T. [Los Alamos National Lab., NM (United States)

    1994-12-31

    Calcite vein and vug fillings at four depths (130-314m), all above the present water table in USW G-1 bore hole at Yucca Mountain, Nevada, contain primary fluid inclusions with variable vapor/liquid raitos: Most of these inclusions are either full of liquid or full of vapor. The liquid-filled inclusions show that most of the host calcite crystallized from fluids at <100{degrees}C. The vapor-filled inclusions provide evidence that a separate vapor phase was present in the fluid during crystallization. Studies of these vapor-filled inclusions on the microscope crushing stage were interpreted in an earlier paper as indicating trapping of an air-water-CO{sub 2} vapor phase at ``<100{degrees}C``. Our new studies reveal the additional presence of major methane in the vapor-filled inclusion, indicating even lower temperatures of trapping, perhaps at near-surface temperatures. They also show that the host calcite crystals grew from a flowing film of water on the walls of fractures open to the atmosphere, the vapor-filled inclusions representing bubbles that exsolved from this film onto the crystal surface.

  19. Shock-induced effects in calcite from Cactus Crater

    Science.gov (United States)

    Vizgirda, J.; Ahrens, T. J.; Tsay, F.-D.

    1980-01-01

    The paper discusses shock metamorphism of calcite from coralline limestone samples retrieved from a borehole drilled into rocks beneath Cactus Crater, a nuclear explosion crater at Eniwetok Atoll. The metamorphism was detected and quantified using electron spin resonance (ESR); the ESR spectra of Mn(+) present as a trace constituent in the coral samples, show a consistent decrease in hyperfine peak splitting with decreasing depth of sample. It is suggested that the decrease in hyperfine peak splitting reflects a decrease in crystal field splitting, and therefore, small increases on cation-anion distances produced by mechanical energy input during the shock process. Two alternative crater models suggested by the ESR results are a depiction of a steady decay of the shock wave, and a delineation of a breccia lens with a breccia-bedrock interface at 20 plus or minus 5 m.

  20. Thermodynamics of magnesian calcite solid-solutions at 25°C and 1 atm total pressure

    Science.gov (United States)

    Busenberg, Eurybiades; Plummer, L. Niel

    1989-01-01

    protodolomite. Group I and II solid-solutions differ significantly in stability. The rate of crystal growth and the chemical composition of the aqueous solutions from which the solids were formed are the main factors controlling stoichiometric solubility of the magnesian calcites and the density of crystal defects. The literature on the occurrence and behavior of magnesian calcites in sea water and other aqueous solutions is also examined.

  1. High-Magnesian Calcite Mesocrystals : A Coordination Chemistry Approach

    NARCIS (Netherlands)

    Lenders, Jos J. M.; Dey, Archan; Bomans, Paul H. H.; Spielmann, Jan; Hendrix, Marco M. R. M.; de With, Gijsbertus; Meldrum, Fiona C.; Harder, Sjoerd; Sommerdijk, Nico A. J. M.

    2012-01-01

    While biogenic calcites frequently contain appreciable levels of magnesium, the pathways leading to such high concentrations remain unclear. The production of high-magnesian calcites in vitro is highly challenging, because Mg-free aragonite, rather than calcite, is the favored product in the presenc

  2. in situ Calcite Precipitation for Contaminant Immobilization

    Energy Technology Data Exchange (ETDEWEB)

    Yoshiko Fujita; Robert W. Smith

    2009-08-01

    in situ Calcite Precipitation for Contaminant Immobilization Yoshiko Fujita (Yoshiko.fujita@inl.gov) (Idaho National Laboratory, Idaho Falls, Idaho, USA) Robert W. Smith (University of Idaho-Idaho Falls, Idaho Falls, Idaho, USA) Subsurface radionuclide and trace metal contaminants throughout the U.S. Department of Energy (DOE) complex pose one of DOE’s greatest challenges for long-term stewardship. One promising stabilization mechanism for divalent trace ions, such as the short-lived radionuclide strontium-90, is co-precipitation in calcite. Calcite, a common mineral in the arid western U.S., can form solid solutions with trace metals. The rate of trace metal incorporation is susceptible to manipulation using either abiotic or biotic means. We have previously demonstrated that increasing the calcite precipitation rate by stimulating the activity of urea hydrolyzing microorganisms can result in significantly enhanced Sr uptake. Urea hydrolysis causes the acceleration of calcium carbonate precipitation (and trace metal co-precipitation) by increasing pH and alkalinity, and also by liberating the reactive cations from the aquifer matrix via exchange reactions involving the ammonium ion derived from urea: H2NCONH2 + 3H2O ? 2NH4+ + HCO3- + OH- urea hydrolysis >X:2Ca + 2NH4+ ? 2>X:NH4 + Ca2+ ion exchange Ca2+ + HCO3- + OH- ? CaCO3(s) + H2O calcite precipitation where >X: is a cation exchange site on the aquifer matrix. This contaminant immobilization approach has several attractive features. Urea hydrolysis is catalyzed by the urease enzyme, which is produced by many indigenous subsurface microorganisms. Addition of foreign microbes is unnecessary. In turn the involvement of the native microbes and the consequent in situ generation of reactive components in the aqueous phase (e.g., carbonate and Ca or Sr) can allow dissemination of the reaction over a larger volume and/or farther away from an amendment injection point, as compared to direct addition of the reactants at

  3. Polar-axis-oriented crystal growth of tetragonal PZT films on stainless steel substrate using pseudo-perovskite nanosheet buffer layer

    Directory of Open Access Journals (Sweden)

    Yoshiki Minemura

    2015-07-01

    Full Text Available Lead zirconate titanate (PZT film with polar axis orientation was grown on a SUS 316L stainless steel substrate with the help of a Ca2Nb3O10 nanosheet (ns-CN layer that had a pseudo-perovskite-type crystal structure. The ns-CN buffer layer was supported on a platinized SUS 316L (Pt/SUS substrate, followed by chemical solution deposition (CSD of the PZT films with tetragonal symmetry (Zr/Ti =40/60. The PZT films consisting of c-domain, with [001]-axis orientation of the perovskite unit cell, were deposited on the ns-CN/Pt/SUS substrate owing to (i epitaxial lattice matching between the unit cell of PZT and substrate surface and (ii in-plane thermal stress applied to the PZT film during cooling-down step of CSD procedure. The c-domain-oriented PZT film on ns-CN/Pt/SUS substrate exhibited enhanced remanent polarization of approximately 52 μC/cm2 and lowered dielectric permittivity of approximately 230, which are superior to those of conventional PZT films with random crystal orientation and comparable to those of epitaxial PZT films grown on (100SrRuO3//(100SrTiO3 substrates.

  4. Polarisation-dependence of anomalous scattering in brominated DNA and RNA molecules, and importance of crystal orientation in SAD and MAD phasing.

    Energy Technology Data Exchange (ETDEWEB)

    Sanishvili, R.; Besnard, C.; Camus, F.; Fleurant, M.; Pattison, P.; Bricogne, G.; Schiltz, M.; Biosciences Division; Ecole Polytechnique Federale de Lausanne; ESRF; Global Phasing Ltd.

    2007-01-01

    In this paper the anisotropy of anomalous scattering at the Br K-absorption edge in brominated nucleotides is investigated, and it is shown that this effect can give rise to a marked directional dependence of the anomalous signal strength in X-ray diffraction data. This implies that choosing the correct orientation for crystals of such molecules can be a crucial determinant of success or failure when using single- and multiple-wavelength anomalous diffraction (SAD or MAD) methods to solve their structure. In particular, polarized absorption spectra on an oriented crystal of a brominated DNA molecule were measured, and were used to determine the orientation that yields a maximum anomalous signal in the diffraction data. Out of several SAD data sets, only those collected at or near that optimal orientation allowed interpretable electron density maps to be obtained. The findings of this study have implications for instrumental choices in experimental stations at synchrotron beamlines, as well as for the development of data collection strategy programs.

  5. Optical Anisotropy and Four Possible Orientations of a Nematic Liquid Crystal on the Same Film of a Photochromic Chiral Smectic Polymer

    Science.gov (United States)

    Blinov, Lev M.; Barberi, Riccardo; Kozlovsky, Mikhail V.; Lazarev, Vladimir V.; de Santo, Maria P.

    Spin coated films of a chiral comb-like liquid crystalline copolymer containing azobenzene chromophores in its side chains are optically isotropic in their twisted smectic-like glassy state. In contact with a nematic liquid crystal (5CB, E7, MBBA) they provide a degenerate planar orientation. When irradiated by unpolarized UV light, they orient the same nematics homeotropically. Treated with linearly polarized UV light they orient nematics homogeneously with the director along the electric vector of the exciting light. After a combined irradiation first with unpolarized UV light and then with linearly polarized visible light, the films again provide a homogeneous liquid crystal orientation, this time with the director perpendicular to the visible light electric vector. The phenomena observed are related to the light induced optical anisotropy. Two main processes are responsible for the anisotropy (1) a UV light depletion of trans-isomers of the azobenzene chromophores from the chosen direction and (2) a reorientation of the chromophores by polarized visible light.

  6. Growth of Large-Size SnS Thin Crystals Driven by Oriented Attachment and Applications to Gas Sensors and Photodetectors.

    Science.gov (United States)

    Wang, Jun; Lian, Gang; Xu, Zhenghao; Fu, Chen; Lin, Zhaojun; Li, Liyi; Wang, Qilong; Cui, Deliang; Wong, Ching-Ping

    2016-04-20

    Freestanding large-size SnS thin crystals are synthesized via two-dimensional oriented attachment (OA) growth of colloidal quantum dots (CQDs) in a novel high-pressure solvothermal reaction. The SnS thin crystals present a uniform rectangular shape with a lateral size of 20-30 um and thickness of time and organic ligands results in polycrystal-to-monocrystal formation and defect annihilation. Furthermore, gas sensor and photodetector devices, based on SnS thin single crystals, are also prepared. The sensing devices present high sensitivity, superior selectivity, low detection limit (≪100 ppb) and reversibility to NO2 at room temperature. The fabricated photodetector devices exhibit a high responsivity of 2.04 × 10(3) A W(1-) and high external quantum efficiency of ∼4.75 × 10(5) % at 532 nm, which are much higher than most of the photodetector devices.

  7. Calcite-forming bacteria for compressive strength improvement in mortar.

    Science.gov (United States)

    Park, Sung-Jin; Park, Yu-Mi; Chun, Woo-Young; Kim, Wha-Jung; Ghim, Sa-Youl

    2010-04-01

    Microbiological calcium carbonate precipitation (MCP) has been investigated for its ability to improve the compressive strength of concrete mortar. However, very few studies have been conducted on the use of calcite-forming bacteria (CFB) to improve compressive strength. In this study, we discovered new bacterial genera that are capable of improving the compressive strength of concrete mortar. We isolated 4 CFB from 7 environmental concrete structures. Using sequence analysis of the 16S rRNA genes, the CFB could be partially identified as Sporosarcina soli KNUC401, Bacillus massiliensis KNUC402, Arthrobacter crystallopoietes KNUC403, and Lysinibacillus fusiformis KNUC404. Crystal aggregates were apparent in the bacterial colonies grown on an agar medium. Stereomicroscopy, scanning electron microscopy, and x-ray diffraction analyses illustrated both the crystal growth and the crystalline structure of the CaCO3 crystals. We used the isolates to improve the compressive strength of concrete mortar cubes and found that KNUC403 offered the best improvement in compressive strength.

  8. In-situ growth of calcite at Devils Hole, Nevada: Comparison of field and laboratory rates to a 500,000 year record of near-equilibrium calcite growth

    Science.gov (United States)

    Plummer, L.N.; Busenberg, E.; Riggs, A.C.

    2000-01-01

    Calcite grew continuously for 500,000 years on the submerged walls of an open fault plane (Devils Hole) in southern Nevada, U.S.A. at rates of 0.3 to 1.3 mm/ka, but ceased growing approximately 60,000 years ago, even though the fault plane remained open and was continuously submerged. The maximum initial in-situ growth rate on pre-weighed crystals of Iceland spar placed in Devils Hole (calcite saturation index, SI, is 0.16 to 0.21 at 33.7??C) for growth periods of 0.75 to 4.5 years was 0.22 mm/ka. Calcite growth on seed crystals slowed or ceased following initial contact with Devils Hole groundwater. Growth rates measured in synthetic Ca-HCO3 solutions at 34??C, CO2 partial pressures of 0.101, 0.0156 (similar to Devils Hole groundwater) and 0.00102 atm, and SI values of 0.2 to 1.9 were nearly independent of P(CO)(2), decreased with decreasing saturation state, and extrapolated through the historical Devils Hole rate. The results show that calcite growth rate is highly sensitive to saturation state near equilibrium. A calcite crystal retrieved from Devils Hole, and used without further treatment of its surface, grew in synthetic Devils Hole groundwater when the saturation index was raised nearly 10-fold that of Devils Hole water, but the rate was only 1/4 that of fresh laboratory crystals that had not contacted Devils Hole water. Apparently, inhibiting processes that halted calcite growth in Devils Hole 60,000 years ago continue today.

  9. Deformation twinning and the role of amino acids and magnesium in calcite hardness from molecular simulation.

    Science.gov (United States)

    Côté, A S; Darkins, R; Duffy, D M

    2015-08-21

    We employ classical molecular dynamics to calculate elastic properties and to model the nucleation and propagation of deformation twins in calcite, both as a pure crystal and with magnesium and aspartate inclusions. The twinning is induced by applying uniaxial strain to the crystal and relaxing all stress components except the uniaxial component. A detailed analysis of the atomistic processes reveal that the twinning mechanism involves small displacements of the Ca ions and cooperative rotations of the CO3 ions. The volume of the twinned region expands under increased uniaxial strain via the propagation of steps along the twin boundaries. The energy cost of the twin boundaries is compensated by the reduced hydrostatic stress and strain energy. The presence of biogenic impurities is shown to decrease the strain required to induce twin formation in calcite and, thus, the yield stress. This increased propensity for twinning provides a possible explanation for the increased hardness and penetration resistance observed experimentally in biominerals.

  10. Calcite growth-rate inhibition by fulvic acid and magnesium ion—Possible influence on biogenic calcite formation

    Science.gov (United States)

    Reddy, Michael M.

    2012-01-01

    Increases in ocean surface water dissolved carbon dioxide (CO2) concentrations retard biocalcification by reducing calcite supersaturation (Ωc). Reduced calcification rates may influence growth-rate dependent magnesium ion (Mg) incorporation into biogenic calcite modifying the use of calcifying organisms as paleoclimate proxies. Fulvic acid (FA) at biocalcification sites may further reduce calcification rates. Calcite growth-rate inhibition by FA and Mg, two common constituents of seawater and soil water involved in the formation of biogenic calcite, was measured separately and in combination under identical, highly reproducible experimental conditions. Calcite growth rates (pH=8.5 and Ωc=4.5) are reduced by FA (0.5 mg/L) to 47% and by Mg (10−4 M) to 38%, compared to control experiments containing no added growth-rate inhibitor. Humic acid (HA) is twice as effective a calcite growth-rate inhibitor as FA. Calcite growth rate in the presence of both FA (0.5 mg/L) and Mg (10−4 M) is reduced to 5% of the control rate. Mg inhibits calcite growth rates by substitution for calcium ion at the growth site. In contrast, FA inhibits calcite growth rates by binding multiple carboxylate groups on the calcite surface. FA and Mg together have an increased affinity for the calcite growth sites reducing calcite growth rates.

  11. Calcite growth-rate inhibition by fulvic acid and magnesium ion—Possible influence on biogenic calcite formation

    Science.gov (United States)

    Reddy, Michael M.

    2012-08-01

    Increases in ocean surface water dissolved carbon dioxide (CO2) concentrations retard biocalcification by reducing calcite supersaturation (Ωc). Reduced calcification rates may influence growth-rate dependent magnesium ion (Mg) incorporation into biogenic calcite modifying the use of calcifying organisms as paleoclimate proxies. Fulvic acid (FA) at biocalcification sites may further reduce calcification rates. Calcite growth-rate inhibition by FA and Mg, two common constituents of seawater and soil water involved in the formation of biogenic calcite, was measured separately and in combination under identical, highly reproducible experimental conditions. Calcite growth rates (pH=8.5 and Ωc=4.5) are reduced by FA (0.5 mg/L) to 47% and by Mg (10-4 M) to 38%, compared to control experiments containing no added growth-rate inhibitor. Humic acid (HA) is twice as effective a calcite growth-rate inhibitor as FA. Calcite growth rate in the presence of both FA (0.5 mg/L) and Mg (10-4 M) is reduced to 5% of the control rate. Mg inhibits calcite growth rates by substitution for calcium ion at the growth site. In contrast, FA inhibits calcite growth rates by binding multiple carboxylate groups on the calcite surface. FA and Mg together have an increased affinity for the calcite growth sites reducing calcite growth rates.

  12. Higher Order Elastic Constants, Gruneisen Parameters and Lattice Thermal Expansion of Trigonal Calcite

    OpenAIRE

    Thresiamma Phlip; Menon, C S; Indulekha, K.

    2005-01-01

    The second- and third-order elastic constants of trigonal calcite have been obtained using the deformation theory. The strain energy density derived using the deformation theory is compared with the strain dependent lattice energy obtained from the elastic continuum model approximation to get the expressions for the second- and third-order elastic constants. Higher order elastic constants are a measure of the anharmonicity of a crystal lattice. The seven second-order elastic constants and the...

  13. Mineral Chemistry of Melanite from Calcitic Ijolite, the Oka Carbonatite Complex, Canada:Implications for Multi-Pulse Magma Mixing

    Institute of Scientific and Technical Information of China (English)

    Wei Chen; Weiqi Zhang; Antonio Simonetti; Shaoyong Jiang

    2016-01-01

    Ti-rich garnet is found within calcitic ijolite from the Oka carbonatite complex in Can-ada, which is characterized by 58%–73% andradite component (2.12 wt.%–4.18 wt.% TiO2) and classi-fied as melanite. The garnet displays complex zoning and contains abundant high field strength ele-ments (HFSEs) and rare earth elements (REEs). Three groups (I, II, III) have been identified based on their petrographic nature. Compared to groups II and III, Group I garnet cores contain higher TiO2, MgO, HFSE, and REE and lower SiO2 abundances. The distinct chemical and petrographic signatures of the investigated garnets cannot be attributed to simple closed system crystallization, but they are consistent with the multi-pulse magma mixing. Combined with previously reported U-Pb ages for apa-tite from the calcitic ijolite, at least three stages of magma evolution and subsequent mixing have been involved in the generation of calcitic ijolite at Oka. The early-formed melt that generated Group I gar-net core was later mixed with at least two small-volume, more evolved melts. The intermediate stage melt formed the remaining garnet along with some pyroxene, calcite, nepheline, and apatite at 127±3.6 Ma. The youngest, most evolved melt generated the majority of pyroxene, calcite, nepheline, and apatite within the calcitic ijolite at 115±3.1 Ma.

  14. Removal of organic magnesium in coccolithophore calcite

    Science.gov (United States)

    Blanco-Ameijeiras, S.; Lebrato, M.; Stoll, H. M.; Iglesias-Rodriguez, M. D.; Méndez-Vicente, A.; Sett, S.; Müller, M. N.; Oschlies, A.; Schulz, K. G.

    2012-07-01

    Coccolithophore calcite refers to the plates of calcium carbonate (CaCO3) produced by the calcifying phytoplankton, coccolithophores. The empirical study of the elemental composition has a great potential in the development of paleoproxies. However, the difficulties to separate coccolithophore carbonates from organic phases hamper the investigation of coccoliths magnesium to calcium ratios (Mg/Ca) in biogeochemical studies. Magnesium (Mg) is found in organic molecules in the cells at concentrations up to 400 times higher than in inorganically precipitated calcite in present-day seawater. The aim of this study was to optimize a reliable procedure for organic Mg removal from coccolithophore samples to ensure reproducibility in measurements of inorganic Mg in calcite. Two baseline methods comprising organic matter oxidations with (1) bleach and (2) hydrogen peroxide (H2O2) were tested on synthetic pellets, prepared by mixing reagent grade CaCO3 with organic matter from the non-calcifying marine algae Chlorella autotrophica and measured with an ICP-AES (inductively coupled plasma-atomic emission spectrometer). Our results show that treatments with a reductive solution [using hydroxylamine-hydrochloride (NH2OH·HCl + NH4OH)] followed by three consecutive oxidations (using H2O2) yielded the best cleaning efficiencies, removing >99% of organic Mg in 24 h. P/Ca and Fe/Ca were used as indicators for organic contamination in the treated material. The optimized protocol was tested in dried coccolithophore pellets from batch cultures of Emiliania huxleyi, Calcidiscus leptoporus and Gephyrocapsa oceanica. Mg/Ca of treated coccolithophores were 0.151 ± 0.018, 0.220 ± 0.040, and 0.064 ± 0.023 mmol/mol, respectively. Comparison with Mg/Ca literature coccolith values, suggests a tight dependence on modern seawater Mg/Ca, which changes as a consequence of different seawater origins (protocol applicable to field and laboratory studies of trace elemental composition in

  15. Ice crystal c-axis orientation and mean grain size measurements from the Dome Summit South ice core, Law Dome, East Antarctica

    Science.gov (United States)

    Treverrow, Adam; Jun, Li; Jacka, Tim H.

    2016-06-01

    We present measurements of crystal c-axis orientations and mean grain area from the Dome Summit South (DSS) ice core drilled on Law Dome, East Antarctica. All measurements were made on location at the borehole site during drilling operations. The data are from 185 individual thin sections obtained between a depth of 117 m below the surface and the bottom of the DSS core at a depth of 1196 m. The median number of c-axis orientations recorded in each thin section was 100, with values ranging from 5 through to 111 orientations. The data from all 185 thin sections are provided in a single comma-separated value (csv) formatted file which contains the c-axis orientations in polar coordinates, depth information for each core section from which the data were obtained, the mean grain area calculated for each thin section and other data related to the drilling site. The data set is also available as a MATLAB™ structure array. Additionally, the c-axis orientation data from each of the 185 thin sections are summarized graphically in figures containing a Schmidt diagram, histogram of c-axis colatitudes and rose plot of c-axis azimuths. All these data are referenced by doi:10.4225/15/5669050CC1B3B and are available free of charge at https://data.antarctica.gov.au" target="_blank">https://data.antarctica.gov.au.<

  16. Heterogeneous growth of calcite at aragonite {001}- and vaterite {001}-melt interfaces: A molecular dynamics simulation study

    Science.gov (United States)

    Nada, Hiroki; Nishimura, Tatsuya; Sakamoto, Takeshi; Kato, Takashi

    2016-09-01

    Crystal growth at the interface between a calcium carbonate (CaCO3) crystal and its melt at a high temperature of 1500 K is investigated by means of a molecular dynamics simulation. The simulation is performed for the interfaces of a calcite {104} plane, aragonite {001}, {100}, and {010} planes, and vaterite {001}, {110}, and {100} planes. The growth from a pure melt and that from a melt containing Mg2+ are examined. Calcite growth occurs on the calcite {104} plane, aragonite growth occurs on the aragonite {100}, and {010} planes, and vaterite growth occurs on the vaterite {110} and {100} planes. However, the heterogeneous growth of calcite occurs on the {001} plane of aragonite and vaterite, irrespective of the presence of Mg2+. The results advance our understanding of geological processes that occur at high temperature, such as the formation of CaCO3 crystals from carbonatite magma and the formation of marble. Moreover, the results provide useful information for the control of CaCO3 crystal formation in material design.

  17. Variations in calcite growth kinetics with surface topography: molecular dynamics simulations and process-based growth kinetics modelling

    NARCIS (Netherlands)

    Wolthers, M.; Di Tommaso, D.; Du, Zhimei; de Leeuw, Nora H.

    2013-01-01

    It is generally accepted that cation dehydration is the rate-limiting step to crystal growth from aqueous solution. Here we employ classical molecular dynamics simulations to show that the water exchange frequency at structurally distinct calcium sites in the calcite surface varies by about two orde

  18. Calcite Supersaturation and Precipitation Kinetics in the Lower Colorado River, Ail-American Canal and East Highline Canal

    Science.gov (United States)

    Suarez, D. L.

    1983-06-01

    In situ pH determinations and analysis of major ions in solution indicated that the lower Colorado River is supersaturated with respect to calcite throughout the entire daily cycle, in both winter and summer. Although the ion activity product was 4 to 6 times greater than the calcite solubility product, there was no detectable precipitation. Chemical analyses of water samples taken along 350 km of the river and canals from Parker Dam to the Salton Sea also revealed no evidence of calcium carbonate precipitation despite the inflow of saline and highly supersaturated irrigation return flows. Laboratory kinetic studies indicated that calcite crystal growth rates with Colorado River water are about 30% of the rate for pure Ca-HCO3 waters and about 70% of that for synthetic Colorado River water. Calcite precipitation by crystal growth in the river is limited by the combination of short residence times and unavailability of reactive calcite. Critical supersaturation levels necessary for heterogeneous nucleation do not occur; a high suspended load limits algal photosynthesis and thus prevents large decreases in daytime H2CO3 levels.

  19. Atomistic simulations of calcium uranyl(VI) carbonate adsorption on calcite and stepped-calcite surfaces.

    Science.gov (United States)

    Doudou, Slimane; Vaughan, David J; Livens, Francis R; Burton, Neil A

    2012-07-17

    Adsorption of actinyl ions onto mineral surfaces is one of the main mechanisms that control the migration of these ions in environmental systems. Here, we present computational classical molecular dynamics (MD) simulations to investigate the behavior of U(VI) in contact with different calcite surfaces. The calcium-uranyl-carbonate [Ca(2)UO(2)(CO(3))(3)] species is shown to display both inner- and outer-sphere adsorption to the flat {101̅4} and the stepped {314̅8} and {31̅2̅16} planes of calcite. Free energy calculations, using the umbrella sampling method, are employed to simulate adsorption paths of the same uranyl species on the different calcite surfaces under aqueous condition. Outer-sphere adsorption is found to dominate over inner-sphere adsorption because of the high free energy barrier of removing a uranyl-carbonate interaction and replacing it with a new uranyl-surface interaction. An important binding mode is proposed involving a single vicinal water monolayer between the surface and the sorbed complex. From the free energy profiles of the different calcite surfaces, the uranyl complex was also found to adsorb preferentially on the acute-stepped {314̅8} face of calcite, in agreement with experiment.

  20. Origin of zoning within dedolomite and calcitized gypsum of the Mississippian Arroyo Penasco Group

    Energy Technology Data Exchange (ETDEWEB)

    Ulmer, D.S.

    1985-01-01

    The Mississippian Arroyo Penasco Group carbonates are the oldest Paleozoic rocks present in north-central New Mexico. These supratidal to shallow,subtidal sediments exhibit complex diagenetic fabrics produced by periods of pre-Pennsylvanian subaerial exposure. Both extensive recrystallization of the Espiritu Santo carbonates and brecciation of the overlying Macho Member of the Tererro Formation resulted from an extended period of Mississippian subaerial exposure of broad, low-relief tidal flats. Cathodoluminescent petrography indicates that the recrystallized limestones consist of calcite pseudomorphs of dolomite and gypsum. Dedolomite and calcitized gypsum crystals, with /sup 13/C//sup 12/C ratios of -2 to +1.5% PDB, range from highly zoned to uniformly luminescent. Electron microprobe analyses reveals variable Mn and Fe contents across the pseudomorphs which are responsible for differences in observed luminosity. These features are interpreted to reflect a period of subaerial exposure after deposition of Macho Member sediments, which caused dissolution of gypsum and dolomite by sulfate and Mg depleted meteoric fluids and produced the collapse breccia. Preservation of zoning within some pseudomorphs required simultaneous dissolution of gypsum and dolomite and precipitation of calcite. C-isotope data indicates a meteoric to mixed phreatic origin for pore fluids which precipitated calcite; repetitive zoning within dolomite and gypsum pseudomorphs is indicative of interactions between marine and meteoric phreatic fluids in the intertidal environment.

  1. Kinetics and Mechanisms of Cadmium Carbonate Heteroepitaxial Growth at the Calcite (101¯4) Surface

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Man; Kovarik, Libor; Arey, Bruce W.; Felmy, Andrew R.; Rosso, Kevin M.; Kerisit, Sebastien N.

    2014-06-01

    Elucidating the kinetics and mechanisms of heteroepitaxial nucleation and growth at mineral-water interfaces is essential to understanding surface reactivity in geochemical systems. In the present work, the formation of heteroepitaxial cadmium carbonate coatings at calcite-water interfaces was investigated by exposing calcite (10-14) surfaces to Cd-bearing aqueous solutions. In situ atomic force microscopy (AFM) was employed as the primary technique. The AFM results indicate that the heteroepitaxial growth of cadmium carbonate proceeds via three different mechanisms depending on the initial supersaturation of the aqueous solution: advancement of existing steps, nucleation and growth of three-dimensional (3D) islands, and nucleation and spread of two-dimensional (2D) nuclei. The 3D islands and 2D nuclei exhibit different morphologies and growth kinetics. The effects of supersaturation on heteroepitaxial growth mechanisms can be interpreted in terms of the free energy barrier for nucleation. At low initial supersaturation, where 3D nucleation dominates, it is hypothesized, from the growth rate and morphology of the 3D islands observed with AFM, that the crystallization of the overgrowth follows a non-classical pathway involving the formation of a surface precursor that is not fully crystalline, whereas high supersaturation favors the formation of crystalline 2D nuclei whose morphology is based on the atomic structure of the calcite substrate. Cross-sectional transmission electron microscopy (TEM) images reveal that the atomic structure of the interface between the cadmium carbonate coating and calcite shows perfect, dislocation-free epitaxy.

  2. Kinetics and mechanisms of cadmium carbonate heteroepitaxial growth at the calcite (10 1bar 4) surface

    Science.gov (United States)

    Xu, Man; Kovarik, Libor; Arey, Bruce W.; Felmy, Andrew R.; Rosso, Kevin M.; Kerisit, Sebastien

    2014-06-01

    Elucidating the kinetics and mechanisms of heteroepitaxial nucleation and growth at mineral-water interfaces is essential to understanding surface reactivity in geochemical systems. In the present work, the formation of heteroepitaxial cadmium carbonate coatings at calcite-water interfaces was investigated by exposing calcite (10 1bar 4) surfaces to Cd-bearing aqueous solutions. In situ atomic force microscopy (AFM) was employed as the primary technique. The AFM results indicate that the heteroepitaxial growth of cadmium carbonate proceeds via three different mechanisms depending on the initial supersaturation of the aqueous solution: advancement of existing steps, nucleation and growth of three-dimensional (3D) islands, and nucleation and spread of two-dimensional (2D) nuclei. The 3D islands and 2D nuclei exhibit different morphologies and growth kinetics. The effects of supersaturation on heteroepitaxial growth mechanisms can be interpreted in terms of the free energy barrier for nucleation. At low initial supersaturation, where 3D nucleation dominates, it is hypothesized, from the growth rate and morphology of the 3D islands observed with AFM, that the crystallization of the overgrowth follows a non-classical pathway involving the formation of a surface precursor that is not fully crystalline, whereas high supersaturation favors the formation of crystalline 2D nuclei whose morphology is based on the atomic structure of the calcite substrate. Cross-sectional transmission electron microscopy (TEM) images reveal that the atomic structure of the interface between the cadmium carbonate coating and calcite shows perfect, dislocation-free epitaxy.

  3. Microstratigraphic logging of calcite fabrics in speleothems as tool for palaeoclimate studies

    Directory of Open Access Journals (Sweden)

    Silvia Frisia

    2015-01-01

    Full Text Available The systematic documentation of calcite fabrics in stalagmites and flowstones provides robustness to palaeoclimate interpretation based on geochemical proxies, but it has been neglected because it is difficult to transform crystal morphologies into numerical values, and construct fabric time series. Here, general criteria that allow for coding fabrics of calcite composing stalagmites and flowstones is provided. Being based on known models of fabric development, the coding ascribes sequential numbers to each fabric, which reflect climate-related parameters, such as changes in drip rate variability, bio-mediation or diagenetic modifications. Acronyms are proposed for Columnar types, Dendritic, Micrite, Microsparite and Mosaic fabrics, whose use could then render possible comparison of calcite fabrics in stalagmites and flowstones from diverse latitudinal and altitudinal settings. The climatic and environmental significance of similarities in the geochemical signals and trends analysed in coeval stalagmites and flowstones (or differences in the signals and trends will be more robust when compared with fabric time series. This is particularly true where, such as in the Holocene, changes in geochemical values may be subtle, yet fabrics may show changes related to variations in supersaturation, drip rate or input of detrital particles or organic compounds. The proposed microstratigraphic logging allows recognition of changes in stable isotope ratio or trace element values that can be ascribed to hydrology and diagenesis, with considerable improvement of reconstructions based on the chemical proxies of stalagmites and flowstones composed of calcite.

  4. Self-construction of core-shell and hollow zeolite analcime icositetrahedra: a reversed crystal growth process via oriented aggregation of nanocrystallites and recrystallization from surface to core.

    Science.gov (United States)

    Chen, Xueying; Qiao, Minghua; Xie, Songhai; Fan, Kangnian; Zhou, Wuzong; He, Heyong

    2007-10-31

    Zeolite analcime with a core-shell and hollow icositetrahedron architecture was prepared by a one-pot hydrothermal route in the presence of ethylamine and Raney Ni. Detailed investigations on samples at different preparation stages revealed that the growth of the complex single crystalline geometrical structure did not follow the classic crystal growth route, i.e., a crystal with a highly symmetric morphology (such as polyhedra) is normally developed by attachment of atoms or ions to a nucleus. A reversed crystal growth process through oriented aggregation of nanocrystallites and surface recrystallization was observed. The whole process can be described by the following four successive steps. (1) Primary analcime nanoplatelets undergo oriented aggregation to yield discus-shaped particles. (2) These disci further assemble into polycrystalline microspheres. (3) The relatively large platelets grow into nanorods by consuming the smaller ones, and meanwhile, the surface of the microspheres recrystallizes into a thin single crystalline icositetrahedral shell via Ostwald ripening. (4) Recrystallization continues from the surface to the core at the expense of the nanorods, and the thickness of the monocrystalline shell keeps on increasing until all the nanorods are consumed, leading to hollow single crystalline analcime icositetrahedra. The present work adds new useful information for the understanding of the principles of zeolite growth.

  5. Slip and Twinning in the [ 1 ¯ $ /line{mathbf{1}} $ 49]-Oriented Single Crystals of a High-Entropy Alloy

    Science.gov (United States)

    Kireeva, I. V.; Chumlyakov, Yu. I.; Pobedennaya, Z. V.; Platonova, Yu. N.; Kuksgauzen, I. V.; Kuksgauzen, D. A.; Poklonov, V. V.; Karaman, I.; Sehitoglu, H.

    2016-12-01

    Using [ overline{1} 49] - oriented single crystals of an FCC Fe20Ni20Mn20Cr20Co20 (at.%) high-entropy alloy subjected to tensile deformation, the temperature dependence of critical resolved shear stresses τcr(T) and the deformation mechanism of slip and twinning are investigated in the early stages of deformation at ɛ ≤ 5% within the temperature interval T = 77-573 K. It is shown that τcr increases with decreasing the testing temperature and the τcr(T) temperature dependence is controlled by the slip of perfect dislocations a/2. The early deformation stages ɛ ≤ 5% are associated with the development of planar slip by pileups of perfect dislocations a/2, stacking faults and mechanical twins, which is observed in the temperature interval from 77 to 423 K. A comparison of the temperature dependence τcr(T) and the development of mechanical twinning is performed between the [ overline{1} 49] -oriented single crystals of the Fe20Ni20Mn20Cr20Co20 high-entropy alloy, the single crystals of the austenitic stainless steel, Fe - 18% Cr - 12% Ni - 2Mo (wt.%) without nitrogen atoms (Steel 316) and Hadfield steel, Fe - 13% Mn - (1-1.3)% C (wt.%).

  6. Evaluation of the effects of 3D diffusion, crystal geometry, and initial conditions on retrieved time-scales from Fe-Mg zoning in natural oriented orthopyroxene crystals

    Science.gov (United States)

    Krimer, Daniel; Costa, Fidel

    2017-01-01

    Volcano petrologists and geochemists increasingly use time-scale determinations of magmatic processes from modeling the chemical zoning patterns in crystals. Most determinations are done using one-dimensional traverses across a two-dimensional crystal section. However, crystals are three-dimensional objects with complex shapes, and diffusion and re-equilibration occurs in multiple dimensions. Given that we can mainly study the crystals in two-dimensional petrographic thin sections, the determined time-scales could be in error if multiple dimensional and geometrical effects are not identified and accounted for. Here we report the results of a numerical study where we investigate the role of multiple dimensions, geometry, and initial conditions of Fe-Mg diffusion in an orthopyroxene crystal with the view towards proper determinations of time scales from modeling natural crystals. We found that merging diffusion fronts (i.e. diffusion from multiple directions) causes 'additional' diffusion that has the greatest influence close to the crystal's corners (i.e. where two crystal faces meet), and with longer times the affected area widens. We also found that the one-dimensional traverses that can lead to the most accurate calculated time-scales from natural crystals are along the b- crystallographic axis on the ab-plane when model inputs (concentration and zoning geometry) are taken as measured (rather than inferred from other observations). More specifically, accurate time-scales are obtained if the compositional traverses are highly symmetrical and contain a concentration plateau measured through the crystal center. On the other hand, for two-dimensional models the ab- and ac-planes are better suited if the initial (pre-diffusion) concentration and zoning geometry inputs are known or can be estimated, although these are a priory unknown, and thus, may be difficult to use in practical terms. We also found that under certain conditions, a combined one-dimensional and two

  7. Physical and stable-isotope evidence for formation of secondary calcite and silica in the unsaturated zone, Yucca Mountain, Nevada

    Science.gov (United States)

    Whelan, J.F.; Paces, J.B.; Peterman, Z.E.

    2002-01-01

    Calcite and silica form coatings on fracture footwalls and cavity floors in the welded tuffs at Yucca Mountain, the potential site of a high-level radioactive waste repository. These secondary mineral deposits are heterogeneously distributed in the unsaturated zone (UZ) with fewer than 10% of possible depositional sites mineralized. The paragenetic sequence, compiled from deposits throughout the UZ, consists of an early-stage assemblage of calcite??fluorite??zeolites that is frequently capped by chalcedony??quartz. Intermediate- and late-stage deposits consist largely of calcite, commonly with opal on buried growth layers or outermost crystal faces of the calcite. Coatings on steep-dipping fractures usually are thin (??? 3 mm) with low-relief outer surfaces whereas shallow-dipping fractures and lithophysal cavities typically contain thicker, more coarsely crystalline deposits characterized by unusual thin, tabular calcite blades up to several cms in length. These blades may be capped with knobby or corniced overgrowths of late-stage calcite intergrown with opal. The observed textures in the fracture and cavity deposits are consistent with deposition from films of water fingering down fracture footwalls or drawn up faces of growing crystals by surface tension and evaporated at the crystal tips. Fluid inclusion studies have shown that most early-stage and some intermediate-stage calcite formed at temperatures of 35 to 85??C. Calcite deposition during the past several million years appears to have been at temperatures < 30??C. The elevated temperatures indicated by the fluid inclusions are consistent with temperatures estimated from calcite ??18O values. Although others have interpreted the elevated temperatures as evidence of hydrothermal activity and flooding of the tuffs of the potential repository, the authors conclude that the temperatures and fluid-inclusion assemblages are consistent with deposition in a UZ environment that experienced prolonged heat input from

  8. Review - Fabrication of crystal-oriented barium-bismuth titanate ceramics in high magnetic field and subsequent reaction sintering

    Directory of Open Access Journals (Sweden)

    Satoshi Tanaka, Yusuke Tomita, Ryoichi Furushima, Hiroyuki Shimizu, Yutaka Doshida and Keizo Uematsu

    2009-01-01

    Full Text Available High magnetic field was applied to fabricate novel lead-free piezoelectric ceramics with a textured structure. A compact of crystallographically oriented grains was prepared by dry forming in a high magnetic field from a mixed slurry of bismuth titanate and barium titanate powders. Bismuth titanate particles with a size of about 1 μ m were used as the host material. In the forming process, the slurry was poured into a mold and set in a magnetic field of 10 T until completely dried. Bismuth titanate particles were highly oriented in the slurry under the magnetic field. The dried powder compact consisted of highly oriented bismuth titanate particles and randomly oriented barium titanate particles. Barium bismuth titanate ceramics with a- and b-axis orientations were successfully produced from the dried compact by sintering at temperatures above 1100 ° C.

  9. STUDY ON MAGNETIC FIELD-INDUCED ORIENTATION OF A CHIRAL SIDE-CHAIN LIQUID CRYSTAL POLYACRYLATE USING INFRARED DICHROISM

    Institute of Scientific and Technical Information of China (English)

    HE Liu; JIN Shunzi; ZHANG Shufan; QI Zongneng; WANG Fosong

    1996-01-01

    Magnetic field-induced orientation of a chiral side chain liquid crystalline polyacrylate (P-11) was studied by using IR dichroism. For the investigated P-11, it has been shown that the magnetic alignment takes place over the entire temperature range between its melting point and clearing point and the orientation level is strongly temperature-dependent, the development with time of the magnetic orientation follows an exponential-type relation,and the smectic phase state influences the thermal relaxation process in the absence of the magnetic field.

  10. Mapping the 3D distribution of CdSe nanocrystals in highly oriented and nanostructured hybrid P3HT-CdSe films grown by directional epitaxial crystallization.

    Science.gov (United States)

    Roiban, L; Hartmann, L; Fiore, A; Djurado, D; Chandezon, F; Reiss, P; Legrand, J-F; Doyle, S; Brinkmann, M; Ersen, O

    2012-11-21

    Highly oriented and nanostructured hybrid thin films made of regioregular poly(3-hexylthiophene) and colloidal CdSe nanocrystals are prepared by a zone melting method using epitaxial growth on 1,3,5-trichlorobenzene oriented crystals. The structure of the films has been analyzed by X-ray diffraction using synchrotron radiation, electron diffraction and 3D electron tomography to afford a multi-scale structural and morphological description of the highly structured hybrid films. A quantitative analysis of the reconstructed volumes based on electron tomography is used to establish a 3D map of the distribution of the CdSe nanocrystals in the bulk of the films. In particular, the influence of the P3HT-CdSe ratio on the 3D structure of the hybrid layers has been analyzed. In all cases, a bi-layer structure was observed. It is made of a first layer of pure oriented semi-crystalline P3HT grown epitaxially on the TCB substrate and a second P3HT layer containing CdSe nanocrystals uniformly distributed in the amorphous interlamellar zones of the polymer. The thickness of the P3HT layer containing CdSe nanoparticles increases gradually with increasing content of NCs in the films. A growth model is proposed to explain this original transversal organization of CdSe NCs in the oriented matrix of P3HT.

  11. Orientation dependency of shear stress-strain curves in B2-ordered Fe3Al single crystals deformed in tension at room temperature

    Institute of Scientific and Technical Information of China (English)

    郑为为; 杨王玥; 孙祖庆

    2002-01-01

    B2-ordered Fe3Al single crystals with various orientations were deformed in tension at room temperature in vacuum. The shape of shear stress-strain curves and work hardening rates were found to be strongly dependent on the orientation. The formation of the five different work hardening stages were considered to be related to the number of operative slip systems, the effect of secondary slip systems and the dissociation of the twofold superdislocation. Stage I is an easy glide stage corresponding to single slip. Stage II, with high hardening rate, often corresponds to the existence of conjugate slip systems. Stage III, with relatively low hardening rate, corresponds to the weaker hardening of secondary slip systems. Stage IV, with the highest hardening rate, is not only related to multiple slip but also the dissociation of twofold superdislocations and the moving of superpartials with an antiphase boundary (APB) trap. Stages V, with a negative hardening rate, may be caused by the cross slip of single dissociated superdislocation. The number of stages and the work hardening rate of the same stage were also found to change significantly, when the tensile orientation lies in different orientation regions.

  12. Cryogenic and non-cryogenic pool calcites indicating permafrost and non-permafrost periods: a case study from the Herbstlabyrinth-Advent Cave system (Germany

    Directory of Open Access Journals (Sweden)

    D. K. Richter

    2010-11-01

    Full Text Available Weichselian cryogenic calcites collected in what is referred to as the Rätselhalle of the Herbstlabyrinth-Advent Cave system are structurally classified as rhombohedral crystals and spherulitic aggregates. The carbon and oxygen isotopic composition of these precipitates (δ13C = +0.6 to −7.3‰ δ18O = −6.9 to −18.0‰ corresponds to those of known slowly precipitated cryogenic cave calcites under conditions of isotopic equilibrium between water and ice of Central European caves. The carbon and oxygen isotopic composition varies between different caves which is attributed to the effects of cave air ventilation before the freezing started.

    By petrographic and geochemical comparisons of Weichselian cryogenic calcite with recent to sub-recent precipitates as well as Weichselian non-cryogenic calcites of the same locality, a model for the precipitation of these calcites is proposed. While the recent and sub-recent pool-calcites isotopically match the composition of interglacial speleothems (stalagmites, etc., isotope ratios of Weichselian non-cryogenic pool-calcites reflect cooler conditions. Weichselian cryogenic calcites show a trend towards low δ18O values with higher carbon isotope ratios reflecting slow freezing of the precipitating solution. In essence, the isotope geochemistry of the Weichselian calcites reflects the climate history changing from overall initial permafrost conditions to permafrost-free and subsequently to renewed permafrost conditions. Judging from the data compiled here, the last permafrost stage in the Rätselhalle is followed by a warm period (interstadial and/or Holocene. During this warmer period, the cave ice melted and cryogenic and non-cryogenic Weichselian calcite precipitates were deposited on the cave ground or on fallen blocks, respectively.

  13. Biosorption of divalent Pb, Cd and Zn on aragonite and calcite mollusk shells

    Energy Technology Data Exchange (ETDEWEB)

    Du Yang; Lian Fei [Key Laboratory of Pollution Process and Environmental Criteria, Ministry of Education, Tianjin Key Laboratory of Urban Ecology Environmental Remediation and Pollution Control, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Zhu Lingyan, E-mail: zhuly@nankai.edu.cn [Key Laboratory of Pollution Process and Environmental Criteria, Ministry of Education, Tianjin Key Laboratory of Urban Ecology Environmental Remediation and Pollution Control, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China)

    2011-07-15

    The potential of using mollusk shell powder in aragonite (razor clam shells, RCS) and calcite phase (oyster shells, OS) to remove Pb{sup 2+}, Cd{sup 2+} and Zn{sup 2+} from contaminated water was investigated. Both biogenic sorbents displayed very high sorption capacities for the three metals except for Cd on OS. XRD, SEM and XPS results demonstrated that surface precipitation leading to crystal growth took place during sorption. Calcite OS displayed a remarkably higher sorption capacity to Pb than aragonite RCS, while the opposite was observed for Cd. However, both sorbents displayed similar sorption capacities to Zn. These could be due to the different extent of matching in crystal lattice between the metal bearing precipitate and the substrates. The initial pH of the solution, sorbent's dosage and grain size affected the removal efficiency of the heavy meals significantly, while the organic matter in mollusk shells affected the removal efficiency to a lesser extent. - Highlights: > Mollusk shells display high removal efficiency to heavy metals in contaminated water. > Surface precipitation leading to crystal growth takes place during the sorption. > Crystal structure similarity between precipitates and substrates affects the sorption. > pH, sorbent dosage and grain size of adsorbent affects the removal efficiency. > Organic matter in mollusk shells affects the removal efficiency to a less extent. - Mollusk shells display high sorption ability to heavy metals and crystal structure similarity between precipitates and substrates affects the sorption.

  14. Tuning calcite morphology and growth acceleration by a rational design of highly stable protein-mimetics

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Chunlong; Qi, Jiahui; Tao, Jinhui; Zuckermann, Ronald; De Yoreo, James J.

    2014-09-05

    In nature, proteins play a significant role in biomineral formation. One of the ultimate goals of bioinspired materials science is to develop highly stable synthetic molecules that mimic the function of these natural proteins by controlling crystal formation. Here, we demonstrate that both the morphology and the degree of acceleration or inhibition observed during growth of calcite in the presence of peptoids can be rationally tuned by balancing the electrostatic interactions (EI) and hydrophobic interactions (HI), with HI playing the dominant role. While either strong EI or HI inhibit growth and suppress (104) face expression, correlations between peptoid-crystal binding energies and observed changes in calcite growth indicate moderate EI allow peptoids to weakly adsorb while moderate HI cause disruption of surface-adsorbed water layers, leading to growth acceleration with retained expression of (104) faces. This study provides fundamental principles for designing peptoids as crystallization promoters, and offers a straightforward screening method based on macroscopic crystal morphology. Because peptoids are sequence-specific, highly stable, and easily synthesized, peptoid-enhanced crystallization offers a broad range of potential applications.

  15. Tuning calcite morphology and growth acceleration by a rational design of highly stable protein-mimetics

    Science.gov (United States)

    Chen, Chun-Long; Qi, Jiahui; Tao, Jinhui; Zuckermann, Ronald N.; Deyoreo, James J.

    2014-09-01

    In nature, proteins play a significant role in biomineral formation. One of the ultimate goals of bioinspired materials science is to develop highly stable synthetic molecules that mimic the function of these natural proteins by controlling crystal formation. Here, we demonstrate that both the morphology and the degree of acceleration or inhibition observed during growth of calcite in the presence of peptoids can be rationally tuned by balancing the electrostatic and hydrophobic interactions, with hydrophobic interactions playing the dominant role. While either strong electrostatic or hydrophobic interactions inhibit growth and reduces expression of the {104} faces, correlations between peptoid-crystal binding energies and observed changes in calcite growth indicate moderate electrostatic interactions allow peptoids to weakly adsorb while moderate hydrophobic interactions cause disruption of surface-adsorbed water layers, leading to growth acceleration with retained expression of the {104} faces. This study provides fundamental principles for designing peptoids as crystallization promoters, and offers a straightforward screening method based on macroscopic crystal morphology. Because peptoids are sequence-specific, highly stable, and easily synthesized, peptoid-enhanced crystallization offers a broad range of potential applications.

  16. Spectroscopy of discrete vertically oriented single-crystals of n-type tetraazaterrylene: understanding the role of defects in molecular semiconductor photovoltaics.

    Science.gov (United States)

    Wise, A J; Zhang, Y; Fan, J; Wudl, F; Briseno, A L; Barnes, M D

    2014-08-14

    Recent synthetic work has realized a novel (n-type) small-molecule acceptor, 7,8,15,16-tetra-aza-terrylene (TAT), single-crystals of which can be grown oriented along the c-axis crystallographic direction, and over-coated with pentacene to form a highly ordered donor/acceptor interface for use in organic photovoltaic devices. However, characterization of single TAT crystals reveals highly variable emission spectra and excited state dynamics - properties which strongly influence photovoltaic performance. Through the use of single-crystal widefield imaging, photoluminescence spectroscopy, time correlated single photon counting, and resonant Raman studies, we conclude that this variability is a result of long-lived low-energy trap-emission from packing defects. Interestingly, we also discovered that TAT crystals whose width exceeds ∼200 nm begin acting as waveguides and optical microcavity resonators for their own photoluminescence. Several strategies are proposed for leveraging the size-dependant optical properties of TAT pillars to further enhance device performance using this active layer design.

  17. Diagenetic Mg-calcite overgrowths on foraminiferal tests in the vicinity of methane seeps

    Science.gov (United States)

    Panieri, Giuliana; Lepland, Aivo; Whitehouse, Martin J.; Wirth, Richard; Raanes, Morten P.; James, Rachael H.; Graves, Carolyn A.; Crémière, Antoine; Schneider, Andrea

    2017-01-01

    Methane is a potent greenhouse gas and some episodes of past global warming appear to coincide with its massive release from seafloor sediments as suggested by carbon isotope records of foraminifera. Here, we present structural, geochemical, and stable carbon isotope data from single foraminiferal calcite tests and authigenic Mg-calcite overgrowths in a sediment core recovered from an area of active methane seepage in western Svalbard at ca. 340 m water depth. The foraminifera are from intervals in the core where conventional bulk foraminiferal δ13 C values are as low as -11.3 ‰. Mg/Ca analyses of the foraminiferal tests reveal that even tests for which there is no morphological evidence for secondary authigenic carbonate can contain Mg-rich interlayers with Mg/Ca up to 220 mmol/mol. Transmission electron microscopy (TEM) of the contact point between the biogenic calcite and authigenic Mg-calcite layers shows that the two phases are structurally indistinguishable and they have the same crystallographic orientation. Secondary ion mass spectrometry (SIMS) analyses reveal that the Mg-rich layers are strongly depleted in 13C (δ13 C as low as -34.1 ‰). These very low δ13 C values indicate that the authigenic Mg-calcite precipitated from pore waters containing methane-derived dissolved inorganic carbon at the depth of the sulfate-methane transition zone (SMTZ). As the depth of the SMTZ can be located several meters below the sediment-seawater interface, interpretation of low foraminiferal δ13 C values in ancient sediments in terms of the history of methane seepage at the seafloor must be undertaken with care.

  18. The origin of carbon isotope vital effects in coccolith calcite

    Science.gov (United States)

    McClelland, H. L. O.; Bruggeman, J.; Hermoso, M.; Rickaby, R. E. M.

    2017-01-01

    Calcite microfossils are widely used to study climate and oceanography in Earth's geological past. Coccoliths, readily preserved calcite plates produced by a group of single-celled surface-ocean dwelling algae called coccolithophores, have formed a significant fraction of marine sediments since the Late Triassic. However, unlike the shells of foraminifera, their zooplankton counterparts, coccoliths remain underused in palaeo-reconstructions. Precipitated in an intracellular chemical and isotopic microenvironment, coccolith calcite exhibits large and enigmatic departures from the isotopic composition of abiogenic calcite, known as vital effects. Here we show that the calcification to carbon fixation ratio determines whether coccolith calcite is isotopically heavier or lighter than abiogenic calcite, and that the size of the deviation is determined by the degree of carbon utilization. We discuss the theoretical potential for, and current limitations of, coccolith-based CO2 paleobarometry, that may eventually facilitate use of the ubiquitous and geologically extensive sedimentary archive. PMID:28262764

  19. Biomineralization processes of calcite induced by bacteria isolated from marine sediments.

    Science.gov (United States)

    Wei, Shiping; Cui, Hongpeng; Jiang, Zhenglong; Liu, Hao; He, Hao; Fang, Nianqiao

    2015-06-01

    Biomineralization is a known natural phenomenon associated with a wide range of bacterial species. Bacterial-induced calcium carbonate precipitation by marine isolates was investigated in this study. Three genera of ureolytic bacteria, Sporosarcina sp., Bacillus sp. and Brevundimonas sp. were observed to precipitate calcium carbonate minerals. Of these species, Sporosarcina sp. dominated the cultured isolates. B. lentus CP28 generated higher urease activity and facilitated more efficient precipitation of calcium carbonate at 3.24 ± 0.25 × 10(-4) mg/cell. X-ray diffraction indicated that the dominant calcium carbonate phase was calcite. Scanning electron microscopy showed that morphologies of the minerals were dominated by cubic, rhombic and polygonal plate-like crystals. The dynamic process of microbial calcium carbonate precipitation revealed that B. lentus CP28 precipitated calcite crystals through the enzymatic hydrolysis of urea, and that when ammonium ion concentrations reached 746 mM and the pH reached 9.6, that favored calcite precipitation at a higher level of 96 mg/L. The results of this research provide evidence that a variety of marine bacteria can induce calcium carbonate precipitation, and may influence the marine carbonate cycle in natural environments.

  20. Biomineralization processes of calcite induced by bacteria isolated from marine sediments

    Directory of Open Access Journals (Sweden)

    Shiping Wei

    2015-06-01

    Full Text Available Biomineralization is a known natural phenomenon associated with a wide range of bacterial species. Bacterial-induced calcium carbonate precipitation by marine isolates was investigated in this study. Three genera of ureolytic bacteria, Sporosarcina sp., Bacillus sp. and Brevundimonas sp. were observed to precipitate calcium carbonate minerals. Of these species, Sporosarcina sp. dominated the cultured isolates. B. lentus CP28 generated higher urease activity and facilitated more efficient precipitation of calcium carbonate at 3.24 ± 0.25 × 10−4 mg/cell. X-ray diffraction indicated that the dominant calcium carbonate phase was calcite. Scanning electron microscopy showed that morphologies of the minerals were dominated by cubic, rhombic and polygonal plate-like crystals. The dynamic process of microbial calcium carbonate precipitation revealed that B. lentus CP28 precipitated calcite crystals through the enzymatic hydrolysis of urea, and that when ammonium ion concentrations reached 746 mM and the pH reached 9.6, that favored calcite precipitation at a higher level of 96 mg/L. The results of this research provide evidence that a variety of marine bacteria can induce calcium carbonate precipitation, and may influence the marine carbonate cycle in natural environments.

  1. Mineralogical, crystallographic, and isotopic constraints on the precipitation of aragonite and calcite at Shiqiang and other hot springs in Yunnan Province, China

    Science.gov (United States)

    Jones, Brian; Peng, Xiaotong

    2016-11-01

    Two active spring vent pools at Shiqiang (Yunnan Province, China) are characterized by a complex array of precipitates that coat the wall around the pool and the narrow ledges that surround the vent pool. These precipitates include arrays of aragonite crystals, calcite cone-dendrites, red spar calcite, unattached dodecahedral and rhombohedral calcite crystals, and late stage calcite that commonly coats and disguises the earlier formed precipitates. Some of the microbial mats that grow on the ledges around the pools have been partly mineralized by microspheres that are formed of Si and minor amounts of Fe. The calcite and aragonite that are interspersed with each other at all scales are both primary precipitates. Some laminae, for example, change laterally from aragonite to calcite over distances of only a few millimetres. The precipitates at Shiqiang are similar to precipitates found in and around the vent pools of other springs found in Yunnan Province, including those at Gongxiaoshe, Zhuyuan, Eryuan, and Jifei. In all cases, the δDwater and δ18Owater indicate that the spring water is of meteoric origin. These are thermogene springs with the carrier CO2 being derived largely from the mantle and reaction of the waters with bedrock. Variations in the δ13Ctravertine values indicate that the waters in these springs were mixed, to varying degrees, with cold groundwater and its soil-derived CO2. Calcite and aragonite precipitation took place once the spring waters had become supersaturated with respect to CaCO3, probably as a result of rapid CO2 degassing. These precipitates, which were not in isotopic equilibrium with the spring water, are characterized by their unusual crystal morphologies. The precipitation of calcite and aragonite, seemingly together, can probably be attributed to microscale variations in the saturation levels that are, in turn, attributable to microscale variations in the rate of CO2 degassing.

  2. Origin of calcite in the glacigenic Virttaankangas complex

    Directory of Open Access Journals (Sweden)

    Nina M. Kortelainen

    2007-01-01

    Full Text Available Groundwaters of the glacigenic Virttaankangas complex in southern Finland are characterized by high pH values ranging up to 9.5. These values are significantly higher than those observed in silicate-rich shallow groundwater formations in crystalline bedrock areas. TheVirttaankangas sediments were discovered to contain small amounts of fine grained, dispersed calcite, which has a high tendency to increase the pH of local groundwaters. The primary goal of this study was to determine the mode of occurrence of calcite and to identifyits sources. The mineralogy of the glacigenic Virttaankangas complex was studied using material from 21 sediment drill cores. Fine-grained calcite is present in trace amounts (<< 1.4 % in the glaciofluvial and glaciolacustrine depositional units of the Virttaankangas complex. The topmost littoral sands were practically devoid of calcite. The isotope records of carbon and oxygen, the angular morphology of the grains and the uniform dispersion of calcite in the complex suggest a clastic origin for calcite, with no evidence for in-situ precipitation. In order to constrain the source of calcite, the isotopic composition of carbon and oxygen in five calcite samples was compared to the isotopic data from five carbonate rock erratics and eight crystalline bedrock samples from the region. Based on carbon and oxygen isotope ratios and chemical compositions, the dispersed calcite grains of the Virttaankangas complex appear to have been derived from the Mesoproterozoic Satakunta Formation, some 30 km NW from the Virttaankangas area. In sandstone, calcite is predominantly present as diagenetic cement in grain interspaces, concretions and interlayers. The source of detrital calcite was unexpected, as prior to this study the Satakunta sandstone hasnot been known to contain calcite.

  3. Research on the growth orientation of pyrite grains in the colloform textures in Baiyunpu Pb-Zn polymetallic deposit, Hunan, China

    Science.gov (United States)

    Gao, Shang; Huang, Fei; Gu, Xiangping; Chen, Zhenyu; Xing, Miaomiao; Li, Yongli

    2017-02-01

    A large number of colloform-textured pyrites were found in Baiyunpu Pb-Zn ore bodies in Xinshao County, Hunan, China. This study investigates the growth orientation of the pyrite grains in these structures by field emission scanning electron microscopy (FE-SEM), in situ micro X-ray diffraction (μXRD) and electron backscatter diffraction (EBSD). The growth proceeded from micro-crystalline cores in the colloform textures. Moreover, the pyrite layers were discrete and separated by locally significant quantities of galena and calcite. The μXRD results suggested clear crystalline characteristics and weakly preferred orientations of the colloform textures. EBSD confirmed that the pyrite grains exist preferred orientations or in the layered zones. According to the crystal growth theory, the formation and variation of crystal preferred orientations (CPOs) in pyrite are mainly restricted by the internal crystal structure of the pyrite and depends on the external environment conditions, such as trace element concentrations and the supersaturation degree. We inferred the evolutionary regularity of lattice planes with different indices in the pyrite crystal structure from morphological, compositional and growth orientation information, which reflect the crystal growth history of the colloform pyrite. This study will advance our understanding of the growth processes of colloform pyrite and environmental evolution in the Baiyunpu Pb-Zn polymetallic deposits.

  4. The nacre protein perlucin nucleates growth of calcium carbonate crystals.

    Science.gov (United States)

    Blank, S; Arnoldi, M; Khoshnavaz, S; Treccani, L; Kuntz, M; Mann, K; Grathwohl, G; Fritz, M

    2003-12-01

    Atomic force microscopy (AFM) in aqueous solution was used to investigate native nacre of the marine snail Haliotis laevigata on the microscopic scale and the interaction of purified nacre proteins with calcium carbonate crystals on the nanoscopic scale. These investigations were controlled by scanning electron microscopy (SEM), light microscopy (LM) and biochemical methods. For investigations with AFM and SEM, nacre was cleaved parallel to the aragonite tablets in this biogenic polymer/mineral composite. Multilamellar organic sheets consisting of a core of chitin with layers of proteins attached on both sides lay between the aragonite layers consisting of confluent aragonite tablets. Cleavage appeared to occur between the aragonite tablet layer and the protein layer. AFM images revealed a honeycomb-like structure to the organic material with a diameter of the 'honeycombs' equalling that of the aragonite tablets. The walls of the structures consisted of filaments, which were suggested to be collagen. The flat regions of the honeycomb-like structures exhibited a hole with a diameter of more than 100 nm. When incubated in saturated calcium carbonate solution, aragonite needles with perfect vertical orientation grew on the proteinacous surface. After treatment with proteinase K, no growth of orientated aragonite needles was detected. Direct AFM measurements on dissolving and growing calcite crystals revealed a surface structure with straight steps the number of which decreased with crystal growth. When the purified nacre protein perlucin was added to the growth solution (a super-saturated calcium carbonate solution) new layers were nucleated and the number of steps increased. Anion exchange chromatography of the water-soluble proteins revealed a mixture of about 10 different proteins. When this mixture was dialysed against saturated calcium carbonate solution and sodium chloride, calcium carbonate crystals precipitated together with perlucin leaving the other proteins

  5. Search For Past Life On Mars: Physical And Chemical Characterization Of Calcite Minerals Of Biotic And Abiotic Origin

    Science.gov (United States)

    Stalport, Fabien; Coll, P.; Cabane, M.; Person, A.; Navarro-Gonzales, R.; Raulin, F.; Valay, M.; Ausset, P.; Szopa, C.; McKay, C. P.

    2006-09-01

    Several lines of evidence suggest that early Mars once had liquid water on its surface, a denser atmosphere and a mild climate. Similar environmental conditions led to the origin of life on the Earth more than 3.5 billion years ago; consequently, life might also have originated on Mars. We contend that inorganic compounds could give us interesting clues as to the existence of possible biological activity in future astrobiological missions to Mars. Consequently, we have investigated the physical and chemical properties of calcite, which could be expected on Mars because liquid water was certainly present on the surface of early Mars and carbon dioxide was abundant in its atmosphere. Calcite is interesting because on Earth this mineral is produced by abiotic processes as well as by biological activity. One may suppose that crystalline defects and trace element in the crystal lattice and the growth speed of biotic calcites must indicate a difference between them and pure abiotic calcites. We investigated twelve different terrestrial calcite samples from various origins: biotic, diagenetic and abiotic. The minerals were studied by X-ray diffraction and electron scanning microscopy to determine their mineralogical and chemical composition, and differential thermal analysis coupled to thermogravimetric analysis (DTA-TG) to determine their thermal behavior. Our results show that the thermal degradation of abiotic calcite starts at a temperature at least 40°C higher than the degradation temperature of any biotic calcite investigated. Consequently, in the case of a Martian in-situ study or in a sample return mission, the analysis of Martian minerals by DTA-TG represents a promising approach to detect evidence of past biological activity on Mars.

  6. Search for past life on Mars: Physical and chemical characterization of minerals of biotic and abiotic origin: part 1 - Calcite

    Science.gov (United States)

    Stalport, Fabien; Coll, Patrice; Cabane, Michel; Person, Alain; González, Rafael Navarro; Raulin, Francois; Vaulay, Marie Jo; Ausset, Patrick; McKay, Chris P.; Szopa, Cyril; Zarnecki, John

    2005-12-01

    Several lines of evidence suggest that early Mars once had liquid water on its surface, a denser atmosphere and a mild climate. Similar environmental conditions led to the origin of life on the Earth more than 3.5 billion years ago; consequently, life might also have originated on Mars. The Viking landers searched for evidence of organic molecules on the surface of Mars, and found that the Martian soil is depleted in organics at ppb levels at the landing sites. We contend that inorganic compounds could give us interesting clues as to the existence of possible biological activity in future astrobiological missions to Mars. Consequently, we have investigated the physical and chemical properties of calcite, which could be expected on Mars because liquid water was certainly present on the surface of early Mars and carbon dioxide was abundant in its atmosphere. Calcite is interesting because on Earth this mineral is produced by abiotic processes as well as by biological activity. One may suppose that crystalline defects and trace element in the crystal lattice and the growth speed of biotic calcites must indicate a difference between them and pure abiotic calcites. We investigated twelve different terrestrial calcite samples from various origins: biotic, diagenetic and abiotic. The minerals were studied by X-ray diffraction and electron scanning microscopy to determine their mineralogical and chemical composition, and differential thermal analysis coupled to thermogravimetric analysis (DTA-TG) to determine their thermal behavior. Our results show that the thermal degradation of abiotic calcite starts at a temperature at least 40°C higher than the degradation temperature of any biotic calcite investigated. Consequently, in the case of a Martian in-situ study or in a sample return mission, the analysis of Martian minerals by DTA-TG represents a promising approach to detect evidence of past biological activity on Mars.

  7. Microstructure of (110)-Oriented Epitaxial SrRuO3 Thin Films Grown on Off-Cut Single Crystal YSZ(100) Substrates

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Xinhua [Max-Planck-Institut fur Mikrostrukturphysik, Germany; Lee, Sung Kyun [Max-Planck-Institut fur Mikrostrukturphysik, Germany; Lee, Ho Nyung [ORNL; Hesse, Dietrich [Max-Planck-Institut fur Mikrostrukturphysik, Germany

    2005-01-01

    The microstructure of (1 1 0){sup pc}-oriented epitaxial SrRuO{sub 3} (SRO) thin films grown by pulsed laser deposition on (1 0 0)YSZ (YSZ: yttria-stabilized zirconia) single crystal substrates with a miscut angle of 5{sup o} has been investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The films grow epitaxially with their pseudocubic (1 1 0) plane parallel to the (1 0 0) surface of the YSZ single crystal substrate, and with an in-plane orientation relationship of [{ovr 1} 1 1]{sub SRO}//[0 1 1]{sub YSZ}. Cross-sectional TEM investigations show that the films have a rough, facetted surface. Generally, four different azimuthal domains are present in (1 1 0)SRO films on (1 0 0)YSZ. Their number can be significantly reduced using annealed offcut YSZ substrates before SRO deposition, and this reduction effect is shown to be much stronger on [0 1 1]-miscut (1 0 0)YSZ than on [0 0 1]-miscut ones. Size and morphology of the azimuthal pseudocubic domains and their domain boundaries, as well as of anti-phase domains and their domain boundaries are studied by plan-view and cross-section TEM.

  8. Microstructure of (110)-oriented epitaxial SrRuO{sub 3} thin films grown on off-cut single crystal YSZ(100) substrates

    Energy Technology Data Exchange (ETDEWEB)

    Zhu Xinhua [Max-Planck Institut fuer Mikrostrukturphysik, Weinberg 2, D-06120 Halle (Germany)]. E-mail: xhzhu@mpi-halle.de; Lee, Sung Kyun [Max-Planck Institut fuer Mikrostrukturphysik, Weinberg 2, D-06120 Halle (Germany); Lee, Ho Nyung [Condensed Matter Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Hesse, Dietrich [Max-Planck Institut fuer Mikrostrukturphysik, Weinberg 2, D-06120 Halle (Germany)

    2005-04-25

    The microstructure of (110){sup pc}-oriented epitaxial SrRuO{sub 3} (SRO) thin films grown by pulsed laser deposition on (100)YSZ (YSZ: yttria-stabilized zirconia) single crystal substrates with a miscut angle of 5{sup o} has been investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The films grow epitaxially with their pseudocubic (110) plane parallel to the (100) surface of the YSZ single crystal substrate, and with an in-plane orientation relationship of [1-bar 11]{sub SRO}//[011]{sub YSZ}. Cross-sectional TEM investigations show that the films have a rough, facetted surface. Generally, four different azimuthal domains are present in (110)SRO films on (100)YSZ. Their number can be significantly reduced using annealed offcut YSZ substrates before SRO deposition, and this reduction effect is shown to be much stronger on [011]-miscut (100)YSZ than on [001]-miscut ones. Size and morphology of the azimuthal pseudocubic domains and their domain boundaries, as well as of anti-phase domains and their domain boundaries are studied by plan-view and cross-section TEM.

  9. Magnetic properties of epitaxial Fe{sub 3}O{sub 4} films with various crystal orientations and tunnel magnetoresistance effect at room temperature

    Energy Technology Data Exchange (ETDEWEB)

    Nagahama, Taro, E-mail: nagahama@eng.hokudai.ac.jp; Matsuda, Yuya; Tate, Kazuya; Kawai, Tomohiro; Takahashi, Nozomi; Hiratani, Shungo; Watanabe, Yusuke; Yanase, Takashi; Shimada, Toshihiro [Graduate School of Engineering, Hokkaido University, Kita13 Nishi8, Kitak-ku, Sapporo 060-8628 (Japan)

    2014-09-08

    Fe{sub 3}O{sub 4} is a ferrimagnetic spinel ferrite that exhibits electric conductivity at room temperature (RT). Although the material has been predicted to be a half metal according to ab-initio calculations, magnetic tunnel junctions (MTJs) with Fe{sub 3}O{sub 4} electrodes have demonstrated a small tunnel magnetoresistance (TMR) effect. Not even the sign of the tunnel magnetoresistance ratio has been experimentally established. Here, we report on the magnetic properties of epitaxial Fe{sub 3}O{sub 4} films with various crystal orientations. The films exhibited apparent crystal orientation dependence on hysteresis curves. In particular, Fe{sub 3}O{sub 4}(110) films exhibited in-plane uniaxial magnetic anisotropy. With respect to the squareness of hysteresis, Fe{sub 3}O{sub 4} (111) demonstrated the largest squareness. Furthermore, we fabricated MTJs with Fe{sub 3}O{sub 4}(110) electrodes and obtained a TMR effect of −12% at RT. The negative TMR ratio corresponded to the negative spin polarization of Fe{sub 3}O{sub 4} predicted from band calculations.

  10. One-on-One and R-on-One Tests on KDP and DKDP Crystals with Different Orientations

    Institute of Scientific and Technical Information of China (English)

    HU Guo-Hang; ZHAO Yuan-An; SUN Shao-Tao; LI Da-Wei; SUN Xun; SHAO Jian-Da; FAN Zheng-Xiu

    2009-01-01

    By testing a substantial number of tripler and z-cut KDP and DKDP crystals,we have observed that at 355 nm,the laser induced damage threshold in the R-on-one test is higher than that in the one-on-one test.It is proved that laser conditioning is an efficient way to improve the damage resistance.The efficiency of laser conditioning becomes increasingly good with smaller ramping fluence steps.We have also found that the damage resistance of the z-cut crystal is higher than the tripler cut,and the pinpoint number is definitely less in the z-cut crystal.The reason for these observations is discussed.

  11. Controlled synthesis of highly orientation-ordered single crystal Cd{sub 1−x}Zn{sub x}S nanorod array

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Junwei, E-mail: Junw.hou@gmail.com [PetroChina Xinjiang Oilfield Company, Research Institute of Experiment and Detection, Karamay, Xinjiang 834000 (China); Lv, Xiaoyi [Colleges of Information Science and Engineering, Xinjiang University, Urumqi 830046 (China); Li, Zhihong [PetroChina Xinjiang Oilfield Company, Research Institute of Experiment and Detection, Karamay, Xinjiang 834000 (China); Zou, Hua [School of Mathematics and Physics, Jiangsu University of Technology, Changzhou 213001 (China); Zeng, Xiaofei [Department of Science, China University of Petroleum Beijing, Beijing 102249 (China)

    2014-12-15

    Graphical abstract: Well-aligned Cd{sub 1−x}Zn{sub x}S nanorod arrays. - Highlights: • Single crystal Cd{sub 1−x}Zn{sub x}S nanorods arrays were fabricated by chemical vapor deposition method. • The as-synthesized products are high uniformity. • The possible growth mechanism and process of arrays nanostructure has been discussed. - Abstract: In this article, a catalyst-free method for the preparation of orientation-ordered single-crystal Cd{sub 1−x}Zn{sub x}S nanorod arrays on graphite substrates has been reported. The morphology and crystal structure of the Cd{sub 1−x}Zn{sub x}S nanorod arrays were studied using scanning electron microscopy and transmission electron microscopy. The results showed that the nanorods with 40–100 nm in diameter and 2000 nm in length grew along the [0 0 1] direction of the hexagonal crystalline phase. A vapor–solid (VS) growth mechanism was proposed for the formation of the Cd{sub 1−x}Zn{sub x}S nanorod arrays. The photoluminescence characterizations showed a strong blue emission at 420 nm for the Cd{sub 1−x}Zn{sub x}S nanorod arrays when the value of x is 0.5. Thus, with a simple CVD technique, the high-density and orientation-ordered nanorod arrays would become a promising candidate in many applications such as building blocks for optoelectronics.

  12. Switching of magnetic easy-axis using crystal orientation for large perpendicular coercivity in CoFe2O4 thin film

    Science.gov (United States)

    Shirsath, Sagar E.; Liu, Xiaoxi; Yasukawa, Yukiko; Li, Sean; Morisako, Akimitsu

    2016-07-01

    Perpendicular magnetization and precise control over the magnetic easy axis in magnetic thin film is necessary for a variety of applications, particularly in magnetic recording media. A strong (111) orientation is successfully achieved in the CoFe2O4 (CFO) thin film at relatively low substrate temperature of 100 °C, whereas the (311)-preferred randomly oriented CFO is prepared at room temperature by the DC magnetron sputtering technique. The oxygen-deficient porous CFO film after post-annealing gives rise to compressive strain perpendicular to the film surface, which induces large perpendicular coercivity. We observe the coercivity of 11.3 kOe in the 40-nm CFO thin film, which is the highest perpendicular coercivity ever achieved on an amorphous SiO2/Si substrate. The present approach can guide the systematic tuning of the magnetic easy axis and coercivity in the desired direction with respect to crystal orientation in the nanoscale regime. Importantly, this can be achieved on virtually any type of substrate.

  13. Relationship between the orientation of texture and heteroepitaxy of diamond and related materials films on silicon single crystal and the valence electron structure of the interface

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Diamond and cubic boron nitride films have already been applied practically because of their excellent properties. The specific orientations of the films have special meaning on their application in optics and microelectronics fields. In this paper, the relative electron density differences of the interface between the different crystal planes of silicon substrate and those of diamond and cubic boron films are calculated with the empirical electron theory in solids and molecules. Analyses on the calculation results show that in the range of the researched films, the smaller the relative electron density difference between the film and the substrate is, the stabler the film is in thermodynamics. Therefore, the electron density difference is the essential factor of determining the orientation of the texture and heteroepitaxy of the films. The deductions accord well with the experimental facts. The calculation methods and the theory not only provide a new angle of view for the research of the growth mechanism of diamond film and cubic boron nitride film on the silicon substrate, but also provide a possible direction for the prediction of the orientation of other films.

  14. Crystal preferred orientation in peridotite ultramylonites deformed by grain size sensitive creep, étang de Lers, Pyrenees, France

    NARCIS (Netherlands)

    Drury, M.R.; Avé Lallemant, H.G.; Pennock, G.M.; Palasse, L.N.

    2011-01-01

    In naturally deformed upper mantle rocks a strong olivine crystallographic preferred orientation (CPO) occurs in rocks with grain sizes larger than about 15 mm. Finer grained peridotites tend to have weak to random olivine CPO. The different types of olivine CPO are usually interpreted in relation t

  15. Geochemistry of speleothems affected by aragonite to calcite recrystallization - Potential inheritance from the precursor mineral

    Science.gov (United States)

    Domínguez-Villar, David; Krklec, Kristina; Pelicon, Primož; Fairchild, Ian J.; Cheng, Hai; Edwards, Lawrence R.

    2017-03-01

    Formerly aragonite speleothems recrystallized to calcite result from solutions subsaturated in aragonite and supersaturated in calcite that infiltrate into the speleothem through the interconnected porosity. In most cases, the crystal replacement takes place through a thin solution film. This diagenetic process can occur under open or semi-closed geochemical conditions. Thus, secondary calcite crystals record the composition of the fluid at the time of diagenesis affected by calcite partition coefficients and fractionation factors (open system) or partly inherit the composition of the primary aragonite (semi-closed system). So, whether or not recrystallized aragonite speleothems can record reliable geochemical signals from the time of speleothem primary deposition still is an open debate. We studied a stalagmite from Eagle Cave (Spain) predominantly composed of secondary calcite that replaced aragonite, although a core of primary aragonite extending 45 mm along the growth direction was preserved at the base of the sample. We obtained Mg and Sr compositional maps, paired U-Th dating and δ18O and δ13C profiles across the diagenetic front. Additionally, two parallel isotope records were obtained along the speleothem growth direction in the aragonite and calcite sectors. Our results support that recrystallization of this speleothem took place in open system conditions for δ18O, δ13C, Mg and Sr, but in semi-closed system conditions for U and Th. The recrystallization of this sample took place during one or several events, likely after the Younger Dryas as a result of climate change influencing drip water composition. Based on compositional zoned patterns, we suggest that the advance of diagenetic fronts in this speleothem had an average rate of 50 ± 45 μm/yr. Such recrystallization rate can transform any aragonite speleothem into calcite within a few centuries. We suggest that the volume of water interacting with the speleothem at the time of recrystallization is

  16. Calcite and dolomite in intrusive carbonatites. II. Trace-element variations

    Science.gov (United States)

    Chakhmouradian, Anton R.; Reguir, Ekaterina P.; Couëslan, Christopher; Yang, Panseok

    2016-04-01

    The composition of calcite and dolomite from several carbonatite complexes (including a large set of petrographically diverse samples from the Aley complex in Canada) was studied by electron-microprobe analysis and laser-ablation inductively-coupled-plasma mass-spectrometry to identify the extent of substitution of rare-earth and other trace elements in these minerals and the effects of different igneous and postmagmatic processes on their composition. Analysis of the newly acquired and published data shows that the contents of rare-earth elements (REE) and certain REE ratios in magmatic calcite and dolomite are controlled by crystal fractionation of fluorapatite, monazite and, possibly, other minerals. Enrichment in REE observed in some samples (up to ~2000 ppm in calcite) cannot be accounted for by coupled substitutions involving Na, P or As. At Aley, the REE abundances and chondrite-normalized (La/Yb)cn ratios in carbonates decrease with progressive fractionation. Sequestration of heavy REE from carbonatitic magma by calcic garnet may be responsible for a steeply sloping "exponential" pattern and lowered Ce/Ce* ratios of calcite from Magnet Cove (USA) and other localities. Alternatively, the low levels of Ce and Mn in these samples could result from preferential removal of these elements by Ce4+- and Mn3+-bearing minerals (such as cerianite and spinels) at increasing f(O2) in the magma. The distribution of large-ion lithophile elements (LILE = Sr, Ba and Pb) in rock-forming carbonates also shows trends indicative of crystal fractionation effects (e.g., concomitant depletion in Ba + Pb at Aley, or Sr + Ba at Kerimasi), although the phases responsible for these variations cannot be identified unambiguously at present. Overall, element ratios sensitive to the redox state of the magma and its complexing characteristics (Eu/Eu*, Ce/Ce* and Y/Ho) are least variable and in both primary calcite and dolomite, approach the average chondritic values. In consanguineous

  17. The role of silicate surfaces on calcite precipitation kinetics

    DEFF Research Database (Denmark)

    Stockmann, Gabrielle J.; Wolff-Boenisch, Domenik; Bovet, Nicolas Emile

    2014-01-01

    The aim of this study is to illuminate how calcite precipitation depends on the identity and structure of the growth substrate. Calcite was precipitated at 25°C from supersaturated aqueous solutions in the presence of seeds of either calcite or one of six silicate materials: augite, enstatite......, labradorite, olivine, basaltic glass and peridotite rock. Calcite saturation was achieved by mixing a CaCl2-rich aqueous solution with a NaHCO3-Na2CO3 aqueous buffer in mixed-flow reactors containing 0.5-2g of mineral, rock, or glass seeds. This led to an inlet fluid calcite saturation index of 0.6 and a p......H equal to 9.1. Although the inlet fluid composition, flow rate, and temperature were identical for all experiments, the onset of calcite precipitation depended on the identity of the seeds present in the reactor. Calcite precipitated instantaneously and at a constant rate in the presence of calcite...

  18. Sorption and desorption of arsenate and arsenite on calcite

    DEFF Research Database (Denmark)

    Sø, Helle Ugilt; Postma, Diederik Jan; Jakobsen, Rasmus

    2008-01-01

    The adsorption and desorption of arsenate (As(V)) and arsenite (As(111)) oil calcite was investigated in a series of batch experiments in calcite-equilibrated solutions. The solutions covered a broad range of pH, alkalinity, calcium concentration and ionic strength. The initial arsenic...

  19. Emission polarization study on quartz and calcite.

    Science.gov (United States)

    Vincent, R. K.

    1972-01-01

    Calculation of the spectral emission polarization of quartz and calcite polished plates for observation angles of 20 and 70 deg by the substitution of complex index of refraction values for each mineral into Fresnel's equations. The emission polarization is shown to be quite wavelength-dependent, demonstrating that selected narrow or medium-width spectral bands exhibit a significantly higher percentage of polarization than a broad spectral band for these two minerals. Field measurements with a broadband infrared radiometer yield polarizations on the order of 2% for a coarse-grained granite rock and beach sand (both quartz-rich). This implies that a more sensitive detector with a selected medium-width filter may be capable of measuring emission polarization accurately enough to make this parameter useful as a remote sensing tool for discrimination among rocks on the basis of texture.

  20. Rocking curve FWHM maps of a chemically etched (0 0 1) oriented HPHT type Ib diamond crystal plate

    Energy Technology Data Exchange (ETDEWEB)

    Zhong, Y; Macrander, A T; Krasnicki, S; Chu, Y S; Maj, J; Assoufid, L; Qian, J [Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439 (United States)

    2007-09-07

    Synchrotron radiation and a CCD detector were employed to map the full width at half maximum (FWHM) of rocking curves for a synthetic (0 0 1) oriented type Ib diamond plate. The plate was sawed from a diamond grown in the high-pressure-high-temperature (HPHT) process. Maps for broadening relative to a reference point on the diamond for the (2 2 4) reflection at 12 keV are reported before and after chemical etching. Significant rocking curve narrowing over most of the diamond was found, and we conclude that the diffraction performance of (0 0 1) oriented type Ib diamonds can be significantly improved over a large area by chemical etching. Stripes in the map before etching corresponded to grooves formed in the process of sawing the plate out of the as-grown stone. The FWHM map did not correlate with the surface height profile measured after {approx}10 {mu}m were removed from the surface by etching.

  1. Calcite surface structure and reactivity: molecular dynamics simulations and macroscopic surface modelling of the calcite-water interface

    NARCIS (Netherlands)

    Wolthers, M.; Di Tommaso, D.; Du, Z.; de Leeuw, N.H.

    2012-01-01

    Calcite–water interactions are important not only in carbon sequestration and the global carbon cycle, but also in contaminant behaviour in calcite-bearing host rock and in many industrial applications. Here we quantify the effect of variations in surface structure on calcite surface reactivity. Fir

  2. Molecular modeling studies of interactions between sodium polyacrylate polymer and calcite surface

    Science.gov (United States)

    Ylikantola, A.; Linnanto, J.; Knuutinen, J.; Oravilahti, A.; Toivakka, M.

    2013-07-01

    The interactions between calcite pigment and sodium polyacrylate dispersing agent, widely used in papermaking as paper coating components, were investigated using classical force field and quantum chemical approaches. The objective was to understand interactions between the calcite surface and sodium polyacrylate polymer at 300 K using molecular dynamics simulations. A quantum mechanical ab initio Hartree-Fock method was also used to obtain detailed information about the sodium polyacrylate polymer structure. The effect of water molecules (moisture) on the interactions was also examined. Calculations showed that molecular weight, branching and the orientation of sodium polyacrylate polymers influence the interactions between the calcite surface and the polymer. The force field applied, and also water molecules, were found to have an impact on all systems studied. Ab initio Hartree-Fock calculations indicated that there are two types of coordination between sodium atoms and carboxylate groups of the sodium polyacrylate polymer, inter- and intra-carboxylate group coordination. In addition, ab initio Hartree-Fock calculations of the structure of the sodium polyacrylate polymer produced important information regarding interactions between the polymers and carboxylated styrene-butadiene latex particles.

  3. Molecular modeling studies of interactions between sodium polyacrylate polymer and calcite surface

    Energy Technology Data Exchange (ETDEWEB)

    Ylikantola, A. [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); Linnanto, J., E-mail: juha.m.linnanto@gmail.com [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); University of Tartu, Institute of Physics, Riia 142, EE-51014 Tartu (Estonia); Knuutinen, J.; Oravilahti, A. [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); Toivakka, M. [Åbo Akademi University, Laboratory of Paper Coating and Converting and Center for Functional Materials, FI-20500 Turku/Åbo (Finland)

    2013-07-01

    The interactions between calcite pigment and sodium polyacrylate dispersing agent, widely used in papermaking as paper coating components, were investigated using classical force field and quantum chemical approaches. The objective was to understand interactions between the calcite surface and sodium polyacrylate polymer at 300 K using molecular dynamics simulations. A quantum mechanical ab initio Hartree–Fock method was also used to obtain detailed information about the sodium polyacrylate polymer structure. The effect of water molecules (moisture) on the interactions was also examined. Calculations showed that molecular weight, branching and the orientation of sodium polyacrylate polymers influence the interactions between the calcite surface and the polymer. The force field applied, and also water molecules, were found to have an impact on all systems studied. Ab initio Hartree–Fock calculations indicated that there are two types of coordination between sodium atoms and carboxylate groups of the sodium polyacrylate polymer, inter- and intra-carboxylate group coordination. In addition, ab initio Hartree–Fock calculations of the structure of the sodium polyacrylate polymer produced important information regarding interactions between the polymers and carboxylated styrene-butadiene latex particles.

  4. Influence of crystallographic orientation on the magnetic properties of NiFe, Co, and Ni epitaxial fcc films grown on single-crystal substrates

    Science.gov (United States)

    Ohtani, Taiki; Kawai, Tetsuroh; Ohtake, Mitsuru; Futamoto, Masaaki

    2013-08-01

    Ni80Fe20 (at. %), Co, and Ni epitaxial thin films of fcc(100) and fcc(111) orientations are prepared on single-crystal substrates by using an ultra-high-vacuum radio-frequency magnetron sputtering system. The influence of the magnetocrystalline anisotropy on the magnetostriction behavior under in-plane rotating magnetic fields is investigated. Triangular waveforms are observed in the magnetostriction measurements under low rotating fields for films that show four-fold symmetry in the in-plane magnetic anisotropies. The magnetostriction behavior is related to the motion of ninety-degree magnetic domain walls in magnetically unsaturated films. The waveform changes from a triangular to a sinusoidal shape when magnetization saturation is approached under increasing magnetic field. On the other hand, films having almost isotropic in-plane magnetic properties show sinusoidal waveforms even when the films are not magnetically saturated.

  5. Calcite biomineralization by bacterial isolates from the recently discovered pristine karstic herrenberg cave.

    Science.gov (United States)

    Rusznyák, Anna; Akob, Denise M; Nietzsche, Sándor; Eusterhues, Karin; Totsche, Kai Uwe; Neu, Thomas R; Frosch, Torsten; Popp, Jürgen; Keiner, Robert; Geletneky, Jörn; Katzschmann, Lutz; Schulze, Ernst-Detlef; Küsel, Kirsten

    2012-02-01

    Karstic caves represent one of the most important subterranean carbon storages on Earth and provide windows into the subsurface. The recent discovery of the Herrenberg Cave, Germany, gave us the opportunity to investigate the diversity and potential role of bacteria in carbonate mineral formation. Calcite was the only mineral observed by Raman spectroscopy to precipitate as stalactites from seepage water. Bacterial cells were found on the surface and interior of stalactites by confocal laser scanning microscopy. Proteobacteria dominated the microbial communities inhabiting stalactites, representing more than 70% of total 16S rRNA gene clones. Proteobacteria formed 22 to 34% of the detected communities in fluvial sediments, and a large fraction of these bacteria were also metabolically active. A total of 9 isolates, belonging to the genera Arthrobacter, Flavobacterium, Pseudomonas, Rhodococcus, Serratia, and Stenotrophomonas, grew on alkaline carbonate-precipitating medium. Two cultures with the most intense precipitate formation, Arthrobacter sulfonivorans and Rhodococcus globerulus, grew as aggregates, produced extracellular polymeric substances (EPS), and formed mixtures of calcite, vaterite, and monohydrocalcite. R. globerulus formed idiomorphous crystals with rhombohedral morphology, whereas A. sulfonivorans formed xenomorphous globular crystals, evidence for taxon-specific crystal morphologies. The results of this study highlighted the importance of combining various techniques in order to understand the geomicrobiology of karstic caves, but further studies are needed to determine whether the mineralogical biosignatures found in nutrient-rich media can also be found in oligotrophic caves.

  6. Shock Waves Trigger Fault Weakening in Calcite-bearing Rocks During Earthquakes

    Science.gov (United States)

    Spagnuolo, E.; Plumper, O.; Violay, M.; Cavallo, A.; Di Toro, G.

    2014-12-01

    The weakening mechanism of calcite-bearing rocks is still poorly understood though many major earthquakes stroke within carbonate sequences. Insights derive from the laboratory: in experiments performed on calcite-bearing gouges, up to 90% drop in friction is associated to grain size reduction to the nanoscale and the formation of crystal-plastic microstructures suggesting the activation of debated weakening mechanisms (e.g., grain boundary sliding and diffusion creep; nanopowder lubrication). Whatever the case, it is unclear how nanoparticles form and what their role is at the initiation of sliding. To investigate initial fault instability we sheared with a rotary shear apparatus SHIVA pre-cut ring-shaped solid cylinders (50/30 mm ext/int diameter) of Carrara marble (99.9% CaCO3). Rock cylinders were slid for few millimetres(0, 1.5 mm and 5mm) at accelerations (6.5 ms-2) and normal stresses (10 MPa) approaching seismic deformation conditions. Initial slip (nano-fracturing have occurred preserving the grain shape (pulverization) and (3) reaction products attributable to high pressure and high temperature conditions (i.e. calcite decomposition into amorphous carbon rimming the nanograins). All the above features are typical of shock-induced changes in minerals. We interpret the above observations as follows: pre-existing grain boundaries or newly formed defects are the nuclei for the generation of dislocations and for their pile-up; the fast release of those piles-up in avalanches under rapid stress loading (fast moving dislocations) may explain the origin of such a shock-like behaviour responsible for large initial frictional weakening. The passage of the shock wave induces pervasive nanofracturing with grain size reduction to the nano-scale and an abrupt temperature rise responsible for calcite decarbonation and formation of carbon amorphous material.

  7. Orientating layers with adjustable pretilt angles for liquid crystals deposited by a linear atmospheric pressure plasma source

    Energy Technology Data Exchange (ETDEWEB)

    Jian, Shih-Jie; Kou, Chwung-Shan [Department of Physics, National Tsing Hua University, Hsinchu 30013, Taiwan (China); Hwang, Jennchang [Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu 30013, Taiwan (China); Lee, Chein-Dhau; Lin, Wei-Cheng [Material and Chemical Research Laboratories/Industrial Technology Research Institute, Hsinchu 30140, Taiwan (China)

    2013-06-15

    A method for controlling the pretilt angles of liquid crystals (LC) was developed. Hexamethyldisiloxane polymer films were first deposited on indium tin oxide coated glass plates using a linear atmospheric pressure plasma source. The films were subsequently treated with the rubbing method for LC alignment. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy measurements were used to characterize the film composition, which could be varied to control the surface energy by adjusting the monomer feed rate and input power. The results of LC alignment experiments showed that the pretilt angle continuously increased from 0 Degree-Sign to 90 Degree-Sign with decreasing film surface energy.

  8. Orientation and Temperature Dependence of Piezoelectric Properties for Sillenite-Type Bi12TiO20 and Bi12SiO20 Single Crystals

    Directory of Open Access Journals (Sweden)

    Chuanying Shen

    2014-06-01

    Full Text Available The full matrix of electro-elastic constants of sillenite-type crystals Bi12TiO20 (BTO and Bi12SiO20 (BSO were determined by the resonance method, with d14 and k14 being on the order of 40–48 pC/N and 31%–36%, respectively. In addition, double-rotated orientation dependence of d33 was investigated, with the maximum values of 25–28 pC/N being achieved in ZXtl45°/54°-cut samples. The electrical resistivity of BSO was found to be two orders higher than that of BTO, being on the order of 7 × 105 Ω cm at 500 °C. The temperature dependence of dielectric and piezoelectric properties were investigated. BSO exhibited a high thermal stability in the temperature range of 25–500 °C, while BTO showed a variation of ~3% in the range of 25–350 °C. The high values of d14 and k14, together with the good thermal stability, make BTO and BSO crystals potential candidates for electromechanical applications in medium temperature range.

  9. Molecular ordering of ethanol at the calcite surface

    DEFF Research Database (Denmark)

    Pasarín, I. S.; Yang, M.; Bovet, Nicolas Emile

    2012-01-01

    -743 ] and molecular dynamics (MD) modeling [ Yang, M., Stipp, S. L. S., and Harding, J. H.Cryst. Growth Des. 2008, 8 (11), 4066-4074 ], have suggested that OH functional groups control polysaccharide attachment. The purpose of this work was to characterize, using X-ray reflectivity (XR) combined with molecular...... dynamics (MD) simulations, the structuring on calcite of a layer of the simplest carbon chain molecule that contains an OH group, ethanol (CH 3-CH2-OH). We found evidence that EtOH forms a highly ordered structure at the calcite surface, where the first layer molecules bond with calcite. The ethanol...

  10. Calcite Twinning in the Ordovician Martinsburg Formation, Delaware Water Gap, New Jersey, USA: Implications for Cleavage Formation and Tectonic Shortening in the Appalachian Piedmont Province

    Directory of Open Access Journals (Sweden)

    John P. Craddock

    2016-02-01

    Full Text Available A traverse across the Stone Church syncline in the Ordovician Martinsburg turbidites reveals an axial planar cleavage (N40°E, SE dips in regional thrust-related folds (N40°E, shallow plunges and five phases of sparry calcite. Calcite fillings are bedding-parallel, cleavage-parallel, and one vein set cross-cuts both earlier phases; the youngest calcite filling is a bedding-parallel fault gouge that crosscuts the cleavage and preserves top-down-to-the-southeast normal fault kinematics. Calcite veins unique to disharmonically-folded calcareous siltstones (Maxwell, 1962 were also analyzed. Stable isotopic analysis (O, C of all of the calcite phases indicates a uniform fluid source (δ13C −2.0, δ18O −13.3 VPDB and, potentially, a similar precipitation and mechanical twinning age. The twinning strains (n = 1341; average Δσ = −32 MPa; average ε1 = −2.9% in the calcite suite are consistent with SE-NW thrust shortening, and sub-horizontal shortening perpendicular to evolving axial planar cleavage planes in the Stone Church syncline. Calcareous siltstone layers within the Martinsburg Fm. turbidites share concordant bedding planes and are unique, chemically (XRF, but folded and cleaved differently than the surrounding clay-rich Martinsburg turbidites. Neither sediment type yielded detrital zircons. Electron backscatter X-ray diffraction (EBSD and calcite twinning results in a folded calcareous siltstone layer preserving a layer-normal SE-NW shortening strain and Lattice Preferred Orientation (LPO. Shortening axes for the five-phase calcite suite trends ~N40°W, consistent with tectonic transport associated with crystalline nappe emplacement of the Reading Prong within the Piedmont province.

  11. Film Thickness Dependence of Crystal Structure in 100-Oriented Epitaxial Pb(Zr0.65Ti0.35)O3 Films Grown on Single-Crystal Substrates with Different Thermal Expansion Coefficients

    Science.gov (United States)

    Ehara, Yoshitaka; Yasui, Shintaro; Ishii, Koji; Funakubo, Hiroshi

    2012-09-01

    100-oriented epitaxial Pb(Zr0.65Ti0.35)O3 films with various film thicknesses from 0.1 to 3 µm were grown on (100)cSrRuO3 ∥ (100)SrTiO3 and (100)cSrRuO3 ∥ (100)LaNiO3 ∥ (001)CaF2 substrates. The out-of-plane/in-plane lattice parameter ratio of the films on the CaF2 substrates was larger than that on the SrTiO3 substrates up to 1.1 µm film thickness, while (90°-α) (α was defined as the internal tilt angle) was almost 0°. Results of analysis of Raman spectra and piezoresponse images suggest that the 1.1-µm-thick film grown on the (100)cSrRuO3 ∥ (100)LaNiO3 ∥ (001)CaF2 substrate had tetragonal symmetry with a polar-axis orientation. Moreover, the saturation polarization values of the films measured from P-E hysteresis loops correspond to the two Ps values estimated from the thermodynamic theory, assuming the change in the polar direction due to the symmetry change to tetragonal, and from the crystal distortion in tetragonal symmetry. This can be explained by the large compressive stress from the CaF2 substrate having a large thermal expansion coefficient.

  12. Climate and cave control on Pleistocene/Holocene calcite-to-aragonite transitions in speleothems from Morocco: Elemental and isotopic evidence

    Science.gov (United States)

    Wassenburg, Jasper A.; Immenhauser, Adrian; Richter, Detlev K.; Jochum, Klaus Peter; Fietzke, Jan; Deininger, Michael; Goos, Manuela; Scholz, Denis; Sabaoui, Abdellah

    2012-09-01

    The occurrence of aragonite in speleothems has commonly been related to high dripwater Mg/Ca ratios, because Mg is known to be a growth inhibitor for calcite. Laboratory aragonite precipitation experiments, however, suggested a more complex array of controlling factors. Here, we present data from Pleistocene to Holocene speleothems collected from both a dolostone and a limestone cave in northern Morocco. These stalagmites exhibit both lateral and stratigraphic calcite-to-aragonite transitions. Aragonite fabrics are well-preserved and represent primary features. In order to shed light on the factors that control alternating calcite and aragonite precipitation, elemental (Mg, Sr, Ba, U, P, Y, Pb, Al, Ti and Th) abundances were measured using LA-ICP-MS, and analysed with Principal Component Analysis. Samples were analyzed at 100-200 μm resolution across stratigraphic and lateral transitions. Carbon and oxygen isotope ratios were analysed at 100 μm resolution covering stratigraphic calcite-to-aragonite transitions. Results show that the precipitation of aragonite was driven by a decrease in effective rainfall, which enhanced prior calcite precipitation. Different geochemical patterns are observed between calcite and aragonite when comparing data from the Grotte de Piste and Grotte Prison de Chien. This may be explained by the increased dripwater Mg/Ca ratio and enhanced prior aragonite precipitation in the dolostone cave versus lower dripwater Mg/Ca ratio and prior calcite precipitation in the limestone cave. A full understanding for the presence of lateral calcite-to-aragonite transitions is not reached. Trace elemental analysis, however, does suggest that different crystallographic parameters (ionic radius, amount of crystal defect sites, adsorption potential) may have a direct effect on the incorporation of Sr, Mg, Ba, Al, Ti, Th and possibly Y and P.

  13. Trace metal distribution and isotope variations in low-temperature calcite and groundwater in granitoid fractures down to 1 km depth

    Science.gov (United States)

    Drake, Henrik; Tullborg, Eva-Lena; Hogmalm, K. Johan; Åström, Mats E.

    2012-05-01

    methods used depended on the crystal homogeneity (one or several calcite generations), discerned by detailed SEM-investigations (back-scatter and cathodo-luminescence). 87Sr/86Sr ratios as well as δ18O signatures in calcite are in the range expected for the precipitates from present-day groundwater, or older groundwater with similar composition (except in sections with a considerable portion of glacial water, where calcite definitely is older than the latest glaciation). Stable carbon isotopes in calcite generally show values typically associated with HCO3- originating from soil organic matter but at intermediate depth frequently with HCO3- originating from in situ microbial anaerobic oxidation of methane (highly depleted δ13C). For one of the studied metals - manganese - there was a strong correlation between the sampled calcite coatings and hypothetical calcite predicted by applying laboratory-based partition coefficients (literature data) on groundwater chemistry for sections corresponding to those where the calcites were sampled. This points to temporal and spatial stability in groundwater Mn/Ca ratios over millions of years, or even more, and show that it is possible to assess, based on laboratory-derived data on Mn partitioning, past groundwater Mn-composition from fracture calcites. For other metals - Fe, Sr, and Mg - which are expected to interact with co-precipitating minerals to a higher degree than Mn, the correlations between measured and predicted calcite were weaker for various reasons.

  14. Relative Shock Effects in Mixed Powders of Calcite, Gypsum, and Quartz: A Calibration Scheme from Shock Experiments

    Science.gov (United States)

    Bell, Mary S.

    2009-01-01

    The shock behavior of calcite and gypsum is important in understanding the Cretaceous/Tertiary event and other terrestrial impacts that contain evaporite sediments in their targets. Most interest focuses on issues of devolatilization to quantify the production of CO2 or SO2 to better understand their role in generating a temporary atmosphere and its effects on climate and biota [e.g., papers in 1,2,3,4]. Devolatilization of carbonate is also important because the dispersion and fragmentation of ejecta is strongly controlled by the expansion of large volumes of gas during the impact process as well [5,6]. Shock recovery experiments for calcite yield seemingly conflicting results: early experimental devolatilization studies [7,8,9] suggested that calcite was substantially outgassed at 30 GPa (> 50%). However, the recent petrographic work of [10,11,12] presented evidence that essentially intact calcite is recovered from 60 GPa experiments. [13] reported results of shock experiments on anhydrite, gypsum, and mixtures of those phases with silica. Their observations indicate little or no devolatilization of anhydrite shocked to 42 GPa and that the fraction of sulfur, by mass, that degassed is approx.10(exp -2) of theoretical prediction. In another (preliminary) report of shock experiments on calcite, anhydrite, and gypsum, [14] observe calcite recrystallization when shock loaded at 61 GPa, only intensive plastic deformation in anhydrite shock loaded at 63 GPa, and gypsum converted to anhydrite when shock loaded at 56 GPa. [15] shock loaded anhydrite and quartz to a peak pressure of 60 GPa. All of the quartz grains were trans-formed to glass and the platy anhydrite grains were completely pseudomorphed by small crystallized anhydrite grains. However, no evidence of interaction between the two phases could be observed and they suggest that recrystallization of anhydrite grains is the result of a solid state transformation. [16] reanalyzed the calcite and anhydrite shock

  15. An AFM study of calcite dissolution in concentrated electrolyte solutions

    Science.gov (United States)

    Ruiz Agudo, E.; Putnis, C. V.; Putnis, A.; Rodriguez-Navarro, C.

    2009-04-01

    Calcite-solution interactions are of a paramount importance in a range of processes such as the removal of heavy metals, carbon dioxide sequestration, landscape modeling, weathering of building stone and biomineralization. Water in contact with minerals often carries significant amounts of solutes; additionally, their concentration may vary due to evaporation and condensation. It is well known that calcite dissolution is affected dramatically by the presence of such solutes. Here we present investigations on the dissolution of calcite in the presence of different electrolytes. Both bulk (batch reactors) experiments and nanoscale (in situ AFM) techniques are used to study the dissolution of calcite in a range of solutions containing alkaly cations balanced by halide anions. Previous works have indicated that the ionic strength has little influence in calcite dissolution rates measured from bulk experiments (Pokrovsky et al. 2005; Glendhill and Morse, 2004). Contrary to these results, our quantitative analyses of AFM observations show an enhancement of the calcite dissolution rate with increasing electrolyte concentration. Such an effect is concentration-dependent and it is most evident in concentrated solutions. AFM experiments have been carried out in a fluid cell using calcite cleavage surfaces in contact with solutions of simple salts of the alkaly metals and halides at different undersaturations with respect to calcite to try to specify the effect of the ionic strength on etch pit spreading rate and calcite dissolution rate. These results show that the presence of soluble salts may critically affect the weathering of carbonate rocks in nature as well as the decay of carbonate stone in built cultural heritage. References: Pokrosky, O.S.; Golubev, S.V.; Schott, J. Dissolution kinetics of calcite, dolomite and magnesite at 25°C and 0 to 50 atm pCO2. Chemical Geology, 2005, 217 (3-4) 239-255. Glendhill, D.K.; Morse, J.W. Dissolution kinetics of calcite in Na

  16. Thermoluminescence glow curve of {gamma}-irradiated calcite

    Energy Technology Data Exchange (ETDEWEB)

    Singh, S.D.; Ingotombi, S. [Manipur Univ. (India). Dept. of Physics

    1995-07-14

    The trapping parameters, namely the activation energy E, frequency factor s and b order of kinetics of the thermoluminescence (TL) peaks of calcites (brown and colourless varieties) irradiated with 4.08 kGy of {gamma}-rays, are determined using the least-squares curve-fitting technique. The electron lifetime {tau} of the peaks of calcite are calculated in order to estimate the upper limit of their utility in TL dating. (author).

  17. Symmetric Euler orientation representations for orientational averaging.

    Science.gov (United States)

    Mayerhöfer, Thomas G

    2005-09-01

    A new kind of orientation representation called symmetric Euler orientation representation (SEOR) is presented. It is based on a combination of the conventional Euler orientation representations (Euler angles) and Hamilton's quaternions. The properties of the SEORs concerning orientational averaging are explored and compared to those of averaging schemes that are based on conventional Euler orientation representations. To that aim, the reflectance of a hypothetical polycrystalline material with orthorhombic crystal symmetry was calculated. The calculation was carried out according to the average refractive index theory (ARIT [T.G. Mayerhöfer, Appl. Spectrosc. 56 (2002) 1194]). It is shown that the use of averaging schemes based on conventional Euler orientation representations leads to a dependence of the result from the specific Euler orientation representation that was utilized and from the initial position of the crystal. The latter problem can be overcome partly by the introduction of a weighing factor, but only for two-axes-type Euler orientation representations. In case of a numerical evaluation of the average, a residual difference remains also if a two-axes type Euler orientation representation is used despite of the utilization of a weighing factor. In contrast, this problem does not occur if a symmetric Euler orientation representation is used as a matter of principle, while the result of the averaging for both types of orientation representations converges with increasing number of orientations considered in the numerical evaluation. Additionally, the use of a weighing factor and/or non-equally spaced steps in the numerical evaluation of the average is not necessary. The symmetrical Euler orientation representations are therefore ideally suited for the use in orientational averaging procedures.

  18. Selective Flotation of Calcite from Fluorite: A Novel Reagent Schedule

    Directory of Open Access Journals (Sweden)

    Zhiyong Gao

    2016-10-01

    Full Text Available Fluorite is an important strategic mineral. In general, fluorite ores will contain a certain amount of calcite gangue mineral. Thus, they need to be separated from each other. For an economic separation, a reverse flotation process is used to float calcite gangue from fluorite. However, little information on the separation is available. In this study, a novel reagent schedule using citric acid (CA as the depressant, sodium fluoride (NaF as the regulator and sulfoleic acid (SOA as the collector, was developed to separate calcite from fluorite. The results demonstrated a high selectivity for the flotation of calcite from fluorite using this new reagent schedule. The best selective separation for a single mineral and mixed binary minerals was obtained when 200 mg/L of NaF, 50 mg/L of CA, and 6 mg/L of SOA were used at pH 9. In addition, a batch flotation experiment was carried out using a run-of-mine feed material. Selective separation was achieved with 85.18% calcite removal while only 11.2% of fluorite was lost. An attempt was made to understand the effect of the new reagent schedule on the flotation of calcite. The results from both microflotation and bench scale flotation demonstrated a great potential for industrial application using this novel reagent schedule to upgrade fluorite ore.

  19. Orientation Dependence of Functional Properties in Heterophase Single Crystals of the Ti36.5Ni51.0Hf12.5 and Ti48.5Ni51.5 Alloys

    Science.gov (United States)

    Panchenko, E. Yu.; Chumlyakov, Yu. I.; Surikov, N. Yu.; Tagiltsev, A. I.; Vetoshkina, N. G.; Osipovich, K. S.; Maier, H.; Sehitoglu, H.

    2016-03-01

    The features of orientation dependence of stress-induced thermoelastic B2-( R)- B19'-martensitic transformations in single crystals of the Ti48.5Ni51.5 and Ni51.0Ti36.5Hf12.5 (at.%) alloys, which contain disperse particles of the Ti3Ni4 and H-phase, respectively, are revealed along with those of their shape-memory effects (SME) and superelasticity (SE). It is experimentally demonstrated that irrespective of the crystal structure of disperse particles measuring more than 100 nm, for their volume fraction f > 16% there is a weaker orientation dependence of the reversible strain in the cases of manifestation of SME and SE. In the orientations of Class I, wherein martensitic detwinning introduces a considerable contribution into transformation strain, the values of SME |ɛ SME | and SE |ɛ SE | decrease by over a factor of two compared to the theoretical lattice strain value |ɛ tr0 | for a B2- B19'-transformation and the experimental values of reversible strain for quenched TiNi crystals. In the orientations of Class 2, wherein detwinning of the martensite is suppressed as is the case in quenched single-phase single crystals, the reversible strain is maintained close to its theoretical value |ɛ tr0 |. Micromechanical models of interaction between the martensite and the disperse particles are proposed, which account for the weaker orientation dependence of |ɛ SME | and |ɛ SE | due to suppression of detwinning of the B19'-martensite crystals by the particles and a transition from a single-variant evolution of the stress-induced martensitic transformations to a multiple-variant evolution of transformations in the cases of increased size of the particles and their larger volume fractions.

  20. Calcite Farming at Hollow Ridge Cave: Calibrating Net Rainfall and Cave Microclimate to Dripwater and Calcite Chemical Variability

    Science.gov (United States)

    Tremaine, D. M.; Kilgore, B. P.; Froelich, P. N.

    2012-04-01

    Stable isotope (δ18O and δ13C) and trace element records in cave speleothems are often interpreted as climate changes in rainfall amount or source, cave air temperature, overlying vegetation and atmospheric pCO2. However, these records are difficult to verify without in situ calibration of changes in cave microclimate (e.g., net rainfall, interior ventilation changes) to contemporaneous variations in dripwater and speleothem chemistry. In this study at Hollow Ridge Cave (HRC) in Marianna, Florida (USA), cave dripwater, bedrock, and modern calcite (farmed in situ) were collected in conjunction with continuous cave air pCO2, temperature, barometric pressure, relative humidity, radon-222 activity, airflow velocity and direction, rainfall amount, and drip rate data [1]. We analyzed rain and dripwater δD and δ18O, dripwater Ca2+, pH, δ13C and TCO2, cave air pCO2 and δ13C, and farmed calcite δ18O and δ13C to examine the relationships among rainwater isotopic composition, cave air ventilation, cave air temperature, calcite growth rate and seasonal timing, and calcite isotopic composition. Farmed calcite δ13C decreases linearly with distance from the front entrance to the interior of the cave during all seasons, with a maximum entrance-to-interior gradient of Δδ13C = -7‰ . A whole-cave "Hendy test" at distributed contemporaneous farming sites reveals that ventilation induces a +1.9 ± 0.96‰ δ13C offset between calcite precipitated in a ventilation flow path and out of flow paths. Farmed calcite δ18O exhibits a +0.82 ± 0.24‰ offset from values predicted by both theoretical calcite-water calculations and by laboratory-grown calcite [2]. Unlike calcite δ13C, oxygen isotopes show no ventilation effects and are a function only of temperature. Combining our data with other speleothem studies, we find a new empirical relationship for cave-specific water-calcite oxygen isotope fractionation across a range of temperatures and cave environments: 1000 ln α = 16

  1. THE ORIENTATION OF CaCO3 ARAGONITE CRYSTALS FROM SEVERAL ORGANISMS%几种生物CaCO3霰石结晶的取向性

    Institute of Scientific and Technical Information of China (English)

    蒋新农; 李敬之; 徐学红

    2001-01-01

    The CaCO3 crystals are widely distributed in organisms. Thecalcite, aragonite and vaterite are the main crystal polymorphisms of CaCO3. In this paper, CaCO3 crystals were obtained from the nacreous layers of Hyriopsis cumingii Lea and Pinctada martensii Dunker, the internal shell of a cuttlefish and the otolith of Pseudosciaena crocea. X-ray diffraction measurement was used to analyze the crystal orientation of CaCO3 crystals: The results showed that each kind of natural CaCO3 crystal has an orientation on specific plane. In detail, the crystal orientations of the nacreous layers are higher than the internal shell, and the orientation of the otolith is the lowest. Except the nacreous layers of Pinctada martensii, whose highest peak is on the crystal plane (312), all the other three natural samples have the highest peak on the crystal plane (012). As to ground CaCO3 crystals, the differences between their corresponding d values are very small, so each ground sample has the CaCO3 aragonite structure characterized by the JCPDS card (5-0453).%CaCO3结晶广泛分布于生物界,其主要结晶形式为方解石、霰石及球霰石。用X-射线衍射法对三角帆蚌及合浦珍珠母贝的珍珠层、墨鱼骨和大黄鱼耳石的CaCO3结晶进行测定,发现各样品均有一定取向性,以三角帆蚌和合浦珍珠母贝珍珠层的取向性为最强,墨鱼骨的取向性次之,大黄鱼耳石的取向性最小,以上材料粉末样的衍射分析表明,各样品对应d值间差异极小,均为X射线衍射卡(5-0453)所表征的CaCO3霰石结构。

  2. Calcite precipitation on glass substrates and active stalagmites in Katerloch Cave (Austria): Constraints from environmental monitoring

    Science.gov (United States)

    Sakoparnig, Marlene; Boch, Ronny; Wang, Xianfeng; Lin, Ke; Spötl, Christoph; Leis, Albrecht; Gollowitsch, Anna; Dietzel, Martin

    2016-04-01

    Located near Graz at the SE-rim of the Alps Katerloch is well-known for its impressive dripstone decoration, e.g. several metres tall and relatively fast growing (0.2-0.7 mm/yr on average) candle-stick-type stalagmites. In the course of an ongoing multi-annual and partially high-resolution cave monitoring program we study modern (active) sites of carbonate deposition focusing on the site-specific growth dynamics and connection of modern regional and cave environmental conditions with petrographic, chemical and stable isotopic information captured in the speleothems. Fresh calcite precipitates on artificial (glass) substrates underneath active drip sites were collected continuously from 2006 to 2014 (eight years!). The samples (up to 7 mm thick) represent cave sections of different temperature and drip sites of partially different characteristics (e.g. drip rate). We also recovered short drill cores (up to 3 cm length, 1 cm diameter) from the top of active stalagmites probably representing the last decades to centuries of calcite crystallization. Moreover, an actively growing stalagmite (K10) comprising both modern and past calcite deposition was collected. 238U-234U-230Th dating using MC-ICP-MS of K10 (71 cm long) revealed several distinct growth intervals (separated by growth interruptions) starting at 129.1 ±1.2 kyr BP (Last Interglacial) up to now, mostly reflecting warm and humid climate intervals. High-resolution (100 μm) isotope profiles micromilled from the multi-annual modern calcite precipitates on artificial substrates revealed low δ13C values of -12.8 to -8.3 ‰ (VPDB) and relatively high δ18O of -6.9 to -4.9 ‰Ṫhe δ18O curves from all collection sites (different growth rate) record a pronounced decrease during their most recent growth period most likely corresponding to a significant decrease towards lower oxygen isotope values observed in drip waters collected in the year 2014 compared with samples from 2005 to 2007. Drip water δ2H /δ18O

  3. Residues Asp164 and Glu165 at the substrate entryway function potently in substrate orientation of alanine racemase from E. coli: Enzymatic characterization with crystal structure analysis.

    Science.gov (United States)

    Wu, Dalei; Hu, Tiancen; Zhang, Liang; Chen, Jing; Du, Jiamu; Ding, Jianping; Jiang, Hualiang; Shen, Xu

    2008-06-01

    Alanine racemase (Alr) is an important enzyme that catalyzes the interconversion of L-alanine and D-alanine, an essential building block in the peptidoglycan biosynthesis. For the small size of the Alr active site, its conserved substrate entryway has been proposed as a potential choice for drug design. In this work, we fully analyzed the crystal structures of the native, the D-cycloserine-bound, and four mutants (P219A, E221A, E221K, and E221P) of biosynthetic Alr from Escherichia coli (EcAlr) and studied the potential roles in substrate orientation for the key residues involved in the substrate entryway in conjunction with the enzymatic assays. Structurally, it was discovered that EcAlr is similar to the Pseudomonas aeruginosa catabolic Alr in both overall and active site geometries. Mutation of the conserved negatively charged residue aspartate 164 or glutamate 165 at the substrate entryway could obviously reduce the binding affinity of enzyme against the substrate and decrease the turnover numbers in both D- to L-Ala and L- to D-Ala directions, especially when mutated to lysine with the opposite charge. However, mutation of Pro219 or Glu221 had only negligible or a small influence on the enzymatic activity. Together with the enzymatic and structural investigation results, we thus proposed that the negatively charged residues Asp164 and Glu165 around the substrate entryway play an important role in substrate orientation with cooperation of the positively charged Arg280 and Arg300 on the opposite monomer. Our findings are expected to provide some useful structural information for inhibitor design targeting the substrate entryway of Alr.

  4. Principal molecular axis and transition dipole moment orientations in liquid crystal systems: an assessment based on studies of guest anthraquinone dyes in a nematic host.

    Science.gov (United States)

    Sims, Mark T; Abbott, Laurence C; Cowling, Stephen J; Goodby, John W; Moore, John N

    2016-12-21

    An assessment of five different definitions of the principal molecular axis along which molecules align in a nematic liquid crystal system has been made by analysing fully atomistic molecular dynamics (MD) simulations of a set of anthraquinone dyes in the cyanobiphenyl-based nematic host mixture E7. Principal molecular axes of the dyes defined by minimum moment of inertia, minimum circumference, minimum area, maximum aspect ratio, and surface tensor models were tested, and the surface tensor model was found to give the best description. Analyses of MD simulations of E7 alone showed that the surface tensor model also gave a good description of the principal molecular axes of the host molecules, suggesting that this model may be applicable more generally. Calculated dichroic order parameters of the guest-host systems were obtained by combining the surface tensor analysis with fixed transition dipole moment (TDM) orientations from time-dependent density functional theory (TD-DFT) calculations on optimised structures of the dyes, and the trend between the dyes generally matched the trend in the experimental values. Additional analyses of the guest-host simulations identified the range of conformers explored by the flexible chromophores within the dyes, and TD-DFT calculations on corresponding model structures showed that this flexibility has a significant effect on the TDM orientations within the molecular frames. Calculated dichroic order parameters that included the effects of this flexibility gave a significantly improved match with the experimental values for the more flexible dyes. Overall, the surface tensor model has been shown to provide a rationale for the experimental alignment trends that is based on molecular shape, and molecular flexibility within the chromophores has been shown to be significant for the guest-host systems: the computational approaches reported here may be used as a general aid in the predictive design of dyes with appropriate molecular

  5. Anisotropic dynamics of water ultraconfined in macroscopically oriented channels of single-crystal beryl: a multifrequency analysis.

    Science.gov (United States)

    Anovitz, Lawrence M; Mamontov, Eugene; ben Ishai, Paul; Kolesnikov, Alexander I

    2013-11-01

    The properties of fluids can be significantly altered by the geometry of their confining environments. While there has been significant work on the properties of such confined fluids, the properties of fluids under ultraconfinement, environments where, at least in one plane, the dimensions of the confining environment are similar to that of the confined molecule, have not been investigated. This paper investigates the dynamic properties of water in beryl (Be(3)Al(2)Si(6)O(18)), the structure of which contains approximately 5-Å-diam channels parallel to the c axis. Three techniques, inelastic neutron scattering, quasielastic neutron scattering, and dielectric spectroscopy, have been used to quantify these properties over a dynamic range covering approximately 16 orders of magnitude. Because beryl can be obtained in large single crystals we were able to quantify directional variations, perpendicular and parallel to the channel directions, in the dynamics of the confined fluid. These are significantly anisotropic and, somewhat counterintuitively, show that vibrations parallel to the c-axis channels are significantly more hindered than those perpendicular to the channels. The effective potential for vibrations in the c direction is harder than the potential in directions perpendicular to it. There is evidence of single-file diffusion of water molecules along the channels at higher temperatures, but below 150 K this diffusion is strongly suppressed. No such suppression, however, has been observed in the channel-perpendicular direction. Inelastic neutron scattering spectra include an intramolecular stretching O-H peak at ~465 meV. As this is nearly coincident with that known for free water molecules and approximately 30 meV higher than that in liquid water or ice, this suggests that there is no hydrogen bonding constraining vibrations between the channel water and the beryl structure. However, dielectric spectroscopic measurements at higher temperatures and lower

  6. Defluoridation of drinking water by boiling with brushite and calcite.

    Science.gov (United States)

    Larsen, M J; Pearce, E I F

    2002-01-01

    Existing methods for defluoridating drinking water involve expensive high technology or are slow, inefficient and/or unhygienic. A new method is now suggested, encompassing brushite and calcite suspension followed by boiling. Our aim was to examine the efficiency of the method and the chemical reactions involved. Brushite, 0.3-0.5 g, and an equal weight of calcite were suspended in 1 litre water containing 5-20 ppm fluoride. The suspensions were boiled in an electric kettle, left to cool and the calcium salts to sediment. Solution ion concentrations were determined and sediments were examined by X-ray diffraction. In distilled water initially containing 5, 10 and 20 ppm fluoride the concentration was reduced to 0.06, 0.4 and 5.9 ppm, respectively. Using Aarhus tap water which contained 2.6 mmol/l calcium the final concentrations were 1.2, 2.5 and 7.7 ppm, respectively, and runs without calcite gave results similar to those with calcite. Without boiling the fluoride concentration remained unaltered, as did the brushite and calcite salts, despite occasional agitation by hand. All solutions were supersaturated with respect to fluorapatite and hydroxyapatite and close to saturation with respect to brushite. Boiling produced well-crystallised apatite and traces of calcite, while boiling of brushite alone left a poorly crystallised apatite. We conclude that boiling a brushite/calcite suspension rapidly converts the two salts to apatite which incorporates fluoride if present in solution, and that this process may be exploited to defluoridate drinking water.

  7. Photoinduced synthesis of single-digit micrometer-size spheroidal calcite composites in the presence of partially hydrolyzed poly(vinyl alcohol)

    Science.gov (United States)

    Nishio, Takashi; Naka, Kensuke

    2015-06-01

    Photoinduced crystallization of calcium carbonate (CaCO3), which was based on the photodecarboxylation of ketoprofen (KP, 2-(3-benzoylphyenyl)propionic acid) under alkaline conditions of pH 8.4 and 10 was studied for preparation of CaCO3 composite particles in single-digit micrometer-sizes. In this method, a homogeneous solution comprising KP, calcium chloride, ammonia, and partially hydrolyzed poly(vinyl alcohol) (PVAPS, degree of saponification: 86.5-89.0 mol%) was used as a precursor solution and was exposed to ultraviolet (UV) irradiation for different time periods. After the UV irradiation for 50 min, calcite spheroids in single-digit micrometer-sizes were obtained as major products at pH 8.4. The obtained calcite spheroids contained organic components of about 10 wt%. The comparison of the characteristics of the CaCO3 obtained at pH 8.4 and 10 suggests that the nucleation and crystallization of both vaterite and calcite continuously took place in a moderated supersaturation owing to the CO2 hydration equilibrium as long as the photodecarboxylation of KP continued. Consequently, the aggregation-based crystal growth in the presence of PVAPS seemed to enable the formation of the spheroidal composites of calcite in single-digit micrometer-sizes.

  8. Desired crystal oriented LiFePO4 nanoplatelets in situ anchored on a graphene cross-linked conductive network for fast lithium storage.

    Science.gov (United States)

    Wang, Bo; Liu, Anmin; Abdulla, Wael Al; Wang, Dianlong; Zhao, X S

    2015-05-21

    Electron transfer and lithium ion diffusion rates are the key factors limiting the lithium ion storage in anisotropic LiFePO4 electrodes. In this work, we employed a facile solvothermal method to synthesize a "platelet-on-sheet" LiFePO4/graphene composite (LFP@GNs), which is LiFePO4 nanoplatelets in situ grown on graphene sheets with highly oriented (010) facets of LiFePO4 crystals. Such a two-phase contact mode with graphene sheets cross-linked to form a three-dimensional porous network is favourable for both fast lithium ion and electron transports. As a result, the designed LFP@GNs displayed a high rate capability (∼56 mA h g(-1) at 60 C) and long life cycling stability (∼87% capacity retention over 1000 cycles at 10 C). For comparison purposes, samples ex situ modified with graphene (LFP/GNs) as well as pure LiFePO4 platelets (LFP) were also prepared and investigated. More importantly, the obtained LFP@GNs can be used as a basic unit for constructing more complex structures to further improve electrochemical performance, such as coating the exposed LFP surface with a thin layer of carbon to build a C@LFP@GN composite to further enhance its cycling stability (∼98% capacity retention over 1000 cycles at 10 C).

  9. Relationship between thermodynamic parameter and thermodynamic scaling parameter for orientational relaxation time for flip-flop motion of nematic liquid crystals.

    Science.gov (United States)

    Satoh, Katsuhiko

    2013-03-07

    Thermodynamic parameter Γ and thermodynamic scaling parameter γ for low-frequency relaxation time, which characterize flip-flop motion in a nematic phase, were verified by molecular dynamics simulation with a simple potential based on the Maier-Saupe theory. The parameter Γ, which is the slope of the logarithm for temperature and volume, was evaluated under various conditions at a wide range of temperatures, pressures, and volumes. To simulate thermodynamic scaling so that experimental data at isobaric, isothermal, and isochoric conditions can be rescaled onto a master curve with the parameters for some liquid crystal (LC) compounds, the relaxation time was evaluated from the first-rank orientational correlation function in the simulations, and thermodynamic scaling was verified with the simple potential representing small clusters. A possibility of an equivalence relationship between Γ and γ determined from the relaxation time in the simulation was assessed with available data from the experiments and simulations. In addition, an argument was proposed for the discrepancy between Γ and γ for some LCs in experiments: the discrepancy arises from disagreement of the value of the order parameter P2 rather than the constancy of relaxation time τ1(*) on pressure.

  10. The Raman spectrum of CaCO{sub 3} polymorphs calcite and aragonite: A combined experimental and computational study

    Energy Technology Data Exchange (ETDEWEB)

    De La Pierre, Marco, E-mail: cedric.carteret@univ-lorraine.fr, E-mail: marco.delapierre@unito.it; Maschio, Lorenzo; Orlando, Roberto; Dovesi, Roberto [Dipartimento di Chimica, Università di Torino and NIS (Nanostructured Interfaces and Surfaces) Centre of Excellence, Via P. Giuria 7, 10125 Torino (Italy); Carteret, Cédric, E-mail: cedric.carteret@univ-lorraine.fr, E-mail: marco.delapierre@unito.it; André, Erwan [Laboratoire de Chimie Physique et Microbiologie pour l’Environnement (LCPME), UMR 7564, Université de Lorraine-CNRS, 405 rue de Vandoeuvre, 54601 Villers-lès-Nancy (France)

    2014-04-28

    Powder and single crystal Raman spectra of the two most common phases of calcium carbonate are calculated with ab initio techniques (using a “hybrid” functional and a Gaussian-type basis set) and measured both at 80 K and room temperature. Frequencies of the Raman modes are in very good agreement between calculations and experiments: the mean absolute deviation at 80 K is 4 and 8 cm{sup −1} for calcite and aragonite, respectively. As regards intensities, the agreement is in general good, although the computed values overestimate the measured ones in many cases. The combined analysis permits to identify almost all the fundamental experimental Raman peaks of the two compounds, with the exception of either modes with zero computed intensity or modes overlapping with more intense peaks. Additional peaks have been identified in both calcite and aragonite, which have been assigned to {sup 18}O satellite modes or overtones. The agreement between the computed and measured spectra is quite satisfactory; in particular, simulation permits to clearly distinguish between calcite and aragonite in the case of powder spectra, and among different polarization directions of each compound in the case of single crystal spectra.

  11. Hydrochemical controls on aragonite versus calcite precipitation in cave dripwaters

    Science.gov (United States)

    Rossi, Carlos; Lozano, Rafael P.

    2016-11-01

    Despite the paleoclimatic relevance of primary calcite to aragonite transitions in stalagmites, the relative role of fluid Mg/Ca ratio, supersaturation and CO32- concentration in controlling such transitions is still incompletely understood. Accordingly, we have monitored the hydrochemistry of 50 drips and 8 pools that are currently precipitating calcite and/or aragonite in El Soplao and Torca Ancha Caves (N. Spain), investigating the mineralogy and geochemistry of the CaCO3 precipitates on the corresponding natural speleothem surfaces. The data reveal that, apart from possible substrate effects, dripwater Mg/Ca is the only obvious control on CaCO3 polymorphism in the studied stalagmites and pools, where calcite- and aragonite-precipitating dripwaters are separated by an initial (i.e. at stalactite tips) Mg/Ca threshold at ≈1.1 mol/mol. Within the analyzed ranges of pH (8.2-8.6), CO32- concentration (1-6 mg/L), supersaturation (SIaragonite: 0.08-1.08; SIcalcite: 0.23-1.24), drip rate (0.2-81 drops/min) and dissolved Zn (6-90 μg/L), we observe no unequivocal influence of these parameters on CaCO3 mineralogy. Despite the almost complete overlapping supersaturations of calcite- and aragonite-precipitating waters, the latter are on average less supersaturated because the waters having Mg/Ca above ∼1.1 have mostly achieved such high ratios by previously precipitating calcite. Both calcite and aragonite precipitated at or near oxygen isotopic equilibrium, and Mg incorporation into calcite was consistent with literature-based predictions, indicating that in the studied cases CaCO3 precipitation was not significantly influenced by strong kinetic effects. In the studied cases, the calcites that precipitate at ∼11 °C from dripwaters with initial Mg/Ca approaching ∼1.1 incorporate ∼5 mol% MgCO3, close to the published value above which calcite solubility exceeds aragonite solubility, suggesting that aragonite precipitation in high-relative-humidity caves is

  12. A Raman spectroscopic comparison of calcite and dolomite.

    Science.gov (United States)

    Sun, Junmin; Wu, Zeguang; Cheng, Hongfei; Zhang, Zhanjun; Frost, Ray L

    2014-01-03

    Raman spectroscopy was used to characterize and differentiate the two minerals calcite and dolomite and the bands related to the mineral structure. The (CO3)(2-) group is characterized by four prominent Raman vibrational modes: (a) the symmetric stretching, (b) the asymmetric deformation, (c) asymmetric stretching and (d) symmetric deformation. These vibrational modes of the calcite and dolomite were observed at 1440, 1088, 715 and 278 cm(-1). The significant differences between the minerals calcite and dolomite are observed by Raman spectroscopy. Calcite shows the typical bands observed at 1361, 1047, 715 and 157 cm(-1), and the special bands at 1393, 1098, 1069, 1019, 299, 258 and 176 cm(-1) for dolomite are observed. The difference is explained on the basis of the structure variation of the two minerals. Calcite has a trigonal structure with two molecules per unit cell, and dolomite has a hexagonal structure. This is more likely to cause the splitting and distorting of the carbonate groups. Another cause for the difference is the cation substituting for Mg in the dolomite mineral.

  13. Texture evolution in calcite gouge formed at sub-seismic slip

    Science.gov (United States)

    Delle Piane, Claudio; Luzin, Vladimir; Timms, Nick E.; Ben Clennell, M.; Giwelli, Ausama

    2016-04-01

    Carbonate rocks are abundant in the upper crust and are notoriously seismogenic with Mw>6 earthquakes nucleating in fault zones in carbonate dominated units around the world. Field observations describe fault zones as characterised by a narrow principal slip zone at their core, containing fine, granular wear material referred to as fault gouge, produced during cumulative slip. The current literature on the link between texture and frictional properties of calcite gouges is very limited and somewhat contradictory: based on the study of a natural calcite gouge a link has been proposed between the presence of a crystallographic preferred orientation (CPO) and past seismic activity on the gouge hosting fault zone. However, similar features in terms of CPO were also identified on gouges experimentally generated at slip velocities well below the seismic ones, therefore questioning their interpretation as diagnostic of past seismic events. We studied the evolution of friction coefficient and texture on calcite gouges experimentally produced by means of high pressure direct shear experiments on large, water saturated, intact blocks of travertine (calcite 99 % wt.). Several blocks were deformed at room temperature up to different amounts of maximum displacements (20 mm, 70 mm and 120 mm) under an imposed sub-seismic slip rate of approximately 0.1 microns/s. Microstructural characterization of the deformed blocks was subsequently carried out on samples representing the highest strained portion s of each blocks (i.e. gouge zones). Local and bulk texture of the original and deformed materials was studied by means of electron backscattered diffraction (EBSD) and neutron diffraction, respectively. Direct shear experiments consistently indicate an evolution of the friction coefficient stabilizing at around values of 0.6 after 15 mm of slip. Macroscopic observations on the deformed blocks indicate that deformation is localised in a narrow band of extreme grain size reduction

  14. Stability of Basalt plus Anhydrite plus Calcite at HP-HT: Implications for Venus, the Earth and Mars

    Science.gov (United States)

    Martin, A. M.; Righter, K.; Treiman, A. H.

    2010-01-01

    "Canali" observed at Venus surface by Magellan are evidence for very long melt flows, but their composition and origin remain uncertain. The hypothesis of water-rich flow is not reasonable regarding the temperature at Venus surface. The length of these channels could not be explained by a silicate melt composition but more likely, by a carbonate-sulfate melt which has a much lower viscosity (Kargel et al 1994). One hypothesis is that calcite CaCO3 and anhydrite CaSO4 which are alteration products of basalts melted during meteorite impacts. A famous example recorded on the Earth (Chicxulub) produced melt and gas rich in carbon and sulfur. Calcite and sulfate evaporites are also present on Mars surface, associated with basalts. An impact on these materials might release C- and S-rich melt or fluid. Another type of planetary phenomenon (affecting only the Earth) might provoke a high pressure destabilization of basalt+anhydrite+calcite. Very high contents of C and S are measured in some Earth s magmas, either dissolved or in the form of crystals (Luhr 2008). As shown by the high H content and high fO2 of primary igneous anhydrite-bearing lavas, the high S content in their source may be explained by subduction of an anhydrite-bearing oceanic crust, either directly (by melting followed by eruption) or indirectly (by release of S-rich melt or fluid that metasomatize the mantle) . Calcite is a major product of oceanic sedimentation and alteration of the crust. Therefore, sulfate- and calcite-rich material may be subducted to high pressures and high temperatures (HP-HT) and release S- and C-rich melts or fluids which could influence the composition of subduction zone lavas or gases. Both phenomena - meteorite impact and subduction - imply HP-HT conditions - although the P-T-time paths are different. Some HP experimental/theoretical studies have been performed on basalt/eclogite, calcite and anhydrite separately or on a combination of two. In this study we performed piston

  15. The equilibrium between diagenetic calcites and dolomites and its impact on reservoir quality in the sandstone reservoir of Kela 2 gas field

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Based on the equilibrium theory of chemical reactions between water and rocks, this paper establishes a thermodynamic phase relationship diagram among calcites, dolomites and water solution under the condition of diagenesis based on the thermodynamic database of related minerals and fluids and dolomite's degree of order parameters. It has been discovered that the equilibrium between calcites and dolomites in the diagenetic environment is strongly impacted by temperature and the Ca/Mg ratios in groundwater, and that the dolomite's degree of order in the diagenetic environment is a function of crystallization temperature and time, not controlled by water solution. Hereby, the authors make a further analysis of the close relationship of chemical reaction between carbonate cements and pore water in the sandstone reservoirs of Kala 2 gas field in Kuche sag. It can be seen that there are different impacts on sandstone reservoir quality among the equilibrium system of calcites, dolomites and pore water at different depths of reservoirs.

  16. Crystal orientation dependence of band matching in all-B2-trilayer current-perpendicular-to-plane giant magnetoresistance pseudo spin-valves using Co{sub 2}Fe(Ge{sub 0.5}Ga{sub 0.5}) Heusler alloy and NiAl spacer

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jiamin; Hono, K., E-mail: kazuhiro.hono@nims.go.jp [National Institute for Materials Science, 1-2-1, Sengen, Tsukuba 305-0047 (Japan); Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-2-1, Sengen, Tsukuba 305-0047 (Japan); Furubayashi, T.; Takahashi, Y. K.; Sasaki, T. T. [National Institute for Materials Science, 1-2-1, Sengen, Tsukuba 305-0047 (Japan)

    2015-05-07

    We have experimentally investigated the crystal orientation dependence of band matching in current-perpendicular-to-plane giant magnetoresistance (CPP-GMR) pseudo-spin-valves using Co{sub 2}Fe(Ge{sub 0.5}Ga{sub 0.5}) (CFGG) Heusler alloy ferromagnetic layer and NiAl spacer. The high quality epitaxial CFGG/NiAl/CFGG all-B2-trilayers structure devices were fabricated on both MgO(001) and sapphire (112{sup ¯}0) single crystal substrates to create (001) and (110) crystal orientations. Same magneto-transport properties were observed from these two differently orientated devices indicating that there is no or little orientation dependence of band matching on MR output. We also found that all-B2-trilayer structure was free of lattice matching influence depending on the crystal orientation, which made it a good candidate for CPP-GMR device.

  17. Climate proxies from Sr/Ca of coccolith calcite: calibrations from continuous culture of Emiliania huxleyi

    Science.gov (United States)

    Stoll, Heather M.; Rosenthal, Yair; Falkowski, Paul

    2002-03-01

    Continuous culture of the coccolithophorid Emiliania huxleyi reveals that coccolith Sr/Ca ratios depend on temperature and growth rate. At a constant temperature of 18°C, coccolith Sr/Ca ratios increased nearly 15% as growth rate increased from 0.1 to 1.5 divisions per day and calcification rate increased from 1.5 to 50 pg calcite per cell per day. When temperature increased from 7 to 26°C, Sr/Ca ratios increased by more than 25% (i.e., 1%/1°C), although the range in growth and calcification rates was the same as for experiments at constant temperature. The temperature dependence of Sr/Ca ratios in coccoliths is consistent with that observed in planktonic foraminifera and abiogenic calcites, suggesting that it is controlled by thermodynamic processes. However, the positive correlation of coccolith Sr/Ca with temperature contrasts with field studies in the equatorial Pacific, where Sr/Ca ratios are highest at the locus of maximum upwelling and productivity despite depressed temperatures. This paradox may reflect different calcification rate effects between E. huxleyi and the other species dominating assemblages in the equatorial Pacific sediments, which may be resolved by new techniques for separation of monospecific coccolith samples from sediments. Models of crystal growth indicate that kinetic effects on Sr partitioning in calcite due to surface enrichment could explain the Sr/Ca variations observed in constant temperature experiments but not the larger amplitude calcification rate effects observed in equatorial Pacific sediments. Despite the dual influence of temperature and growth rate on coccolith Sr/Ca, coccolith Sr/Ca correlates with "b," the slope of the dependence of carbon isotope fractionation in biomarkers (ɛ p) on CO 2(aq) at a range of growth rates and temperatures. Consequently, using coccolith Sr/Ca in combination with alkenone ɛ p may improve paleo-CO 2 determinations.

  18. Shell microstructure and its inheritance in the calcitic helcionellid Mackinnonia

    Directory of Open Access Journals (Sweden)

    Michael J. Vendrasco

    2015-02-01

    Full Text Available Mackinnonia davidi from the Cambrian (Series 2 of Australia has a prismatic outer shell layer and, as newly described here, a calcitic semi-nacre inner layer. The pattern is the same as in stenothecids such as Mellopegma, providing more evidence for a strong phylogenetic signal in the shell microstructure of Cambrian molluscs. In addition, calcite now appears to have been common in helcionellids and other molluscs during the early and middle Cambrian, with many species exhibiting foliated calcite. This is surprising given the dominance of aragonite in molluscs, both modern and from post-Cambrian fossil deposits with exceptional shell microstructure preservation, including localities from the Ordovician of the Cincinnati region, USA.

  19. Isotopic and elemental proxies in mollusc and brachiopod calcite

    DEFF Research Database (Denmark)

    Ullmann, Clemens Vinzenz

    This thesis summarizes the findings of studies conducted at the University of Copenhagen from September 2010 to September 2013, aiming at a better understanding of the geochemical signatures in marine, biogenic calcite. Throughout the history of the Earth, the climatic conditions and the chemical...... for a meaningful interpretation of isotopic and elemental ratios in shell materials. Without this knowledge the correct interpretation of the shell composition in terms of past environments is impossible. Calcite shells of brachiopods, bivalves and belemnites were analyzed here for shell ultra...

  20. Diagenetic alteration in low-Mg calcite from macrofossils

    DEFF Research Database (Denmark)

    Ullmann, Clemens Vinzenz; Korte, Christoph

    2015-01-01

    microscopy) and chemical (trace element abundances, isotopic ratios) screening techniques used to assess the alteration degree of low-Mg calcite macrofossils and summarize the findings on diagenetic trends observed for elemental and isotopic systems in such materials. For a robust evaluation...... of the preservation state of biogenic calcite, it is advisable to combine a set of complementary techniques. Absolute limiting values of element and isotope ratios for discarding diagenetically altered materials cannot be universally applied, but should rather be evaluated on a case to case basis. The evaluation can...

  1. Geochemical signatures of fluid paleo-transfer in fracture filling calcite from low permeability rock masses: examples taken from Bure's and Tournemire's site in France and northern Switzerland; Signatures geochimiques de paleocirculations aqueuses dans la calcite de remplissage de fracture de massifs argileux peu permeables et de leurs encaissants: exemples pris sur les sites de Bure, Tournemire et Suisse du nord

    Energy Technology Data Exchange (ETDEWEB)

    Lecocq, D

    2002-12-15

    Fractures in rock masses represent preferential path for fluid transfer and, as such, are the most efficient way for migration of radionuclides at a regional scale. The impact of fracturing on hydrogeological system is a major challenge for underground radioactive waste storage projects. In this context, geochemistry of fracture-filling calcite is used to better understand physical and chemical properties of palaeo-fluids. A new methodology has been developed to analyze Mg, Mn, Fe, Sr and Rare Earth Elements REE (La, Ce, Nd, Sm, Eu, Dy and Yb) in calcite by Secondary Ion Mass Spectrometry. Analyses of calcite crystals have been performed in fractures from Jurassic clays and limestones in France (Bure and Tournemire sites) and northern Switzerland (Mt Terri's tunnel and deep borehole). On each case, several geochemical signatures are observed, according to REE partitioning and Mn and Fe concentrations. In the Bure site, a dependence of calcite geochemistry from fracture host rock has been evidenced. On the other hand, speciation of REE in solution equilibrated with clayey or calcareous rocks at circum-neutral pH (7 to 8) is not significantly influenced by the media: speciation is dominated by carbonate species in both cases and phosphate complexes can modify heavy REE availability in relatively to light REE. These results point out that in fractures in clays, calcite crystallizes at equilibrium with a fluid expulsed during diagenesis from clay minerals, recording the effect of clays and accessory phases. In limestone fractures, calcite records a later event related to the past functioning of the present aquifer, and the fluid has reached equilibrium with the rock minerals. In secondary filling calcite from Toarcian Argilites faults close to Tournemire's tunnel, three successive generations of calcite are observed in an extensive fault, and a fourth in a compressive one. In Aalenian Opalinus Clays veins, comparison between existing isotopic data and Mn, Fe

  2. Ion microprobe assessment of the heterogeneity of Mg/Ca, Sr/Ca and Mn/Ca ratios in Pecten maximus and Mytilus edulis (bivalvia shell calcite precipitated at constant temperature

    Directory of Open Access Journals (Sweden)

    P. S. Freitas

    2009-07-01

    Full Text Available Small-scale heterogeneity of biogenic carbonate elemental composition can be a significant source of error in the accurate use of element/Ca ratios as geochemical proxies. In this study ion microprobe (SIMS profiles showed significant small-scale variability of Mg/Ca, Sr/Ca and Mn/Ca ratios in new shell calcite of the marine bivalves Pecten maximus and Mytilus edulis that was precipitated during a constant-temperature culturing experiment. Elevated Mg/Ca, Sr/Ca and Mn/Ca ratios were found to be associated with the deposition of elaborate shell features, i.e. a shell surface stria in P. maximus and surface shell disturbance marks in both species, the latter a common occurrence in bivalve shells. In both species the observed small-scale elemental heterogeneity most likely was not controlled by variable transport of ions to the extra-pallial fluid, but by factors such as the influence of shell organic content and/or crystal size and orientation, the latter reflecting conditions at the shell crystal-solution interface. In the mid and innermost regions of the P. maximus shell the lack of significant small-scale variation of Mg/Ca ratios, which is consistent with growth at constant temperature, suggest a potential application as a palaeotemperature proxy. Cross-growth band element/Ca ratio profiles in the interior of bivalve shells may provide more promising palaeo-environmental tools than sampling from the outer region of bivalve shells.

  3. Carboxylated Agarose (CA)-Silk Fibroin (SF) Dual Confluent Matrices Containing Oriented Hydroxyapatite (HA) Crystals: Biomimetic Organic/Inorganic Composites for Tibia Repair.

    Science.gov (United States)

    Hu, Jing-Xiao; Ran, Jia-Bing; Chen, Si; Jiang, Pei; Shen, Xin-Yu; Tong, Hua

    2016-07-11

    By in situ combining the dual cross-linking matrices of the carboxylated agarose (CA) and the silk fibroin (SF) with the hydroxyapatite (HA) crystals, the CA-SF/HA composites with optimal physicochemical and biological properties were obtained, which were designed to meet the clinical needs of load-bearing bone repair. With the synergistic modulation of the dual organic matrices, the HA nanoparticles presented sheet and rod morphologies due to the preferred orientation, which successfully simulated the biomineralization in nature. The chemical reactivity of the native agarose (NA) was significantly enhanced via carboxylation, and the CA exhibited higher thermal stability than the NA. In the presence of SF, the composites showed optimal mechanical properties that could meet the standard of bone repair. The degradation of the composites in the presence of CA and SF was significantly delayed such that the degradation rate of the implant could satisfy the growth rate of the newly formed bone tissue. The in vitro tests confirmed that the CA-SF/HA composite scaffolds enabled the MG63 cells to proliferate and differentiate well, and the CA/HA composite presented greater capability of promoting the cell behaviors than the NA/HA composite. After 24 days of implantation, newly formed bone was observed at the tibia defect site and around the implant. Extensive osteogenesis was presented in the rats treated with the CA-SF/HA composites. In general, the CA-SF/HA composites prepared in this work had the great potential to be applied for repairing large bone defects.

  4. Orientation effects on the bandgap and dispersion behavior of 0.91Pb(Zn1/3Nb2/3)O3-0.09PbTiO3 single crystals

    Institute of Scientific and Technical Information of China (English)

    He Chong-Jun; Fu Xin-Duo; Xu Feng; Wang Ji-Ming; Zhu Kong-Jun; Du Chao-Ling; Liu You-Wen

    2012-01-01

    0.91Pb(Znl/3Nb2/3)O3-0.09PbTiO3(PZN-9%PT)single crystals with different orientations are investigated by using a spectroscopic ellipsometer,and the refractive indices and the extinction coefficients are obtained.The Sellmeier dispersion equations for the refractive indices are obtained by the least square fitting,which can be used to calculate the refractive indices in a low absorption wavelength range.Average Sellmeier oscillator parameters Eo,λo,So,and Ed are calculated by fitting with the single-term oscillator equation,which are related directly to the electronic energy hand structure.The optical energy bandgaps are obtained from the absorption coefficient spectra.Our results show that the optical properties of [001] and [111] poled crystals are very similar,but quite different from those of the [011]poled crystal.

  5. Reconstructing Cambro-Ordovician Seawater Composition using Clumped Isotope Paleothermometry on Calcitic and Phosphatic Brachiopods

    Science.gov (United States)

    Bergmann, K.; Robles, M.; Finnegan, S.; Hughes, N. C.; Eiler, J. M.; Fischer, W. W.

    2012-12-01

    A secular increase in δ18O values of marine fossils through early Phanerozoic time raises questions about the evolution of climate and the water cycle. This pattern suggests two end-member hypotheses 1) surface temperatures during early Paleozoic time were very warm, in excess of 40°C (tropical MAT), or 2) the isotopic composition of seawater increased by up to 7-8‰. It has been difficult to evaluate these hypotheses because the δ18O composition of fossils depends on both temperature and the δ18O of water. Furthermore, primary isotopic signatures can be overprinted by diagenetic processes that modify geological materials. This too could explain the decrease in δ18O values of marine fossils with age. Carbonate clumped isotope thermometry can constrain this problem by providing an independent measure of crystallization temperature and, when paired with classical δ18O paleothermometry, can determine the isotopic composition of the fluid the mineral last equilibrated with. Combined with traditional tools, this method has the potential to untangle primary isotopic signatures from diagenetic signals. We measured the isotopic ordering of CO3 groups (Δ47) substituted into the phosphate lattice of phosphatic brachiopods in Cambrian strata. Phosphatic fossils are generally less soluble than carbonates in surface and diagenetic environments, and so are hypothesized to provide a more robust record of primary growth conditions. They also provide an archive prior to the rise of thick shelled calcitic fossils during the Ordovician Radiation. Additionally, measurements of the δ18O of the CO3 groups can be compared with the δ18O of PO4 groups to test whether their mutual fractionation is consistent with primary growth and the apparent temperature recorded by carbonate clumped isotope measurements. We are constructing a phosphatic brachiopod calibration for carbonate clumped isotope thermometry, and Δ47 values of CO2 extracted from modern phosphatic brachiopods suggest

  6. New inversion of calcite twin data for paleostress tested and calibrated on numerically-generated and natural data

    Science.gov (United States)

    Parlangeau, Camille; Lacombe, Olivier; Schueller, Sylvie; Daniel, Jean-Marc

    2016-04-01

    The inversion of calcite twin data is a powerful tool to reconstruct paleostresses sustained by carbonate rocks during their geological history. Following Etchecopar's (1984) pioneering work, this study presents a new technique of inversion of calcite twin data, which allows reconstructing the 5 parameters of the deviatoric stress tensor. In order to determine the applicability domain of the technique as well as to estimate the uncertainties on the reconstructed stress tensors, we first carried out tests on numerically generated calcite twin data and tested the separability of superimposed stress tensors with various degrees of similarity and the influence of optical bias, heterogeneities and occurrence of different grain size classes as met in natural samples. For monophase datasets with homogeneous grain size, the errors on the different stress parameters (orientation of principal stress axes, stress ratio and differential stresses) are negligible except for the differential stress (error of 5%). In cases displaying distinct grain sizes, misfits remain negligible but may reach 20% for the differential stress if the differential stress applied is greater than 60-65 MPa. Incorporation of optical bias slightly increases uncertainties up to 25% for the differential stress, 5% for the stress ratio and 8° for the orientation of the principal stress axes. For polyphase datasets with homogeneous grain size, the misfit on the orientation of the principal stress axes increases up to 10°, the stress ratio remains well constrained and the misfit on differential stress reaches 20% (applied differential stress > 70 MPa). Incorporation of optical bias increases the misfit of the orientation of the principal stress axes (average misfit: 6-8°; maximum: 17°), the misfit on stress ratio (average misfit: 2%; maximum: 26%) and the misfit on the differential stress (average misfit: 15%; maximum: 30%) These tests demonstrate that it is better to analyze twin data from subsets of

  7. Crystal orientation dependent optical transmittance and band gap of Na{sub 0.5}Bi{sub 0.5}TiO{sub 3}–BaTiO{sub 3} single crystals

    Energy Technology Data Exchange (ETDEWEB)

    He, Chongjun, E-mail: hechongjun@nuaa.edu.cn [College of Science, Nanjing University of Aeronautics and Astronautics, Nanjing 211106 (China); Deng, Chenguang; Wang, Jiming; Gu, Xiaorong; Wu, Tong [College of Science, Nanjing University of Aeronautics and Astronautics, Nanjing 211106 (China); Zhu, Kongjun [State Key Laboratory of Mechanics and Control of Mechanical Structures, College of Aerospace Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing 210016 (China); Liu, Youwen, E-mail: ywliu@nuaa.edu.cn [College of Science, Nanjing University of Aeronautics and Astronautics, Nanjing 211106 (China); Key Laboratory of Radar Imaging and Microwave Photonics, Ministry of Education, Nanjing University of Aeronautics and Astronautics, Nanjing 210016 (China)

    2016-02-15

    Optical transmittance spectra of lead-free ferroelectric (1−x)Na{sub 0.5}Bi{sub 0.5}TiO{sub 3}–xBaTiO{sub 3} (NBT–xBT) single crystals poled along different directions have been studied comprehensively. After poled along [001] direction, the transmittance of tetragonal NBT–8%BT crystal is about 70%, which is much higher than that of NBT–2%BT crystal with rhombohedral structure and NBT–5%BT crystal with morphotropic phase boundary (MPB) composition. However, after poled [111] direction, the transmittance of tetragonal NBT–8%BT crystal is the smallest among them. These properties are manifest in view of the crystal structure. Both direct and indirect optical energy band gaps, as well phonon energies were obtained from absorption coefficient spectra by Tauc equations. The band gaps of [001]-poled NBT–xBT crystals increase with BT content, yet the [111]-poled crystals have opposite trends.

  8. PVC mixtures’ mechanical properties with the addition of modified calcite as filler

    OpenAIRE

    Vučinić Dušica R.; Jovanović Vladimir D.; Kolonja Božo M.; Sekulić Živko T.; Mihajlović Slavica R.

    2012-01-01

    In this study mechanical properties of PVC mixtures (PVC, stabilizer, lubricant, filler) such as tensile strength, tensile elongation, breaking strength, and breaking elongation were investigated. Unmodified calcite, as well as calcite modified by stearic acid, were used as fillers in wet and dry processes. The PVC mixtures containing the calcite modified by wet procedure have better mechanical properties compared to those with the calcite modified by the dry process. Tensile and breaki...

  9. Mechanical properties of polyvinyl chloride mixtures with the addition of modified calcite as filler

    OpenAIRE

    Mihajlović, Slavica R.; Sekulić, Živko T.; Vučinić, Dušica R.; Jovanović, Vladimir D.; Kolonja, Božo M.

    2012-01-01

    In this study, mechanical properties of PVC mixtures (PVC, stabilizer, lubricant and filler) such as tensile strength, tensile elongation, breaking strength and breaking elongation were investigated. Unmodified calcite, as well as calcite modified by stearic acid, were used as fillers in wet and dry processes. The PVC mixtures containing the calcite modified by wet procedure had better mechanical properties compared to those with the calcite modified by the dry process. Tensile and breaking s...

  10. Structural incorporation of Neptunyl(V) into Calcite: Interfacial Reactions and Kinetics

    OpenAIRE

    Heberling, Frank

    2010-01-01

    In this experimental work the calcite-water interface is characterized by means of zetapotential and surface diffraction measurements. Based on the experimental results a new Basic Stern Surface Complexation model for calcite is developed. Neptunyl(V) adsorption at the calcite surface and incorporation into the calcite structure is studied by batch type adsorption- and mixed flow reactor experiments. Adsorption and incorporation species of Neptunyl are investigated by EXAFS spectroscopy.

  11. Lithofacies palaeogeography and sedimentology Beef and cone-in-cone calcite fibrous cements associated with the end-Permian and end-Triassic mass extinctions:Reassessment of processes of formation

    Institute of Scientific and Technical Information of China (English)

    Stephen Kershaw; Li Guo

    2016-01-01

    This paper reassesses published interpretation that beef and cone-in-cone (B-CIC) fibrous calcite cements were precipitated contemporaneously just below the sea floor in uncon-solidated sediment, in limestones associated with the end-Permian (P/T) and end-Triassic (T/J) mass extinctions. That interpretation introduced the concept of a sub-seafloor car-bonate factory associated with ocean acidification by raised carbon dioxide driven by volcanic eruption, coinciding with mass extinction. However, our new fieldwork and petrographic analysis, with literature comparison, reveals several problems with this concept. Two key points based on evidence in the T/J transition of the UK are:(1) that B-CIC calcite deposits form thin scattered layers and lenses at several horizons, not a distinct deposit associated with volcanic activity; and (2) B-CIC calcite is more common in Early Jurassic sediments after the extinction and after the end of the Central Atlantic Magmatic Province volcanism proposed to have supplied the carbon dioxide required. Our samples from Late Triassic, Early Jurassic and Early Cretaceous limestones in southern UK show that B-CIC calcite occurs in both marine and non-marine sediments, therefore ocean processes are not mandatory for its formation. There is no proof that fibrous calcite was formed before lithification, but our Early Jurassic samples do prove fibrous calcite formed after compaction, thus interpretation of crystal growth in uncon-solidated sediment is problematic. Furthermore, B-CIC crystals mostly grew both upwards and downwards equally, contradicting the interpretation of the novel carbonate factory that they grew preferentially upwards in soft sediment. Finally, Early Jurassic and Early Cretaceous examples are not associated with mass extinction. Three further key points derived from the literature include: (1) B-CIC calcite is wide-spread geographically and stratigraphically, not clustered around mass extinctions or the Paleocene

  12. Sorption and catalytic oxidation of Fe(II) at the surface of calcite

    NARCIS (Netherlands)

    Mettler, S.; Wolthers, M.; Charlet, L.; Von Gunten, U.

    2009-01-01

    The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps: (a

  13. S-SAD phasing of monoclinic histidine kinase from Brucella abortus combining data from multiple crystals and orientations: an example of data-collection strategy and a posteriori analysis of different data combinations.

    Science.gov (United States)

    Klinke, Sebastián; Foos, Nicolas; Rinaldi, Jimena J; Paris, Gastón; Goldbaum, Fernando A; Legrand, Pierre; Guimarães, Beatriz G; Thompson, Andrew

    2015-07-01

    The histidine kinase (HK) domain belonging to the light-oxygen-voltage histidine kinase (LOV-HK) from Brucella abortus is a member of the HWE family, for which no structural information is available, and has low sequence identity (20%) to the closest HK present in the PDB. The `off-edge' S-SAD method in macromolecular X-ray crystallography was used to solve the structure of the HK domain from LOV-HK at low resolution from crystals in a low-symmetry space group (P21) and with four copies in the asymmetric unit (∼108 kDa). Data were collected both from multiple crystals (diffraction limit varying from 2.90 to 3.25 Å) and from multiple orientations of the same crystal, using the κ-geometry goniostat on SOLEIL beamline PROXIMA 1, to obtain `true redundancy'. Data from three different crystals were combined for structure determination. An optimized HK construct bearing a shorter cloning artifact yielded crystals that diffracted X-rays to 2.51 Å resolution and that were used for final refinement of the model. Moreover, a thorough a posteriori analysis using several different combinations of data sets allowed us to investigate the impact of the data-collection strategy on the success of the structure determination.

  14. Constitutive Response of Microbial Induced Calcite Precipitation Cemented Sands

    Science.gov (United States)

    Feng, Kai

    In the last decade, microbial induced calcite precipitation (MICP) emerged as a novel technique for implementing soil improvement in an environmentally-friendly and economically beneficial manner. However, the mechanical behavior and constitutive response of these materials are still not fully explored by researchers. In this dissertation, the characteristics of MICP cemented sands are investigated through numerical modelling and experimental tests, including macro and micro tests under both static and dynamic loading. In the first part, the mechanical behavior of MICP cemented sands were probed using monotonic load testing and the existence of calcite precipitation was verified by scanning electron microscopy, with this behavior compared to traditionally cemented soil and naturally cemented soil. Both MICP cementation and traditional cementation were verified to be effective in the increase of stiffness and strength, and unique characteristic of MICP cemented soil was highlighted.

  15. Adsorption of polar aromatic hydrocarbons on synthetic calcite

    DEFF Research Database (Denmark)

    Madsen, Lene; Grahl-Madsen, Laila; Grøn, Christian

    1996-01-01

    studied by adsorption experiments. The results clearly demonstrate the differences in the adsorption behaviour between probes with different functional groups of varying polarity and acidity. The maximum adsorption decreases in the order: benzoic acid, benzyl alcohol and benzylamine. The order...... of magnitude of Delta G degrees for the adsorption process implies the formation of a strong bond between the calcite surface and the adsorbate molecules. Copyright (C) 1996 Elsevier Science Ltd....

  16. Meteoric calcitization of magnesite in Miocene lacustrine deposits (Calatayud basin, NE Spain)

    Science.gov (United States)

    Cañaveras, J. C.; Sánchez-Moral, S.; Sanz-Rubio, E.; Hoyos, M.

    1998-08-01

    Sedimentary magnesite deposits are commonly present in evaporite successions in the Tertiary Calatayud basin (NE Spain). Outcropping evaporite sequences, mainly composed of secondary gypsum after anhydrite-glauberite, show centimetre-thick layers of magnesite passing laterally into calcite pseudospar. Petrographic and stable isotope data indicate that calcite pseudospar formed via late-stage calcitization of magnesite under near-surface conditions. Calcitization occurred by the interaction between magnesite and Ca-enriched waters derived from the dissolution of gypsum and/or glauberite. The geochemical simulation of this process, petrographic evidence, and the correlation between the magnesite/calcite ratio and the δ18O values of both magnesite and calcite samples across the reaction front are in agreement with the existence of neoformed 18O-depleted magnesite during the waning stages of the calcitization process.

  17. Is bicarbonate stable in and on the calcite surface?

    DEFF Research Database (Denmark)

    Andersson, Martin Peter; Rodriguez Blanco, Juan Diego; Stipp, Susan Louise Svane

    2016-01-01

    We have used density functional theory with the COSMO-RS implicit solvent model to predict the pKa for the deprotonation of bicarbonate to carbonate, i.e. HCO3− CO32− + H+, when HCO3− is included in, and adsorbed on, a calcite surface. We have used cluster models (80–100 atoms) to represent...... the flat {10.4} surface, acute steps, obtuse steps, two types of kinks on the acute step and two types of kinks on the obtuse steps. Based on the predicted pKa values, which range from −6.0 to 2.4 depending on the surface site, we conclude that bicarbonate deprotonates to carbonate when it is in calcite...... even when pH in solution is very low. This is true for all surface sites, even for solutions where 2.4 calcite, the predicted pKa for deprotonation is 7.5, which is ∼3 pH units lower than in aqueous solution...

  18. Rate of radiocarbon retention onto calcite by isotope exchange

    Energy Technology Data Exchange (ETDEWEB)

    Lempinen, Janne; Lehto, Jukka [Helsinki Univ. (Finland). Lab. of Radiochemistry

    2016-11-01

    Radiocarbon ({sup 14}C) is a top priority class radionuclide associated with the long-term safety of spent nuclear fuel disposal. Dissolved inorganic radiocarbon can be retained in bedrock via isotope exchange with calcite (CaCO{sub 3}) at solubility equilibrium with groundwater. In the present study, the rate of the isotope exchange process was investigated on synthetic calcite using batch experiments. Experiments were performed in solutions with a calcium concentration of 0.0002-0.1 M, including two synthetic reference groundwaters. The radiocarbon activity in the solutions decreased exponentially as a function of time, thus following first-order kinetics. The rate of isotope exchange was quantified from an exponential fit to the activity data over time. The rate of radiocarbon retention increased as a function of the calcium activity. The isotope exchange half-life was only 4.3 days at calcium ion activities over 0.01. This half-life is very much shorter than the half-life of {sup 14}C or the time scale of groundwater movements; consequently calcite can effectively retain radiocarbon from brackish and saline groundwaters.

  19. Arsenite sorption and co-precipitation with calcite

    CERN Document Server

    Roman-Ross, Gabriela; Turrillas, Xavier; Fernandez-Martinez, Alejandro; Charlet, Laurent

    2008-01-01

    Sorption of As(III) by calcite was investigated as a function of As(III) concentration, time and pH. The sorption isotherm, i.e. the log As(III) vs. log [As(OH)3 degrees / Assat] plot is S-shaped and has been modelled on an extended version of the surface precipitation model. At low concentrations, As(OH)3 degrees is adsorbed by complexation to surface Ca surface sites, as previously described by the X-ray standing wave technique. The inflexion point of the isotherm, where As(OH)3 degrees is limited by the amount of surface sites (ST), yields 6 sites nm-2 in good agreement with crystallographic data. Beyond this value, the amount of sorbed arsenic increases linearly with solution concentration, up to the saturation of arsenic with respect to the precipitation of CaHAsO3(s). The solid solutions formed in this concentration range were examined by X-ray and neutron diffraction. The doped calcite lattice parameters increase with arsenic content while c/a ratio remains constant. Our results made on bulk calcite on...

  20. Phase Transition and Orientational Disorder of the Cation in [(PyO)(H/D)][AuCl{sub 4}] (PyO = C{sub 5}H{sub 5}NO) Crystal

    Energy Technology Data Exchange (ETDEWEB)

    Asaji, T., E-mail: asaji@chs.nihon-u.ac.jp; Akiyama, E. [Nihon University, Department of Chemistry, Graduate School of Integrated Basic Sciences (Japan); Tajima, F.; Eda, K.; Hashimoto, M. [Kobe University, Department of Chemistry, Faculty of Science (Japan); Furukawa, Y. [Hiroshima University, Department of Science Education, Graduate School of Education (Japan)

    2004-12-15

    An orientational disorder of the cation in [(PyO)D][AuCl{sub 4}] crystal was investigated by the {sup 35}Cl NQR and {sup 1}H NMR measurements. A structural phase transition was found at ca. 70 K from the temperature dependence of the NQR frequencies both in [(PyO)D][AuCl{sub 4}] and [(PyO)H][AuCl{sub 4}]. Temperature dependence of the spin-lattice relaxation time T{sub 1} of the NQR of [AuCl{sub 4}]{sup -} could be interpreted by an electric field gradient modulation due to the motion of the cation. Characteristics of T{sub 1} of {sup 35}Cl NQR as well as that of {sup 1}H NMR suggest a dynamic orientational disorder of the cation.

  1. Origin of gem corundum in calcite marble: The Revelstoke occurrence in the Canadian Cordillera of British Columbia

    Science.gov (United States)

    Dzikowski, Tashia J.; Cempírek, Jan; Groat, Lee A.; Dipple, Gregory M.; Giuliani, Gaston

    2014-06-01

    The calcite marble-hosted gem corundum (ruby, sapphire) occurrence near Revelstoke, British Columbia, Canada, occurs in the Monashee Complex of the Omineca Belt of the Canadian Cordillera. Corundum occurs in thin, folded and stretched layers with green muscovite + Ba-bearing K-feldspar + anorthite (An0.85-1) ± phlogopite ± Na-poor scapolite. Other silicate layers within the marble are composed of: (1) diopside + tremolite ± quartz and (2) garnet (Alm0.7-0.5Grs0.2-0.4) + Na-rich scapolite + diopside + tremolite + Na,K-amphiboles. Non-silicate layers in the marble are either magnetite- or graphite-bearing. Predominantly pink (locally red or purple) opaque to transparent corundum crystals have elevated Cr2O3 (≤ 0.21 wt.%) and variable amounts of TiO2; rare blue rims on the corundum crystals contain higher amounts of TiO2 (≤ 0.53 wt.%) and Fe2O3 (≤ 0.07 wt.%). The associated micas have elevated Cr, V, Ti, and Ba contents. Petrography of the silicate layers show that corundum formed from muscovite at the peak of metamorphism (~ 650-700 °C at 8.5-9 kbar). Because the marble is almost pure calcite (dolomite is very rare), the corundum was preserved because it did not react with dolomite to spinel + calcite during decompression. The scapolite-bearing assemblages formed during or after decompression of the rock at ~ 650 °C and 4-6 kbar. Gem-quality corundum crystals formed especially on borders of the mica-feldspar layers in an assemblage with calcite. Whole rock geochemistry data show that the corundum-bearing silicate (mica-feldspar) layers formed by mechanical mixing of carbonate with the host gneiss protolith; the bulk composition of the silicate layers was modified by Si and Fe depletion during prograde metamorphism. High element mobility is supported by the homogenization of δ18O and δ13C values in carbonates and silicates for the marble and silicate layers. The silicate layers and the gneiss contain elevated contents of Cr and V due to the volcanoclastic

  2. PVC mixtures’ mechanical properties with the addition of modified calcite as filler

    Directory of Open Access Journals (Sweden)

    Vučinić Dušica R.

    2012-01-01

    Full Text Available In this study mechanical properties of PVC mixtures (PVC, stabilizer, lubricant, filler such as tensile strength, tensile elongation, breaking strength, and breaking elongation were investigated. Unmodified calcite, as well as calcite modified by stearic acid, were used as fillers in wet and dry processes. The PVC mixtures containing the calcite modified by wet procedure have better mechanical properties compared to those with the calcite modified by the dry process. Tensile and breaking strength of the PVC mixture containing the calcite modified with 1.5% stearic acid using wet process, are higher for 2.8% and 5.2%, respectively, compared to the PVC mixture containing the calcite modified with the same amount of acid used in the dry process. The tensile strength difference between the mixtures increases with the increase of the concentration of used stearic acid up to 3%. The strength of PVC mixture with the calcite modified by wet process is 3.1% higher compared to the mixture containing calcite modified by dry process. The results showed that the bonding strength between calcite and the adsorbed organic component affected tensile strength, tensile elongation and breaking strength of the PVC mixtures. The best filler was obtained by wet modification using 1.5% stearic acid solution that provided the formation of a stearate monolayer chemisorbed on calcite. The PVC mixtures containing the calcite modified by wet process using 1.5% stearic acid solution exhibited the best mechanical properties. This calcite was completely hydrophobic with dominant chemically adsorbed surfactant, which means that stearate chemisorbed on calcite provided stronger interaction in the calcite-stearic acid-PVC system.

  3. Biomimetic mineralization of CaCO3 on a phospholipid monolayer: from an amorphous calcium carbonate precursor to calcite via vaterite.

    Science.gov (United States)

    Xiao, Junwu; Wang, Zhining; Tang, Yecang; Yang, Shihe

    2010-04-06

    A phospholipid monolayer, approximately half the bilayer structure of a biological membrane, can be regarded as an ideal model for investigating biomineralization on biological membranes. In this work on the biomimetic mineralization of CaCO(3) under a phospholipid monolayer, we show the initial heterogeneous nucleation of amorphous calcium carbonate precursor (ACC) nanoparticles at the air-water interface, their subsequent transformation into the metastable vaterite phase instead of the most thermodynamically stable calcite phase, and the ultimate phase transformation to calcite. Furthermore, the spontaneity of the transformation from vaterite to calcite was found to be closely related to the surface tension; high surface pressure could inhibit the process, highlighting the determinant of surface energy. To understand better the mechanisms for ACC formation and the transformation from ACC to vaterite and to calcite, in situ Brewster angle microscopy (BAM), ex situ scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and X-ray diffraction analysis were employed. This work has clarified the crystallization process of calcium carbonate under phospholipid monolayers and therefore may further our understanding of the biomineralization processes induced by cellular membranes.

  4. Evolution of a calcite marble shear zone complex on Thassos Island, Greece: microstructural and textural fabrics and their kinematic significance

    Science.gov (United States)

    Bestmann, Michel; Kunze, Karsten; Matthews, Alan

    2000-11-01

    The deformation history of a monophase calcite marble shear zone complex on Thassos Island, Northern Greece, is reconstructed by detailed geometric studies of the textural and microstructural patterns relative to a fixed reference system (shear zone boundary, SZB). Strain localization within the massive marble complex is linked to decreasing P- T conditions during the exhumation process of the metamorphic core complex. Solvus thermometry indicates that temperatures of 300-350°C prevailed during part of the shear zone deformation history. The coarse-grained marble protolith outside the shear zone is characterized by symmetrically oriented twin sets due to early coaxial deformation. A component of heterogeneous non-coaxial deformation is first recorded within the adjacent protomylonite. Enhanced strain weakening by dynamic recrystallization promoted strong localization of plastic deformation in the ultramylonite of the calcite shear zone, where high strain was accommodated by non-coaxial flow. This study demonstrates that both a pure shear and a simple shear strain path can result in similar crystallographic preferred orientations (single c-axis maximum perpendicular to the SZB) by different dominant deformation mechanisms. Separated a-axis pole figures (+ a- and - a-axis) show different density distributions with orthorhombic texture symmetry in the protolith marble and monoclinic symmetry in the ultramylonite marble consistently with the observed grain fabric symmetry.

  5. Carbonate "clumped" isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

    Directory of Open Access Journals (Sweden)

    J. Kimball

    2015-12-01

    between the corals of different mineralogy is in the same direction as published theoretical predictions for the offset between calcite and aragonite, although the magnitude of the offset is different. One possibility is that the deep-sea coral results reflect that crystals may attain nominal mineral equilibrium clumped isotope signatures only under conditions of extremely slow growth. In that case, a possible explanation for the attainment of disequilibrium bulk isotope signatures and equilibrium clumped isotope signatures by deep-sea corals is that extraordinarily slow growth rates can promote the occurrence of isotopic reordering in the interfacial region of growing crystals. We also cannot rule out a component of a biological "vital-effect" influencing clumped isotope signatures in one or both orders of coral. Based on published experimental data and theoretical calculations, these biological "vital" effects could arise from kinetic isotope effects due to the source of carbon used for calcification, temperature- and pH-dependent rates of CO2 hydration and/or hydroxylation, calcifying fluid pH, the activity of carbonic anhydrase, the residence time of dissolved inorganic carbon in the calcifying fluid, and calcification rate. A third possible explanation is the occurrence of variable acid digestion fractionation factors. Although a recent study has suggested that dolomite, calcite, and aragonite may have similar clumped isotope acid digestion fractionation factors, the influence of acid digestion kinetics on Δ47 is a subject that warrants further investigation.

  6. Carbonate "clumped" isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

    Science.gov (United States)

    Kimball, Justine; Eagle, Robert; Dunbar, Robert

    2016-12-01

    between the corals of different mineralogy is in the same direction as published theoretical predictions for the offset between calcite and aragonite although the magnitude of the offset is different. One possibility is that the deep-sea coral results reflect high-Mg and aragonite crystals attaining nominal mineral equilibrium clumped isotope signatures due to conditions of extremely slow growth. In that case, a possible explanation for the attainment of disequilibrium bulk isotope signatures and equilibrium clumped isotope signatures by deep-sea corals is that extraordinarily slow growth rates can promote the occurrence of isotopic reordering in the interfacial region of growing crystals. We also cannot rule out a component of a biological "vital effect" influencing clumped isotope signatures in one or both orders of coral. Based on published experimental data and theoretical calculations, these biological vital effects could arise from kinetic isotope effects due to the source of carbon used for calcification, temperature- and pH-dependent rates of CO2 hydration and/or hydroxylation, calcifying fluid pH, the activity of carbonic anhydrase, the residence time of dissolved inorganic carbon in the calcifying fluid, and calcification rate. A third possible explanation is the occurrence of variable acid digestion fractionation factors. Although a recent study has suggested that dolomite, calcite, and aragonite may have similar clumped isotope acid digestion fractionation factors, the influence of acid digestion kinetics on Δ47 is a subject that warrants further investigation.

  7. First-principles study of boron speciation in calcite and aragonite

    Science.gov (United States)

    Balan, Etienne; Pietrucci, Fabio; Gervais, Christel; Blanchard, Marc; Schott, Jacques; Gaillardet, Jérome

    2016-11-01

    Despite the importance of boron as a proxy of past ocean pH, the crystal-chemical factors controlling its incorporation in the structure of calcium carbonates are still poorly understood. This is partly linked to an imperfect knowledge of the coordination, protonation state and local environment of boron species in these minerals. In the present study, we use first-principles quantum mechanical tools to model selected trigonal and tetragonal boron species in calcite and aragonite. The stable geometry of the models is obtained from standard energy minimization schemes or using a more advanced metadynamics exploration of their configurational space. The computation of 11B NMR chemical shifts and quadrupolar coupling parameters enables a straightforward comparison of the models to existing experimental NMR data. The results show that B in calcium carbonates does occur as structural species substituted for CO32- anions. The B speciation depends on the polymorph considered. In calcite, structural boron is present as partially deprotonated trigonal BO2(OH)2- species coexisting with a fraction of substituted B(OH)4- groups. In aragonite, the B(OH)4- substitution for CO32- anions is dominant. Different species, including entrapped B(OH)3 molecules and substituted BO33- groups also occur in biogenic samples. The diversity of B speciation reflects a diversity of B incorporation mechanisms and sheds light on previous studies confronting B isotopic composition determination with NMR observations. The mechanisms of boron incorporation in calcium carbonates are probably more complex than usually assumed in the literature using boron isotopes as a proxy of paleo-atmospheric CO2 reconstructions. Although not invalidating the empirical paleo-pH proxy, these results call for a better understanding of the fundamental mechanisms of boron incorporation in carbonates.

  8. 晶体相场法研究应力状态及晶体取向对微裂纹尖端扩展行为的影响∗%Study on the effect of stress state and crystal orientation on micro-crack tip propagation b ehavior in phase field crystal metho d

    Institute of Scientific and Technical Information of China (English)

    2015-01-01

    A nanometer scale mechanism for micro crack propagation under uniaxial tension in single crystals is investigated using phase field crystal (PFC) simulation. The uniaxial tensile loading is strain controlled. And three initial typical stresses of pre-existing center crack in (111) crystal plane of face centered cubic structure are chosen to study the effects of initial stress state on micro-crack propagation. Moreover, the influences of different crystal orientations, when the crystal suffers from uniaxial tension, are also investigated. Due to the influence of time scale and length scale in the PFC method, the motion of dislocations, vacancies, shear band and twinning structure should be observed and described during the propagation process of micro cracks. In addition, the free energy curves of different processes are drawn and discussed in order to explain the different behaviors of the crystal in the propagation of cracks. Simulation results show that the propagation behavior of micro cracks can be closely associated with the initial stress state. It is found that the propagation behavior mainly occurs in the ⟨0¯11⟩(111) slip system. Besides, the crystal orientation has a significant effect on the mechanism of activation and evolution. In the pre-stretching system, slip dislocation is induced near the micro-crack tip, and then its slide in [0¯11] direction will cause the cleavage of a certain crystal plane, and promote the micro cracks to extend. However, to a certain level, the propagating direction of the micro-crack tip will turn to another slip direction [10¯1]. As a result, zigzag edge appears. By contrast, in the pre-shear system, the tip of the micro crack propagates in a cleavage mode, and results in the appearance of slip dislocation [10¯1] near the micro-crack tip. Afterwards, the motion of slip dislocation promotes the production of vacancies. And owing to the aggregation and combination of vacancies, secondary cracks form and propagate in

  9. Pyrite-pyrrhotite intergrowths in calcite marble from Bistriški Vintgar, Slovenia

    Science.gov (United States)

    Zavašnik, J.

    2016-02-01

    Roman marble quarry in Bistrica gorge in southern Pohorje Mt. (north-eastern Slovenia) is situated in a 20 m thick lens of layered marble, at the contact zone between granodiorite and metamorphites. Grey and yellowish non-homogenous calcite marble is heavily included by mica, quartz, feldspars, zoisite, pyrite and amphiboles. In the present research, we have studied numerous pyrite (FeS2) crystals associated with yellowish-bronze non-stoichiometric pyrrhotite (Fe1-xS), not previously reported from this locality. SEM investigation revealed unusual sequence of crystallisation: primary skeletal pyrrhotite matrix is sparsely overgrown by well-crystalline pyrite, both being overgrown by smaller, well-developed hexagonal pyrrhotite crystals of the second generation. With TEM we identify the pyrrhotite as 5T-Fe1-xS phase, where x is about 0.1 and is equivalent to Fe9S10. The pyrite-pyrrhotite coexistence allows us a construction of fO2-pH diagram of stability fields, which reflects geochemical conditions at the time of marble re-crystallisation.

  10. EDITORIAL: Optical orientation Optical orientation

    Science.gov (United States)

    SAME ADDRESS *, Yuri; Landwehr, Gottfried

    2008-11-01

    priority of the discovery in the literature, which was partly caused by the existence of the Iron Curtain. I had already enjoyed contact with Boris in the 1980s when the two volumes of Landau Level Spectroscopy were being prepared [2]. He was one of the pioneers of magneto-optics in semiconductors. In the 1950s the band structure of germanium and silicon was investigated by magneto-optical methods, mainly in the United States. No excitonic effects were observed and the band structure parameters were determined without taking account of excitons. However, working with cuprous oxide, which is a direct semiconductor with a relative large energy gap, Zakharchenya and his co-worker Seysan showed that in order to obtain correct band structure parameters, it is necessary to take excitons into account [3]. About 1970 Boris started work on optical orientation. Early work by Hanle in Germany in the 1920s on the depolarization of luminescence in mercury vapour by a transverse magnetic field was not appreciated for a long time. Only in the late 1940s did Kastler and co-workers in Paris begin a systematic study of optical pumping, which led to the award of a Nobel prize. The ideas of optical pumping were first applied by Georges Lampel to solid state physics in 1968. He demonstrated optical orientation of free carriers in silicon. The detection method was nuclear magnetic resonance; optically oriented free electrons dynamically polarized the 29Si nuclei of the host lattice. The first optical detection of spin orientation was demonstrated by with the III-V semiconductor GaSb by Parsons. Due to the various interaction mechanisms of spins with their environment, the effects occurring in semiconductors are naturally more complex than those in atoms. Optical detection is now the preferred method to detect spin alignment in semiconductors. The orientation of spins in crystals pumped with circularly polarized light is deduced from the degree of circular polarization of the recombination

  11. From nanometer aggregates to micrometer crystals

    DEFF Research Database (Denmark)

    Schultz, Logan Nicholas; Dideriksen, Knud; Lakshtanov, Leonid;

    2014-01-01

    and crystal shapes. Grain coarsening of calcite, CaCO3, is relevant for biomineralization and commercial products and is an important process in diagenesis of sediments to rock during geological time. We investigated coarsening of pure, synthetic calcite powder of sub-micrometer diameter crystals and aged...... demonstrated steady growth of nanometer crystallites. The results can be described by theory where grains coarsen preferentially by aggregation at early times and high temperatures and by Ostwald ripening at later stages. Crystal form and dimension are influenced by the transition from one growth mechanism......Grain size increases when crystals respond to dynamic equilibrium in a saturated solution. The pathway to coarsening is generally thought to be driven by Ostwald ripening, that is, simultaneous dissolution and reprecipitation, but models to describe Ostwald ripening neglect solid-solid interactions...

  12. 3D imaging using X-Ray tomography and SEM combined FIB to study non isothermal creep damage of (111) oriented samples of γ / γ ′ nickel base single crystal superalloy MC2

    KAUST Repository

    Jouiad, Mustapha

    2012-01-01

    An unprecedented investigation consisting of the association of X-Ray tomography and Scanning Electron Microscopy combined with Focus Ion Beam (SEM-FIB) is conducted to perform a 3D reconstruction imaging. These techniques are applied to study the non-isothermal creep behavior of close (111) oriented samples of MC2 nickel base superalloys single crystal. The issue here is to develop a strategy to come out with the 3D rafting of γ\\' particles and its interaction whether with dislocation structures or/and with the preexisting voids. This characterization is uncommonly performed away from the conventional studied orientation [001] in order to feed the viscoplastic modeling leading to its improvement by taking into account the crystal anisotropy. The creep tests were performed at two different conditions: classical isothermal tests at 1050°C under 140 MPa and a non isothermal creep test consisting of one overheating at 1200°C and 30 seconds dwell time during the isothermal creep life. The X-Ray tomography shows a great deformation heterogeneity that is pronounced for the non-isothermal tested samples. This deformation localization seems to be linked to the preexisting voids. Nevertheless, for both tested samples, the voids coalescence is the precursor of the observed damage leading to failure. SEM-FIB investigation by means of slice and view technique gives 3D views of the rafted γ\\' particles and shows that γ corridors evolution seems to be the main creep rate controlling parameter. © 2012 Trans Tech Publications, Switzerland.

  13. Function development through microstructure control. Control of crystal axis orientation of zinc oxide and its optical properties; Soshiki seigyo ni yoru kino hatsugen. Sanka aen no haikosei seigyo to kogakuteki kino

    Energy Technology Data Exchange (ETDEWEB)

    Fujitsu, S. [Shonan Institute of Technology, Kanagawa (Japan); Watanabe, Y. [Science University of Tokyo, Tokyo (Japan)

    1998-04-01

    Described herein are light beam deflectors of thin piezoelectric films, and synthesis, photoconductance and nonlinear optical measurement of light-distributing, transparent zinc oxide, viewed from application of zinc oxide to optical purposes. Supersonic waves, when passing through a transparent medium, leaves compressional waves of strain, causing cyclic changes in refractive index. This phenomenon can be used for diffraction of light. A light beam deflector is one of the examples of using this phenomenon applied to a thin piezoelectric film of zinc oxide. The authors have developed a process to synthesize transparent, polycrystalline zinc oxide of high C-axis orientation. A seed of sintered zinc oxide is placed at the center of an electrical oven, and a substrate in the temperature-gradient zone. The seed evaporates, when heated to around 1200degC, to leave the zinc oxide crystal grains on the substrate, which grow preferentially in the C-axis direction at around 300{mu}m/h. Zinc oxide is known as a compound of anisotropy in properties by crystal orientation, and shows piezoelectric and photoconducting properties. 8 refs., 7 figs.

  14. Effect of airborne particle on SO 2-calcite reaction

    Science.gov (United States)

    Böke, Hasan; Göktürk, E. Hale; Caner-Saltık, Emine N.; Demirci, Şahinde

    1999-02-01

    In modern urban atmosphere, sulphur dioxide (SO 2) attacks calcite (CaCO 3) in calcareous stone-producing gypsum (CaSO 4·2H 2O) which forms crust at rain sheltered surfaces and accelerates erosion at areas exposed to rain. The airborne particles collected on stone surfaces have always been considered to enhance the gypsum crust formation and thus it is believed that they should be removed from the surface to decrease the effects of SO 2. In this study, our aim was to investigate this event by carrying out a series of experiments in laboratory using pure calcium carbonate powder to represent calcareous stone. Sodium montmorillonite, activated carbon, ferric oxide, vanadium pentoxide and cupric chloride were mixed in the pure calcium carbonate powder as substitutes of the airborne particles in the polluted atmosphere. The samples have been exposed at nearly 10 ppmv SO 2 concentrations at 90% relative humidity conditions in a reaction chamber for several days. The mineralogical composition of the exposed samples were determined by X-ray diffraction (XRD) analysis and infrared spectrometer (IR). Sulphation reaction products, calcium sulphite hemihydrate, gypsum and unreacted calcite, were determined quantitatively using IR. Exposed samples have also been investigated morphologically using a scanning electron microscope (SEM). Experimental results reveal that calcium sulphite hemihydrate is the main reaction product of the SO 2-calcite reaction. It turns out that airborne particles play an important catalytic role in the oxidation of calcium sulphite hemihydrate into gypsum, although their presence does not very significantly affect the extent of sulphation reaction. This behaviour of airborne particles is explained by the presence of liquid film on the calcium carbonate surface where a series of reactions in the gas-liquid-solid interfaces takes place.

  15. Principles of calcite dissolution in human and artificial otoconia.

    Directory of Open Access Journals (Sweden)

    Leif Erik Walther

    Full Text Available Human otoconia provide mechanical stimuli to deflect hair cells of the vestibular sensory epithelium for purposes of detecting linear acceleration and head tilts. During lifetime, the volume and number of otoconia are gradually reduced. In a process of degeneration morphological changes occur. Structural changes in human otoconia are assumed to cause vertigo and balance disorders such as benign paroxysmal positional vertigo (BPPV. The aim of this study was to investigate the main principles of morphological changes in human otoconia in dissolution experiments by exposure to hydrochloric acid, EDTA, demineralized water and completely purified water respectively. For comparison reasons artificial (biomimetic otoconia (calcite gelatin nanocomposits and natural calcite were used. Morphological changes were detected in time steps by the use of environmental scanning electron microscopy (ESEM. Under in vitro conditions three main dissolution mechanisms were identified as causing characteristic morphological changes of the specimen under consideration: pH drops in the acidic range, complex formation with calcium ions and changes of ion concentrations in the vicinity of otoconia. Shifts in pH cause a more uniform reduction of otoconia size (isotropic dissolution whereas complexation reactions and changes of the ionic concentrations within the surrounding medium bring about preferred attacks at specific areas (anisotropic dissolution of human and artificial otoconia. Owing to successive reduction of material, all the dissolution mechanisms finally produce fragments and remnants of otoconia. It can be assumed that the organic component of otoconia is not significantly attacked under the given conditions. Artificial otoconia serve as a suitable model system mimicking chemical attacks on biogenic specimens. The underlying principles of calcite dissolution under in vitro conditions may play a role in otoconia degeneration processes such as BPPV.

  16. The sensitized luminescence of manganese-activated calcite

    Science.gov (United States)

    Schulman, J.H.; Evans, L.W.; Ginther, R.J.; Murata, K.J.

    1947-01-01

    Synthetic manganese-activated calcites are shown to be practically inert to ultraviolet excitation in the range 2000-3500A, while they are luminescent under cathode-ray excitation. The incorporation of small amounts of an auxiliary impurity along with the manganese produces the strong response to ultraviolet radiation hitherto ascribed to CaCO3:Mn itself. Three such impurities have been studied: lead, thallium, and cerium. The first two induce excitation in the neighborhood of the mercury resonance line, while the cerium introduces a response principally to longer wave ultraviolet. The strong response to 2537A excitation shown by some natural calcites is likewise found to be due to the presence of lead along with the manganese, rather than to the manganese alone. The data do not warrant ascribing the longer wave-length ultraviolet-excited luminescence of all natural calcites to the action of an auxiliary impurity. The essential identity of the cathode-ray excited luminescence spectra of CaCO 3:Mn, CaCO3: (Pb+Mn), CaCO3:(Tl+Mn), and CaCO3:(Ce+Mn) with the 2537A-excited spectra of the latter three is evidence that the luminescent center in all cases is the manganese ion or the MnO6 group. It is shown that a "cascade" mechanism for the action of the auxiliary impurities, lead, thallium, and cerium, is incorrect; and that the phenomenon must be considered as a case of sensitized luminescence. Owing to the nature of cathode-ray excitation, the manganese activator can be excited by this agent even in the absence of a second impurity. For optical excitation, however, an absorption band for the ultraviolet must be established by building into the CaCO3:Mn a second impurity or "sensitizer.".

  17. Study of Biomass Calcite as Fine Aggregate of Concrete

    Institute of Scientific and Technical Information of China (English)

    WANG Jian; YU Yan

    2012-01-01

    The possibility of using crushed oyster shell to partly replace the fine aggregate of concrete was evaluated. The compressive strength and slump of concrete mixture with different amount of crushed oyster shell were tested and thus the appropriate dosage was determined. Additionally, the compatibility with super plasticizer and the stability in NazSO4 solution were also discussed to prove the feasibility of oyster shell as fine aggregate of concrete. The microstructure of concrete was observed with XRD and SEM techniques. This research provides the basis for the application of waste biomass calcite.

  18. Electronic structures of organometallic complexes of f elements LXXXIII: First comparison of experimental and calculated (on the basis of density functional theory) polarized Raman spectra of an oriented organometallic single crystal: Tris(pentamethylcyclopentadienyl)lanthanum.

    Science.gov (United States)

    Amberger, Hanns-Dieter; Reddmann, Hauke; Mueller, Thomas J; Evans, William J

    2014-10-15

    The polarized Raman spectra of an oriented La(η(5)-C5Me5)3 (1) single crystal (where the principal axes of the two molecules per unit cell are uniformly oriented) as well as the mid (ca. 90K) and far infrared spectra of pellets have been recorded. Applying the selection rules of C3h symmetry to the spectra obtained, the irreducible representations (irreps) of numerous lines/bands of intra-ligand character were derived. In the range theory (DFT) were performed. In the intra-ligand range >400cm(-1), the obtained results agree well with the experimental findings. Because of the strong mixing at lower wavenumbers, even the separation of calculated skeletal and intra-ligand modes and the identification of the former was only successful by comparing the calculated FIR and averaged Raman spectra of compound 1 with those of La(η(5)-C5Me4H)3 (2). Making use of both the calculated frequencies of normal modes and their polarizability tensors, the polarized Raman spectra of an oriented single crystal of 1 in the range <400cm(-1) were calculated and compared to the experimental ones. Because of an overestimation of the mixing of normal vibrations of A' symmetry, the experimental intensities of the lines of the symmetric stretch ν1(A') were not reproduced by the calculation for compound 1 but by that for Sm(η(5)-C5Me5)3 (3). Skeletal and intra-ligand modes were separated and designated. Neglecting νC-H modes, the DFT calculation for 1 achieved an r.m.s. deviation of 17.9cm(-1) for 72 assignments.

  19. Crytallographic orientation and magmetostriction of FeGa crystals%Fe_(81) Ga_(19)合金晶体生长取向与磁致伸缩性能

    Institute of Scientific and Technical Information of China (English)

    李川; 刘敬华; 陈立彪; 蒋成保; 徐惠彬

    2011-01-01

    Fe81Ga19 single crystals and polycrystals with different orientations are prepared by zone melting directional solidification. Pole figures show that the deviation degrees between [001] orientation and axis are 12°, 5° and 3°, and the in corresponding axial magnetostrictions parallel to external magnetic field are 254×10-6, 271×10-6 and 291×10-6. The[001]orientation single crystal is determined by back-reflection Laue, and the magnetostriction is 312×10-6. The results reveal the relationship between crystallographic orientation and magnetostriction, and the increase of magnetostrictions with deviation degree decreasing. The deviation degrees between [001]orientation and axis of polycrystals are determined by Electron Backscattered Diffraction to be 18.4°, 15.2° and 14.8°, and thir corresponding magnetostrictions are 180×10-6m, 230×10-6 and 235×10-6.%通过区熔定向凝固法,生长出[001]易磁化方向与晶体轴向之间存在不同取向差的Fe81Ga19合金单晶体和Fe81Ga19合金多晶体.极图测试结果显示,Fe81Ga19合金单晶体的[001]方向与轴向取向差分别为12°,5°和3°.采用电阻应变片法测定相应磁致伸缩应变,与外加磁场方向平行的轴向磁致伸缩应变分别为254×10-6,271×10-6和291×10-6.由劳埃法确定并切取[001]取向Fe81Ga19合金单晶体,磁致伸缩应变达到312×10-6.采用背散射取向分析方法(EBSD),确定了定向生长Fe81Ga19合金取向多晶体不同晶粒[001]易磁化方向与晶体轴向之间取向差,其分别为18.4°,15.2°和14.8°,轴向磁致伸缩应变分别为180×10-6,230×10-6和235×10-6.

  20. Highly effective strain-induced band-engineering of (111) oriented, direct-gap GeSn crystallized on amorphous SiO2 layers

    Science.gov (United States)

    Li, Haofeng; Wang, Xiaoxin; Liu, Jifeng

    2016-03-01

    We demonstrate highly effective strain-induced band-engineering of (111) oriented direct-gap Ge1-xSnx thin films (0.074 GeSn films also demonstrate high thermal stability, offering both excellent direct-gap optoelectronic properties and fabrication/operation robustness for integrated photonics.

  1. Highly Ordered 1D Fullerene Crystals for Concurrent Control of Macroscopic Cellular Orientation and Differentiation toward Large-Scale Tissue Engineering.

    Science.gov (United States)

    Minami, Kosuke; Kasuya, Yuki; Yamazaki, Tomohiko; Ji, Qingmin; Nakanishi, Waka; Hill, Jonathan P; Sakai, Hideki; Ariga, Katsuhiko

    2015-07-15

    A highly aligned 1D fullerene whisker (FW) scaffold in a centimeter area is fabricated by interfacial alignment. The resulting aligned FW scaffold enables concurrent control over cellular orientation and differentiation to muscle cells. This aligned FW scaffold is made by a facile method, and hence the substrate is a promising alternative to other cell scaffolds for tissue engineering.

  2. Oriented crystalline monolayers and bilayers of 2 x 2 silver(1) grid architectures at the air-solution interface: Their assembly and crystal structure elucidation

    DEFF Research Database (Denmark)

    Weissbuch, J.; Baxter, P.N.W.; Kuzmenko, I.;

    2000-01-01

    Oriented crystalline monolayers, similar to 14 Angstrom thick, of a 2 x 2 Ag+ grid complex, self-assembled at the air-solution interface starting from an water-insoluble ligand 3,6-bis[2-(6-phenylpyridine)]pyridazine spread on silver-ion-containing solutions,were examined by grazing-incidence X-r...

  3. Prediction of calcite Cement Distribution in Shallow Marine Sandstone Reservoirs using Seismic Data

    Energy Technology Data Exchange (ETDEWEB)

    Bakke, N.E.

    1996-12-31

    This doctoral thesis investigates how calcite cemented layers can be detected by reflection seismic data and how seismic data combined with other methods can be used to predict lateral variation in calcite cementation in shallow marine sandstone reservoirs. Focus is on the geophysical aspects. Sequence stratigraphy and stochastic modelling aspects are only covered superficially. Possible sources of calcite in shallow marine sandstone are grouped into internal and external sources depending on their location relative to the presently cemented rock. Well data and seismic data from the Troll Field in the Norwegian North Sea have been analysed. Tuning amplitudes from stacks of thin calcite cemented layers are analysed. Tuning effects are constructive or destructive interference of pulses resulting from two or more closely spaced reflectors. The zero-offset tuning amplitude is shown to depend on calcite content in the stack and vertical stack size. The relationship is found by regression analysis based on extensive seismic modelling. The results are used to predict calcite distribution in a synthetic and a real data example. It is found that describing calcite cemented beds in shallow marine sandstone reservoirs is not a deterministic problem. Hence seismic inversion and sequence stratigraphy interpretation of well data have been combined in a probabilistic approach to produce models of calcite cemented barriers constrained by a maximum amount of information. It is concluded that seismic data can provide valuable information on distribution of calcite cemented beds in reservoirs where the background sandstones are relatively homogeneous. 63 refs., 78 figs., 10 tabs.

  4. Diagenetic environments of calcite veins hosted in marine carbonate rocks in middle Yangtze region of South China%中扬子海相碳酸盐岩中方解石脉成岩环境研究

    Institute of Scientific and Technical Information of China (English)

    王芙蓉; 何生; 杨兴业

    2011-01-01

    Analyses of thin slices, cathodoluminescence and carbon-oxygen isotope of calcite veins hosted in marine carbonate rocks distributed around Jingshan County in the middle Yangtze region of South China indicated that, two crystal forms including radial calcite and isometric texture calcite could be identified in calcite veins in the Triassic and the cathodoluminescence intensity was different. The Permian and Ordovician fractures were mainly filled with isometric texture calcite veins and the cathodoluminescence intensity was similar with that of the surrounding rocks. The δl3 CPDB value of calcite veins ranged from -6. 76‰ to 4. Ol‰and the δ18 OPDB value ranged from -17. 95‰to -5. 67‰, indicating the marine phreatic environment and the mixing phreatic environment for calcite veins deposition. Calcite veins in the Triassic were sedimentary origin, and part of calcite veins in the Permian and the Ordovician suffered latter diagenetic fluid dissolution. Fluid generated from organic-matter maturation effected the formation of calcite veins in the Permian to some degree.%通过对中扬子京山县城周边露头碳酸盐岩中方解石脉的普通薄片、阴极发光以及碳氧同位索等资料分析,认为该区露头三叠系裂隙中充填放射状和等轴粒状的方解石且阴极发光强度有差异,二叠系和奥陶系裂隙中主要为等轴粒状方解石,阴极发光与围岩相似.方解石脉的δ13CPDB位于-6.76‰~4.01‰之间,δ18OPDB在-17.95‰~-5.67‰之间,基本为海水潜流带一混合水潜流带沉积环境.三叠系方解石脉基本上为沉积碳酸盐岩,二叠系和奥陶系部分方解石脉受后期成岩流体的影响,其中二叠系有饥质成熟产生的流体对该层系方解石脉的形成有一定影响.

  5. Isotopic analysis for degradation diagnosis of calcite matrix in mortar.

    Science.gov (United States)

    Dotsika, E; Psomiadis, D; Poutoukis, D; Raco, B; Gamaletsos, P

    2009-12-01

    Mortar that was used in building as well as in conservation and restoration works of wall paintings have been analysed isotopically (delta(13)C and delta(18)O) in order to evaluate the setting environments and secondary processes, to distinguish the structural components used and to determine the exact causes that incurred the degradation phenomena. The material undergoes weathering and decay on a large proportion of its surface and in depth, due to the infiltration of water through the structural blocks. Mineralogical analysis indicated signs of sulphation and dissolution/recrystallisation processes taking place on the material, whereas stable isotopes provided information relative to the origin of the CO(2) and water during calcite formation and degradation processes. Isotopic change of the initial delta(13)C and delta(18)O in carbonate matrix was caused by alteration of the primary source of CO(2) and H(2)O in mortar over time, particularly by recrystallisation of calcite with porewater, evaporated or re-condensed water, and CO(2) from various sources of atmospheric and biogenic origin. Human influence (surface treatment) and biological growth (e.g. fungus) are major exogenic processes which may alter delta(18)O and delta(13)C in lime mortar.

  6. Environmental controls on the Emiliania huxleyi calcite mass

    Science.gov (United States)

    Horigome, M. T.; Ziveri, P.; Grelaud, M.; Baumann, K.-H.; Marino, G.; Mortyn, P. G.

    2013-06-01

    Although ocean acidification is expected to impact (bio)calcification by decreasing the seawater carbonate ion concentration, [CO32-], there exists evidence of non-uniform response of marine calcifying plankton to low seawater [CO32-]. This raises questions on the role of environmental factors other than acidification and on the complex physiological responses behind calcification. Here we investigate the synergistic effect of multiple environmental parameters, including temperature, nutrient (nitrate and phosphate) availability, and seawater carbonate chemistry on the coccolith calcite mass of the cosmopolitan coccolithophore Emiliania huxleyi, the most abundant species in the world ocean. We use a suite of surface (late Holocene) sediment samples from the South Atlantic and southwestern Indian Ocean taken from depths lying well above the modern lysocline. The coccolith calcite mass in our results presents a latitudinal distribution pattern that mimics the main oceanographic features, thereby pointing to the potential importance of phosphorus and temperature in determining coccolith mass by affecting primary calcification and possibly driving the E. huxleyi morphotype distribution. This evidence does not necessarily argue against the potentially important role of the rapidly changing seawater carbonate chemistry in the future, when unabated fossil fuel burning will likely perturb ocean chemistry beyond a critical point. Rather our study highlights the importance of evaluating the combined effect of several environmental stressors on calcifying organisms to project their physiological response(s) in a high CO2 world and improve interpretation of paleorecords.

  7. 择优蚀坑表征立方晶系冷轧电工硅钢取向性%Grain orientation characterization of cold-rolled electrical steel sheets in the cubic crystal system by etch figures

    Institute of Scientific and Technical Information of China (English)

    李岩; 董秀文; 于志伟; 孔平

    2016-01-01

    In order to determine the value of import, the tax collecting and perform different ways of supervision regulations according to the grain orientation characterization of the electrical steel sheets, the etch figures of cold-rolled electrical steel sheets based on the preferential etch behavior were investigated by means of etch figure method. The relationships between the etch figures and grain orientation were analyzed from the viewpoint of crystallography. The results show that the geometric morphology of the etch figures on the rolling surface is disordered orientation for the non-oriented electrical steel sheets, and their corresponding miller indexes are (001), (011) and (111), respectively, and other miller indexes by their evolution formation. On the rolling surface of the grain-oriented electrical steel sheets, the etch figures are regular geometric morphology, miller index is (011), or other miller indexes by the evolution formation. The morphology of etch figures on the grain boundary related to the orientation difference between the adjacent grain, big orientation difference, will form{100},{110}and{111}crystal system of etch figures, whereas if small, will form{110}crystal system of etch figures. For grain-oriented steel sheets, the geometric morphology of etch figures is not affected by the grain boundary. The basal edges of the etch figures are parallel each other, and the deviation angle is less than 5 degrees. Their basal edges, extending direction are same as the rolling direction of the steel sheets, and the deviation angle shall not exceed 5 degrees also.%为确定电工硅钢的晶粒取向性,应用蚀坑技术研究了冷轧无取向硅钢、取向硅钢因择优腐蚀所形成的蚀坑与晶粒取向的关系,分析了{100}面系蚀坑形貌的演变过程,从晶体学角度建立了蚀坑形貌与晶面指数的对应关系.结果发现:无取向硅钢形成不同形貌的蚀坑,其晶面指数为( 001)、( 011)和( 111) ,或是由它们

  8. Structure and interactions of calcite spherulites with {alpha}-chitin in the brown shrimp (Penaeus aztecus) shell

    Energy Technology Data Exchange (ETDEWEB)

    Heredia, A. [Instituto de Ciencias Nucleares, Departamento de Quimica de Radiaciones y Radioquimica, UNAM, Circuito Exterior C.U. Apdo., Postal 70-543, 04510 Mexico, D.F. (Mexico); Physikalisches Institut and Center for Nanotechnology, Universitaet Muenster, Gievenbecker Weg 11, 48149 Muenster (Germany); Aguilar-Franco, M. [Instituto de Fisica, Depto de Fisicoquimica, UNAM, Circuito Exterior s/n, Ciudad Universitaria Apartado Postal 20-364 01000 Mexico D.F. (Mexico); Magana, C. [Instituto de Fisica, Depto de Estado Solido, UNAM, Circuito Exterior s/n, Ciudad Universitaria Apartado Postal 20-364 01000 Mexico D.F. (Mexico); Flores, C. [Instituto de Investigaciones en Materiales, Depto de Estado Solido, Laboratorio de Biomateriales, UNAM, Circuito Exterior C.U. S/N CP 04510 Mexico, D.F. (Mexico); Pina, C. [Instituto de Investigaciones en Materiales, Depto de Estado Solido, Laboratorio de Biomateriales, UNAM, Circuito Exterior C.U. S/N CP 04510 Mexico, D.F. (Mexico); Velazquez, R. [Centro de Fisica Aplicada Tecnologia Avanzada, UNAM, Km. 15 Carretera Queretaro-San Luis Potosi, C.P. 76230, Queretaro, Qro. (Mexico); Schaeffer, T.E. [Physikalisches Institut and Center for Nanotechnology, Universitaet Muenster, Gievenbecker Weg 11, 48149 Muenster (Germany); Bucio, L. [Instituto de Fisica, Depto de Estado Solido, UNAM, Circuito Exterior s/n, Ciudad Universitaria Apartado Postal 20-364 01000 Mexico D.F. (Mexico); Basiuk, V.A. [Instituto de Ciencias Nucleares, Departamento de Quimica de Radiaciones y Radioquimica, UNAM, Circuito Exterior C.U. Apdo., Postal 70-543, 04510 Mexico, D.F. (Mexico)

    2007-01-15

    White spots form in the brown shrimp (Penaeus aztecus, Decapoda) shell during frozen storage. The mineral formed consists of calcite incorporated into an amorphous {alpha}-chitin matrix. We studied mechanisms of interaction of amorphous {alpha}-chitin macromolecules with hkl crystal planes to form highly ordered structures, as well as the role of specific sites in the biopolymer, which can be related to nucleation and spheroidal crystal growth. We used low vacuum scanning electron microscopy (LVSEM), X-ray powder diffraction (XRD), atomic force microscopy (AFM), Fourier-transform infrared spectroscopy (FT-IR), and molecular mechanics modeling (MM+ method). AFM images showed fingerprint distances in the biopolymer and a highly layered structure in the crystalline material. The presence of {alpha}-chitin, with a specific spatial distribution of radicals, is thought to be responsible for nucleation and to thermodynamically stabilize ions to form the spherulite crystalline phase, which are usually oval to spherical (0.10 to 200 {mu}m in diameter). Our models of crystal-biopolymer interaction found high affinity of CO{sub 3} {sup 2-} anions in the (104) crystalline plane (the main plane in calcite monocrystals) to NH- groups of the biopolymer, as well as of the C=O in the biopolymer to Ca{sup 2+} cations in the crystalline structure. These interactions explain the spherical growth and inhibition in some planes. The specific physicochemical interactions (docking of groups depending on their geometrical distribution) suggest that the biomineral structure is controlled by the biopolymer on a local scale. This information is useful for further design and improvement of (hybrid) materials for versatile application, from nanotechnology to biomedicine and engineering.

  9. Impact of cooling condition on the crystal structure and surface quality of preferred c-axis-oriented AIN films for SAW devices

    Institute of Scientific and Technical Information of China (English)

    ZHANG Geng-yu; YANG Bao-he; ZHAO Jian; LI Cui-ping; LI Ming-ji

    2011-01-01

    AIN films with preferred c-axis orientation are deposited on Si substrates using the radio frequency (RF) magnetron sputtering method. The post-processing is carried out under the cooling conditions including high vacuum, low vacuum under deposition gas ambient and low vacuum under dynamic N2 ambient. Structures and morphologies of the films are analyzed by X-ray diffraction (XRD) and atomic force microscopy (AFM). The hardness and Young's modulus are investigated by the nanoindenter. The experimental results indicate that the (100) and (110) peak intensities decrease in the XRD spectra and the root-mean-square of roughness (Rrms) of the film decreases gradually with the increase of the cooling rate. The maximum values of the hardness and Young's modulus are obtained by cooling in low vacuum under deposition gas ambient. The reason for orientation variation of the films is explained from the perspective of the Al-N bond formation.

  10. Thermal properties of halogen-ethane glassy crystals: Effects of orientational disorder and the role of internal molecular degrees of freedom

    Energy Technology Data Exchange (ETDEWEB)

    Vdovichenko, G. A.; Krivchikov, A. I.; Korolyuk, O. A. [B. Verkin Institute for Low Temperature Physics and Engineering of NAS Ukraine, 47 Lenin Ave., 61103 Kharkov (Ukraine); Tamarit, J. Ll., E-mail: josep.lluis.tamarit@upc.edu; Pardo, L. C.; Rovira-Esteva, M. [Grup de Caracterització de Materials, Departament de Física i Enginyeria Nuclear, ETSEIB, Universitat Politècnica de Catalunya, Diagonal 647, 08028 Barcelona, Catalonia (Spain); Bermejo, F. J. [Instituto de Estructura de la Materia, CSIC, Consejo Superior de Investigaciones Cientificas, Serrano 123, 28006 Madrid (Spain); Hassaine, M.; Ramos, M. A. [Laboratorio de Bajas Temperaturas, Departamento de Física de la Materia Condensada, Condensed Matter Physics Center (IFIMAC) and Instituto Nicolás Cabrera, Universidad Autónoma de Madrid, Francisco Tomás y Valiente 7, 28049 Madrid (Spain)

    2015-08-28

    The thermal conductivity, specific heat, and specific volume of the orientational glass former 1,1,2-trichloro-1,2,2-trifluoroethane (CCl{sub 2}F–CClF{sub 2}, F-113) have been measured under equilibrium pressure within the low-temperature range, showing thermodynamic anomalies at ca. 120, 72, and 20 K. The results are discussed together with those pertaining to the structurally related 1,1,2,2-tetrachloro-1,2-difluoroethane (CCl{sub 2}F–CCl{sub 2}F, F-112), which also shows anomalies at 130, 90, and 60 K. The rich phase behavior of these compounds can be accounted for by the interplay between several of their degrees of freedom. The arrest of the degrees of freedom corresponding to the internal molecular rotation, responsible for the existence of two energetically distinct isomers, and the overall molecular orientation, source of the characteristic orientational disorder of plastic phases, can explain the anomalies at higher and intermediate temperatures, respectively. The soft-potential model has been used as the framework to describe the thermal properties at low temperatures. We show that the low-temperature anomaly of the compounds corresponds to a secondary relaxation, which can be associated with the appearance of Umklapp processes, i.e., anharmonic phonon-phonon scattering, that dominate thermal transport in that temperature range.

  11. Interactions of arsenic with calcite surfaces revealed by in-situ nanoscale imaging

    Science.gov (United States)

    Renard, Francois; Putnis, Christine; Montes-Hernandez, German; Ruiz-Agudo, Encarnacion; Hövelmann, Jörn; Sarret, Géraldine

    2015-04-01

    Arsenic dissolved in water represents a key environmental and health challenge because several million people are under the threat of contamination. In calcareous environments calcite may play an important role in arsenic solubility and transfer in water. Arsenic-calcite interactions remain controversial, especially for As(III) which was proposed to be either incorporated as such, or as As(V) after oxidation. Here, we provide the first time-lapse in-situ study of calcite dissolution and growth in the presence of solutions with various amounts of As(III) or As(V). This was performed at room temperature and pH range 6-9 using a flow through cell connected to an atomic force microscope (AFM), to study the evolution of the (10-14) calcite cleavage surface morphology. Reaction products were then characterized by Raman spectroscopy. In parallel, co-precipitation experiments with either As(III) or As(V) were performed in batch reactors, and the speciation of arsenic in the resulting solids was studied by X-ray absorption spectroscopy (XAS). For As(V), AFM results showed that it interacts strongly with the calcite surface, and XAS results showed that As(V) was mostly incorporated in the calcite structure. For As(III), AFM results showed much less impact on calcite growth and dissolution and less incorporation was observed. This was confirmed by XAS results that indicate that As(III) was partly oxidized into As(V) before being incorporated into calcite and the resulting calcite contained 36% As(III) and 64% As(V). All these experimental results confirm that As(V) has a much stronger interaction with calcite than As(III) and that calcite may represent an important reservoir for arsenic in various geological environments.

  12. The influence of nano-scale second-phase particles on deformation of fine grained calcite mylonites

    Science.gov (United States)

    Herwegh, Marco; Kunze, Karsten

    2002-09-01

    Grey and white carbonate mylonites were collected along thrust planes of the Helvetic Alps. They are characterised by very small grain sizes and non-random grain shape (SPO) and crystallographic preferred orientation (CPO). Presumably they deformed in the field of grain size sensitive flow by recrystallisation accommodated intracrystalline deformation in combination with granular flow. Both mylonites show a similar mean grain size, but in the grey mylonites the grain size range is larger, the grain shapes are more elongate and the dynamically recrystallised calcite grains are more often twinned. Grey mylonites have an oblique CPO, while the CPO in white mylonites is symmetric with respect to the shear plane. Combustion analysis and TEM investigations revealed that grey mylonites contain a higher amount of highly structured kerogens with particle sizes of a few tens of nanometers, which are finely dispersed at the grain boundaries. During deformation of the rock, nano-scale particles reduced the migration velocity of grain boundaries by Zener drag resulting in slower recrystallisation rates of the calcite aggregate. In the grey mylonites, more strain increments were accommodated by individual grains before they became refreshed by dynamic recrystallisation than in white mylonites, where grain boundary migration was less hindered and recrystallisation cycles were faster. Consequently, grey mylonites represent 'deformation' microfabrics while white mylonites are characterised by 'recrystallisation' microfabrics. Field geologists must utilise this different deformation behavior when applying the obliquity in CPO and SPO of the respective mylonites as reliable shear sense indicators.

  13. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    Energy Technology Data Exchange (ETDEWEB)

    Gorman, Brian P [Colorado School of Mines, Golden, CO (United States)

    2015-09-02

    Project Description: The general objective of the proposed research is to determine the kinetics and mechanisms of calcite reactions with saline waters over a wide range of saline water composition, pCO2, and modest ranges in T and P. This will be accomplished by studying both reaction rates and solubility from changes in solution chemistry, and making nanoscale observations of calcite precipitate surface morphology and composition at the micro-to-nano-scale to provide an understanding of controlling reaction mechanisms and pathways. The specific objectives necessary to reach the general objective are: a) determination of how pCO2, Ca2+, ionic strength and “foreign” ions influence reaction rates; and b) investigate the influence of these parameters on apparent kinetic solubility from dissolution and precipitation reactions. This information will clearly be central to the construction of reliable reaction-transport models to predict reservoir and formation response to increased CO2 in saline waters. This program was initially collaborative with John Morse at Texas A&M, however his passing shortly after the beginning of this program resulted in abbreviated research time and effort. Summary of Results: Early studies using electron microscopy and spectroscopy indicated that carbonate precipitation from natural seawater (NSW) conditions onto aragonite substrates was mediated by a surface amorphous calcium carbonate layer. It was hypothesized that this ACC layer (observed after < 5days reaction time) was responsible for the abnormal reaction kinetics and also served as a metastable seed layer for growth of epitaxial aragonite. Further studies of the ACC formation mechanism indicated a strong dependence on the Mg concentration in solution. Subsequent studies at shorter times (10 hrs) on calcite substrates and in a wide range of supersaturation conditions did not indicate any ACC layer. Instead, an epitaxial layer by layer

  14. Nucleation and Epitaxy-Mediated Phase Transformation of a Precursor Cadmium Carbonate Phase at the Calcite/Water Interface

    Energy Technology Data Exchange (ETDEWEB)

    Riechers, Shawn L.; Rosso, Kevin M.; Kerisit, Sebastien N.

    2017-02-24

    Mineral nucleation can be catalyzed by the presence of mineral substrates; however, the mechanisms of heterogeneous nucleation remain poorly understood. A combination of in situ time-sequenced measurements and nano-manipulation experiments were performed using atomic force microscopy (AFM) to probe the mechanisms of heteroepitaxial nucleation of otavite (CdCO3) on calcite (CaCO3) single crystals that exposed the (10-14) surface. Otavite and calcite are isostructural carbonates that display a 4% lattice mismatch, based on their (10-14) surface areas. AFM observations revealed a two-stage process in the nucleation of cadmium carbonate surface precipitates. As evidenced by changes in height, shape, growth behavior, and friction signal of the precipitates, a precursor phase was observed to initially form on the surface and subsequently undergo an epitaxy-mediated phase transformation to otavite, which then grew epitaxially. Nano-manipulation experiments, in which the applied force was increased progressively until precipitates were removed from the surface, showed that adhesion of the precursor phase to the substrate was distinctively weaker than that of the epitaxial phase, consistent with that of an amorphous phase. These findings demonstrate for the first time that heterogeneous mineral nucleation can follow a non-classical pathway like that found in homogenous aqueous conditions.

  15. EFFECT OF MAGNESIUM AS SUBSTITUTE MATERIAL IN ENZYME MEDIATED CALCITE PRECIPITATION (EMCP FOR SOIL IMPROVEMENT TECHNIQUE

    Directory of Open Access Journals (Sweden)

    Heriansyah ePutra

    2016-05-01

    Full Text Available The optimization of enzyme-mediated calcite precipitation (EMCP was evaluated as a soil improvement technique. In our previous works, purified urease was utilized to bio-catalyze the hydrolysis of urea, which causes the supplied Ca2+ to precipitate with CO32- as calcium carbonate. In the present work, magnesium chloride was newly added to the injecting solutions to delay the reaction rate and to enhance the amount of carbonate precipitation. Soil specimens were prepared in PVC cylinders and treated with concentration-controlled solutions composed of urea, urease, calcium, and magnesium chloride. The mechanical properties of the treated soil specimens were examined through unconfined compressive strength (UCS tests. A precipitation ratio of the carbonate up to 90% of the maximum theoretical precipitation was achieved by adding a small amount of magnesium chloride. Adding magnesium chloride as a delaying agent was indeed found to reduce the reaction rate of the precipitation, which may increase the volume of the treated soil if used in real fields because of the slower precipitation rate and the resulting higher injectivity. A mineralogical analysis revealed that magnesium chloride decreases the crystal size of the precipitated materials and that another carbonate of aragonite is newly formed. Mechanical test results indicated that carbonate precipitates within the soils and brings about a significant improvement in strength. A maximum UCS of 0.6 MPa was obtained from the treated samples.

  16. Demonstration of Crystal Structure.

    Science.gov (United States)

    Neville, Joseph P.

    1985-01-01

    Describes an experiment where equal parts of copper and aluminum are heated then cooled to show extremely large crystals. Suggestions are given for changing the orientation of crystals by varying cooling rates. Students are more receptive to concepts of microstructure after seeing this experiment. (DH)

  17. A global deglacial negative carbon isotope excursion in speleothem calcite

    Science.gov (United States)

    Breecker, D.

    2015-12-01

    δ13C values of speleothem calcite decreased globally during the last deglaciation defining a carbon isotope excursion (CIE) despite relatively constant δ13C values of carbon in the ocean-atmosphere system. The magnitude of the CIE varied with latitude, increasing poleward from ~2‰ in the tropics to as much as 7‰ at high latitudes. This recent CIE provides an interesting comparison with CIEs observed in deep time. A substantial portion of this CIE can be explained by the increase in atmospheric pCO2 that accompanied deglaciation. The dependence of C3 plant δ13C values on atmospheric pCO2 predicts a 2‰ δ13C decrease driven by the deglacial pCO2 increase. I propose that this signal was transferred to caves and thus explains nearly 100% of the CIE magnitude observed in the tropics and no less than 30% at the highest latitudes in the compilation. An atmospheric pCO2 control on speleothem δ13C values, if real, will need to be corrected for using ice core data before δ13C records can be interpreted in a paleoclimate context. The decrease in the magnitude of the equilibrium calcite-CO2 carbon isotope fractionation factor explains a maximum of 1‰ of the CIE at the highest northern latitude in the compilation, which experienced the largest deglacial warming. Much of the residual extratropical CIE was likely driven by increasing belowground respiration rates, which were presumably pronounced at high latitudes as glacial retreat exposed fresh surfaces and/or vegetation density increased. The largest increases in belowground respiration would have therefore occurred at the highest latitudes, explaining the meridional trend. This work supports the notion that increases in atmospheric pCO2 and belowground respiration rates can result in large CIEs recorded in terrestrial carbonates, which, as previously suggested, may explain the magnitude of the PETM CIE as recorded by paleosol carbonates.

  18. Complex vibrational analysis of an antiferroelectric liquid crystal based on solid-state oriented quantum chemical calculations and experimental molecular spectroscopy.

    Science.gov (United States)

    Drużbicki, Kacper; Mikuli, Edward; Kocot, Antoni; Ossowska-Chruściel, Mirosława Danuta; Chruściel, Janusz; Zalewski, Sławomir

    2012-08-02

    The experimental and theoretical vibrational spectroscopic study of one of a novel antiferroelectric liquid crystals (AFLC), known under the MHPSBO10 acronym, have been undertaken. The interpretation of both FT-IR and FT-Raman spectra was focused mainly on the solid-state data. To analyze the experimental results along with the molecular properties, density functional theory (DFT) computations were performed using several modern theoretical approaches. The presented calculations were performed within the isolated molecule model, probing the performance of modern exchange-correlations functionals, as well as going beyond, i.e., within hybrid (ONIOM) and periodic boundary conditions (PBC) methodologies. A detailed band assignment was supported by the normal-mode analysis with SQM ab initio force field scaling. The results are supplemented by the noncovalent interactions analysis (NCI). The relatively noticeable spectral differences observed upon Crystal to AFLC phase transition have also been reported. For the most prominent vibrational modes, the geometries of the transition dipole moments along with the main components of vibrational polarizability were analyzed in terms of the molecular frame. One of the goals of the paper was to optimize the procedure of solid-state calculations to obtain the results comparable with the all electron calculations, performed routinely for isolated molecules, and to test their performance. The presented study delivers a complex insight into the vibrational spectrum with a noticeable improvement of the theoretical results obtained for significantly attracting mesogens using modern molecular modeling approaches. The presented modeling conditions are very promising for further description of similar large molecular crystals.

  19. Unusual micrometric calcite-aragonite interface in the abalone shell Haliotis (Mollusca, Gastropoda).

    Science.gov (United States)

    Dauphin, Yannicke; Cuif, Jean-Pierre; Castillo-Michel, Hiram; Chevallard, Corinne; Farre, Bastien; Meibom, Anders

    2014-02-01

    Species of Haliotis (abalone) show high variety in structure and mineralogy of the shell. One of the European species (Haliotis tuberculata) in particular has an unusual shell structure in which calcite and aragonite coexist at a microscale with small patches of aragonite embedded in larger calcitic zones. A detailed examination of the boundary between calcite and aragonite using analytical microscopies shows that the organic contents of calcite and aragonite differ. Moreover, changes in the chemical composition of the two minerals seem to be gradual and define a micrometric zone of transition between the two main layers. A similar transition zone has been observed between the layers in more classical and regularly structured mollusk shells. The imbrication of microscopic patches of aragonite within a calcitic zone suggests the occurrence of very fast physiological changes in these taxa.

  20. Sorption of phosphate onto calcite; results from batch experiments and surface complexation modeling

    DEFF Research Database (Denmark)

    Sø, Helle Ugilt; Postma, Dieke; Jakobsen, Rasmus;

    2011-01-01

    The adsorption of phosphate onto calcite was studied in a series of batch experiments. To avoid the precipitation of phosphate-containing minerals the experiments were conducted using a short reaction time (3h) and low concentrations of phosphate (⩽50μM). Sorption of phosphate on calcite...... was studied in 11 different calcite-equilibrated solutions that varied in pH, PCO2, ionic strength and activity of Ca2+, CO32- and HCO3-. Our results show strong sorption of phosphate onto calcite. The kinetics of phosphate sorption onto calcite are fast; adsorption is complete within 2–3h while desorption...... of a high degree of super-saturation with respect to hydroxyapatite (SIHAP⩽7.83). The amount of phosphate adsorbed varied with the solution composition, in particular, adsorption increases as the CO32- activity decreases (at constant pH) and as pH increases (at constant CO32- activity). The primary effect...

  1. Influence of surface conductivity on the apparent zeta potential of calcite

    CERN Document Server

    Li, Shuai; Heberling, Frank; Devau, Nicolas; Jougnot, Damien; Chiaberge, Christophe

    2016-01-01

    Zeta potential is a physicochemical parameter of particular importance in describing the surface electrical properties of charged porous media. However, the zeta potential of calcite is still poorly known because of the difficulty to interpret streaming potential experiments. The Helmholtz-Smoluchowski (HS) equation is widely used to estimate the apparent zeta potential from these experiments. However, this equation neglects the influence of surface conductivity on streaming potential. We present streaming potential and electrical conductivity measurements on a calcite powder in contact with an aqueous NaCl electrolyte. Our streaming potential model corrects the apparent zeta potential of calcite by accounting for the influence of surface conductivity and flow regime. We show that the HS equation seriously underestimates the zeta potential of calcite, particularly when the electrolyte is diluted (ionic strength < 0.01 M) because of calcite surface conductivity. The basic Stern model successfully predicted ...

  2. Dynamic theory of morphological characteristics of crystals of ɛ and γ phases, including Headley-Brooks orientation relationships upon the α-ɛ and α-ɛ-γ martensitic transformations

    Science.gov (United States)

    Kashchenko, M. P.; Chashchina, V. G.

    2015-10-01

    Different variants of the formation of martensite crystals upon the α-γ transformation caused by the tension-compression deformation of {110}α planes have been considered according to the dynamic theory of martensitic transformations. In contrast to previous works, here we take into account the deviation (angle θ) of the principal directions of deformation from the symmetry axes α. It has been shown that the requirement of the symmetry of the arrangement of atoms in the basal plane {0001}ɛ is satisfied in the range of angular deviations-arctan √ {2/3} ≤slant θ ≤slant arctan √ {2/3}. The algorithm for calculating the morphological characteristics is illustrated based on the example of an elastically isotropic medium, which does not require assigning concrete values of elastic moduli. The estimations performed make it possible, in particular, to explain the physical nature of the Headley-Brooks orientation relationships as a result of the inheritance of one of the variants of permissible material orientation relationships for the α-ɛ transformation in the course of the ɛ-γ transformation at θ 35°. The changes in the other morphological signs are also discussed.

  3. Interactions of arsenic with calcite surfaces revealed by in situ nanoscale imaging

    Science.gov (United States)

    Renard, François; Putnis, Christine V.; Montes-Hernandez, German; Ruiz-Agudo, Encarnacion; Hovelmann, Jörn; Sarret, Géraldine

    2015-06-01

    Arsenic dissolved in water represents a key environmental and health challenge because several million people are under the threat of contamination. In calcareous environments calcite may play an important role in arsenic solubility and transfer in water. Arsenic-calcite interactions remain controversial, especially for As(III) which was proposed to be either incorporated as such, or as As(V) after oxidation. Here, we provide the first time-lapse in situ study of the evolution of the (10-14) calcite cleavage surface morphology during dissolution and growth in the presence of solutions with various amounts of As(III) or As(V) at room temperature and pH range 6-11 using a flow-through cell connected to an atomic force microscope (AFM). Reaction products were then characterized by Raman spectroscopy. In parallel, co-precipitation experiments with either As(III) or As(V) were performed in batch reactors, and the speciation of arsenic in the resulting solids was studied by X-ray absorption spectroscopy (XAS). For As(V), AFM results showed that it interacts strongly with the calcite surface, and XAS results showed that As(V) was mostly incorporated in the calcite structure. For As(III), AFM results showed much less impact on calcite growth and dissolution and less incorporation was observed. This was confirmed by XAS results that indicate that As(III) was partly oxidized into As(V) before being incorporated into calcite and the resulting calcite contained 36% As(III) and 64% As(V). All these experimental results confirm that As(V) has a much stronger interaction with calcite than As(III) and that calcite may represent an important reservoir for arsenic in various geological environments.

  4. Fluid Inclusions of Calcite and Sources of Ore-forming Fluids in the Huize Zn-Pb-(Ag-Ge) District, Yunnan, China

    Institute of Scientific and Technical Information of China (English)

    HAN Runsheng; LIU Congqiang; HUANG Zhilong; MA Deyun; LI Yuan; HU Bin; MA Gengsheng; LEI Li

    2004-01-01

    The Huize Zn-Pb- (Ag-Ge) district is a typical representative of the well-known medium-to large-sized carbonate-hosted Zn-Pb- (Ag-Ge) deposits, occurring in the Sichuan-Yunnan-Guizhou Pb-Zn Ore-forming Zone.Generally, fluid inclusions within calcite, one of the major gangue minerals, are dominated by two kinds of small (1-10μm) inclusions including pure-liquid and liquid. The inclusions exist in concentrated groups along the crystal planes of the calcite. The ore-forming fluids containing Pb and Zn, which belong to the Na+-K+-Ca2+-C1--F--SO42- type, are characterized by temperatures of 164-221 ℃, medium salinity in 5-10.8 wt% NaCl, and medium pressure at 410xl0s to 661 x 10s Pa. The contents of Na+-K+ and Cl--F-, and ratios of Na+/K+-Cl-/F- in fluid inclusions present good linearity. The ratios of Na+/K+ (4.66-6.71) and C1-/F- (1 8.21-31.04) in the fluid inclusions of calcite are relatively high, while those of Na+/K+ (0.29-5.69) and Cl-/F- (5.00-26.0) in the inclusions of sphalerite and pyrite are relatively low. The ratio of Na+/K+increases in accord with those of C1-/F, which indicates that ore-forming fluid of deep source participates in the mineralization. The waters of fluid inclusions have δD values from -43.5‰ to -55.4‰ of calcite. The δ18Ov-sMow values of the ore-forming fluids, calculated values, range from 17.09‰ to 18.56‰ of calcite and 17.80‰ to 23.14‰ for dolomite.δ13 Cv-PDB values range from -1.94‰ to -3.31‰ for calcite and -3.35‰ to 0.85‰ for the ore-bearing dolomite. These data better demonstrate that the ore-forming fluids were mainly derived from metamorphic water and magmatic hot fluid, in relation to the metamorphism of the Kunyang Group in the basement and magmatic hydrothermalism. The deposit itself might have resulted from ascending cycles of ore-forming fluid, enriched in Pb and Zn. The Huize Zn-Pb- (Ag-Ge)deposits related to carbonate-hosted Zn-Pb sulphides.

  5. Preferred orientation of ettringite in concrete fractures

    KAUST Repository

    Wenk, Hans-Rudolf

    2009-05-15

    Sulfate attack and the accompanying crystallization of fibrous ettringite [Ca6Al2(OH)12(SO4) 3·26H2O] cause cracking and loss of strength in concrete structures. Hard synchrotron X-ray microdiffraction is used to quantify the orientation distribution of ettringite crystals. Diffraction images are analyzed using the Rietveld method to obtain information on textures. The analysis reveals that the c axes of the trigonal crystallites are preferentially oriented perpendicular to the fracture surfaces. By averaging single-crystal elastic properties over the orientation distribution, it is possible to estimate the elastic anisotropy of ettringite aggregates. © 2009 International Union of Crystallography.

  6. The surface reactivity of chalk (biogenic calcite) with hydrophilic and hydrophobic functional groups

    Science.gov (United States)

    Okhrimenko, D. V.; Dalby, K. N.; Skovbjerg, L. L.; Bovet, N.; Christensen, J. H.; Stipp, S. L. S.

    2014-03-01

    The surface properties of calcium carbonate minerals play an important role in a number of industrial and biological processes. Properties such as wettability and adsorption control liquid-solid interface behaviour and thus have a strong influence on processes such as biomineralisation, remediation of aquifers and oil recovery. We investigated how two model molecules of different polarity, namely water and ethanol, interact with reservoir and outcrop chalk samples and we compared their behaviour with that of pure, inorganically precipitated calcite. Thermodynamic quantities, such as the work of wetting, surface energy and isosteric adsorption enthalpy, were determined from vapour adsorption isotherms. The chalks were studied fresh and after extraction of organic residues that were originally present in these samples. The work of wetting correlates with the amount of organic matter present in the chalk samples but we observed a fundamental difference between the adsorption properties of chalk and pure, inorganically precipitated calcite toward the less polar, ethanol molecule. Further analysis of the chemical composition of the organic matter extracted from the chalk samples was made by gas chromatography (GC-MS). Monitoring surface composition by X-ray photoelectron spectroscopy (XPS) before and after extraction of the organic material, and with atomic force microscopy (AFM), showed that nanometer sized clay crystals observed on the chalk particle surfaces could be an important part of the reason for the differences. Removal of the extractable portion of the hydrocarbons liberates adsorption sites that have different wetting properties than the rest of the chalk and these have an energy distribution that is similar to clays. Thus, the results exemplify the complexity of biogenic calcite adsorption behaviour and demonstrate that chalk wetting in drinking water aquifers as well as oil reservoirs is controlled partly by the nanoparticles of clay that have grown on the

  7. Fabrication of porous calcite using chopped nylon fiber and its evaluation using rats.

    Science.gov (United States)

    Ishikawa, Kunio; Tram, Nguyen Xuan Thanh; Tsuru, Kanji; Toita, Riki

    2015-02-01

    Although porous calcite has attracted attention as bone substitutes, limited studies have been made so far. In the present study, porous calcite block was fabricated by introducing chopped nylon fiber as porogen. Ca(OH)2 powder containing 10 wt% chopped nylon fiber was compacted at 150 MPa, and sintered to burn out the fiber and to carbonate the Ca(OH)2 under stream of 1:2 O2-CO2. Sintering of Ca(OH)2 at 750 °C or lower temperature resulted in incomplete burning out of the fiber whereas sintering at 800 °C or higher temperature resulted in the formation of CaO due to the thermal decomposition of Ca(OH)2. However, sintering at 770 °C resulted in complete burning out of the fiber and complete carbonation of Ca(OH)2 to calcite without forming CaO. Macro- and micro-porosities of the porous calcite were approximately 23 and 16%, respectively. Diameter of the macropores was approximately 100 μm which is suitable for bone tissue penetration. Porous calcite block fabricated by this method exhibited good tissue response when implanted in the bone defect in femur of 12-weeks-old rat. Four weeks after implantation, bone bonded on the surface of calcite. Furthermore, bone tissue penetrated interior to the macropore at 8 weeks. These results demonstrated the good potential value of porous calcite as artificial bone substitutes.

  8. Aragonite-calcite transformation in fossil snail shells of loess sequences in Loess Plateau, Central China

    Institute of Scientific and Technical Information of China (English)

    SHENG Xuefen; CHEN Jun; CAI Yuanfeng; CHEN Yang; JI Junfeng

    2005-01-01

    The methods of X-ray diffraction (XRD) and ICP-AES are applied to analyzing the mineral composition of modern and fossil snail shells in Luochuan section and Xifeng section. The results show that the mineral phase of calcium carbonate in modern snail shells is aragonite, but for some fossil snail shells in certain layers of loess sequences, a part of aragonite is transformed into calcite. In Luochuan and Xifeng sections, the stratigraphic borderline of aragonite-calcite transformation appearing obviously is between L5 and L6. Under the earth surface condition, the aragonite-calcite transformation is influenced by the factor of temperature only in a long time scale. It seems that the pressure is not the factor influencing the aragonite-calcite transformation. The results also show that existing age of snail shells is possibly the dominant and principal factor for the aragonite-calcite transformation. To a certain extent, the degree of aragonite-calcite transformation in snail shell is controlled by the content of trace element, such as Mg2+. The trace element can improve the stability of snail shell aragonite and impede the process of aragonite transforming into calcite.

  9. Orienteering injuries

    OpenAIRE

    Folan, Jean M.

    1982-01-01

    At the Irish National Orienteering Championships in 1981 a survey of the injuries occurring over the two days of competition was carried out. Of 285 individual competitors there was a percentage injury rate of 5.26%. The article discusses the injuries and aspects of safety in orienteering.

  10. Uranium isotope fractionation during coprecipitation with aragonite and calcite

    Science.gov (United States)

    Chen, Xinming; Romaniello, Stephen J.; Herrmann, Achim D.; Wasylenki, Laura E.; Anbar, Ariel D.

    2016-09-01

    Natural variations in 238U/235U of marine calcium carbonates might provide a useful way of constraining redox conditions of ancient environments. In order to evaluate the reliability of this proxy, we conducted aragonite and calcite coprecipitation experiments at pH ∼7.5 and ∼8.5 to study possible U isotope fractionation during incorporation into these minerals. Small but significant U isotope fractionation was observed in aragonite experiments at pH ∼8.5, with heavier U isotopes preferentially enriched in the solid phase. 238U/235U of dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00007 + 0.00002/-0.00003, 1.00005 ± 0.00001, and 1.00003 ± 0.00001. In contrast, no resolvable U isotope fractionation was observed in an aragonite experiment at pH ∼7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among different aqueous U species is the most likely explanation for these findings. Certain charged U species are preferentially incorporated into calcium carbonate relative to the uncharged U species Ca2UO2(CO3)3(aq), which we hypothesize has a lighter equilibrium U isotope composition than most of the charged species. According to this hypothesis, the magnitude of U isotope fractionation should scale with the fraction of dissolved U that is present as Ca2UO2(CO3)3(aq). This expectation is confirmed by equilibrium speciation modeling of our experiments. Theoretical calculation of the U isotope fractionation factors between different U species could further test this hypothesis and our proposed fractionation mechanism. These findings suggest that U isotope variations in ancient carbonates could be controlled by changes in the aqueous speciation of seawater U, particularly changes in seawater pH, PCO2 , Ca2+, or Mg2+ concentrations. In general, these effects are likely to be small (<0.13‰), but are nevertheless potentially significant because of the small natural range of

  11. Crystal orientation effects on implantation of low-energy hydrogen, helium and hydrogen/helium mixtures in plasma-facing tungsten surfaces

    Science.gov (United States)

    Linn, Brian C.

    The development of plasma-facing materials (PFM) is one of the major challenges in. realizing fusion reactors. Materials deployed in PFMs must be capable of withstanding the high-flux of low-energy hydrogen and helium ions omitted from the plasma. while not hindering the plasma. Tungsten is considered a promising candidate material due to desirable material properties including its high melting temperature, good thermal conductivity and relatively low physical and chemical sputtering yields. This thesis uses molecular dynamic simulations to investigate helium and hydrogen bombardment of tungsten and the underlying physical effects (e.g. sputtering, erosion, blistering). Non-cumulative and cumulative bombardment simulations of helium, hydrogen, and hydrogen/helium bombardment of tungsten were modeled using the molecular dynamics code LAMMPS. Two orientations of monocrystalline bcc tungsten surfaces were considered, (001) and (111). Simulations were performed for temperatures ranging from 600K up to 1500K and helium / hydrogen incident energies of 20eV to 100eV . The results of these simulations showed the effect of temperature and incident particle energy on retention rates and implantation/deposition profiles in tungsten.

  12. Elastic anisotropy of Tambo gneiss from Promontogno, Switzerland: a comparison of crystal orientation and microstructure-based modeling and experimental measurements

    Science.gov (United States)

    Vasin, R. N.; Kern, H.; Lokajíček, T.; Svitek, T.; Lehmann, E.; Mannes, D. C.; Chaouche, M.; Wenk, H.-R.

    2017-01-01

    SUMMARYFelsic and mafic gneisses constitute large proportions of the upper and lower continental crust. Gneisses often demonstrate high anisotropy of elastic properties associated with preferred orientations of sheet silicates. Here we study the elastic anisotropy of a sample of Tambo gneiss from Promontogno in the Central Alps. We apply optical microscopy, time-of-flight neutron diffraction, neutron and X-ray tomography to quantify mineral composition and microstructures and use them to construct self-consistent models of elastic properties. They are compared to results of ultrasonic measurements on a cube sample in a multi anvil apparatus and on a spherical sample in an apparatus that can measure velocities in multiple directions. Both methods provide similar results. It is shown that models of microstructure-derived elastic properties provide a good match with ultrasonic experiment results at pressures above 100 MPa. At a pressure of 0.1 MPa the correspondence between the model and the experiment is worse. This may be caused by an oversimplification of the model with respect to microfractures or uncertainties in the experimental determination of S-wave velocities and elastic tensor inversion. The study provides a basis to determine anisotropic elastic properties of rocks either by ultrasonic experiments or quantitative models based on microstructures. This information can then be used for interpretation of seismic data of the crust.

  13. Recurrent Pure Calcite Urolithiasis Confirmed by Endoscopic Removal and Infrared Spectroscopy in a Malnourished Anorectic Female

    Science.gov (United States)

    Andreassen, Kim Hovgaard; Sloth Osther, Palle Jörn

    2016-01-01

    Abstract Often when calcite is found as a component of urinary calculi, they are considered false calculi or artifacts. We present a case of true calcite urolithiasis. The stone material was removed percutaneously from a severely malnourished anorectic woman and analyzed by infrared spectroscopy (IRS). In addition, calcite urolithiasis was confirmed in several recurrent stone events by IRS. Laxative abuse with magnesium oxide was believed to be the underlying cause of stone formation, and ammonium chloride given as one weekly dose turned out to be effective for stone prevention. PMID:27579419

  14. Comparison of galvanic displacement and electroless methods for deposition of gold nanoparticles on synthetic calcite

    Indian Academy of Sciences (India)

    Chamarthi K Srikanth; P Jeevanandam

    2012-11-01

    Gold nanoparticles have been deposited on synthetic calcite substrate by galvanic displacement reaction and electroless deposition methods. A comparative study has shown that electroless deposition is superior compared to galvanic displacement reaction for uniform deposition of gold nanoparticles on calcite. Characterization of the samples, prepared by two different deposition methods, was carried out by X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy (FE–SEM) and diffuse reflectance spectroscopy (DRS) measurements. FE–SEM studies prove that smaller nanoparticles of gold are deposited uniformly on calcite if electroless deposition method was employed and DRS measurements show the characteristic surface plasmon resonance of gold nanoparticles.

  15. Stimulated Globular Scattering of Laser Radiation in Photonic Crystals: Temperature Dependences

    CERN Document Server

    Gorelik, V S; Tcherniega, N V; Vodchits, A I

    2007-01-01

    Stimulated globular scattering (SGS) characteristics (frequency shifts, threshold, conversion efficiency) have been studied in photonic crystals (synthetic opal matrices and opal nanocomposites) at different temperatures. Results have been compared with stimulated Raman scattering investigations in calcite single crystals. In both cases temperature lowering from +20 C to -196 C resulted in the stimulated scattering energy increase and its redistribution to the higher order components.

  16. Ultrasonic Observation of the Calcite-Aragonite Transition

    Science.gov (United States)

    Ahrens, T. J.; Katz, S.

    1963-01-01

    Elastic-wave velocities were measured as a function of pressure by ultrasonic pulse Interferometry in Solenhofen and Manilus limestone specimens to pressures of 27 and 38 kb. Longitudinal velocities decrease sharply from 5.3 km/sec at a mean pressure of 4 kb to a minimum of 4.8 km/sec at 8 kb. Transverse velocities decrease from 3.1 to 2.9 km/sec. At the minimum bulk and rigidity moduli are 25 and 20 per cent below their 4-kb values. A density increase of 1.7 per cent is associated with this minimum. The observed effects are attributed to the calcite-aragonite transition, and they may be due to an inherent property of the material, a component of which undergoes a polymorphic transition, the low- and high-pressure phases coexisting over a considerable pressure range. This may be an additional mechanism to account for low-velocity zones in the earth?s interior.

  17. Microbiologically Induced Calcite Precipitation Mediated by Sporosarcina pasteurii.

    Science.gov (United States)

    Bhaduri, Swayamdipta; Debnath, Nandini; Mitra, Sushanta; Liu, Yang; Kumar, Aloke

    2016-04-16

    The particular bacterium under investigation here (S. pasteurii) is unique in its ability, under the right conditions, to induce the hydrolysis of urea (ureolysis) in naturally occurring environments through secretion of an enzyme urease. This process of ureolysis, through a chain of chemical reactions, leads to the formation of calcium carbonate precipitates. This is known as Microbiologically Induced Calcite Precipitation (MICP). The proper culture protocols for MICP are detailed here. Finally, visualization experiments under different modes of microscopy were performed to understand various aspects of the precipitation process. Techniques like optical microscopy, Scanning Electron Microscopy (SEM) and X-Ray Photo-electron Spectroscopy (XPS) were employed to chemically characterize the end-product. Further, the ability of these precipitates to clog pores inside a natural porous medium was demonstrated through a qualitative experiment where sponge bars were used to mimic a pore-network with a range of length scales. A sponge bar dipped in the culture medium containing the bacterial cells hardens due to the clogging of its pores resulting from the continuous process of chemical precipitation. This hardened sponge bar exhibits superior strength when compared to a control sponge bar which becomes compressed and squeezed under the action of an applied external load, while the hardened bar is able to support the same weight with little deformation.

  18. Alkaline flocculation of Phaeodactylum tricornutum induced by brucite and calcite.

    Science.gov (United States)

    Vandamme, Dries; Pohl, Philip I; Beuckels, Annelies; Foubert, Imogen; Brady, Patrick V; Hewson, John C; Muylaert, Koenraad

    2015-11-01

    Alkaline flocculation holds great potential as a low-cost harvesting method for marine microalgae biomass production. Alkaline flocculation is induced by an increase in pH and is related to precipitation of calcium and magnesium salts. In this study, we used the diatom Phaeodactylum tricornutum as model organism to study alkaline flocculation of marine microalgae cultured in seawater medium. Flocculation started when pH was increased to 10 and flocculation efficiency reached 90% when pH was 10.5, which was consistent with precipitation modeling for brucite or Mg(OH)2. Compared to freshwater species, more magnesium is needed to achieve flocculation (>7.5mM). Zeta potential measurements suggest that brucite precipitation caused flocculation by charge neutralization. When calcium concentration was 12.5mM, flocculation was also observed at a pH of 10. Zeta potential remained negative up to pH 11.5, suggesting that precipitated calcite caused flocculation by a sweeping coagulation mechanism.

  19. Nanoscale observations of the effect of citrate on calcium oxalate precipitation on calcite surfaces.

    Science.gov (United States)

    Burgos-Cara, Alejandro; Ruiz-Agudo, Encarnacion; Putnis, Christine V.

    2016-04-01

    Calcium oxalate (CaC2O4ṡxH2O) minerals are naturally occurring minerals found in fossils, plants, kidney stones and is a by-product in some processes such as paper, food and beverage production [1,2]. In particular, calcium oxalate monohydrate phase (COM) also known as whewellite (CaC2O4ṡH2O), is the most frequently reported mineral phase found in urinary and kidney stones together with phosphates. Organic additives are well known to play a key role in the formation of minerals in both biotic and abiotic systems, either facilitating their precipitation or hindering it. In this regard, recent studies have provided direct evidence demonstrating that citrate species could enhance dissolution of COM and inhibit their precipitation. [3,4] The present work aims at evauate the influence of pH, citrate and oxalic acid concentrations in calcium oxalate precipitation on calcite surfaces (Island Spar, Chihuahua, Mexico) through in-situ nanoscale observation using in situ atomic force microscopy (AFM, Multimode, Bruker) in flow-through experiments. Changes in calcium oxalate morphologies and precipitated phases were observed, as well as the inhibitory effect of citrate on calcium oxalate precipitation, which also lead to stabilization an the amorphous calcium oxalate phase. [1] K.D. Demadis, M. Öner, Inhibitory effects of "green"additives on the crystal growth of sparingly soluble salts, in: J.T. Pearlman (Ed.), Green Chemistry Research Trends, Nova Science Publishers Inc., New York, 2009, pp. 265-287. [2] M. Masár, M. Zuborová, D. Kaniansky, B. Stanislawski, Determination of oxalate in beer by zone electrophoresis on a chip with conductivity detection, J. Sep. Sci. 26 (2003) 647-652. [3] Chutipongtanate S, Chaiyarit S, Thongboonkerd V. Citrate, not phosphate, can dissolve calcium oxalate monohydrate crystals and detach these crystals from renal tubular cells. Eur J Pharmacol 2012;689:219-25. [4] Weaver ML, Qiu SR, Hoyer JR, Casey WH, Nancollas GH, De Yoreo JJ

  20. From high-temperature orientationally disordered mixed crystals to low-temperature complex formation in the two-component system (CH3)3CBr + Cl3CBr.

    Science.gov (United States)

    Barrio, María; Negrier, Philippe; Tamarit, Josep Ll; Mondieig, Denise

    2011-02-24

    The phase diagram of the two-component systems (CH(3))(3)CBr + Cl(3)CBr has been experimentally determined by means of differential scanning calorimetry and X-ray powder diffraction techniques from the low-temperature ordered phases to the liquid state. Before melting, both components have the same orientationally disordered (OD) face-centered cubic (FCC) and rhombohedral (R) phases, and the two-phase equilibria [FCC + L] and [R + FCC] are accounted for by means of the existence of an isomorphic relationship between the OD phases of pure compounds. The thermodynamic assessment of such equilibria enables us to get the excess properties of the involved OD phases and to rationalize the existence of a maximum and a minimum in the [R + FCC] equilibrium on the basis of the contribution of the entropic term in the excess Gibbs energy function. At low temperature, two complexes, (CH(3))(3)CBr:Cl(3)CBr (1:1) and (CH(3))(3)CBr:2Cl(3)CBr (1:2), appear. The structures of 1:1 and 1:2 complexes have been determined to be monoclinic (P2(1)/n, c, Z = 4) and hexagonal (P6(3), Z = 6). Within both "ordered" structures, the Cl(3)CBr entities of the asymmetric unit were found to be disordered so that sites have fractional occupancies of 0.75 and 0.25 for Cl and Br atoms, in the same way that it occurs for the low-temperature monoclinic (C2/c, Z = 32) phase of Cl(3)CBr. Finally, the existence of complexes is connected with the special intermolecular interactions appearing between a methyl group and a halogen, as previously inferred by Calvet et al. [T. Calvet et al. J. Chem. Phys. 1999, 110, 4841].

  1. Orientation and the Young Orienteer

    Science.gov (United States)

    Walsh, S. E.; Martland, J. R.

    Orientation within orienteering is dependent on the use of two basic strategies; that is, either a compass or Magnetic-North-based strategy, which relies on the use of one set of information; or the use of a map and landmark-based strategy which relies on the use of at least two sets of information. Walsh and found that, when given the choice, young children use the compass-based strategy when following complex potentially disorientating routes.The efficacy of these two basic orientation strategies was investigated within three different orienteering environments: (1) a familiar known environment; (2) a familiar unknown environment and (3) an unfamiliar unknown environment.Subjects, age range from 9 to 10think aloud particularly the introduction of basic skills to young performers. They support the argument that is essential to introduce the map and compass simultaneously and that relocation and orientation skills should be coached concurrently.

  2. Some Debye temperatures from single-crystal elastic constant data

    Science.gov (United States)

    Robie, R.A.; Edwards, J.L.

    1966-01-01

    The mean velocity of sound has been calculated for 14 crystalline solids by using the best recent values of their single-crystal elastic stiffness constants. These mean sound velocities have been used to obtain the elastic Debye temperatures ??De for these materials. Models of the three wave velocity surfaces for calcite are illustrated. ?? 1966 The American Institute of Physics.

  3. High School Forum: "Invitations to Enquiry": The Calcite/Acid Reaction.

    Science.gov (United States)

    Herron, J. Dudley, Ed.; Driscoll, D. R.

    1979-01-01

    Describes a high school chemistry experiment which involves the reaction between calcite and hydrochloric and sulfuric acids. This reaction can be carried out as a projected demonstration and on an individual basis. (HM)

  4. Calcium sulfoaluminate (Ye'elimite) hydration in the presence of gypsum, calcite, and vaterite

    Energy Technology Data Exchange (ETDEWEB)

    Hargis, Craig W. [Department of Civil and Environmental Engineering, University of California, Berkeley, CA (United States); Telesca, Antonio [School of Engineering, University of Basilicata, Potenza (Italy); Monteiro, Paulo J.M., E-mail: monteiro@ce.berkeley.edu [Department of Civil and Environmental Engineering, University of California, Berkeley, CA (United States)

    2014-11-15

    Six calcium sulfoaluminate-based cementitious systems composed of calcium sulfoaluminate, calcite, vaterite, and gypsum were cured as pastes and mortars for 1, 7, 28 and 84 days. Pastes were analyzed with X-ray diffraction, thermogravimetric and differential thermal analyses. Mortars were tested for compressive strength, dimensional stability and setting time. Furthermore, pastes with a water/cementitious material mass ratio of 0.80 were tested for heat evolution during the first 48 h by means of isothermal conduction calorimetry. It has been found that: (1) both calcite and vaterite reacted with monosulfoaluminate to give monocarboaluminate and ettringite, with vaterite being more reactive; (2) gypsum lowered the reactivity of both carbonates; (3) expansion was reduced by calcite and vaterite, irrespective of the presence of gypsum; and (4) both carbonates increased compressive strength in the absence of gypsum and decreased compressive strength less in the presence of gypsum, with vaterite's action more effective than that of calcite.

  5. Calcite dissolution along a transect in the western tropical Indian Ocean: A multiproxy approach

    Digital Repository Service at National Institute of Oceanography (India)

    Naik, S.S.; Naidu, P.D.

    Three paleocarbonate ion proxies, size index, planktonic foraminifera shell weight, and calcite crystallinity, have been employed here to a set of core top samples from the western tropical Indian Ocean in the water depth ranges from 1086 to 4730 m...

  6. Anisotropic dynamics of water ultra-confined in macroscopically oriented channels of single-crystal beryl: A multi-frequency analysis

    Energy Technology Data Exchange (ETDEWEB)

    Anovitz, Lawrence {Larry} M [ORNL; Mamontov, Eugene [ORNL; Ishai, Paul ben [The Hebrew University of Jerusalem, Israel; Kolesnikov, Alexander I [ORNL

    2013-01-01

    The properties of fluids can be significantly altered by the geometry of their confining environments. While there has been significant work on the properties of such confined fluids, the properties of fluids under ultraconfinement, environments where, at least in one plane, the dimensions of the confining environment are similar to that of the confined molecule, have not been investigated. This paper investigates the dynamic properties of water in beryl (Be3Al2Si6O18), the structure of which contains approximately 5-A-diam channels parallel to the c axis. Three techniques, inelastic neutron scattering, quasielastic neutron scattering, and dielectric spectroscopy, have been used to quantify these properties over a dynamic range covering approximately 16 orders of magnitude. Because beryl can be obtained in large single crystals we were able to quantify directional variations, perpendicular and parallel to the channel directions, in the dynamics of the confined fluid. These are significantly anisotropic and, somewhat counterintuitively, show that vibrations parallel to the c-axis channels are significantly more hindered than those perpendicular to the channels. The effective potential for vibrations in the c direction is harder than the potential in directions perpendicular to it. There is evidence of single-file diffusion of water molecules along the channels at higher temperatures, but below 150 K this diffusion is strongly suppressed. No such suppression, however, has been observed in the channel-perpendicular direction. Inelastic neutron scattering spectra include an intramolecular stretching O-H peak at 465 meV. As this is nearly coincident with that known for free water molecules and approximately 30 meV higher than that in liquid water or ice, this suggests that there is no hydrogen bonding constraining vibrations between the channel water and the beryl structure. However, dielectric spectroscopic measurements at higher temperatures and lower frequencies

  7. The Influence of Exotic Calcite on the Mechanical Behavior of Quartz Bearing Fault Gouge

    Science.gov (United States)

    Carpenter, B. M.; Di Stefano, G.; Collettini, C.

    2014-12-01

    The interseismic recovery of frictional strength is a fundamental part of the seismic cycle. This restrengthening, and related phenomena, plays a key role in determining the stability and mode of tectonic faulting. Recent experimental data has shown that gouge mineralogy has a strong influence on the rate of frictional healing, with calcite-dominated gouges showing the highest rates. Combining these data with widespread observations of calcite as cement or veins in non-carbonate hosted faults, indicates that the presence of calcite within a fault gouge could play an important role in shallow- and mid-crustal earthquakes. We report on laboratory experiments designed to explore the mechanical behavior of quartz/calcite mixtures as a means to better understand the evolution of fault behavior in faults where carbonate materials are present. We sheared mixtures of powdered Carrara marble (>98% CaCO3) and disaggregated Ottawa sand (99.8% SiO2) at constant normal stress of 5 MPa under saturated conditions at room temperature. We performed slide-hold-slide tests, 1-3,000 seconds, and velocity stepping tests, 0.1-1000 μm/s, to measure the amount of frictional healing and velocity dependence of friction respectively. Small subsets of experiments were conducted at different boundary conditions. Preliminary results show that the presence of calcite in quartz-based fault gouge has a hardening effect, both in overall frictional strength, where the strength of our mixtures increases with increasing calcite content, and in single experiments, where mixtures with low percentages of calcite show a consistent strain-hardening trend. We also observe that the rates of frictional healing and creep relaxation increase with increasing calcite content. Finally, our results show that the addition of as little as 2.5% calcite within a fault gouge results in a 30% increase in the rate of frictional healing, with further increases in calcite content resulting in larger increases in the rate

  8. Analyzing Orientations

    Science.gov (United States)

    Ruggles, Clive L. N.

    Archaeoastronomical field survey typically involves the measurement of structural orientations (i.e., orientations along and between built structures) in relation to the visible landscape and particularly the surrounding horizon. This chapter focuses on the process of analyzing the astronomical potential of oriented structures, whether in the field or as a desktop appraisal, with the aim of establishing the archaeoastronomical "facts". It does not address questions of data selection (see instead Chap. 25, "Best Practice for Evaluating the Astronomical Significance of Archaeological Sites", 10.1007/978-1-4614-6141-8_25) or interpretation (see Chap. 24, "Nature and Analysis of Material Evidence Relevant to Archaeoastronomy", 10.1007/978-1-4614-6141-8_22). The main necessity is to determine the azimuth, horizon altitude, and declination in the direction "indicated" by any structural orientation. Normally, there are a range of possibilities, reflecting the various errors and uncertainties in estimating the intended (or, at least, the constructed) orientation, and in more formal approaches an attempt is made to assign a probability distribution extending over a spread of declinations. These probability distributions can then be cumulated in order to visualize and analyze the combined data from several orientations, so as to identify any consistent astronomical associations that can then be correlated with the declinations of particular astronomical objects or phenomena at any era in the past. The whole process raises various procedural and methodological issues and does not proceed in isolation from the consideration of corroborative data, which is essential in order to develop viable cultural interpretations.

  9. Molecular dynamics simulation of adsorption of an oil-water-surfactant mixture on calcite surface

    Institute of Scientific and Technical Information of China (English)

    Lu Guiwu; Zhang Xuefen; Shao Changjin; Yang Hong

    2009-01-01

    An interface super molecular structure model for oil-water-surfactant mixture and calcite was established. By using a molecular dynamics method, the effects of rhamnolipid, sodium dodecyl benzene sulfonate and sodium hexadecyl sulfonate on the interface adsorption behavior of oil molecules were investigated. It was found that these three surfactants could reduce oil-calcite interface binding energy, and play a role of oil-displacing agent.

  10. Origin of sulfate in barite and calcite cements in the Jebel Madar salt dome (Oman)

    Science.gov (United States)

    Vandeginste, V.; John, C. M.; Gilhooly, W. P.

    2012-12-01

    Jebel Madar is a 500-m high mountain rising in the desert at the Oman Foothills. The Jebel consists of Triassic to Cretaceous carbonate host rocks forming the carapace of a salt dome. Halokinesis caused major fracturing and faulting at Jebel Madar, and the resulting structures acted as the main pathways for fluids that generated diagenetic cements composed of both barite and calcite. The spatial distribution of calcite and barite occurrences shows that calcite is formed in large abundance along the three main faults, whereas barite is more concentrated along faults further away from the three main ones. The stable carbon and oxygen isotope composition of calcite and fluid inclusion data from both calcite and barite show a distinct evolution of the fluid with a highly saline component towards more mixing with meteoric water. This is in agreement with clumped isotopes data on calcite cements indicating an evolution towards lower temperatures, consistent with doming of the Jebel and greater input of lower-temperature descending meteoric fluids. Here, we present sulphur and oxygen isotopic data on barite that suggest a link between the barite formation and the Precambrian salt underlying Jebel Madar. The average δ34S measured in barite is 33‰ CDT (1σ = 5‰; n = 33), which falls at the lower end of the δ34S range reported for the Ara Group anhydrite. The average δ18O in the same barite samples is 23‰ VSMOW (1σ = 2‰; n = 33). Data from the barite will be compared with sulphur isotopes from the carbonate-associate sulfate in the calcite cements. The overall goal of our research is to gain a better insight in the formation process of barite and calcite in Jebel Madar and its link with salt tectonics. We would like to acknowledge the financial support of QCCSRC (funded jointly by Qatar Petroleum, Shell and the Qatar Science & Technology Park) and the GSA Laubach fund for this study.

  11. The coordination of sulfur in synthetic and biogenic Mg calcites: The red coral case

    Science.gov (United States)

    Perrin, J.; Rivard, C.; Vielzeuf, D.; Laporte, D.; Fonquernie, C.; Ricolleau, A.; Cotte, M.; Floquet, N.

    2017-01-01

    Sulfur has been recognized in biogenic calcites for a long time. However, its structural position is matter of debate. For some authors, sulfur is a marker of the organic matrix while it is part of the calcite structure itself for others. To better understand the place of sulfur in calcite, sulfated magnesian calcites (S-MgCalcite) have been synthetized at high pressure and temperature and studied by μ-XANES spectroscopy. S-MgCalcite XANES spectra show two different types of sulfur: sulfate (SO42-) as a predominant species and a small contribution of sulfite (SO32-), both substituting for carbonate ions in the calcite structure. To address the question of the position of sulfur in biogenic calcites, the oxidation states of sulfur in the skeleton and organic tissues of Corallium rubrum have been investigated by micro X-ray fluorescence (μ-XRF) and sulfur K-edge micro X-ray absorption near edge structure (μ-XANES) spectroscopy at the European Synchrotron Radiation Facility (ESRF, Grenoble, France) on beamline ID21. In the skeleton, sulfur is mainly present as oxidized sulfur SO42- (+VI), plus a weak sulfite contribution. XANES spectra indicate that sulfur is inorganically incorporated as sulfur structurally substituted to carbonate ions (SSS). Although an organic matrix is present in the red coral skeleton, reduced organic sulfur could not be detected by μ-XANES spectroscopy in the skeleton probably due to low organic/inorganic sulfur ratio. In the organic tissues surrounding the skeleton, several sulfur oxidation states have been detected including disulfide (S-S), thioether (R-S-CH3), sulfoxide (SO2), sulfonate (SO2O-) and sulfate (SO42-). The unexpected occurrence of inorganic sulfate within the organic tissues suggests the presence of pre-organized organic/inorganic complexes in the circulatory system of the red coral, precursors to biomineralization ahead of the growth front.

  12. The mechanical and microstructural behaviour of calcite-dolomite composites: An experimental investigation

    OpenAIRE

    Kushnir, Alexandra R. l.; Kennedy, L. A.; Misra, Santanu; Benson, Philip; White, J C

    2015-01-01

    The styles and mechanisms of deformation associated with many variably dolomitized limestone shear systems are strongly controlled by strain partitioning between dolomite and calcite. Here, we present experimental results from the deformation of four composite materials designed to address the role of dolomite on the strength of limestone. Composites were synthesized by hot isostatic pressing mixtures of dolomite (Dm) and calcite powders (% Dm: 25%-Dm, 35%-Dm, 51%-Dm, and 75%-Dm). In all comp...

  13. Sturgeon and paddlefish (Acipenseridae) sagittal otoliths are composed of the calcium carbonate polymorphs vaterite and calcite.

    Science.gov (United States)

    Pracheil, B M; Chakoumakos, B C; Feygenson, M; Whitledge, G W; Koenigs, R P; Bruch, R M

    2017-02-01

    This study sought to resolve whether sturgeon (Acipenseridae) sagittae (otoliths) contain a non-vaterite fraction and to quantify how large a non-vaterite fraction is using neutron diffraction analysis. This study found that all otoliths examined had a calcite fraction that ranged from 18 ± 6 to 36 ± 3% by mass. This calcite fraction is most probably due to biological variation during otolith formation rather than an artefact of polymorph transformation during preparation.

  14. Chiral morphology of calcite through selective binding of amino acids

    Science.gov (United States)

    Orme, Christine

    2002-03-01

    Many living organisms contain biominerals and composites with finely tuned properties, reflecting a remarkable level of control over the nucleation, growth and shape of the constituent crystals. Peptides and proteins play an important role in achieving this control. Using in situ AFM we find that site-specific binding of amino acid residues to surface steps changes the step-edge free energies, giving rise to direction-specific binding energies unique to individual amino acid enantiomers and leading to chiral modifications that propagate from atomic length scales to macroscopic length scales. Molecular modeling studies support an energetic basis for the differences in binding. Our results emphasize that the mechanism under-lying crystal modification through organic molecules is best understood by considering both stereochemical recognition as well as the effects of binding on the interfacial energies of the growing crystal.

  15. Reaction-induced fracturing in a hot pressed calcite-periclase aggregate

    Science.gov (United States)

    Kuleci, H.; Ulven, O. I.; Rybacki, E.; Wunder, B.; Abart, R.

    2017-01-01

    The chemo-mechanical feedbacks associated with hydration of periclase immersed in a calcite matrix were investigated experimentally. Dense calcite-periclase aggregates with calcite to periclase ratio of 90/10 and 95/5 by volume were prepared by hot isostatic pressing. Subsequent hydration experiments were performed in a hydrothermal apparatus at temperatures of 580-610 °C and a pressure of 200 MPa for run durations of 5-60 min. The rate of the periclase to brucite transformation was primarily controlled by the access of fluid. Where fluid was present, the reaction was too fast for the associated positive volume increase of the solids of about 100% to be accommodated by creep of the calcite matrix, and fracturing was induced. The newly formed cracks greatly enhanced the access of fluid leading to a positive feedback between hydration and fracturing. Mostly the newly formed cracks follow pre-existing grain boundaries in the calcite matrix. Comparison of experimental results with numerical 2D discrete element modelling (DEM) of crack formation revealed that the geometry of the crack pattern around a reacting particle depends on the shape of the original periclase particle, on the mechanical strength of the particle-matrix interface and on the mechanical strength and arrangement of grain boundaries in the calcite matrix in the immediate vicinity of the swelling particle.

  16. Ion beam modifications of defect sub-structure of calcite cleavages

    Indian Academy of Sciences (India)

    E Venkateshwar Rao; M Ramakrishna Murthy

    2008-04-01

    Experimental investigations on the defect sub-structure and surface modifications, brought about by He+ ion-bombardment of calcite cleavages (100), have been carried out. Optical and scanning electron microscopic investigations revealed drastic modifications on the surface morphology, local symmetry and defect concentration. Additional structural defects on ion-bombardment of calcite surfaces also have been observed. Changes in shape and form of chemical etch pits are found to be a function of ion-beam energy, as studied by optical microscopy. Radiation damage in calcite has been attributed mainly due to desorption of CO$^{-2}_{3}$ ions from the calcite surfaces, on irradiation. Measurements of surface conductivity on irradiated calcite surfaces have been made employing a four-probe technique. Enhancement of surface conductivity has been considered to be due to an increase in concentration of CO$^{-2}_{3}$ ions formed, on ion irradiation and subsequent thermal stimulation. Planar plastic anisotropy has been studied on irradiated calcite cleavages by measurement of microhardness.

  17. NMR characterization of hydrocarbon adsorption on calcite surfaces: A first principles study

    Energy Technology Data Exchange (ETDEWEB)

    Bevilaqua, Rochele C. A.; Miranda, Caetano R. [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, UFABC, Santo André, SP (Brazil); Rigo, Vagner A. [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, UFABC, Santo André, SP (Brazil); Universidade Tecnológica Federal do Paraná, UTFPR, Cornélio Procópio, PR (Brazil); Veríssimo-Alves, Marcos [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, UFABC, Santo André, SP (Brazil); Departamento de Física, ICEx, Universidade Federal Fluminense, UFF, Volta Redonda, RJ (Brazil)

    2014-11-28

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca{sup 2+}. Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO{sub 3} (101{sup ¯}4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for {sup 43}Ca, {sup 13}C, and {sup 17}O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated.

  18. Low-Temperature Plasticity of Naturally Deformed Calcite Rocks

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Optical, cathodoluminescence and transmission electron microscope (TEM) analyses were conducted onfour groups of calcite fault rocks, a cataclastic limestone, cataclastic coarse-grained marbles from two fault zones, and afractured mylonite. These fault rocks show similar microstructural characteristics and give clues to similar processes ofrock deformation. They are characterized by the structural contrast between macroscopic cataclastic (brittle) andmicroscopic mylonitic (ductile) microstructures. Intragranular deformation microstructures (i.e. deformation twins, kinkbands and microfractures) are well preserved in the deformed grains in clasts or in primary rocks. The matrix materials areof extremely fine grains with diffusive features. Dislocation microstructures for co-existing brittle deformation andcrystalline plasticity were revealed using TEM. Tangled dislocations are often preserved at the cores of highly deformedclasts, while dislocation walls form in the transitions to the fine-grained matrix materials and free dislocations, dislocationloops and dislocation dipoles are observed both in the deformed clasts and in the fine-grained matrix materials. Dynamicrecrystallization grains from subgrain rotation recrystallization and subsequent grain boundary migration constitute themajor parts of the matrix materials. Statistical measurements of densities of free dislocations, grain sizes of subgrains anddynamically recrystallized grains suggest an unsteady state of the rock deformation. Microstructural andcathodoluminescence analyses prove that fluid activity is one of the major parts of faulting processes. Low-temperatureplasticity, and thereby induced co-existence of macroscopic brittle and microscopic ductile microstmctures are attributedto hydrolytic weakening due to the involvement of fluid phases in deformation and subsequent variation of rock rheology.During hydrolytic weakening, fluid phases, e.g. water, enhance the rate of dislocation slip and climb, and

  19. Preparation of highly (001)-oriented photoactive tungsten diselenide (WSe{sub 2}) films by an amorphous solid-liquid-crystalline solid (aSLcS) rapid-crystallization process

    Energy Technology Data Exchange (ETDEWEB)

    Bozheyev, Farabi; Friedrich, Dennis; Nie, Man; Rengachari, Mythili; Ellmer, Klaus [Helmholtz-Zentrum Berlin fuer Materialien und Energie, Institute for Solar Fuels, Hahn-Meitner-Platz 1, 14109, Berlin (Germany)

    2014-09-15

    Highly (001)-textured tungsten diselenide WSe{sub 2} thin films have been prepared by a two-step process on quartz glass and TiN metallic back contacts, respectively. At first, X-ray amorphous, selenium-rich WSe{sub 2+x} films were deposited by reactive magnetron sputtering at room temperature onto a thin metal promoter film (Ni or Pd) and afterwards annealed in an H{sub 2}Se/Ar atmosphere. X-ray diffraction and scanning electron microscopy show that highly (001)-oriented WSe{sub 2} films can be grown, which is caused by the formation of liquid promoter-metal selenide droplets which dissolve tungsten or tungsten selenide at temperatures, higher than the eutectic temperature in the promoter metal-selenium system, followed by oversaturation and eventually crystallization of WSe{sub 2} platelets. Time-resolved microwave conductivity measurements show that the films are photoactive. The sum of the carrier mobilities of the best films μ{sub e} + μ{sub h} is in the range of 1-7 cm{sup 2} V{sup -1} s{sup -1}. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Pyroelectricity and Spontaneous Polarization in [111] Oriented 0.955 Pb(Zn1/3Nb2/3)O3-0.045PbTiO3 Single Crystals

    Institute of Scientific and Technical Information of China (English)

    SHEN Ming-Rong; YAO Dong-Lai; CAO Wen-Wu

    2005-01-01

    @@ We report that the measurements of the pyroelectric current of the pre-poled [111]-oriented 0. 955 Pb(Zn1/3Nb2/3)O3-0.045 PbTiO3 (PZN-4.5%PT) single crystals can shed some light on the phase transition and spontaneous polarization characters of this material in a similar way to measures of remanent polarization and dielectric properties. The pyroelectric current is measured and the corresponding spontaneous polarization is calculated as a function of temperature with various poling fields added during cooling the sample from 200℃ to room temperature. Critical electric field of 0.061 k V/cm is found to be essential to induce the intermediate ferroelectric orthorhombic phase between the ferroelectric rhombohedral and tetragonal phases. Below the critical field, the polarization increases almost linearly with the increase of poling field. At the critical field, the polarization at 30℃ increases abruptly from 14μC/cm2 for a poling field of 0.06kV/cm to 29.5μC/cm2 for a poling field of 0.061 kV/cm, and afterwards, increases slowly and saturates to 31 μC/cm2 for poling fields beyond 0.55 kV/cm.

  1. 基于蜡晶磁取向的原油磁防蜡机理研究%Study of Crude Oil Magnetic Paraffin Control Mechanism Based on Magnetic Orientation of Wax Crystals

    Institute of Scientific and Technical Information of China (English)

    张伟伟; 段玥晨; 李霞; 张广玉; 张三川

    2016-01-01

    In the process of oil production, wax deposition often occurs on the pipe wall and impedes the normal production in the oilfield. Magnetic paraffin control is a highly effi-cient and clean method for wax inhibition and viscosity reduction of crude oil,but its mecha-nism is still not clarified until now.In order to reveal the microscopic mechanism of magnetic paraffin control, the energy transition mechanism of magnetic treatment has been investigated based on magnetic-field-induced molecular reorientation mechanism.Furthermore,the ef-fect of magnetic field on the orientation of paraffin molecules was also analyzed.Results show that diamagnetic anisotropy is the reason that macromolecular wax could respond to magnetic treatment.In addition,the ordered structure of paraffin molecules can enhance magnetic ef-fect of molecular reorientation significantly. Magnetic orientation can produce three kinds of effects,that is,reduce the wax crystal granularity,orientation arrangement and form the or-derly flow of oil flow,etc.A combination of these three aspects will be significant inhibiting the production of wax crystal network structure, which results in the gelation temperature decrease,low temperature crude oil liquidity increased.%采油生产过程中油管内壁极易结蜡结垢,清防蜡一直是困扰油田正常生产的技术难题。磁防蜡作为一种节能高效的原油防蜡技术,在油田防蜡降黏方面得到了越来越广泛的应用,但是原油磁防蜡的机理至今仍未明确。为揭示原油磁防蜡的微观作用机理,在“磁致分子取向”机理的基础上,探讨磁场作用于原油时的能量转化机制,并据此研究磁场对原油中蜡分子的取向作用规律。结果表明:分子抗磁各向异性是原油中的高分子蜡成分能够响应磁场作用的根源,而蜡分子的有序聚集结构又显著增强了磁场对蜡的取向作用。磁取向作用能够产生三种效

  2. Thermal and Evolved Gas Behavior of Calcite Under Mars Phoenix TEGA Operating Conditions

    Science.gov (United States)

    Ming, D.W.; Niles, P.B.; Morris, R.V.; Boynton, W.V.; Golden, D.C.; Lauer, H.V.; Sutter, B.

    2009-01-01

    The Mars Phoenix Scout Mission with its diverse instrument suite successfully examined several soils on the Northern plains of Mars. The Thermal and Evolved Gas Analyzer (TEGA) was employed to detect organic and inorganic materials by coupling a differential scanning calorimeter (DSC) with a magnetic-sector mass spectrometer (MS). Martian soil was heated up to 1000 C in the DSC ovens and evolved gases from mineral decomposition products were examined with the MS. TEGA s DSC has the capability to detect endothermic and exothermic reactions during heating that are characteristic of minerals present in the Martian soil. Initial TEGA results indicated the presence of endothermic peaks with onset temperatures that ranged from 675 C to 750 C with corresponding CO2 release. This result suggests the presence of calcite (CaCO3. CaO + CO2). Organic combustion to CO2 is not likely since this mostly occurs at temperatures below 550 C. Fe-carbonate and Mg-carbonate are not likely because their decomposition temperatures are less than 600 C. TEGA enthalpy determinations suggest that calcite, may occur in the Martian soil in concentrations of approx.1 to 5 wt. %. The detection of calcite could be questioned based on previous results that suggest Mars soils are mostly acidic. However, the Phoenix landing site soil pH was measured at pH 8.3 0.5, which is typical of terrestrial soils where pH is controlled by calcite solubility. The range of onset temperatures and calcite concentration as calculated by TEGA is poorly con-strained in part because of limited thermal data of cal-cite at reduced pressures. TEGA operates at calcite literature thermal data was obtained at 1000 mbar or higher pressures.

  3. Effect of Mg on the Grain Growth and Dislocation Creep of Calcite

    Science.gov (United States)

    Xu, L.

    2004-12-01

    We tested the effect of variations in the amount of the solute impurity (Mg) on grain growth and strength of calcite aggregate. Synthetic marbles were produced by hot isostatic pressing mixtures of powders of calcite and dolomite at 850° C and 300 MPa confining pressure for different intervals (2 to 30 hrs). The HIP treatment resulted in homogeneous aggregates of calcite with Mg content from 0.5 to 17 mol%. Stress stepping tests and constant strain rate tests were used to examine the effect of Mg content on the dislocation creep of calcite. The grain growth rate under static conditions was decreased with Mg content from 7 to 17 mol%, indicating perhaps that grain boundary mobility is suppressed by the solute drag effect. In the diffusion creep at stresses below 40 Mpa, the strength of calcite decreases with increasing Mg content owing to the difference in grain size at 800° C and 300 MPa confining pressure. The contribution of dislocation creep increases with increasing stress, and the transition between diffusion and dislocation creep occurs at higher stresses for the samples with higher magnesium content and smaller grain size. The creep data were fit assuming a composite flow law consisting of a linear combination of diffusion and dislocation creep and a single-valued grain size. The best agreement was obtained by using a dislocation creep law with exponential dependence of strain rate on stress (e.g. Peierls law). More evidence from microstructure is needed to identify the dominant deformation mechanism conclusively. Most of the samples were compressed up to strains of 0.25; small recrystallized grains are formed resulting in a bimodal grain size distribution in some of the deformed samples. Preliminary data shows that the recrystallized grain sizes are smaller for Mg-calcite compared with that of pure calcite. This study will help to understand the effect of impurities on grain-growth kinetics and strain weakening in localized shear zones.

  4. The influence of final repository relevant electrolyte on the interaction of trivalent lanthanides and actinides with calcite; Der Einfluss endlagerrelevanter Elektrolyte auf die Wechselwirkung dreiwertiger Lanthanide und Actinide mit Calcit

    Energy Technology Data Exchange (ETDEWEB)

    Hofmann, Sascha

    2015-10-21

    Calcite, a naturally occurring and very abundant mineral, is considered a potential retentive geochemical barrier regarding nuclear waste disposal. In this work, the reactivity of calcite towards trivalent Ln and An has been determined by spectroscopic, microscopic and X-ray scattering techniques. This, in connection with the use of luminescent probes Eu(III) and Cm(III), allowed for the understanding of electrolyte influences on the retention potential of calcite.

  5. Orienteering club

    CERN Document Server

    Club d'orientation

    2015-01-01

    Course d'orientation La reprise des courses d’orientation était attendue dans la région puisque près de 150 coureurs ont participé à la première épreuve automnale organisée par le club d’orientation du CERN sur le site de La Faucille. Les circuits ont été remportés par Yann Locatelli du club d’Orientation Coeur de Savoie avec 56 secondes d’avance sur Damien Berguerre du club SOS Sallanches pour le parcours technique long, Marie Vuitton du club CO CERN (membre également de l’Equipe de France Jeune) pour le parcours technique moyen avec presque 4 minutes d’avance sur Jeremy Wichoud du club Lausanne-Jorat, Victor Dannecker pour le circuit technique court devant Alina Niggli, Elliot Dannecker pour le facile moyen et Alice Merat sur le facile court, tous membres du club O’Jura. Les résultats comp...

  6. A ubiquitous hydrothermal episode recorded in the sheet-crack cements of a Marinoan cap dolostone of South China: Implication for the origin of the extremely 13C-depleted calcite cement

    Science.gov (United States)

    Zhou, Guanghong; Luo, Taiyi; Zhou, Mingzhong; Xing, Lecai; Gan, Tian

    2017-02-01

    Sheet-crack - primarily filled with chalcedony, quartz and calcite - is a type of significant sedimentary structure in almost all documented cap carbonates in platform-to-slope settings, which sharply overlie the global Marinoan (∼635 Ma) glacial tillite. The Jiulongwan section, located in the Yangtze Gorges areas, South China, is significant for the first discovery of extremely 13C-depleted (δ13C down to -41‰) calcite cements in sheet-crack structure (Jiang et al., 2003a), which provides direct evidence for the methane seep hypothesis (Kennedy et al., 2001). Focusing on the calcite cements in the same section, Bristow et al. (2011) proposed a hydrothermal origin based on high temperatures (378 °C) determined by carbonate clumped isotope thermometry (CCIT). In this study, we provide evidence for the hydrothermal model using fluid inclusion technology (FIT) to quartz cements in the Jiulongwan section. The widespread sheet-crack structures in South China have uniform mineral paragenetic assemblages, which apparently reflect three stages of a hydrothermal fluid activity, including dolomitization at the early stage, silicification comprising chalcedony and quartz at the middle stage, and calcitization characterized by carbonaceous calcite filling preexisting voids at the late stage. Primary aqueous fluid inclusions from quartz crystals have homogenization temperatures of approximately 160-220 °C (mean, 192 °C, n = 31), while the salinity histogram contains two peaks at low salinity (6.3-8.3 wt.% NaCl equiv.) and high salinity (18.0-20.8 wt.% NaCl equiv.), reflecting precipitation caused by mixing of high- and low-salinity fluids. A modified and detailed hydrothermal model is proposed indicating that the sheet-crack structure resulted from successive thermal fluid activity after karstic dissolution due to postglacial isostatic rebound. This model is compatible with the unified sequence of glacio-eustatic events after the termination of Marinoan glaciation (Zhou

  7. Templated CaCO3 Crystallization by Submicrometer and Nanosized Fibers.

    Science.gov (United States)

    Neira-Carrillo, Andrónico; Gentsch, Rafael; Börner, Hans G; Acevedo, Diego Fernando; Barbero, Cesar Alfredo; Cölfen, Helmut

    2016-09-01

    Electrospun submicrometer-sized poly(ε-caprolactone) (PCL) meshes and nanosized multiwalled carbon nanotubes (MWCNTs) were used as a template for preparing porous and interconnected inorganic-organic hybrid materials composed of CaCO3. Herein, we describe the proportion and incorporation method of submicrometer-sized plasma-treated PCL meshes over areas >1 mm(2) with CaCO3 using three crystallization methods including the use of poly(acrylic acid) (PAA). We found that flexible and rigid acid-functionalized MWCNTs showed a clear capacity and effects to penetrate calcite particles. MWCNTs interacted differently with the individual growth planes of CaCO3, indicating that fibers can undergo changes depending on sulfonate or carboxylate groups, adopt different orientations in solution, and thereby elicit changes in CaCO3 morphology. In summary, the use of PCL and acidic MWCNT fibers as an additive for substrate templates and experimental crystallization provides a viable approach for studying various aspects of biomineralization, including the production of controlled particles, control of porosities, and defined morphologies at microscale and nanoscale levels.

  8. Radiation does response of calcium carbonate crystal in marine shells samples

    Directory of Open Access Journals (Sweden)

    Changkian, S.

    2002-01-01

    Full Text Available A study of the evolution of element, crystal structure and thermoluminescence signal versus gamma irradiation dose were carried out for calcite shells samples. The composition of element was studied by X-ray fluorescence spectrometer. As identified by X-ray diffraction and SEM/EDS analysis, two polymorphs of calcium-carbonate were extracted: calcite and aragonite. The evolution of TL signal versus gamma irradiation dose using the TL reader (Harshaw 2000 was initially dependent on crystal structure and fading effect of the thermoluminescence signal .

  9. Selective Separation of Fluorite, Barite and Calcite with Valonea Extract and Sodium Fluosilicate as Depressants

    Directory of Open Access Journals (Sweden)

    Zijie Ren

    2017-02-01

    Full Text Available Fluorite, barite and calcite are important industry minerals. However, they often co-exist, presenting difficulty in selectively separating them due to their similar surface properties. In this study, valonea extract and sodium fluosilicate were used as depressants to selectively separate them by flotation, with sodium oleate as the collector. The single mineral flotation results showed that valonea extract displayed the strongest depression on calcite, while sodium fluosilicate displayed the strongest depression on barite. These two depressants allowed selective separation of the three minerals through sequential flotation. The flotation of mixed minerals showed that 94% of the calcite was successfully depressed by the valonea extract, and 95% recovery of the fluorite was achieved in the subsequent flotation with sodium fluosilicate depressing barite. The different depressant–mineral interactions were investigated via electro-kinetic studies and molecular dynamics (MD simulations using the Materials Studio 6.0 program. The valonea extract exhibited the strongest adsorption on the calcite surface, and sodium fluosilicate exhibited the strongest adsorption on the barite surface, which prevented oleate species from reacting with Ca2+ or Ba2+ surface sites. This study provides useful guidance for how to process fluorite, barite and calcite resources.

  10. Phosphorus speciation in calcite speleothems determined from solid-state NMR spectroscopy

    Science.gov (United States)

    Mason, Harris E.; Frisia, Silvia; Tang, Yuanzhi; Reeder, Richard J.; Phillips, Brian L.

    2007-02-01

    Variations in speleothem P concentration show cyclic patterns that have important implications for high resolution palaeoclimate and palaeoenvironmental reconstructions. However, little is known about the speciation of P in calcite speleothems. Here we employ solid-state 31P and 1H magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopic techniques as a non-destructive method for analyzing the distribution of P in speleothems. The 31P MAS NMR results show three peaks indicating the presence of three primary types of phosphate species in samples from the Grotta di Ernesto (northeastern Italy): a broad peak at a chemical shift δP-31 = 3.1 to 3.7 ppm from individual phosphate ions incorporated within calcite, a narrow set of peaks near δP-31 = - 0.9 ppm from crystalline monetite and a narrow peak at δP-31 = 2.9 ppm from an unidentified crystalline phosphate phase. Essentially identical results were obtained for a synthetic calcite/phosphate coprecipitate. Spectra collected for a sample from Grotte de Clamouse (southern France) show only a broad peak near 3.5 ppm suggesting a possible limit for phosphate incorporation into the calcite structure. These data suggest that P in this system can interact to form calcium phosphate surface precipitates during infiltration events and are subsequently enclosed during calcite growth.

  11. Competitive adsorption of arsenate and phosphate onto calcite; experimental results and modeling with CCM and CD-MUSIC

    DEFF Research Database (Denmark)

    Sø, Helle Ugilt; Postma, Dieke; Jakobsen, Rasmus;

    2012-01-01

    The competitive adsorption of arsenate and phosphate onto calcite was studied in batch experiments using calcite-equilibrated solutions. The solutions had circum-neutral pH (7–8.3) and covered a wide span in the activity of Ca2+ and View the MathML source. The results show that the adsorption...... that adsorption of arsenate onto calcite is of minor importance in most groundwater aquifers, as phosphate is often present at concentration levels sufficient to significantly reduce arsenate adsorption. The CD-MUSIC model for calcite was used successfully to model adsorption of arsenate and phosphate separately...

  12. Surface Crystallization of a MgO/Y2O3/SiO2/Al2O3/ZrO2 Glass: Growth of an Oriented β-Y2Si2O7 Layer and Epitaxial ZrO2

    Science.gov (United States)

    Wisniewski, Wolfgang; Seidel, Sabrina; Patzig, Christian; Rüssel, Christian

    2017-03-01

    The crystallization behavior of a glass with the composition 54.7 SiO2·10.9 Al2O3·15.0 MgO·3.4 ZrO2·16.0 Y2O3 is studied using X-ray diffraction (XRD), scanning electron microscopy (SEM) including electron backscatter diffraction (EBSD) and (scanning) transmission electron microscopy [(S)TEM] including energy-dispersive X-ray spectrometry (EDXS). This glass shows the sole surface crystallization of four different yttrium silicates of the composition Y2Si2O7 (YS). The almost simultaneous but independent nucleation of α-, β-, δ-, and ε-YS at the surface is followed by growth into the bulk, where ε-YS quickly dominates a first crystallized layer. An accumulation of Mg at the growth front probably triggers a secondary nucleation of β-YS, which forms a thin compact layer before fragmenting into a highly oriented layer of fine grained crystals occupying the remaining bulk. The residual glass between the YS growth structures allows the crystallization of indialite, yttrium stabilized ZrO2 (Y-ZrO2) and very probably μ-cordierite during cooling. Hence, this glass basically shows the inverted order of crystallization observed in other magnesium yttrium alumosilicate glasses containing less Y2O3. An epitaxial relationship between Y-ZrO2 and ε-YS is proven and multiple twinning relationships occur in the YS phases.

  13. Orienteering Club

    CERN Document Server

    Club d'orientation

    2013-01-01

    Courses d’orientation Une bonne dizaine de clubs étaient représentés samedi dernier à La Faucille pour participer à la  2e manche de la coupe genevoise organisée par le club du CERN. Les 120 coureurs ont pu découvrir des parcours classés "technique". Ceux du Haut-Jura familiarisés à ce type de terrain ont pu sortir leur épingle du jeu et se sont octroyé la victoire sur 4 des 5 circuits. Samedi 21 septembre, la montagne du Haut-Jura était encore plébiscitée puisque les coureurs étaient attendus à Saint Cergue sur la carte des Pralies. Pour les résultats complets de La Faucille et les informations sur la prochaine étape, consultez le site du club http://cern.ch/club-orientation.

  14. Calcium carbonate crystallization in the presence of modified polysaccharides and linear polymeric additives

    Science.gov (United States)

    Matahwa, H.; Ramiah, V.; Sanderson, R. D.

    2008-10-01

    Crystallization of calcium carbonate was performed in the presence of grafted polysaccharides, polyacrylamide (PAM) and polyacrylic acid (PAA). The grafted polysaccharides gave crystal morphologies that were different from the unmodified polysaccharides but similar to the ones given by homopolymers of the grafted chains. PAM-grafted α-cellulose gave rectangular platelets that aggregated to form 'spherical' crystals on the surface of the fiber, whereas PAA grafted α-cellulose gave spherical crystals on the surface of the fiber. X-ray diffraction (XRD) spectroscopy showed that PAM-grafted α-cellulose, PAM as well as the control (no polymeric additive) gave calcite crystals at both 25 and 80 °C. However, the PAA-grafted α-cellulose and PAA homopolymer gave calcite and vaterite crystals at 25 °C with calcite and aragonite crystals along with traces of vaterite being formed at 80 °C. The fiber surface coverage by these crystals was more on the acrylic- and acrylamide-grafted cellulose than on the ungrafted α-cellulose. The evolution of CaCO 3 polymorphs as well as crystal morphology in PAA-grafted starch was similar to that of PAA-grafted α-cellulose at the two temperatures employed.

  15. Orientation Club

    CERN Multimedia

    Club d'orientation

    2014-01-01

    COURSE ORIENTATION Résultats de samedi 10 mai    C’est sur une carte entièrement réactualisée dans les bois de Versoix, que plus de 100 coureurs sont venus participer à la course d’orientation, type longue distance, préparée par des membres du club du CERN. Le terrain plutôt plat nécessitait une orientation à grande vitesse, ce qui a donné les podiums suivants :  Technique long avec 17 postes : 1er Jurg Niggli, O’Jura en 52:48, 2e Beat Muller, COLJ Lausanne-Jorat en 58:02, 3e Christophe Vuitton, CO CERN en 58:19 Technique moyen avec 13 postes : 1er Jean-Bernard Zosso, CO CERN, en 46:05 ; 2e Yves Rousselot, Balise 25 Besançon, en 55:11 ; 3e Laurent Merat, O'Jura, en 55:13 Technique court avec 13 postes : 1er Julien Vuitton, CO CERN en 40:59, 2e Marc Baumgartner, CO CERN en 43:18, 3e Yaelle Mathieu en 51:42 Su...

  16. Orienteering Club

    CERN Multimedia

    Club d'orientation

    2013-01-01

    Courses d’orientation ce printemps Le Club d’orientation du CERN vous invite à venir découvrir la course d’orientation et vous propose, en partenariat avec d’autres clubs de la région, une dizaine de courses populaires. Celles-ci ont lieu les samedis après-midi, elles sont ouvertes à tous, quel que soit le niveau, du débutant au sportif confirmé, en famille ou en individuel, en promenade ou en course. Si vous êtes débutant vous pouvez profiter d’une petite initiation offerte par l’organisateur avant de vous lancer sur un parcours. Divers types de parcours sont à votre choix lors de chaque épreuve : facile court (2-3 km), facile moyen (3-5 km), technique court (3-4 km), technique moyen (4-5 km) et technique long (5-7 km). Les dates à retenir sont les suivantes : Samedi 23 mars: Pully (Vd) Samedi 13 avril: Pougny...

  17. Effects of L-Aspartic acid on the step retreat kinetics of calcite

    Science.gov (United States)

    Yoshino, Toru; Kagi, Hiroyuki

    2012-01-01

    Effects of L-Aspartic acid (L-Asp) on step retreat kinetics in the dissolution of calcite were investigated. The step retreat velocities under surface-controlled kinetics were determined from in-situ atomic force microscopic observations using an improved flow-through system. Comparison of the present results with those obtained under a mixed kinetics condition revealed that the addition of L-Asp promotes the transport process in the calcite dissolution through acid-base and/or complex forming reactions in the diffusion boundary layer. Additionally, promotion of the acute and obtuse step retreats by the L-Asp additive was observed under surface-controlled kinetics. This report is the first to clarify that L-Asp promotes surface processes in the dissolution of calcite.

  18. A calcite permeable reactive barrier for the remediation of Fluoride from spent potliner (SPL) contaminated groundwater

    DEFF Research Database (Denmark)

    Turner, B.D.; Binning, Philip John; Sloan, S.W.

    2008-01-01

    The use of calcite (CaCO3) as a substrate for a permeable reactive barrier (PRB) for removing fluoride from contaminated groundwater is proposed and is illustrated by application to groundwater contaminated by spent potliner leachate (SPL), a waste derived from the aluminium smelting process....... The paper focuses on two issues in the implementation of calcite permeable reactive barriers for remediating fluoride contaminated water: the impact of the groundwater chemical matrix and CO2 addition on fluoride removal. Column tests comparing pure NaF solutions, synthetic SPL solutions, and actual SPL...... results show that approximately 99% of 2300 mg/L fluoride can be removed when CO2 is injected directly into the barrier. This can be compared to approximately 30-50% removal when the influent solution is equilibrated with atmospheric CO2 before contact with calcite....

  19. Coccolithophore responses to environmental variability in the South China Sea: species composition and calcite content

    Science.gov (United States)

    Jin, Xiaobo; Liu, Chuanlian; Poulton, Alex J.; Dai, Minhan; Guo, Xianghui

    2016-08-01

    Coccolithophore contributions to the global marine carbon cycle are regulated by the calcite content of their scales (coccoliths) and the relative cellular levels of photosynthesis and calcification rates. All three of these factors vary between coccolithophore species and with response to the growth environment. Here, water samples were collected in the northern basin of the South China Sea (SCS) during summer 2014 in order to examine how environmental variability influenced species composition and cellular levels of calcite content. Average coccolithophore abundance and their calcite concentration in the water column were 11.82 cells mL-1 and 1508.3 pg C mL-1, respectively, during the cruise. Water samples can be divided into three floral groups according to their distinct coccolithophore communities. The vertical structure of the coccolithophore community in the water column was controlled by the trophic conditions, which were regulated by mesoscale eddies across the SCS basin. The evaluation of coccolithophore-based calcite in the surface ocean also showed that three key species in the SCS (Emiliania huxleyi, Gephyrocapsa oceanica, Florisphaera profunda) and other larger, numerically rare species made almost equal contributions to total coccolith-based calcite in the water column. For Emiliania huxleyi biometry measurements, coccolith size positively correlated with nutrients (nitrate, phosphate), and it is suggested that coccolith length is influenced by light and nutrients through the regulation of growth rates. Larger-sized coccoliths were also linked statistically to low pH and calcite saturation states; however, it is not a simple cause and effect relationship, as carbonate chemistry was strongly co-correlated with the other key environmental factors (nutrients, light).

  20. Thickness and structure of the water film deposited from vapour on calcite surfaces

    DEFF Research Database (Denmark)

    Bohr, Jakob; Wogelius, Roy A.; Morris, Peter M.

    2010-01-01

    Synchrotron X-ray reflectivity (SXR) was used to measure the thickness of the water film that adsorbs on a {10¯14} cleavage surface of calcite (CaCO3) in a sample chamber where relative humidity could be controlled within the range from......Synchrotron X-ray reflectivity (SXR) was used to measure the thickness of the water film that adsorbs on a {10¯14} cleavage surface of calcite (CaCO3) in a sample chamber where relative humidity could be controlled within the range from...

  1. A generalised chemical precipitation modelling approach in wastewater treatment applied to calcite

    DEFF Research Database (Denmark)

    Mbamba, Christian Kazadi; Batstone, Damien J.; Flores Alsina, Xavier

    2015-01-01

    , the present study aims to identify a broadly applicable precipitation modelling approach. The study uses two experimental platforms applied to calcite